CA2250226A1 - Bleaching composition - Google Patents

Abstract

There is provided a bleaching composition having enhanced hydrophilic stain removal capability comprising a metal-containing bleach catalyst, an oxygenreleasing bleach system; and an amino tricarboxylic acid or salt thereof having general formula (I), where R1, R2, and R3 are alkyl groups or substituted alkyl groups of chain length C1 to C4; n is 0 or 1; and X is an organic substituent group.

Description

CA 022~0226 1998-09-28 W O97136991 pcTrus97lo5363 BLEACHING COMPO~ITION

Technical ~leld The present invention relates to a bleaching composition adapted for use in a cleaning method exhibiting improved soil and stain removal.

Ba~k~round to the invention Compositions designed for use in cle~ning, particularly in automatic dishwashing and laundry methods are well known and a consistent effort has been made by detergent manufacturers to improve the cle~nin~ and/or rinsing efficiency of said compositions as reflected by many patent publications.

The satisfactory removal of hydrophilic bleachable stains such as tea, coffee and red wine is a particular challenge to the formulator of a bleaching composition. The removal of tea stains is especially difficult Traditionally, the removal of such hydrophilic bleachable stains has been enabled by the use of bleach components such as oxygen bleaches, including hydrogen peroxide and organic peroxyacids. The organic peroxyacids are often obtained by the in situ perhydrolysis reaction between hydrogen peroxide and an organic peroxyacid bleach precursor.
Additionally bleaching compositions cont~ining bleach catalysts have more recently been used.

Bleach compositions including a metal cont~ining bleach catalyst, and more specifically a m~ng~n~se cor-t~ining bleach catalyst, have been described, ~ . . . .

CA 022~0226 1998-09-28 for example, in European Patent Applications Nos. EP-A-544,519, EP-A-544,490, EP-A-544,440, EP-A-458,397, EP-A-458,398 and U.S. Patents Nos. US 5,194,416, US 5,246,621 and US 5,244,594.

Whilst the general problem of the removal of hydrophilic stains has been broadly considered in the art, specific aspects of the problem are the subject of active investigation. It has been found that hard water ions (for example Ca2+ and Mg2+) present in the washing machine feed water, contribute to the difficulty in the removal of hydrophilic stains from stained articles in the wash. Chemical interactions (calcium bridges) between the hard water ions and the hydrophilic soils are believed to makes the soils harder to remove.

It has now surprisingly been found that enh~nrerl removal of stains, particularly hydrophilic stains from the surface of wash articles can be achieved by a bleaching composition cont~ining an amino tricarboxylic acid (ATCA) and a metal-cont~inin~ bleach catalyst.

It is thus an objective of this invention to provide a bleaching composition comprising a metal-cont~ining bleach catalyst, a peroxygen bleach and an amino tricarboxylic acid exhibiting improved soil and stain removal.

S~lmm~ry of the invention According to the present invention there is provided a ble~çhing composition comprising (a) a metal-cont~ining bleach catalyst;

(b) an oxygen-releasing bleach system; and (c) an amino tricarboxylic acid or salt thereof wherein said amino tricarboxylic acid has the general formula:

CA 022~0226 1998-09-28 N - CH --- (R3) - C OH

where R1, R2 and R3 are alkyl groups or substituted alkyl groups of chain length C1 to C4; n is 0 or 1; and X is an organic substituent group.

Detailed Description of the Invention The present invention relates to a bleaching composition adapted for use in a cleaning method, exhibits improved soil and stain removal.

Metal-cont~ining bleach catalyst The bleach compositions described herein has as an essential component a metal cont~inin~ bleach catalyst. Preferably the metal cont~inin~ bleach catalyst is a transition metal cont~inin~ bleach catalyst, more preferably a m~n~nese or cobalt-cont~inin~ bleach catalyst.

A suitable type of bleach catalyst is a catalyst comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or all-minl~m cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylene~ minetetraacetic acid, ethylene(li~min~tetra(methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S.
Pat. 4,430,243.

Preferred types of bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include MnIV2(u-0)3(1,4,7-trimethyl-1,4,7-CA 022~0226 1998-09-28 W O 97/36991 PCTrUS97/05363 triazacyclononane)2-(PF6)2, MnIII2(u-O)l(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(ClO4)2, MnIV4(u-o)6( l ,4,7-triazacyclononane)4-(C104)2, MnIIIMnIV4(u-O)l(u-OAc)2 (1,4,7-trimethyl-1,4,7-triazacyclononane)2-(ClO4)3, and mixtures thereof. Others are described in European patent 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 the compositions herein may also be selected as appropriate for the present invention. For examples of suitable bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S.
Pat. 5,194,416 which teaches mononuclear manganese (IV) complexes such as Mn(1,4,7-trimethyl- 1,4,7-triazacyclononane)(OCH3)3 (PF6) .

Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is a water-soluble complex of m~ng~n~se (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, m~nnitol, xylithol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof.

U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand. Said li~n-ls are of the formula:

R 1 -N=c-B-c=N-R4 wherein R1, R2, R3, and R4 can each be selected from H, substituted alkyl and aryl groups such that each R1-N=C-R2 and R3-C=N-R4 forrn a five or six-membered ring. Said ring can further be substituted. B is a bridging group selected from O, S. CR5R6, NR7 and C=O, wherein R5, R6, and R7 can each be H, alkyl, or aryl groups, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, ... . .

CA 022~0226 1998-09-28 W O 97/36991 PCT~US97/05363 pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings. Optionally, said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro. Particularly preferred is the ligand 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)bispyridylamine-cobalt (II), trisdipyridyl~mine-cobalt(II) perchlorate, Co(2,2-bispyridylamine)2O2ClO4, Bis-(2,2'-bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and mixtures thereof.

Preferred examples include binuclear Mn complexes with tetra-N-dentate and bi-N-dentate ligands, including N4MnIII(u-O)2MnIVN4)+and [Bipy2MnII~(u-O)2MnIVbipy2] -(Cl04)3.

Other suitable bleach catalysts are described, for example, in European patent application, publication no. 408,131 (cobalt complex catalysts), European patent applications, publication nos.
384,503, and 306,089 (metallo-porphyrin catalysts), U.S.
4,728,455 (m~ng~n~se/multidentate ligand catalyst), U.S.
4,711,748 and European patent application, publication no.
224,952, (absorbed m~ng~nese on aluminosilicate catalyst), U.S.
4,601,845 (aluminosilicate support with manganese and zinc or m~n~osium salt), U.S. 4,626,373 (m~ng~nese/ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), German Pat.
specification 2,054,019 (cobalt chelant catalyst) C~n~ n 866,191 (llallsilion metal-cont~ining salts), U.S. 4,430,243 (chelants with m~ng~nese cations and non-catalytic metal cations), and U.S.
4,728,455 (m~n~nese gluconate catalysts).

Other preferred examples include cobalt (III) catalysts having the formula:

Co[(NH3)nM'mB bT tQqPp] Yy CA 022~0226 1998-09-28 W O 97/36991 6 PCTrUS97/05363 wherein cobalt is in the +3 oxidation state; n is an integer from 0 to 5 (preferably 4 or 5; most preferably 5); M' represents a monodentate ligand; m is an integer from 0 to 5 (preferably 1 or 2;
most preferably 1); B' represents a bidentate ligand; b is an integer from 0 to 2; T' represents a tridentate ligand; t is 0 or 1; Q is a tetradentate ligand; q is 0 or 1; P is a pentadentate ligand; p is 0 or 1; and n + m + 2b + 3t + 4q + Sp--6; Y iS one or more appropriately selected counteranions present in a number y, where y is an integer from 1 to 3 (preferably 2 to 3; most preferably 2 when Y is a -1 charged anion), to obtain a charge-balanced salt, preferred Y are selected from the group consisting of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate, and combinations thereof; and wherein further at least one of the coordination sites attached to the cobalt is labile under automatic dishwashing use conditions and the rem~ining coordination sites stabilize the cobalt under automatic dishwashing conditions such that the reduction potential for cobalt (III) to cobalt (II) under ~lk~line conditions is less than about 0.4 volts (preferably less than about 0.2 volts) versus a normal hydrogen electrode.

Preferred cobalt catalysts of this type have the formula:

[C~(NH3)n(M )m] Yy wherein n is an integer from 3 to 5 (preferably 4 or 5; most preferably 5); M' is a labile coor~in~in~ moiety, preferably selected from the group consisting of chlorine, bromine, hydroxide, water, and (when m is greater than 1) combinations thereof; m is an integer from 1 to 3 (preferably 1 or 2; most preferably 1); m+n = 6; and Y is an appropriately selected counteranion present in a number y, which is an integer from 1 to 3 (preferably 2 to 3; most preferably 2 when Y is a -1 charged anion), to obtain a charge-balanced salt.

.

CA 022~0226 1998-09-28 WO 97/36991 ~CT/US97105363 The preferred cobalt catalyst of this type useful herein are cobalt pent~mine chloride salts having the formula [Co(NH3)sCl] Yy~
and especially [Co(NH3)sCl]C12.

More preferred are the present invention compositions which utilize cobalt (III) bleach catalysts having the formula:

[Co(NH3)n(M)m(B)b] Ty wherein cobalt is in the +3 oxidation state; n is 4 or 5 (preferably S); M is one or more ligands coor~lin~te~l to the cobalt by one site;
m is 0, 1 or 2 (preferably 1); B is a ligand coordinated to the cobalt by two sites; b is 0 or 1 (preferably 0), and when b=0, then m~n = 6, and when b=1, then m=0 and n--4; and T is one or more appropriately selected counteranions present in a number y, where y is an integer to obtain a charge-b~l~n~e~l salt (preferably y is 1 to 3; most preferably 2 when T is a -1 charged anion); and wherein further said catalyst has a base hydrolysis rate constant of less than 0.23 M-l s-l (2~~C).

Preferred T are selected from the group consisting of chloride, iodide, I3-, formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PF6-, BF4-, B(Ph)4-, phosphate, phosphite, silicate, tosylate, methanesulfonate, and combinations thereof. Optionally, T can be protonated if more than one anionic group exists in T, e.g., HPo42-, HCO3-, H2PO4-, etc. Further, T may be selected from the group consisting of non-traditional inorganic anions such as anionic surfactants (e.g., linear alkylbenzene sulfonates (~AS), alkyl sulfates (AS), alkylethoxysulfonates (AES), etc.) and/or anionic polymers (e.g., polyacrylates, polymethacrylates, etc.).

