CA1230797A

CA1230797A - Detergent compositions

Info

Publication number: CA1230797A
Application number: CA000461754A
Authority: CA
Inventors: Nigel J. Kermode; Charles D. Bragg; Alastair J. Pretty
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1983-08-27
Filing date: 1984-08-24
Publication date: 1987-12-29
Also published as: DE3472571D1; EP0137669A1; JPH0635596B2; EP0137669B1; JPS60106895A; IE57606B1; IE842178L

Abstract

DETERGENT COMPOSITIONS
ABSTRACT
Detergent compositions comprising from about 5% to about 60%
organic surfactant, from about 7% to about 80% detergency builder essentially free of phosphate and a bleach system. The detergency builder has defined calcium builder capacity and defined magnesium:calcium selectivity and is preferably a mixture of an aluminosilicate and a polycarboxylate. The bleach system comprises peroxy bleaching agent, heavy metal scavenging agent and preferably a bleach activator. The compositions combine excellent bleach stability, fabric damage characteristics and detergency performance.

Description

~3[379~

DETERGENT COMPOSITIONS
.

The present invention relates to detergent compositions. In particular, it relates ~o built laundry detergent co~positions which are es6entially free of phosphate and have exc~llent cleaning, whiteness maintenance and stain-removal performance together with improved bleach stability and fabric-care characteristics.
The role of phosphate detergency builders as adjuncts for organic, water-soluble, synthetic detergents and their value in improving the overall performance of such detergents are well-known. In recent years, however, the use of high levels ~f phosphate builders, such as the tripolyphosphates, has come under scrutiny because of the su6picion that soluble phosph~te specLes accelerate the eutrophication or ageing process of water bodies.
me need exists, therefore for a built laundry detergent composition which is free of phosphate but which i~ comparable to a conventional tripolyphosphate-built composition in overall detergency effectiveness.
The mechanism whereby detergency builders function to improve the detergency action of water-soluble organic detergent compounds is not precisely known, but appears to depend on a combination of such factors as water-softening action, soil su6pension and anti-redeposition effects, clay swelling and peptization and pH
adjustment. However, present theory doe~ not allow the prediction of which compound~ will serve as effective detergency builders. Sodium alumino~ilicates, commonly known as zeolites have been proposed for use as phosphate builder substitute6 since they are able to soften water by removing calcium ions (see, for example, BE-A-814,B74 and BE-A-813581). Zeolite6 are unable to 3~ duplicate the full range of builder functions demonstrated by phosphates, however, and in practice, they have been restricted to the role of a partial phosphate substitute.

"~.

~;~3~'79~7 One way of boosting the overall detergency of zero-phosphate formulations is through the use of bleaching auxiliaries such as the inorganic or organic peroxy bleaches and organic bleach activators. Although careful rebalancing of builder and bleach types and levels can indeed provide some improvement in performance, such formulations remain fundamentally weak in three areas, firstly bleach stability, secondly fabric damage characteristics, and thirdly, greasy and particulate soil removal especially at low wash temperatures.
Applicants have now found, however, that a zero phosphate builder system having defined building capacity and defined selectivity for magnesium versus calcium, in combination with certain heavy-metal scavenging agents results in excellent through-the-wash bleach stability a~d fabric damage characteristics. Moreover, applicants have further discovered that certain organic peroxy acid bleach precursors of defined--chain length are operable in combination with the zero-phosphate builder system to provide at least phosphate-equivalent cleaning performance across the range of wash temperature-s with particularly outstanding performance-on greasy and particulate soils at low wash temperatures.
According to a first aspect of the invention, therefore, there is provided a detergent composition comprising a) from about 5% to about 60% of organic surfactant selected from anionic, nonionic, zwitterionic, ampholytic and cationic surfactants and mixtures thereof, b) from about 7% to about 80% of a detergency builder essentially free of phoRphate having a calcium builder 3~ capacity at pH 10 and 25C of at least 1.5 moles/kg and a magnesiumscalcium selectivity factor of at least 0.2 and comprising (i)from 2% to 30% of polycarboxylate polymer selected from compounds having the empiricai formula I