The M moieties include, but are not limited to, ~or example, F-, S04-2, NCS-, SCN-, S203-2, NH3, PO43~, and carboxylates (which preferably are mono-carboxylates, but more than one CA 022~0226 1998-09-28 W O 97/36991 PCTrUS97/05363 carboxylate may be present in the moiety as long as the binding to the cobalt is by only one carboxylate per moiety, in which case the other carboxylate in the M moiety may be protonated or in its salt form). Optionally, M can be protonated if more than one anionic group exists in M (e.g., HPo42-, HCO3-, H2PO4-, HOC(O)CH2C(O)O-, etc.) Preferred M moieties are substituted and unsubstituted C1-C30 carboxylic acids having the formulas:

RC(O)O-wherein R is preferably selected from the group consisting of hydrogen and Cl-C30 (preferably C1-C1g) unsubstituted and substituted alkyl, C6-C30 (preferably C6-C1g) unsubstituted and substituted aryl, and C3-C30 (preferably Cs-Clg) unsubstituted and substituted heteroaryl, wherein substituents are selected from the group consisting of -NR'3, -NR'4+, -C(O)OR', -OR', -C(O)NR'2, wherein R' is selected from the group consisting of hydrogen and C1-C6 moieties. Such substituted R therefore include the moieties -(CH2)nOH and -(CH2)nNR'4+, wherein n is an integer from 1 to about 16, preferably from about 2 to about 10, and most preferably from about 2 to about 5.

Most preferred M are carboxylic acids having the formula above wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, straight or branched C4-C12 alkyl, and benzyl. Most preferred R is methyl. Preferred carboxylic acid M
moieties include formic, benzoic, octanoic, nonanoic, ~ec~noic, dodecanoic, malonic, maleic, succinic, adipic, phthalic, 2-ethylhexanoic, naphthenoic, oleic, palmitic, triflate, tartrate, stearic, butyric, citric, acrylic, aspartic, fumaric, lauric, linoleic, lactic, malic, and especially acetic acid.

The B moieties include carbonate, di- and higher carboxylates (e.g., oxalate, malonate, malic, succinate, maleate), picolinic acid, CA 022~0226 1998-09-28 W O 97/36991 PCTrUS97/05363 and alpha and beta amino acids (e.g., glycine, ~l~nine, beta-~l~nine, phenyl~l~nine).

Cobalt bleach catalysts useful herein are known, being described for example along with their base hydrolysis rates, in M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg.
Bioinorg. Mech., (1983), 2, pages 1-94. For example, Table 1 at page 17, provides the base hydrolysis rates (designated therein as koH) for cobalt pent~mine catalysts complexed with oxalate (koH= 2.5 x 10-4 M-l s-1 (25~C)), NCS- (koH= 5.0 x 10-4 M-1 s-1 (25~C)), formate (koH= 5.8 x 10-4 M-1 s-l (25~C)), and acetate (koH= 9.6 x 10-4 M-l s-l (25~C)). The most preferred cobalt catalyst useful herein are cobalt pent~mine acetate salts having the formula [Co(NH3)sOAc] Ty, wherein OAc represents an acetate moiety, and especially cobalt pent~mine acetate chloride, ~Co(NH3)sOAc]Cl2; as well as [Co(NH3)sOAc](OAc)2;
[Co(NH3)5OAc](PF6)2; [Co(NH3)sOAc](so4); [Co-(NH3)sOAc](BF4)2; and [Co(NH3)sOAc](NO3)2 (herein "PAC").

These cobalt catalysts are readily prepared by known procedures, such as taught for example in the Tobe article hereinbefore and the references cited therein, in U.S. Patent 4,810,410, to Diakun et al, issued March 7,1989, J. Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, W.L.
Jolly (Prentice-Hall; 1970), pp. 461-3; Inorg. Chem., 18, 1497-1502 (1979); Inor~. Chem., 21, 2881-2885 (1982); Inorg. Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Physical Chemistry, 56, 22-25 (1952); as well as the synthesis examples provided hereinafter.

These catalysts may be coprocessed with adjunct materials so as to reduce the color impact if desired for the aesthetics of the product, or to be included in enzyme-cont~inin~ particles as exemplified CA 022~0226 1998-09-28 WO 97/36991 PCT/US97/0~363 hereinafter, or the compositions may be manufactured to contain catalyst " speckles " .

Oxy~en-releasin~ bleach system An essential component of the detergent composition is an oxygen-releasing bleach system. In one preferred aspect the bleach system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound. The production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In an alternative preferred aspect a preformed organic peroxyacid is incorporated directly into the composition. Compositions cont~ining mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.

Inor~anic perhydrate bleaches The compositions in accord with the invention preferably include a hydrogen peroxide source, as an oxygen-releasing bleach. Suitable hydrogen peroxide sources irlclude the inorganic perhydrate salts.

The inorganic perhydrate salts are normally incorporated in the form of the sodium salt at a level of from 1% to 40% by weight, more preferably from 2 % to 30% by weight and most preferably from 5 % to 25 % by weight of the compositions.

Examples of inorganic perhydrate salts include perborate, percarbonate,perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are normally the alkali metal salts. The inorganic perhydrate salt may be included as the crystalline solid without additional protection. For certain perhydrate salts however, the preferred executions of such granular compositions utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product.

CA 022~0226 1998-09-28 Sodium perborate can be in the form of the monohydrate of nominal formula NaBO2H2O2 or the tetrahydrate NaBO2H2O2.3H2O.

Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates for inclusion in compositions in accordance with the invention.
Sodium percarbonate is an addition compound having a formula corresponding to 2Na2CO3.3H2O2, and is available commercially as a crystalline solid. Sodium percarbonate, being a hydrogen peroxide addition compound tends on dissolution to release the hydrogen peroxide quite rapidly which can increase the tendency for localised high bleach concentrations to arise. The percarbonate is most preferably incorporated into such compositions in a coated form which provides in-product stability.

A suitable coating material providing in product stability comprises mixed salt of a water soluble alkali metal sulphate and carbonate. Such coatings together with coating processes have previously been described in GB-1,466,799, granted to Interox on 9th March 1977. The weight ratio of the mixed salt coating material to percarbonate lies in the range from 1: 200 to 1: 4, more preferably from 1: 99 to 1: 9, and most preferably from 1:
49 to 1: 19. Preferably, the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na2SO4.n.Na2CO3 wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.

Other coatings which contain silicate (alone or with borate salts or boric acids or other inorganics), waxes, oils, fatty soaps can also be used advantageously within the present invention.

Potassium peroxymonopersulfate is another inorganic perhydrate salt of utility in the compositions herein.

CA 022~0226 1998-09-28 Peroxyacid bleach precursor Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as X-C L

where L is a leaving group and X is essentially any functionality, such that on perhydrolysis the structure of the peroxyacid produced is X - C -- OOH

Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5 ~ to 20% by weight, more preferably from 1 % to 10%
by weight, most preferably from 1.5% to 5% by weight of the compositions.

Suitable peroxyacid bleach precursor compounds typically contain one ormore N- or O-acyl groups, which precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789.
Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

Leaving ~roups The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.

W O 97/3091 13 PCTrUS97/05363 Preferred L groups are selected from the group consisting of:

--~~ - ~~Y and --0~

O ~ O

1 3 U ' R3 Y
y R3 r -O--CH=C--CH=CH2 --O--CH=C--CH=CH2 -~C--R1 ,C H2-C, Y 1~l O O
R3 o r --O--C=CHR4 , and N i--CH--R4 R3 o and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group cont~inin~ from 1 to 14 carbon atoms, R3 is an alkyl chain cont~inin~ from 1 to 8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing group.
Any of Rl, R3 and R4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium groups.

The preferred solubilizing groups are -S03-M+, -C02-M+, -S04-M+, -N +(R )~X~ and O < --N(R )3 and most preferably -S03-M and -C02-M wherein R3 is an alkyl chain cont~inin~ from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator. and X

CA 022~0226 1998-09-28 is an anion which provides 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, methylsulfate or acetate anion.

Perbenzoic acid precursor Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.

Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, including for example benzoyl oxybenzene sulfonate:

~o~SO3-Also suitable are the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, including for example:

OAc AcO ~Lo ~,OAc OAc OBz Ac = COCH3; Bz = Benzoyl Perbenzoic acid precursor compounds of the imide type include N-benzoylsuccinimide, tetrabenzoyl ethylene ~ mine and the N-benzoyl substituted ureas. Suitable imidazole type perbenzoic acid precursors include N-CA 022~0226 1998-09-28 W O 97/36991 15 PCTrUS97/05363 benzoyl imidazole and N-benzoyl benzimidazole and other useful N-acyl group-cont~ining perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Other perbenzoic acid precursors include the benzoyl diacyl peroxides, the benzoyl tetraacyl peroxides, and the compound having the formula:
O O

~0 O~COOH

Phthalic anhydride is another suitable perbenzoic acid precursor compound herein:

~0 Suitable N-acylated lactam perbenzoic acid precursors have the formula:

O Cl--CH2--ICH2 CH2~cH2 ]n wherein n is from 0 to 8, preferably from 0 to 2, and R6 is a benzoyl group.

Perbenzoic acid derivative precursors Perbenzoic acid derivative precursors provide substituted perbenzoic acids on perhydrolysis.

CA 022~0226 1998-09-28 W O 97t36991 16 PCT~US97/05363 Suitable substituted perbenzoic acid derivative precursors include any of the herein disclosed perbenzoic precursors in which the benzoyl group is substituted by essentially any non-positively charged (i.e.; non-cationic) functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl and amide groups.

A preferred class of substituted perbenzoic acid precursor compounds are the amide substituted compounds of the following general formulae:

O R5 O or R5 O O

wherein Rl is an aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is an arylene, or alkarylene group cont~inin~ from 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group con~ining 1 to 10 carbon atoms and L can be essentially any leaving group. Rl preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. R1 may be aryl, substituted aryl or alkylaryl cont~inin~ branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R2. The substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R5 is preferably H or methyl. Rl and R5 should not contain more than 18 carbon atoms in total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.

Cationic peroxyacid precursors Cationic peroxyacid precursor compounds produce cationic peroxyacids onperhydrolysis.

Typically, cationic peroxyacid precursors are formed by substitutlng the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl CA 022~0226 1998-09-28 W O 97/36991 17 PCTrUS97/05363 ammonium group, preferably an ethyl or methyl ammonium group.
Cationic peroxyacid precursors are typically present in the compositions as a salt with a suitable anion, such as for example a halide ion or a methylsulfate ion.

The peroxyacid precursor compound to be so cationically substituted maybe a perbenzoic acid, or substituted derivative there~f, precursor compound as described hereinbefore. Alternatively, the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter Cationic peroxyacid precursors are described in U.S. Patents 4,904,406;4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022;
5,106,528; U.K. 1,382,594; EP475,512, 458,396and284,292; andinJP
87-318,332.

Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.

A preferred cationically substituted benzoyl oxybenzene sulfonate is the 4-(trimethyl ammonium) methyl derivative of benzoyl oxybenzene sulfonate:

, ~4O~So3-\N+
/ \

A preferred cationically substituted alkyl oxybenzene sulfonate has theformula:

CA 022~0226 1998-09-28 ~ ,.SO
O ~ 3 " +
N

Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams, particularly trimethyl ammonium methylene benzoyl caprolactam:

o o N '-; ~, ,, , " ~
Other preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene alkyl caprolactams:

o O
~ --N~--N+ (CH2)n where n is from 0 to 12, particularly from 1 to 5.

Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl ammonium) ethyl sodium 4-sulphophenyl carbonate chloride.

Alkyl percarboxylic acid bleach precursors Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis. Preferred precursors of this type provide peracetic acid on perhydrolysis.

Preferred alkyl percarboxylic precursor compounds of the imide type include the N-,N,NlNl tetra acetylated alkylene ~ mines wherein the CA 022~0226 1998-09-28 W O 97/36991 PCTrUS97/05363 alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms.
Tetraacetyl ethylene diamine (TAED) is particularly preferred.

Other preferred alkyl percarboxylic acid precursors include sodium 3,S,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and penta acetyl glucose.

Amide substituted alkyl peroxyacid precursors Amide substituted alkyl peroxyacid precursor compounds are also suitable, including those of the following general formulae:

R 1-- C N ---R2 C L R 1 N C R2 ~ C L
O R5 0 or R5 0 0 wherein R1 is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene group cont~ining from 1 to 14 carbon atoms, and R5 is H or an alkyl group cont~inin~ 1 to 10 carbon atoms and L can be essentially any leaving group. R1 preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. Rl may be straight chain or branched alkyl corlt~ining branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R2. The substitution can include alkyl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. RS is preferably H
or methyl. Rl and R5 should not contain more than 18 carbon atoms in total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.

W O 97/36991 PCT~US97/05363 Benzoxazin or~anic peroxyacid precursors Also suitable are precursor compounds of the benzoxazin-type, as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula:
o ~N~ C R~

including the substituted benzoxazins of the type R4~[~ R, 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, alkyl amino, COOR6 (wherein R6 is H or an alkyl group) and carbonyl functions.

An especially preferred precursor of the benzoxazin-type is:

~N~C~

CA 022~0226 1998-09-28 W O 97136991 21 PCTrUS97/05363 Preformed organic peroxyacid The organic peroxyacid bleaching system may contain, in addition to, oras an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid, typically at a level of from 0.5% to 25~
by weight, more preferably from 1% to 10% by weight of the composition.

A preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:

O R5 O or R5 O o wherein Rl is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group cont~ining from 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group con~inin~ 1 to 10 carbon atoms. Rl preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. Rl may be straight chain or branched alkyl, substituted aryl or alkylaryl cont~inin,~
branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R2. The substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R5 is preferably H or methyl. Rl and R5 should not contain more than 18 carbon atoms in total. Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid, and diperoxyhex~lec~nP-lioc acid. Dibenzoyl peroxide is a preferred organic peroxyacid herein. Mono- and diperazelaic acid, mono- and diperbrassylic -acid, and N-phthaloylaminoperoxicaproic acid are also suitable herein.

CA 022~0226 1998-09-28 W O97/36991 22 PCT~US97/05363 Amino Tricarboxylic Acid (ATCA) The amino tricarboxylic acid (ATCA) is selected from the group having the general formula as shown below.
o X O

o where Rl, R2 or R3 are an alkyl group or substituted alkyl group of chain length C1 to C4. X is an organic substitutent group, that is a substituent typically encountered in organic compounds. X can thus for example be an alkyl, aryl, alkenyl or alkaryl group optionally substituted by any functionality including for example, amino, hydroxyl, amide and ether functionalities. X may also be an organic functional group including for example an amine, hydroxyl, amide, ester or ether group. X is preferably an alkyl group, most preferably a methyl or ethyl group. ATCA is preferably methyl glycine diacetic acid, that is where R1=R2= a -CH2-group and X=CH3.

ATCA can be present at levels of greater than 0.001% by weight, preferably from 0.001 ~O to 40% by weight, most preferably from 0.1% to 15 % by weight of detergent composition.

ATCA acts as a cation complexing chelant. ATCA forms water-soluble chelates with calcium, magnesium, lead, copper, zinc, cadmium, mercury, manganese, iron, aluminium and other cationic polyvalent ions. The stability constant (measured as log K MeZ) of ATCA-calcium chelate is greater than 5.0, preferably greater then 6Ø The stability constant of the CA 022~0226 1998-09-28 W O97/36991 PCT~US97/05363 23 preferred ATCA compound, methyl glycine diacetic acid (MGDA) is 7Ø
The stability constant, log K MeZ is measured in a solution of ionic strength of 0.1, at a temperature of 25~C. The figure of > 5.0 for logKMez indicates that the ratio of the concentration of the undissociated [CaATCA~] to the dissociated complex [Ca2+][ATCA3-], is ~105:1 Deter~ent Composition The bleaching composition preferably forms part of a detergent composition cont~ining detergent components selected from surfactants, other bleaching agents, ~lk~linity sources, water-soluble builder compounds, lime soap dispersants, organic polymeric compounds including polymeric dye transfer inhibiting agents, crystal growth inhibitors, heavy metal ion sequestrants, enzymes and enzyme stabilisers, corrosion inhibitors, suds suppressors, solvents, fabric softening agents, optical brighteners and hydrotropes.

Surfactant A highly preferred component of the compositions used in this invention is a surfactant system comprising surfactant selected from anionic, cationic, nonionic ampholytic and zwitterionic surfactants and mixtures thereof.
Automatic dishwashing machine products should be low foaming in character and thus the foaming of the surfactant system must be suppressed or more preferably be low foaming, typically nonionic in character. The surfactant system is typically present at a level of from 0.2% to 30~ by weight, more preferably from 0.5% to 10% by weight, most preferably from 1 % to 5 % by weight of the compositions.

A typical listing of anionic, nonionic, ampholytic and zwitterionic classes, and species of these surfactants, is given in U.S.P. 3,929,678 issued to Laughlin and Heuring on December, 30, 1975. A list of suitable cationic surfactants is given in U.S.P. 4,259,217 issued to Murphy on March 31,1981. A listing of surfactants typically included in automatic CA 022~0226 l998-09-28 W O 97/36991 PCT~US97/05363 dishwashing detergent compositions is given for example, in EP-A-0414 549 and PCT Applications Nos. WO 93/08876 and WO 93/08874 .

Nonionic surfactant Essentially any nonionic surfactants useful for detersive pulposes can be included in the compositions. Preferred, non-limiting classes of useful nonionic surfactants are listed below.

Nonionic ethoxylated alcohol surfactant The alkyl ethoxylate condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use herein. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
Particularly preferred are the condensation products of alcohols having an alkyl group cont~ining from 8 to 20 carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of alcohol.

Nonionic ethoxylated/propoxylated fatty alcohol surfactant The ethoxylated C6-C1g fatty alcohols and C6-C1g mixed ethoxylated/propoxylated fatty alcohols are suitable surfactants for use herein, particularly where water soluble. Preferably the ethoxylated fatty alcohols are the C1o-Clg ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to 50, most preferably these are the C12-C1g ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40.
Preferably the mixed ethoxylated/propoxylated fatty alcohols have an alkyl chain length of from 10 to 18 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to 10.

CA 022'70226 1998-09-28 Nonionic EO/PO condensates with propylene ~Iycol The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use herein. The hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility. Examples of compounds of this type include certain of the commercially-available PluronicTM surfactants, marketed by BASF.

Nonionic EO condensation products with propylene oxide/ethvlene cli~mine adducts The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenef~ mine are suitable for use herein. The hydrophobic moiety of these products consists of the reaction product of ethylen~ mine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000.
Examples of this type of nonionic surfactant include certain of the comrnercially available TetronicTM compounds, marketed by BASF.

Anionic surfactant Essentially any anionic surfactants useful for detersive purposes are suitable. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di-and triethanol~mine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are preferred.

Other anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl -succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and llnc~ rated C12-C18 monoesters) diesters of sulfosuccinate (especially saturated and llnc~ rated C6-C14 diesters), N-acyl sarcosinates.

CA 022~0226 1998-09-28 W O 97/36991 PCT~US97/05363 Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.

Anionic sulfate surfactant Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the Cs-C17 acyl-N-(C1-C4 alkyl) and -N-(C1-C2 hydroxyalkyl) gl~lc~mine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).

Alkyl sulfate surfactants are preferably selected from the linear and branched primary C10-cl8 alkyl sulfates, more preferably the C1 1-Cls branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.

Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C1o-Clg alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C11-C1g, most preferably C11-Cls alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.

A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.

Anionic sulfonate surfactant Anionic sulfonate surfactants suitable for use herein include the salts of Cs-C20 linear alkylbenzene sulfonates. alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl CA 022~0226 1998-09-28 W O97/36991 PCTrUS97/05363 glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.

Anionic carboxylate surfactant Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.

Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH20)X CH2C00-M+ wherein R is a C6 to Clg alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M
is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHR1-CHR2-O)-R3 wherein R is a C6 to Clg alkyl group, x is from 1 to 25, Rl and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.

Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon. Preferred secondary soap surf~ct~nt~ for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps may also be included as suds suppressors.

Alkali metal sarcosinate surfactant Other suitable anionic surfactants are the alkali metal sarcosinates offormula R-CON (R1) CH2 COOM, wherein R is a Cs-C17 linear or branched alkyl or alkenyl group, Rl is a C1-C4 alkyl group and M is an CA 022~0226 1998-09-28 W O 97/36991 28 PCT~US97/05363 alkali metal ion. Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.

Water-soluble builder compound The compositions of the present invention may contain as a highly preferred component a water-soluble builder compound, typically present at a level of from 1% to 80% by weight, preferably from 10% to 70~ by weight, most preferably from 20% to 60~ by weight of the composition.

Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, carbonates, bicarbonates, borates, phosphates, and mixtures thereof.

The carboxylate or polycarboxylate builder can be monomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.

Suitable carboxylates cont~inin~ one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
Polycarboxylates cont~inin~ two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates cont~inin~ three carboxy groups include, in particular, water-so~uble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No. 1,387,447.

CA 022~0226 1998-09-28 Polycarboxylates cont~ining four carboxy groups include oxydisuccinatesdisclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
Polycarboxylates cont~ininp sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran - cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran - cis -dicarboxylates, 2,2,5,5-tetrahydrofuran - tetracarboxylates, 1,2,3,4,5,6-hexane - hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343.

Of the above, the preferred polycarboxylates are hydroxycarboxylates cont~ining up to three carboxy groups per molecule, more particularly citrates.

The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.

Borate builders, as well as builders cont~inin~ borate-forming materials that can produce borate under detergent storage or wash conditions can also be used but are not preferred at wash conditions less that about 50~C, especially less than about 40~C.

Examples of carbonate builders are the ~lk~line earth and alkali metal carbonates, including sodium carbonate and sesqui-carbonate and mixtures thereof with ultra-fine calcium carbonate as disclosed in Gerrnan Patent Application No. 2,321,001 published on November 15, 1973.