_ _ Rl - yp - ( X - CR3) R2 _ C02M n wherein X is 0 or CH2, Y is a comonomer or mixture oS comonomer~, Rl and R2 are bleach and alkali-stable polymer-end group~, R3 i8 H, OH or Cl_4 alkyl, M i8 ~, alkali metal, alkaline earth metal, ammonium or substituted am~onium groups, p is from O to 2, and n is at least 10, and mixtures thereof (ii)-from 5% to 50% of a water insoluble ion-exchange material having the formula II

Mz[Al02)z (SiO2)y] xH20 II

wherein M i8 a calcium-exchange cation, z and y are at least 6; the molar ratio of z to y is in the range from about 1.0 to about 0.5; and x is from about 10 to about 264; the aluminosilicate having a calcium ion exchange capacity of at least 200 milligrams equivalent of CaC03/gram, a calcium ion exchange rate of at least about 2 grains of Ca2+/gallon/minute/gram/gallon, and a particle size diameter of from about 0.1 microns to about 10 microns, and c) a bleach system compri~ing (i) from 5% to 35~ of inorganic or organic peroxy bleaching agent, (ii) from 0% to 10% of organic peroxy acid bleach precursor, and (iii) a heavy metal scavenging agent.
In another aspect o$ the invention there is provided a detergent composition comprising _ 4 ~ '7~7 a) ~rom about 5% to about 60~ of organic surfactant selected fron anionic, nonionic, zwitterionic, ampholytic and cationic surfacants and Lixtures thereof, b) from about 7% to about 80% of a detergency builder essentially free of phosphate having a calcium builder capacity at 25C of at least l.S moles/kg and a magnesium:calcium selectivity factor of at least 0.2, and c) a bleach system comprising (i) from S~ to 35~ of inorganic or organic peroxy bleaching agent, (ii) from 0.5~ to 10% of organic peroxy acid bleach precursor having the general formula IV, and A 1l R~-C-L IV

wherein R4 is an alkyl group containing 6 to 12 carbon atoms wherein the longest linear alkyl chain extending from and including the carboxyl carbon contains from 5 to 10 carbon atoms and L is a leaving group, the conjugate acid of which has a PKa in the range from 6 to 13, and (iii) a heavy metal ~cavenging agent.
The compositions of the invention contain an organic surfactant, an essentially non-phosphate detergent builder and a bleach system. The detergent builder has defined calcium building capacity and defined magnesium;calcium building eelectivity. The compositions can be liquid or solid, granular spray-dried compositions being preferred.