CA 022~0226 1998-09-28 Specific examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate~ sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.

Partially soluble or insoluble builder compound The detergent compositions of the present invention may contain a partially soluble or insoluble builder compound, typically present at a level of from 1 % to 80~ by weight, preferably from 10% to 70% by weight, most preferably from 20 % to 60% weight of the composition.

Examples of largely water insoluble builders include the sodium aluminosilicates .

Suitable aluminosilicate zeolites have the unit cell formula Naz[(AlO2)z(SiO2)y~. xH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material are in hydrated form and are preferably crystalline, cont~inin~ from 10% to 28%, more preferably from 18% to 22% water in bound form.

The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula Na 12 [Al~2) 12 (sio2)l2]. xH2O

wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na86 [(Al~2)86(Si~2)106]- 276 H2O. Zeolite MAP, as disclosed in P-B-384,070 is a preferred zeolite builder herein.

CA 022~0226 1998-09-28 WO 97/36991 31 PCT~US97/0~363 Water-soluble bismuth compound The compositions used in this invention may contain a water-soluble bismuth compound, preferably present at a level of from 0.005% to 20%, more preferably from 0.01 % to 5 %, most preferably from 0.1 % to 1 % by weight of the compositions.

The water-soluble bismuth compound may be essentially any salt or complex of bismuth with essentially any inorganic or organic counter anion. Preferred inorganic bismuth salts are selected from the bismuth trihalides, bismuth nitrate and bismuth phosphate. Bismuth acetate and citrate are preferred salts with an organic counter anion.

Water-soluble sulfate salt The compositions may optionally contain a water-soluble sulfate salt, preferably present at a level of from 0.1 % to 40 %, more preferably from 1 % to 30%, most preferably from 5 % to 25 % by weight of the compositions.

The water-soluble sulfate salt may be essentially any salt of sulfate with any counter cation. Preferred salts are selected from the sulfates of the alkali and ~lk~line earth metals, particularly sodium sulfate.

Corrosion inhibitor compound The compositions may contain corrosion inhibitors preferably selected from organic silver coating agents, particularly paraffin, nitrogen-cont~ining corrosion inhibitor compounds and Mn(II) compounds, particularly Mn(II) salts of organic ligands.

Organic silver coating agents are described in PCT Publication No.
WO94/16047 and copending UK Application No. UK 9413729.6.
Nitrogen-cont~;nin~ corrosion inhibitor compounds are disclosed in copending European Application no. EP 93202095.1. Mn(II) compounds CA 022~0226 1998-09-28 W O 97/36991 32 PCT~US97105363 for use in corrosion inhibition are described in copending UK Application No. 9418567.5.

Or~anic silver coatin~ agents Organic silver coating agent may be incorporated in automatic dishwashing compositions herein at a level of from 0.05% to 10%, preferably from 0.1% to 5 % by weight of the total composition.

The functional role of the silver coating agent is to form 'in use' a protective coating layer on any silverware components of the washload to which the compositions of the invention are being applied. The silver coating agent should hence have a high aff1nity for attachment to solid silver surfaces, particularly when present in as a component of an aqueous washing and bleaching solution with which the solid silver surfaces are being treated.

Suitable organic silver coating agents herein include fatty esters of mono-or polyhydric alcohols having from 1 to about 40 carbon atoms in the hydrocarbon chain.

The fatty acid portion of the fatty ester can be obtained from mono- orpoly-carboxylic acids having from 1 to about 40 carbon atoms in the hydrocarbon chain. Suitable examples of monocarboxylic fatty acids include behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid, lauric acid, acetic acid, propionic acid, butyric acid, isobutyric acid, Valerie acid, lactic acid, glycolic acid and ~ dihydroxyisobutyric acid.
Examples of suitable polycarboxylic acids include: n-butyl-malonic acid, isocitric acid, citric acid, maleic acid, malic acid and succinic acid.

The fatty alcohol radical in the fatty ester can be represented by mono- or polyhydric alcohols having from 1 to 40 carbon atoms in the hydrocarbon chain. Examples of suitable fatty alcohols include; behenyl, arachidyl, cocoyl, oleyl and lauryl alcohol, ethylene glycol, glycerol, ethanol, CA 022~0226 1998-09-28 W O97/36991 PCTrUS97/05363 isopropanol, vinyl alcohol, diglycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan.

Preferably, the fatty acid and/or fatty alcohol group of the fatty ester adjunct material have from 1 to 24 carbon atoms in the alkyl chain.

Preferred fatty esters herein are ethylene glycol, glycerol and sorbitan esters wherein the fatty acid portion of the ester norrnally comprises a species selected from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.

The glycerol esters are also highly preferred. These are the mono-, di- or tri-esters of glycerol and the fatty acids as defined above.

Specific examples of fatty alcohol esters for use herein include: stearyl acetate, palmityl di-lactate, cocoyl isobutyrate, oleyl maleate, oleyl dimaleate, and tallowyl proprionate. Fatty acid esters useful herein include: xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate, glycerol monostearate, ethylene glycol monostearate, sorbitan esters. Suitable sorbitan esters include sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monobehenate, sorbitan mono-oleate, sorbitan dilaurate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate, and also mixed tallowalkyl sorbitan mono- and di-esters.

Glycerol monostearate, glycerol mono-oleate, glycerol monopalmitate, glycerol monobehenate, and glycerol distearate are preferred glycerol esters herein.

Suitable organic silver coating agents include triglycerides, mono or diglycerides, and wholly or partially hydrogenated derivatives thereof, and any mixtures thereof. Suitable sources of fatty acid esters include vegetable and fish oils and ~nim~l fats. Suitable vegetable oils include soy bean oil, cotton seed oil, castor oil, olive oil, peanut oil, safflower oil, sunflower oil, rapeseed oil, grapeseed oil, palm oil and corn oil.

CA 022~0226 1998-09-28 W O 97/36991 PCT~US97/05363 Waxes, including microcrystalline waxes are suitable organic silver coating agents herein. Preferred waxes have a melting point in the range from about 35~C to about 110~C and comprise generally from 12 to 70 carbon atoms. Preferred are petroleum waxes of the paraffin and microcrystalline type which are composed of long-chain saturated hydrocarbon compounds.

Alginates and gelatin are suitable organic silver coating agents herein.

Dialkyl amine oxides such as C12-C20 methylamine oxide, and dialkyl quaternary ammonium compounds and salts, such as the C12-C20 methylammonium halides are also suitable.

Other suitable organic silver coating agents include certain polymeric materials. Polyvinylpyrrolidones with an average molecular weight of from 12,000 to 700,000, polyethylene glycols (PEG) with an average molecular weight of from 600 to 10,000, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, and cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose are examples of such polymeric materials.

Certain perfume materials, particularly those demonstrating a high substantivity for metallic surfaces, are also useful as the organic silver coating agents herein.

Soil release a~ent Polymeric soil release agents can also be used as an organic silver coating agent. Such soil release agents are also preferred ingredients of laundry detergent compositions herein, for their soil release capability.

Suitable polymeric soil release agents include those soil release agents having: (a) one or more nonionic hydrophile components consisting CA 022~0226 1998-09-28 essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30 oxypropylene units, said hydrophile segments preferably comprising at least about 25 %
oxyethylene units and more preferably, especially for such components having about 20 to 30 oxypropylene units, at least about 50% oxyethylene units; or (b) one or more hydrophobe components comprising (i) C3 oxyalkylene terephth~lAte segments, wherein, if said hydrophobe components also comprise oxyethylene terephthalate, the ratio of oxyethylene terephthalate:C3 oxyalkylene terephthalate units is about 2: 1 or lower, (ii) C4-C6 alkylene or oxy C4-C6 alkylene segments, or mixtures therein, (iii) poly (vinyl ester) segments, preferably polyvinyl acetate, having a degree of polymerization of at least 2, or (iv) C1-C4 alkyl ether or C4 hydroxyalkyl ether substituents, or mixtures therein, wherein said substituents are present in the form of C1-C4 alkyl ether or C4 hydroxyalkyl ether cellulose derivatives, or mixtures therein, or a combination of (a) and (b).

Typically, the polyoxyethylene segments of (a)(i) will have a degree ofpolymerization of from about 200, although higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100.
Suitable oxy C4-C6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as MO3S(CH2)nOCH2CH2O-, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink.

Polymeric soil release agents useful herein also include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate or propylene tereph~h~l~te with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and inclllde hydroxyethers of cellulose such as CA 022~0226 1998-09-28 W O 97/36991 36 PCT~US97105363 METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C 1-C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al.

Soil release agents characterised by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., C1-C6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones. See European Patent Application 0 219 048, published April 22, 1987 by Kud, et al.

Another suitable soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephth~l~te. The molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to B~ r issued July 8, 1975.

Another suitable polymeric soil release agent is a polyester with repeat units of ethylene terephth~l~te units contains 10-15~ by weight of ethylene terephtl~ te units together with 90-80 % by weight of polyoxyethylene terephth~l~te units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000.

Another suitable polymeric soil release agent is a sulfonated product of a subst~nti~lly linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone. These soil release agents are described fully in U.S. Patent 4,968,451, issued November 6, 1990 to J.J.
Scheibel and E.P. Gosselink. Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink. Other polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October CA 022~0226 1998-09-28 W O 97/36991 PCTrUS97/05363 31, 1989 to Maldonado et al, which discloses anionic, especially sul-foarolyl, end-capped terephthalate esters.

Another soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2-propylene units. The repeat units form the backbone of the oligomer and are preferably termin~te~ with modified isethionate end-caps. A particularly preferred soil release agent of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulfonate.

A preferred organic silver coating agent is a paraffin oil, typically apredominantly branched aliphatic hydrocarbon having a number of carbon atoms in the range of from 20 to 50; preferred paraffin oil selected from predomin~ntly branched C2s 45 species with a ratio of cyclic to noncyclic hydrocarbons of from 1:10 to 2:1, preferably from 1:5 to 1:1. A paraffin oil meeting these characteristics, having a ratio of cyclic to noncyclic hydrocarbons of about 32:68, is sold by Wintershall, Salzbergen, Gerrnany, under the trade name WINOG 70.

Nitrogen-cont~inin~ corrosion inhibitor compounds Suitable nitrogen-cont~inin~ corrosion inhibitor compounds include imidazole and derivatives thereof such as benzimidazole, 2-heptadecyl imidazole and those imidazole derivatives described in Czech Patent No.
139, 279 and British Patent GB-A-1,137,741, which also discloses a method for m~kin~ imidazole compounds.

Also suitable as nitrogen-cont~inin~ corrosion inhibitor compounds are pyrazole compounds and their derivatives, particularly those where the pyrazole is substituted in any of the 1, 3, 4 or 5 positions by substituents Rl, R3, R4 and Rs where Rl is any of H, CH20H, CONH3, or COCH3, R3 and Rs are any of C1-C20 alkyl or hydroxyl, and R4 is any of H, NH2 or NO2.

CA 022~0226 l998-09-28 W O97/36991 38 PCTrUS97/05363 Other suitable nitrogen-cont~ining corrosion inhibitor compounds include benzotriazole, 2-mercaptobenzothiazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole, thionalide, morpholine, melamine, distearylamine, stearoyl stearamide, cyanuric acid, aminotriazole, aminotetrazole and indazole.

Nitrogen-cont~ining compounds such as amines, especially distearylamineand ammonium compounds such as ammonium chloride, amrnonium bromide, ammonium sulphate or (li~mmonium hydrogen citrate are also suitable.

Mn(II) corrosion inhibitor compounds The compositions may contain an Mn(II) corrosion inhibitor compound.
The Mn(II) compound is preferably incorporated at a level of from 0.005%
to 5% by weight, more preferably from 0.01% to 1~, most preferably from 0.02% to 0.4% by weight of the compositions. Preferably, the Mn(II) compound is incorporated at a level to provide from 0.1 ppm to 250 ppm, more preferably from 0.5 ppm to 50 ppm, most preferably from 1 ppm to 20 ppm by weight of Mn(II) ions in any bleaching solution.

The Mn (II) compound may be an inorganic salt in anhydrous, or any hydrated forms. Suitable salts include m~ng~n~se sulphate, m~ng~n.ose carbonate, m~ng~n~se phosphate, m~n~nese nitrate, manganese acetate and m~ng~nese chloride. The Mn(II) compound may be a salt or complex of an organic fatty acid such as m~ng~nese acetate or m~ng~ne~se stearate.

The Mn(II) compound may be a salt or complex of an organic ligand. In one preferred aspect the organic ligand is a heavy metal ion sequestrant. In another preferred aspect the organic ligand is a crystal growth inhibitor.

Other corrosion inhibitor compounds Other suitable additional corrosion inhibitor compounds include, mercaptans and diols, especially mercaptans with 4 to 20 carbon atoms CA 022~0226 1998-09-28 including lauryl mercaptan, thiophenol, thionapthol~ thionalide and thioanthranol. Also suitable are saturated or lln~t~-rated Clo-C20 fatty acids, or their salts, especially aluminium tristearate. The C12-C20 hydroxy fatty acids, or their salts, are also suitable. Phosphonated octa-decane and other anti-oxidants such as betahydroxytoluene (BHT) are also suitable.

Copolymers of butadiene and maleic acid, particularly those supplied under the trade reference no. 07787 by Polysciences Inc have been found to be of particular utility as corrosion inhibitor compounds.

Total Available Oxy~en (AvO) Level It has been found that, for optimal anti-silver tarnishinp; performance, the level of available oxygen in the present compositions, measured in units of % available oxygen by weight of the composition, is preferably controlled;
the level of available oxygen should hence preferably be in the range from 0.3% to 2.5%, preferably from 0.5~ to 1.7%, more preferably from 0.6%
to 1.5%, most preferably from 0.7% to 1.2%, measured according to the method described hereunder.

Rate of Release of AvO

The rate of release of available oxygen is preferably also controlled; the rate of release of available oxygen from the compositions herein preferably should be such that, when using the method described hereinafter, the available oxygen is not completely released from the composition until after 3.5 minutes, preferably the available oxygen is released in a time interval of from 3.5 min~tes to 10.0 minutes, more preferably from 4.0 mim1tes to 9.0 minutes, most preferably from 5.0 mimltes to 8.5 minlltes.

Method for Measuring Level of Total Available Oxy~en (AvO) and Rate of Release of AvO in a Deter~ent Composition CA 022~0226 1998-09-28 W O 97/36991 PCTrUS97/05363 Method 1. A beaker of water (typically 2L) is placed on a stirrer Hotplate, and the stirrer speed is selected to ensure that the product is evenly dispersed through the solution.

2. The detergent composition (typically 8g of product which has been sampled down from a bulk supply using a Pascal sampler), is added and simultaneously a stop clock is started.

3. The temperature control should be adjusted so as to m~int~in a constant temperature of 20~C throughout the experiment.

4. Samples are taken from the detergent solution at 2 mimlte time intervals for 20 min~ltes, starting after 1 mim1te, and are titrated by the "titration procedure" described below to determine the level of available oxygen at each point.

Titration Procedure 1. An aliquot from the detergent solution (above) and 2ml sulphuric acid are added into a stirred beaker 2. Approximately 0.2g arnrnonium molybdate catalyst (tetra hydrate form) are added 3. 3mls of 10% sodium iodide solution are added 4. Titration with sodium thiosulphate is conducted until the end point.
The end point can be seen using either of two procedures. First procedure consists simply in seeing the yellow iodine colour fading to clear. The second and preferred procedure consists of ~l(lin~ soluble starch when the CA 022~0226 1998-09-28 WO 97/36991 PCTIUS97/0~363 yellow colour is becoming faint, turning the solution blue. More thiosulphate is added until the end point is reached (blue starch complex is decolourised).

The level of AvO, measured in units of % available oxygen by weight, for the sample at each time interval corresponds to the amount of titre according to the following equation Vol S203(ml) x Molarity (S203) x 8 Sample mass (g) AvO level is plotted versus time to determine the maximum level of AvO,and the rate of release of AvO

Controlled rate of release - means A means may be provided for controlling the rate of release of oxygen bleach to the wash solution.

Means for controlling the rate of release of the bleach may provide forcontrolled release of peroxide species to the wash solution. Such means could, for example, include controlling the release of any inorganic perhydrate salt, acting as a hydrogen peroxide source, to the wash solution.

Suitable controlled release means can include coating any suitable component with a coating designed to provide the controlled release. The coating may therefore, for example, comprise a poorly water soluble material, or be a coating of sufficient thickness that the kinetics of dissolution of the thick coating provide the controlled rate of release.

CA 022~0226 1998-09-28 W O 97/36991 PCTrUS97/05363 The coating material may be applied using various methods. Any coating material is typically present at a weight ratio of coating material to bleach of from 1:99 to 1:2, preferably from 1:49 to 1:9.

Suitable coating materials include triglycerides (e.g. partially) hydrogenated vegetable oil, soy bean oil, cotton seed oil) mono or diglycerides, microcrystalline waxes, gelatin, cellulose, fatty acids and any mixtures thereof.

Other suitable coating materials can comprise the alkali and ~lk~line earth metal sulphates, silicates and carbonates, including calcium carbonate and silicas.

A preferred coating material, particularly for an inorganic perhydrate salt bleach source, comprises sodium silicate of SiO2: Na2O ratio from 1.8: 1 to 3 .0: 1 , preferably 1 .8:1 to 2.4:1 , and/or sodium metasilicate, preferablyapplied at a level of from 2% to 10%, (normally from 3% to 5%) of SiO2 by weight of the inorganic perhydrate salt. Magnesium silicate can also be included in the coating.

Any inorganic salt coating materials may be combined with organic binder materials to provide composite inorganic salt/organic binder coatings.
Suitable binders include the C1o-C20 alcohol ethoxylates cont~ining from 5 - 100 moles of ethylene oxide per mole of alcohol and more preferably the C1s-C20 primary alcohol ethoxylates cont~inin~ from 20 - 100 moles of ethylene oxlde per mole of alcohol.

Other preferred binders include certain polymeric materials.
Polyvinylpyrrolidones with an average molecular weight of from 12,000 to 700,000 and polyethylene glycols (PEG) with an average molecular weight of from 600 to 5 x 106 preferably 1000 to 400,000 most preferably 1000 to 10,000 are examples of such polymeric materials. Copolymers of maleic anhydride with ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the polymer are further examples of polymeric materials useful as binder agents. These polymeric CA 022~0226 1998-09-28 materials may be used as such or in combination with solvents such as water, propylene glycol and the above mentioned Clo-C20 alcohol ethoxylates cont~ining from 5 - 100 moles of ethylene oxide per mole.
Further examples of binders include the C1o-C20 mono- and diglycerol ethers and also the Clo-C20 fatty acids.

Cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their salts are other examples of binders suitable for use herein.

One method for applying the coating material involves agglomeration.
Preferred agglomeration processes include the use of any of the organic binder materials described hereinabove. Any conventional agglomerator/mixer may be used including, but not limited to pan, rotary drum and vertical blender types. Molten coating compositions may also be applied either by being poured onto, or spray atomized onto a moving bed of bleaching agent.

Other means of providing the required controlled release include mechanical means for altering the physical characteristics of the bleach to control its solubility and rate of release. Suitable protocols could include compaction, mechanical injection, manual injection, and adjustment of the solubility of the bleach compound by selection of particle size of any particulate component.

Whilst the choice of particle size will depend both on the composition of the particulate component, and the desire to meet the desired controlled release kinetics, it is desirable that the particle size should be more than 500 micrometers, preferably having an average particle diameter of from 800 to 1200 micrometers.

Additional protocols for providing the means of controlled release include the suitable choice of any other components of the detergent composition matrix such that when the composition is introduced to the wash solution CA 022~0226 1998-09-28 W O97/36991 PCTrUS97/05363 the ionic strength environment therein provided enables the required controlled release kinetics to be achieved.

Alkalinity system The compositions preferably contain an ~lk~linity system cont~ining sodium silicate having an SiO2: Na2O ratio of from 1.8 to 3.0, preferably from 1.8 to 2.4, most preferably 2.0, present preferably at a level of less than 20%, preferably from 1% to 15%, most preferably from 3% to 12% by weight of SiO2. The alkali metal silicate may be in the forrn of either the anhydrous salt or a hydrated salt.

The ~lk~linity system also preferably contains sodium metasilicate, present at a level of at least 0.4% SiO2 by weight. Sodium metasilicate has a nominal SiO2: Na2O ratio of 1Ø The weight ratio of said sodium silicate to said sodium metasilicate, measured as SiO2, is preferably from 50:1 to 5:4, more preferably from 15:1 to 2:1, most preferably from 10:1 to 5:2.

Heavy metal ion sequestrant The detergent compositions of the invention preferably contain as an optional component a heavy metal ion sequestrant. By heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and m~gnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, m~ng~nese and copper.

Heavy metal ion sequestrants are generally present at a level of from 0.005% to 20%, preferably from 0.1 % to 10%, more preferably from 0.25 % to 7.5 % and most preferably from 0.5 % to 5 % by weight of the compositions. The weight ratio of heavy metal ion sequestrant to ATCA is preferably from 1:20 to 20:1, more preferably from 1:10 to 10:1, most preferably from 5: 1 to 1:5.