~23~ 7 The compositions of the invention contain from about 7% to about 80%, preferably from about 10% to about 60%, more preferably from about 15% to about 50% of a det0rgency builder which i8 essentially free of phosphate, i.e. which contains less than about 2%, preferably less than about 1/2% phosphate on a compositional baB i 8 -The detergency builder herein has a calcium buildingcapacity at pH 10 and 25C of at least 1.5, preferably at least 2.0, more preferably at least 3.5 moles Ca2 /kg of builder and a magnesium:calcium selectivi~y factor of at least 0.2, preferably at least 0.25, more preferably at least 0.3.
The building capacity and selectivity factor are measured as follows.
Calcium building capacity (CO) is measured using a Corning calcium ion selective electrode (from Scientific Products, Corning Medical, Corning Ltd., Halstead, Essex, England) with an Orion Double Junction Reference Electrode Model 90-02 (Orion Research Inc., Cambridge, Mass., U.S.A.) as reference. A
calcium ion solution (0.05 M) is titrated into a solution (0.4%) containing the builder under test at pH 10 and 25C. The free calcium ion concentration i8 detexmined as a function of added calcium ions using the calcium electrode precalibrated against a number of standard calcium solutions. The calciu~ ion solution is added until free calcium reaches 5 x 10 3M.
Calcium building capacity is calculated graphically from the molar quantity of added calcium ions corresponding to the intercept at zero free calcium ion concentration of the gradient ~ through 5 x 10 3M and is reported in moles Ca2 /kg of builder.
Magnesium2calcium ~electlvity factor i~ again determined using the calcium ion selective electrode. In this case, 3~ h~wever, the hardness solution contains both calcium and magnesium ion~ (0.03 M each) and the calcium building capacity 80 measured (Cl), or more accurately the reduction in calcium building capacity (CO - Cl), correlates with the selectivity of the builder for magnesium as compared with calcium. The ~electivity factor herein is defined by the quotient ( O Cl)/cO-The essentially zero-phoBphate detergency builder preferably -co~prise~ a mixture of a polycarboxylate polymer and a water-insoluble, ion-exchangeable aluminosilicate. The polycarbo~ylate i8 pre~erably selected to have a magnesium building capacity of at least 2.0 preferably at least 3.0, more preferably at least 3.5 moles/kg as measured at both 25 C and 90C: in other words, the builder should have substantial magnesium building capacity acro~s the range of wash temperatures. Magneæium building capacity can be measured as 1~ for calcium building capacity above but using an Orion Divalent Cation Electrode. Alternatively, magnesium building capacity can be measured on the basis of a turbidity method as follows.
A solution o~ magnesium ions to.4M) is titrated into a solution of the polycarboxylate (1~) at pH 10.3 and at the specified temperature. The solution additionally contains 1.6:1 ratio sodium silicate (0.5%) aq indicator. Precipitation of magnesium silicate above the building limit of the polycarboxylate is monitored using a Mettler phototitrator.
Magnesium building capacity is calculated from the molar quantity of added magnesium corresponding to the point of maximum change in gradient in the turbidity vs added magnesium plot and is reported here in moles Mg2 /kg of polycarboxylate.
Preferred polycarboxylates fall into several categories. A
first category belongs to the class of copolymeric polycarboxylates which, formally at least, are formed from an unsaturated polycarboxylic acid such as maleic acid, citraconic acid, itaconic acid and mesaconic acid as first monomer, and an unsaturated monocarboxylic acid such as acrylic acid or an alpha -Cl 4 alkyl acrylic acid as second monomer. Referring to formula I, therefore, preferred polycarbQxylates of this type are those in which X i~ CH2, R i~ H or Cl_4 alkyl, especially methyl, p i9 from about 0.1 to about 1.9, preferably from about 0.2 to about 1.5, n averages from about 10 to abo~t 1500, preferably from about 50 to about 1000, more preferably from 100 to 800, especially from 120 to 400 and Y comprises monomer units of formula III

~3~79~

CH CH ----C02M C~2M
A second category belongs to the class of poly (alpha-hydroxyacrylates) in which, referring to formula I, X
is CH2, R3 is OH, p is from O to 0.1, prefexably O and n averages from about 50 to 1500, preferably from about 100 to 1000. Y, if present, can be a polycarboxylic acid such as III above, or an ethylene oxide moiety.
A third category belongæ to the cla~s of acetal polycarboxylates in which, referring to formula I, X is O, R3 is H, p is from O to 0.1, preferably O and n averages from lO to 500. If present, Y again can be a polycarboxylic acid such as III above or an ethyleneoxide moiety.
A fourth category belonys to the cla~s of homopolymeric polyacrylates in which referring to formula I, X i~ CH2, R is ~ or Cl 4 alkyl, p is O and n averageC from about 10 to 1500, preferably from about 500 to 1000.
A fifth category of polycarboxylate has the formula I in which X is CH2, R3 is H or Cl_4 alkyi, especially methyl, p i9 from 0.01 to 0.09, preferably from 0.02 to 0.06, n averages from about 10 to about 1500, preferably from about 15 to about 300 and Y is a polycarboxylate formed from maleic acid, citraconic acid, itaconic acid or mesaconic acid, highly preferred being maleic acid-derived comonomers of formula III above.
The alkali-stable polymer end groups in formula I
suitably include alkyl groups, oxyalkyl groups and alkyl carboxylic acid groups and salts and ester~ thereof.
In the above, n, the degree of polymerization of the polymer can be determined from the weight average polymer molecular weight by dividing the latter by the average monomer molecular weight. Thu~, for a maleic-acrylic copolymer having a weight average molecular weight of 15,500 and comprising 30 mole ~ of maleic acid derived units, n is 182 (i.e. 15,500 / (116 x 0.3 ~ 72 x 0.7).