CA 022~0226 1998-09-28 Heavy metal ion sequestrants, which are acidic in nature, having for example phosphonic acid or carboxylic acid functionalities, may be present either in their acid form or as a complex/salt with a suitable counter cation such as an alkali or ~lk~line metal ion, ammonium, or substituted ammonium ion, or any mixtures thereof. Preferably any salts/complexes are water soluble. The molar ratio of said counter cation to the heavy metal ion sequestrant is preferably at least 1:1.

Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylene phosphonates. Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene ~ mine tri (methylene phosphonate) hexamethylene ~i~mine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate.

Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylen.odi~minotetracetic acid, ethylenetriamine pentacetic acid, ethylenedi~mine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylene~ mine disuccinic acid or any salts thereof.

Especially preferred is ethylenedi~mine-N,N'-disuccinic acid (EDDS) or the alkali metal, ~lk~line earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof. Preferred EDDS compounds are the free acid forrn and the sodium or magnesium salt or complex thereof.

Crystal growth inhibitor component The detergent compositions preferably contain a crystal growth inhibitor component, preferably an organodiphosphonic acid component, incorporated preferably at a level of from 0.01% to 5%, more preferably from 0.1 % to 2 % by weight of the compositions.

CA 022~0226 1998-09-28 W O 97/36991 PCTrUS97105363 By organo diphosphonic acid it is meant herein an organo diphosphonic acid which does not contain nitrogen as part of its chemical structure. This definition therefore excludes the organo aminophosphonates, which however may be included in compositions of the invention as heavy metal ion sequestrant components.

The organo diphosphonic acid is preferably a C1-C4 diphosphonic acid, more preferably a C2 diphosphonic acid, such as ethylene diphosphonic acid, or most preferably ethane 1-hydroxy-1,1-diphosphonic acid (HEDP) and may be present in partially or fully ionized form, particularly as a salt or complex.

Enzyme Another optional ingredient useful in the compositions is one or more enzymes. Preferred enzymatic materials include the commercially available lipases, amylases, neutral and ~lk~line proteases, esterases, cellulases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.

Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001% to 4% active enzyme by weight of the composition.

Preferred amylases include, for example, a-amylases obtained from a special strain of B licheniformis, described in more detail in GB-1,269,839 (Novo). Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl and BAN by Novo Industries A/S.

CA 022~0226 1998-09-28 W O 97/36991 PCT~US97/05363 Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition.

Lipolytic enzyme (lipase) may be present at levels of active lipolytic enzyme of from 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, most preferably from 0.001 % to 0.5 % by weight of the compositions. The lipase may be fungal or bacterial in origin. Lipase from chemically or genetically modified mutants of these strains are also useful herein. A preferred lipase is described in Granted European Patent, EP-B-0218272.

An especially preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Asper~illus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo lndustries A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.

Enzyme Stabilizing System Preferred enzyme-cont~ining compositions herein may comprise from about0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such stabilizing systems can comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, chlorine bleach scavengers and mixtures thereof. Such stabilizing systems can also comprise reversible enzyme inhibitors, such as reversible protease inhibitors.

Clay softenin~ system CA 022~0226 1998-09-28 W O 97/36991 PCT~US97/05363 The detergent compositions where formulated for laundry usage may contain a clay softening system comprising a clay mineral compound and optionally a clay flocculating agent.

The clay mineral compound is preferably a smectite clay compound.
Smectite clays are disclosed in the US Patents Nos. 3,862,058, 3,948,790, 3,954,632 and 4,062,647. European Patents Nos. EP-A-299,575 and EP-A-313,146 in the name of the Procter and Gamble Company describe suitable organic polymeric clay flocc~ ting agents.

Lime soap dispersant compound The compositions of the invention may contain a lime soap dispersant compound, preferably present at a level of from 0.1 % to 40 % by weight, more preferably 1 % to 20% by weight, most preferably from 2~ to 105 by weight of the compositions.

A lime soap dispersant is a material that prevents the precipitation of alkali metal, ammonium or amine salts of fatty acids by calcium or m~gnPsium ions. Preferred lime soap dispersant compounds are disclosed in PCT
Application No. W093/08877.

Suds suppressing system The compositions of the invention, when formulated for use in machine washing compositions, preferably comprise a suds suppressing system present at a level of from 0.01 % to 15 %, preferably from 0.05 % to 10%, most preferably from 0.1 % to 5 % by weight of the composition.

Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds, 2-alkyl and alcanol antifoam compounds. Preferred suds suppressing systems and antifoam compounds are disclosed in PCT

CA 022~0226 1998-09-28 W O 97136991 49 PCT~US97/05363 Application No. W093/08876 and copending European Application No.
93870132.3.

Polymeric dye transfer inhibiting a~ents The compositions herein may also comprise from 0.01% to 10 ~, preferably from 0.05 % to 0.5 % by weight of polymeric dye transfer inhibiting agents.

The polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.

a) Polyamine N-oxide polymers Polyamine N-oxide polymers suitable for use herein contain units havingthe following structure formula:

wherein P is a polymerisable unit, and O O O

A is NC, CO, C,--O--, --S--, --N--; x is O or l;

R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group is part of these groups.

CA 022~0226 1998-09-28 The N-O group can be represented by the following general structures:
o o (R1 )X - N - (R2)y (R3 )z or =N (R1 )x wherein Rl, R2 and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups. The N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.

Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, a}icyclic or heterocyclic groups. One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group.
Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O group is attached to the polymerisable unit. A preferred class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group.
Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyridine, pyrrole, imidazole and derivatives thereof.

The polyamine N-oxides can be obtained in almost any degree of polymerisation. The degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power.

CA 022~0226 1998-09-28 W O 97/36991 51 PCT~US97/05363 Typically, the average molecular weight is within the range of 500 to 1,000,000.
b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole Suitable herein are copolymers of N-vinylimidazole and N-vinylpyrrolidone having an average molecular weight range of from 5,000 to 50,000. The preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2.
c) Polyvinylpyrrolidone The detergent compositions herein may also utilise polyvinylpyrrolidone("PVP") having an average molecular weight of from 2,500 to 400,000.
Suitable polyvinylpyrrolidones are commercially available from ISP
Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000).
PVP K-15 is also available from ISP Corporation. Other suitable polyvinylpyrrolidones which are commercially available from BASF
Corporation include Sokalan HP 165 and Sokalan HP 12.
d) Polyvinyloxazolidone The detergent compositions herein may also utilise polyvinyloxazolidones as polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000.

e) Polyvinylimidazole The detergent compositions herein may also utilise polyvinylimidazole as polymeric dye transfer inhibiting agent. Said polyvinylimidazoles preferably have an average molecular weight of from 2,500 to 400,000.

CA 022~0226 1998-09-28 WO 97/36991 PCTrUS97/05363 Optical bri~htener The detergent compositions herein particularly where formulated for laundry usage also optionally contain from about 0.005 ~ to 5 % by weight of certain types of hydrophilic optical brighteners.

Hydrophilic optical brighteners useful herein include those having the structural formula:

N 0~ 1 ~C=C~N~(~N

R2 SO3M SO3M R, 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.

When in the above formula, 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-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation.
Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.

When in the above formula, 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-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is cornmercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.

CA 022~0226 1998-09-28 W O 97/36991 PCT~US97/05363 When in the above formula, R1 is anilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4l-bis~(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.

Cationic fabric softening agents Cationic fabric softening agents can also be incorporated into compositions in accordance with the present invention. Suitable cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0 011 340.

Cationic fabric softening agents are typically incorporated at total levels of fromO.5% to 15% byweight, normallyfrom 1% toS% byweight.

Other optional in~redients Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.

pH of the compositions The detergent compositions used in the present invention are preferably not formulated to have an unduly high pH, in preference having a pH measured as a 1% solution in distilled water of from 8.0 to 12.5, more preferably from 9.0 to 11.8, most preferably from 9.5 to 11.5.

CA 022~0226 1998-09-28 W O 97/36991 PCT~US97/05363 Form of the compositions The detergent compositions used in this invention can be formulated in any desirable form such as powders, gr~n~ tes, pastes, liquids, gels, bars and tablets, granular and tablet forms being preferred.

The bulk density of the granular detergent compositions in accordance with the present invention is typically of at least 650 g/litre, more usually at least 700 g/litre and more preferably from ~00 g/litre to 1200 g/litre.

The particle size of the components of granular compositions in accordance with the invention should preferably be such that no more that 5 % of particles are greater than 1 .4mrn in diameter and not more than 5 % of particles are less than 0.15mm in diameter.

Compacted solids may be manufactured using any suitable compacting process, such as tabletting, briquetting or extrusion, preferably tabletting.
Preferably tablets are manufactured using a standard rotary tabletting press using compression forces of from 5 to 13 KN/cm2, more preferably from 5 to 1 lKN/cm2 so that the compacted solid has a minimum hardness of 176N
to 275N, preferably from 195N to 245N, measured by a C100 hardness test as supplied by I. Holland instruments. This process may be used to prepare homogeneous or layered tablets of any size or shape. Preferably tablets are symmetrical to ensure the uniform dissolution of the tablet in the wash solution According to the present invention the compacted solid form detergent composition may find utility in all types of automatic dish and laundry washing machines including industrial and domestic machines.

Generally, if the compositions are in liquid form the liquid should be thixotropic (ie; exhibit high viscosity when subjected to low stress and lower viscosity when subjected to high stress), or at least have very high viscosity, for example, of from 1,000 to 10,000,000 centipoise.

.. . .

CA 022~0226 1998-09-28 W O 97t36991 PCTrUS97/05363 Machine dishwashing method Any suitable methods for machine washing or cleaning soiled tableware, particularly soiled silverware are envisaged.

preferred machine dishwashing method comprises treating soiled articles selected from crockery, glassware, hollowware, silverware and cutlery and mixtures thereof, with an aqueous liquid having dissolved or dispensed therein an effective amount of a machine dishwashing composition in accord with the invention. By an effective amount of the machine dishwashing composition it is meant from 8g to 60g of product dissolved or dispersed in a wash solution of volume from 3 to 10 litres, as are typical product dosages and wash solution volumes comrnonly employed in conventional machine dishwashing methods.

Laundry washing method Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention. By an effective amount of the detergent composition it is meant from 40g to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.

In a preferred use aspect a dispensing device is employed in the washing method. The dispensing device is charged with the detergent product, and is used to introduce the product directly into the drum of the washing machine before the commencement of the wash cycle. Its volume capacity should be such as to be able to contain sufficient detergent product as would normally be used in the washing method.

CA 022~0226 1998-09-28 W 097t36991 PCTrUSg7/05363 Once the washing machine has been loaded with laundry the dispensing device cont~ining the detergent product is placed inside the drum. At the commencement of the wash cycle of the washing machine water is introduced into the drum and the drum periodically rotates. The design of the dispensing device should be such that it permits cont~inment of the dry detergent product but then allows release of this product during the wash cycle in response to its agitation as the drum rotates and also as a result of its contact with the wash water.