~'~3Q'7~7 In case of doubt, weight-average polymer ~olecular --weights can be determined herein by gel permeation chromotography using Waters ~Porasil (RTM) GPC 60 A2 and ~ ondagel (RTM) E-125, E-500 and E-1000 in series, temperature-controlled column~ at 40C against ~odium polystyrene sulphonate polymer standards, available from Poly~er Laboratories Ltd., Shropshire, UK, the polymer standards being calibrated as their sodium salts, and the eluant being 0.15M sodium dihydrogen phosphate and O.O~M
tetramethyl ammonium hydroxide at pH 7.0 in 80/20 water/acetonitrile.
Mixtures of polycarboxylates are also suitable herein, especially mixtures comprising a high molecular weight component having an n value of at least 100, preferably at least 120, and a low molecular weight component having an n value of less than 100, preferably from 10 to 90, more preferably from 20 to 80. Such mixtures are optimum from the viewpoint of providing excellent bleach stability and anti-incrustation performance in the context of a

2~ zero-phosphate detergent formula.
In mixtures of this type, the weight ratio of high ~olecular weight component to low molecular weight component is generally at least 1:1, preferably from about 1.1:1 to about 20:1, more preferably from about 1.5:1 to about 10.1, especially from about 2:1 to about 8:1. Preferred polycarboxylates of the low molecular weight type are polycarboxylates of the fourth category (homopolyacrylates) listed above.
Of all the above, highly preferred polycarboxylates herein are those of the first category in which n averages fro~ 100 to 800, preferably from 120 to 400 and mixtures thereof with polycarboxylates of the fourth category in which n averages from 10 to 90, preferably from 20 to 80.
According to a further aspect of the invention, therefore, there is provided a detergent composition co~prising - g ~L23C~'7~37 a) from about 5~ to about 60% of organic surfactant selected from anionic, nonionic, zwitterionic, ampholytic and cationic surfacants and mixtures thereof, b) from about 7~ to about 80% of a detergency builder essentially free of phosphate having a calcium builder capacity at 25C of at least 1.5 moles/kg and a magnesium:calcium selectivity factor of at least 0.2, wherein the builder comprises from 24 to 30~ of a mixture of (i) a copolymeric polycarboxylate having the general formula I:

Rl ~ Y - ( X - CR3) ~ R2 I _ _ C02M n wherein X is CH2, Y i8 a maleic-acid derived unit, Rl and R2 are bleach and alkali stable polymer-end groups, R3 is H, M i8 H, alkali metal, alkaline earth metal, ammonium or substituted ammonium, p i8 from about 0.1 to about 1.9 and n . averages from 120 to 400, and (ii) a homopolymeric polyacrylate having the general I in which X, Rl, R2, R3 and M are each as defined in (i) above, p is 0 and n averages ~rom 10 to 90, preferably from 20 to 80, the weight ratio o~
copolymeric polycarboxylate to homopolymeric polyacrylate being at lea~t 1l1, and c) a bleach system comprising . (i) from 5% to 35% of inorganic or organic peroxy bleaching agent, (ii) from 0% to 10% of organic peroxy acid bleach precursor, and (iii) a heavy metal scavenging agent.

~3~ 3'7 -- 10 ~
The aluminosilicate ion-e~change materials herein are preferably those having the unit cell formula M [(A102)z (SiO2)y] xH20 wherein M i5 a calcium-exchange cation, z and y are at lea~t 6: the molar ratio of z to y i8 from about 1.0 to about 0.5 and x i8 at leaQt 5, preferably from about 7.5 to about 276, more preferably from about 10 to about 2Ç4. The aluminosilicate materials are in hydrated from and are preferably crystalline containing from about 10% to about 28%, more preferably from about 18% to about 22% water.

The aluminosilicate ion exchange material~ are further characterized by a particle size diameter of from about 0.1 micron to about 10 microns, preferably from about 0.2 micron to about 4 microns. The term "particle ~ize diameter"
herein represents the average particle size diameter of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope. The aluminosilicate ion exchange materials herein are usually further characterised by their calcium ion exchange capacity, which is at least about 200 mg. equivalent of CaC03 water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from about 300 mg e~./g to about 352 mg eq./g. The aluminosilicate ion exchange materials herein are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca++/gallon/minute/gram/gallon of aluminosllicate (anhydroue basis), and generally lies within the range of from about 2 grains/gallon/minute/gram/gallon to about 6 grains/gallon/minute/gram/gallon, based on calcium ion hardness. Optimum aluminosilicates for builder purposes exhibit a calcium ion exchange rate of at least about 4 grains/gallon/minute/gram/gallon.

3a~7 Alumino~ilicate ion exchange materials useful in the practice of this invention are commerciall~ available and can be naturally occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is discussed in U.S.-A-3,985,669. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, æeolite X, Zeolite HS and mixtures thereofO In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material is Zeolite A and has the formula 12[A12)12 (Si2)12] XH20 wherein x is from about 20 to about 30, especially about 27.
Zeolite X of formula Na86 [(A102)86~sio2)lo6] 276 H20 is also suitable, as well as Zeolite HS of formula Na6 [(A102)6(sio2)6] 7-5 H20)-The polycarboxylate and aluminosilicate components constitute from about 2~ to about 30% and from about 5% to about 50% by weight of composition respectively, more preferably from about 3% to about 10% and from about 10% to about 25% respectively. As a percentage of the builder, polycarboxylate and aluminosilicate constitute from about 5% to about 60% and from 20~ to 95% respectively, preferably from about 10% to about 40% and from 25~ to 75% respectively.
Importantly, the selection of polycarboxylate and the relative amounts of polycarboxylate and aluminosilicate should be such as to meet the critical magnesium;calcium selectivity factor. Usually, the weight ratio o~ polycarboxylatesaluminosilicate is from about 2sl to ls20, preferably from about 1:1 to ls5. Preferred mixtures herein are such, however, that at a 1:1 ratio, the builder displays

3~ a magnesium:calcium selectivity factor of at lea~t about 0.3, preferably at least about 0.35, more preferably at least about 0.4.
The polycarboxylate and aluminosilicate components of the present compositions can be replaced at least in part by other non-phosphate builder materials provided that the total builder system meets the constraints of calcium builder capacity and magnesium:calcium selectivity factor specified earlier.

- 12 - ~3~7 Specific example~ o~ non-phosphorus, inorganic builders are --sodium and potassium carbonate, bicarbonate, ~esquicarbonate, tetraborate decahydrate, and silicate having a molar ratio of Si~2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1~0 to about 3.2, more preferably from about 1.6 to about 2.4. "Seeded carbonate" builders as disclosed in Be-A-798,856 are also suitable. Water-soluble, non-phosphorus organic builders useful herein include the variou~ alkali metal, ammonium and substituted ammonium carboxylates, monomeric polycarboxylates, polyhydroxysulfonates and nitrilotriacetates.
Examples of monomeric polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammoniu~ salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.

Other useful builders hérein are ~odium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, nitrilotriacetate, cis-cyclohexanehexacarboxylate, cis-cyclopentanetetracarboxylate, and phloroglucinol trisulfonate. Such additional non-phosphorus inorganic builders 2~ can be included in levels of from about 0.5~ to about 8%, preferably from about 1% to about 4~ by weight of composition.
The detergent compositions herein contain from about 5% to about 60% by weight of an organic surfactant selected from anionic, nonionic, zwitterionic, ampholytic and cationic surfactants, and mixtures thereof. The surfactant preferably represents from about 8% to about 30%, more preferably from about 10% to about 20~ by weight in the case of solid compositions and from about 10% to about 50~, ~ore preferably from about 15~ to about 40% in the case of liquid compositions.
Surfactants useful herein are listed in US-A-4,222,905 and US-A-4,239,659.
The anionic surfactant can be any one or more of the materials used conventionally in laundry detergents. Suitable synthetic anionic surfactants are water-soluble salts of alkyl benzene sulphonates, alkyl sulphate~, alkyl polyethoxy ether sulphates, paraffin sulphonates, alpha-olefin sulphonates, 1~3~7 - alpha-sulpho-carbo~ylate~ and their esters, alkyl glyceryl ether-sulphonates, fatty acid monoglyceride sulphate~ and sulphonates, alkyl phenol polyethoxy ethër sulphate~, 2-acyloxy alkane-l-sulphonate, and beta-alkylo~y alkane sulphonate.
A particularly suitable class of anionic surfactants includes water-soluble salts, particularly the alkali metal, ammonium and alkanolammonium salts or organic sulphuric reaction products having in their molecular structure an alkyl or alkaryl group containing from about 8 to about 22, especially from about 10 to about 20 carbon atoms and a sulphonic acid or sulphuric acid ester group. (Included in the term "alkyl" i8 the alkyl portion of acyl groups). Examples of this group of synthetic detergents which form part of the detergent compositions of the present invention are the sodium and potassium alkyl sulphates,.
especially those obtained by sulphating the higher alcohols (C8 18) carbon atoms produced by reducing the glycerides of tallow or coconut oil and sodium and potassium alkyl benzene sulphonates, in which the alkyl group contains from about 9 to about 15, especially about 11 to about 13, carbon atoms, in 2~ straight chain or branched chain configuration, e.g. those of the type described in U.S-A- 2,220,099 and U.S-A- 2,477,383 and those prepared from alkylbenzenes obtained by alkylation with straight chain chloroparaffins (using aluminium trichloride catalysis) or straight chain olefins (using hydrogen fluoride catalysis). Especially valuable are linear straight chain alkyl benzene sulphonates in which the average of the alkyl group is about 11.8 carbon atoms, abbreviated as Cll 8 LAS, and C12-C15 methyl branched alkyl sulphates.
Other anionic detergent compounds herein include the sodium 3~ C10_18 alkyl glyceryl ether sulphonates, eapecially those ethers of higher alcohols derlved from tallow and coconut oil;
sodium coconut oil fatty acid monoglyceride sulphonates and sulphates; and sodium or potassium ~alts of alkyl phenol ethylene oxide ether sulphate containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain about 8 to about 12 carbon atoms.