To allow for release of the detergent product during the wash the device may possess a number of openings through which the product may pass.
Alternatively, the device may be made of a material which is permeable to liquid but impermeable to the solid product, which will allow release of dissolved product. Preferably, the detergent product will be rapidly released at the start of the wash cycle thereby providing transient localised high concentrations of product in the drum of the washing machine at this stage of the wash cycle.

Preferred dispensing devices are reusable and are designed in such a way that container integrity is m~int~ined in both the dry state and during the wash cycle. Especially preferred dispensing devices for use with the composition of the invention have been described in the following patents;
GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345 and EP-A-0288346. An article by J.Bland published in Manufacturing Chemist, November 1989, pages 41-46 also describes especially preferred dispensing devices for use with granular laundry products which are of a type commonly know as the "granulette". Another preferred dispensing device for use with the compositions of this invention is disclosed in PCT
Patent Application No. WO94/11562.

Especially preferred dispensing devices are disclosed in European Patent Application Publication Nos. 0343069 & 0343070. The latter Application discloses a device comprising a flexible sheath in the form of a bag extending from a support ring defining an orifice, the orifice being adapted to admit to the bag sufficient product for one washing cycle in a washing CA 022~0226 1998-09-28 W O 97/36991 PCTrUS97/05363 process. A portion of the washing medium flows through the orifice into the bag, dissolves the product, and the solution then passes outwardly through the orifice into the washing medium. The support ring is provided with a masking arrangement to prevent egress of wetted, undissolved, product, this arrangement typically comprising radially extending walls extending from a central boss in a spoked wheel configuration, or a similar structure in which the walls have a helical form.

Alternatively, the dispensing device may be a flexible container, such as a bag or pouch. The bag may be of fibrous construction coated with a water impermeable protective material so as to retain the contents, such as is disclosed in European published Patent Application No. 0018678.
Alternatively it may be formed of a water-insoluble synthetic polymeric material provided with an edge seal or closure designed to rupture in aqueous media as disclosed in European published Patent Application Nos.
0011500, 0011501, 0011502, and 0011968. A convenient form of water frangible closure comprises a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene.

Examples Abbreviations used in Examples In the detergent compositions, the abbreviated component identifications have the following me~ning~:

LAS : Sodium linear C12 alkyl benzene sulfonate TAS : Sodium tallow alkyl sulfate C45AS : Sodium C 14-C 15 linear alkyl sulfate CxyEzS : Sodium C1x-Cly branched alkyl sulfate condensed with z moles of ethylene oxide C45E7 : A C14 15 predomin~ntly linearprimary alcohol condensed with an average of 7 moles of ethylene oxide CA 022~0226 1998-09-28 W O97/36991 PCTrUS97/05363 C25E3 : A C14 15 branched primary alcohol condensed with an average of 3 moles of ethylene oxide C25E5 : A C12 15 branched primary alcohol condensed with an average of S moles of ethylene oxide CEQ : RlCOOCH2CH2.N+(CH3)3 with R1 = C11-QAS : R2.N+(CH3)2(C2H4OH with R2 = Cl2-C14 Soap : Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut oils TFAA : C16-C1g alkyl N-methyl glucamide TPKFA : C12-C14 topped whole cut fatty acids Zeolite A : Hydrated Sodium Aluminosilicate of formula Na12(A102SiO2)12.27H2O having a primary particle size in the range from 0.1 to 10 micrometers Zeolite MAP : Hydrated sodium aluminosilicate MAP having a silicon to aluminium ratio of 1.07:1.
NaSKS-6 : Crystalline layered silicate of formula ~-Na2si2o5 Citric Acid : Anhydrous citric acid Bicarbonate : Anhydrous sodium bicarbonate with a particle size distribution between 400 ~m and 1200 ~m MA/AA : Copolymerof 1:4 maleic/acrylic acid, average molecular weight about 70,000 CMC : Sodium carboxymethyl cellulose Alcalase : Proteolytic enzyme of activity 3AU/g sold by NOVO Tntlll~tries A/S
Cellulase : Cellulytic enzyme of activity 1000 CEVU/g sold by NOVO Industries A/S under the tradename Carezyme Lipase : Lipolytic enzyme of activity 100kLU/g sold by NOVO Industries A/S under the tradename Lipolase Endolase : Endoglucase enzyme of activity 3000 CEVU/g sold by NOVO Industries A/S

CA 022~0226 1998-09-28 Photoactivated bleach : Sulfona~ed Zinc Phythlocyanine encapsulated in dextrin soluble polymer Brightener 1 : Disodium 4,4'-bis(2-sulphostyryl)biphenyl Brightener 2 : Disodium 4,4'-bis (4-anilino-6-morpholino-1 . 3 . 5-triazin-2-yl)amino) stilbene-2: 2 ' -disulfonate PVNO : Polyvinylpyridine N-oxide PVPVI : Copolymer of polyvinylpyrolidone and vinylimidazole SRP 1 : Sulfobenzoyl end capped esters with oxyethylene oxy and terephtaloyl backbone SRP 2 : Diethoxylated poly (1, 2 propylene terephtlate) short block polymer Silicone antifoam : Polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said form controller to said dispersing agent of 10:1 to 100:1 NOBS : Nonanoyloxybenzene sulfonate in the form of the sodium salt STPP : Sodium tripolyphosphate MGDA : Methyl Glycine Diacetic acid Citrate : Tri-sodium citrate dihydrate Carbonate : Anhydrous sodium carbonate Silicate : Amorphous Sodium Silicate (SiO2:Na2O ratio = 2.0) Metasilicate : Sodium metasilicate (SiO2:Na2O ratio = 1.0) PB 1 : Anhydrous sodium perborate monohydrate PB4 : Sodium perborate tetrahydrate of nominal formula NaBo2.3H2o-H2o2 Percarbonate : Anhydrous sodium percarbonate of nominal formula 2.Na2co3.3H2o2 CA 022~0226 1998-09-28 W 097/36991 PCTrUS97/05363 Nonionic : C13-C1s mixed ethoxylated/propoxylated fatty alcohol with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5 sold under the tradename Plurafac LF404 by BASF GmbH (low foaming) TAED : Tetraacetyl ethylene ~ mine HEDP : Ethane 1-hydroxy-1,1-diphosphonic acid DETPMP : Diethyltri~mine penta (methylene) phosphonate, marketed by monsanto under the tradename Dequest 2060 PAAC : Pent~mine acetate cobalt (III) salt Mn Catalyst : MnIV2(m-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(pF6)2 Paraf~ln : Paraffin oil sold under the tradename Winog 70 by Wintershall.
Protease : Proteolytic enzyme of activity 4KNPU/g sold under the tradename Savinase by Novo Industries A/S
Amylase : Amylolytic enzyme of activity 60KNU/g sold under tradename Termamyl 60T by Novo Industries A/S
BTA : Benzotriazole Bismuth nitrate : Bismuth nitrate salt PA30 : Polyacrylic acid of average molecular weight approximately 8,000 Terpolymer : Terpolymer of average molecular weight approx. 7,000, comprising acrylic:maleic:ethylacrylic acid monomer units at a weight ratio of 60:20:20 480N : Random copolymer of 3:7 acrylic/meth~crylic acid, average molecular weight about 3,500 Sulphate : Anhydrous sodium sulphate.
NaDCC : Sodium dichloroisocyanurate KOH : 100% active solution of Potassium Hydroxide CA 022~0226 1998-09-28 W O 97/36991 PCTAUS97tO5363 BSA : Amylotic enzyme sold under the tradename LE17 by Novo Industries A/S (approx l ~o enzyme activity) pH : Measured as a 1 ~ solution in distilled water at 20~C

In the following examples all levels are quoted as % by weight of the composition:

Example 1 The following compact high density (0.96Kg/l) dishwashing detergent compositions A to F were prepared in accord with the invention:

A B C D E F
STPP 24.80 24.80 25.00 28.39 28.50 20.00 Citrate - - - - 10.00 10.00 Carbonate - - 17.50 17.50 MGDA - 2.50 2.00 2.00 3.00 2.00 Silicate 20.36 20.36 14.81 14.81 14.81 Metasilicate 2.50 2.50 2.50 PB1 7.79 7.79 9.74 14.28 9.74 Percarbonate - - - - - 6.70 Non-ionic 1.50 1.50 2.00 1.50 2.00 2.60 TAED 2.39 2.39 2.39 - - 4.00 HEDP 0.46 0.46 1.00 - 0.83 DETPMP - - 0.65 PAAC 0.2 0.2 0.1 0.2 0.2 0.3 BzP - - - 4 44 Paraffin 0.50 0.50 0.50 0.50 - 0.20 Protease 2.20 2.20 2.20 2.20 2.00 0.50 Amylase 1.50 1.50 1.20 1.50 1.00 1.10 CA 022~0226 1998-09-28 BTA 0.30 0.30 0.30 0.30 - -Bismuth Nitrate - - 0.30 - - -Terpolymer - - - 4.00 480N 2.77 2.77 6.00 - 6.67 Sulphate 8.44 8.44 20.77 - 23.24 1.00Misc inc moisture to balance pH (1~ solution) 10.90 10.90 11.00 10.80 10.90 9.60 Example 2 The following granular dishwashing detergent compositions examples G
to L of bulk density 1.02Kg/L were prepared in accord with the invention:

G H I J K L
STPP 30.00 30.00 30.00 27.90 34.50 26.70 Carbonate 30.50 23.50 30.50 23.00 30.50 2.80 MGDA - 2.00 2.00 5.00 5.00 2.00 Silicate 7.40 7.40 7.40 12.00 8.00 18.34 PB1 4.40 4.40 4.40 4.40 4.40 4.40 Nonionic 0.75 0.75 0.75 1.90 1.20 0.50 TAED 1.00 1.00 - - 1.00 PAAC 0.02 0.2 0.004 0.02 0.2 0.2 BzP - 1.40 - - - -Paraffin 0.25 0.25 0.25 Protease 1.10 1.10 1.10 - 2.20 Amylase 0.38 0.38 0.38 - 0.80 BTA 0.15 - 0.15 Sulphate 23.90 21.90 21.90 26.40 12.40 Misc inc moisture - to balance pH (1% solution) 10.80 10.80 10.80 10.70 10.70 12.30 CA 022~0226 l998-09-28 W O 97/36991 PCTrUS97/05363 Example 3 The following detergent composition tablets in accord with the present invention of 25g weight were prepared by compression of a granular dishwashing detergent composition at a pressure of 13KN/cm2 using a st~nA~rd 12 head rotary press:

M N O
STPP 45.00 38.80 32.50 Citrate - - 15.00 Carbonate - 5.00 MGDA - 4.00 2.00 Silicate 26.40 14.80 25.00 Protease 1.76 2.20 0.60 Amylase 1.20 - 0.60 PB1 1.56 7.79 PB4 6.92 - 11.40 PAAC 0.2 2.0 0.002 Nonionic 1.20 2.00 1.10 TAED 4.33 2.39 0.80 HEDP 0.67 0.67 DETPMP 0.65 Paraffin 0.42 0.50 BTA 0.24 0.30 PA30 3.2 - -Sulphate 25.05 12.70 1.20 Misc inc moisture to balance pH (1 ~ solution) 10.60 10.60 11.00 W O 97/36991 PCTrUS97tO5363 Example 4 The following liquid detergent compositions in accord with the present invention P to Q, of density 1.40Kg/L were prepared:

P Q
STPP 31.30 18.00 Carbonate 2.70 2.00 MGDA 2.00 2.00 Silicate - 4.40 PB1 8.00 10.00 PAAC 2.00 0.2 Nonionic 2.50 1.00 Paraffin 2.20 Protease 0.60 0.50 Amylase 0.80 0.40 480N 0.50 4.00 KOH - 6.00 Sulphate 1.60 Misc inc moisture to b~l~n~e pH (1 % solution) 9. 10 10.00 Example 5 The following granular laundry detergent compositions A' to C' of bulk density 750 g/litre were prepared in accord with the invention:

A' B' C' LAS 5.25 5.61 4.76 TAS 1.25 1.86 1.57 C45AS - 2.24 3.89 C25AE3S - 0.76 1.18 C45E7 3.25 - 5.0 C25E3 - 5.5 CEQ 0.8 2.0 2.0 STPP 19.7 19.5 19.5 MGDA 2.0 2.0 2.0 Zeolite A - 19.5 19.5 NaSKS-6/citric acid - 10.6 10.6 (79:21) Carbonate 6.1 21.4 21.4 Bicarbonate - 2.0 2.0 Silicate 6. 8 Sodium sulfate 39. 8 - 14 .3 PB4 5.0 12.7 Mn Catalyst 0.05 0.01 0.01 TAED 0.5 3.1 DETPMP 0.25 0.2 0.2 HEDP - 0.3 0.3 Protease 0.26 0.85 0.85 Lipase 0.15 0.15 0.15 Cellulase 0.28 0.28 0.28 Amylase 0.1 0.1 0.1 MA/AA 0.8 1.6 1.6 CMC 0.2 0.4 0.4 Photoactivated bleach 15 ppm 27 ppm 27 ppm (ppm) Brightener 1 0.08 0.19 0.19 Brightener 2 - 0.04 0.04 Perfume 0.3 0-3 0-3 Silicone antifoam 0.5 2.4 2.4 Minors/misc to 100%

Example 6 The following detergent formulations, according to the present invention were prepared:

D' E' F' Blown Powder STPP 24.0 - 24.0 Zeolite A - 24.0 CA 022~0226 1998-09-28 W O 97/36991 67 PCTrUS97/05363 MGDA 2.0 2.0 2.0 C45AS 9.0 6.0 13.0 MA/AA 2.0 4.0 2.0 LAS 6.0 8.0 11.0 TAS 2.0 - -Silicate 7.0 3.0 3.0 CMC 1.0 1.0 0.5 Brightener 2 0.2 0.2 0.2 Soap 1.0 1.0 1.0 DTPMP 0.4 0.4 0.2 Spray On C45E7 2.5 2.5 2.0 C25E3 2.5 2.5 2.0 Silicone antifoam 0.3 0.3 0.3 -Perfume 0.3 0.3 0.3 Dry additives Carbonate 6.0 13.0 15.0 PB4 18.0 18.0 10.0 PB1 4.0 4.0 0 Mn Catalyst 0.01 0.01 0.01 TAED 3.0 3.0 1.0 Photoactivated bleach 0.02 0.02 0.02 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.25 0.30 0.15 Dry mixed sodium 3.0 3.0 5.0 sulfate B~l~nre (Moisture & 100.0 100.0 100.0 Miscellaneous) ~ensity (g/litre) 630 670 670 W O 97/36991 PCT~US97/05363 Example 7 The following nil bleach-cont~ining detergent formulations of particular use in the washing of colored clothing, according to the present invention were prepared:

G' H' Blown Powder STPP 15.0 15.0 MGDA 2.0 2.0 Sodium sulfate 0.0 5.0 LAS 3.0 3.0 DTPMP 0.4 0.5 CMC 0.4 0.4 MA/AA 4.0 4.0 Agglomerates LAS 6.0 5.0 TAS 3.0 2.0 Silicate 4.0 4.0 Zeolite A 10.0 15.0 CMC
MA/AA - -Carbonate 9.0 7.0 Spray On Perfume 0.3 0.3 C45E7 4.0 4.0 C25E3 2.0 2.0 Dry additives MA/AA
NaSKS-6 Citrate 10.0 Bicarbonate 7.0 3.0 Carbonate 8.0 5.0 Mn Catalyst 0.2 0.2 PVPVI/PVNO 0.5 0.5 W O 97/36991 PCTrUS97/05363 Alcalase 0.5 0.3 Lipase 0.4 0.4 Amylase 0.6 0.6 Cellulase 0.6 0.6 Silicone antifoam 5.0 5.0 Dry additives Sodium sulfate 0.0 9.0 Balance (Moisture and 100.0 100.0 Miscellaneous) Density (g/litre) 700 700 Example 8 The following detergent formulations, according to the present invention were prepared:

I' J' K' L' LAS 20.0 14.0 24.0 22.0 QAS 0.7 1.0 - 0.7 TFAA - 1.0 C25E5/C45E7 - 2.0 - 0.5 C45E3S - 2.5 - -STPP 30.0 18.0 30.0 22.0 Silicate 9.0 5.0 10.0 8.0 Carbonate 13.0 7.5 - 5.0 MGDA 2.0 2.0 2.0 2.0 Bicarbonate - 7.5 DTPMP 0.7 1.0 SRP 1 0.3 0.2 - 0.1 MA/AA 2.0 1.5 2.0 1.0 CMC 0.8 0.4 0.4 0.2 Protease 0.8 1.0 0.5 0.5 -Amylase 0.8 0.4 - 0.25 Lipase 0.2 0.1 0.2 0.1 Cellulase 0.15 0.05 W O 97/36991 PCTrUS97/05363 Photoactivated 70ppm 45ppm - 10ppm bleach (ppm) Brightener 10.2 0.2 0.08 0.2 PBl 6.0 2.0 Mn Catalyst 0.3 0.3 0.2 0.2 NOBS 2.0 1.0 Balance 100 100 100 100 (Moisture and Miscellaneous) .

W O 97/36991 PCT~US97105363 Example 9 The following detergent formulations, according to the present invention were prepared:

M' N' O' Blown Powder STPP 30.0 22.0 6.0 MGDA 2.0 2.0 2.0 Sodium sulfate 19.0 5.0 7.0 MA/AA 3.0 3.0 6.0 LAS 14.0 12.0 22.0 C45AS 8.0 7.0 7.0 Silicate - 1.0 5.0 Soap - - 2.0 Brightener 1 0.2 0.2 0.2 Carbonate 8.0 16.0 20.0 DTPMP - 0.4 0.4 Spray On C45E7 1.0 1.0 1.0 Dry additives PVPVI/PVNO 0.5 0.5 0.5 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.1 0.1 0.1 Cellulase 0.1 - 0.1 0.1 NOBS - 6.1 4.5 PBl 1.0 5.0 6.0 Mn Catalyst 0.3 0.1 0.1 Sodium sulfate - 6.0 Balance (Moisture 100 100 100 and Miscellaneous) CA 022~0226 1998-09-28 W O 97/36991 PCTrUS97/05363 Example 10 The following high density and bleach-cont~ining detergent formulations, according to the present invention were prepared:

P Q' R' Blown Powder STPP 15.0 15.0 15.0 MGDA 2.0 2.0 2.0 Sodium sulfate 0.0 5.0 0.0 LAS 3.0 3.0 3.0 QAS - 1.5 1.5 DTPMP 0.4 0.4 0.4 C M C 0.4 0.4 0.4 MA/AA 4.0 2.0 2.0 Agglomerates LAS 5.0 5.0 5.0 TAS 2.0 2.0 1.0 Silicate 3.0 3.0 4.0 Zeolite A 8.0 8.0 8.0 Carbonate 8.0 8.0 4.0 Spray On Perfume 0.3 0.3 0.3 C45E7 2.0 2.0 2.0 C25E3 2.0 - -Dry additives Citrate 5.0 - 2.0 Bicarbonate - 3.0 Carbonate 8.0 15.0 10.0 TAED 6.0 2.0 5.0 PB1 14.0 7.0 10.0 MGDA 0.1 0.2 0.2 ~Mn Catalyst 0.2 0.3 0.4 Polyethylene oxide of M W - - 0.2 5,000,000 W O 97/36991 PCTrUS97/05363 Bentonite clay - - 10.0 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0 4 Amylase 0.6 0.6 0.6 Cellulase 0.6 0.6 0.6 Silicone antifoam 5.0 5.0 5.0 Dry additives Sodium sulfate 0.0 3.0 0.0 Balance (Moisture and 100.0 100.0 100.0 Miscellaneous) Density (g/litre) 850 850 850

Claims (11)

WHAT IS CLAIMED IS:

1. A bleaching composition comprising a) a metal-containing bleach catalyst;

(b) an oxygen-releasing bleach system; and (c) an amino tricarboxylic acid or salt thereof wherein said amino tricarboxylic acid has the general formula:

where R1, R2 and R3 are alkyl groups or substituted alkyl groups of chain length C1 to C4; n is 0 or 1; and X is an organic substituent group.

2. A bleaching composition according to Claim 1 wherein said metal-containing bleach catalyst is a manganese or cobalt-containing bleach catalyst.

3. A bleaching composition according to either of Claims 1 or 2 wherein said metal-containing bleach catalyst is present at levels of between 0.001%
and 5% by weight of bleaching composition.

4. A bleaching composition according to any of Claims 1 to 3 wherein said oxygen-releasing bleach system comprises a hydrogen peroxide source and a peroxyacid bleach precursor compound.

5. A bleaching composition according to Claim 4 wherein said hydrogen peroxide source is an inorganic perhydrate salt.

6. A bleaching composition according to Claim 5 wherein said inorganic perhydrate salt is present at a level from 1 % to 95 % by weight of the bleaching composition.

7. A bleaching composition according to any of Claims 1 to 6 wherein said amino tricarboxylic acid is methyl glycine diacetic acid.

8. A bleaching composition according to any of Claims 1 to 7 wherein the amino tricarboxylic acid is present at a level of greater than 0.0001% by weight of the bleaching composition.

9. A bleaching composition according to any of Claims 1 to 8 wherein the amino tricarboxylic acid is in the form of its sodium or potassium salt.

10. Use of the bleaching composition according to any of Claims 1 to 9 in a machine dishwashing method.

11. Use of the bleaching composition according to any of Claims 1 to 9 in a machine dishwashing method.