- 14 ~ 3!D'797 Other useful-anionic detergent compounds hersin include the -water-soluble salts or esters of alpha-sulphonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the e~ter group;
water-soluble salts of 2-acyloxy-alkane-1-sulphonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety;
alkyl ether sulphates containing from about 10 to 18, especially about 1~ to 16, carbon ato~s in the alkyl group and from about 1 to 12, especially 1 to 6, more especially 1 to 4 moles of ethylene oxide; water-soluble salts of olefin sulphonates containing from about 12 to 24, preferably aout 14 to 16, carbon atoms, especially those made by reaction with sulphur trioxide followed by neutralization under conditions such that any sultones present are hydrolysed to the corresponding hydroxy alXane sulphonates; water-soluble salts of paraffin sulphonates containing from about 8 to 24, especially 14 to 18 carbon atoms, and beta-alkyloxy alkane sulphonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
The alkane chains of the foregoing non-soap anionic surfactants can be derived from natural sources such as coconut oil or tallow, or can be made synthetically as for example using the Ziegler or Oxo processes. Water solubility can be achieved by using alkali metal, ammonium or alkanolammonium cations;
sodium is preferred. Suitable fatty acid soaps can be selected from the ordinary alkali metal (sodium, potassium), ammonium, and alkylolammonium salts of higher fatty acids containing from about 8 to about 2~, preferably from about 10 to about 22 and especially from about 16 to about 22 carbon atoms in the alkyl chain. Suitable fatty acids can be obtained from natural sources such as, for instance, from soybean oil, castor oil, tallow, whale and fish oils, grease, lard and mixtures thereof). me fatty acids also can be synthetically prepared (e.g., by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-Tropsch process). Resin acids are suitable such as rosin and those resin acids in tall oil.

3'7~7 Napthenic acids are also suitable. Sodium and potassium soaps can be made by direct saponification of the fats and oils or by the neutralization of the free fatty acids which are prepared in a separate manufacturing process. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from tallow and hydrogenated fish oil.
Mixtures of anionic surfactants are particularly suitable herein, especially mixtures of sulfonate and sulfate ~urfactants in a weight ratio of from about 5:1 to about 1:5, preferably 1~ from about 5:1 to about 1:1, more preferably from about 5:1 to about 1.5:1. Especially preferred i-~ a mixture of an alkyl benzene sulfonate having from 9 to 15, especially 11 to 13 carbon atoms in the alkyl radical, the cation being an alkali metal, preferably sodium; and either an alkyl sulfate having from 10 to 20, preferably 12 to 18 carbon atoms in the alkyl radical or an ethoxy sulfate having from 10 to 20, preferably ~0 to 16 carbon atom-q in the alkyl radical and an average degree of ethoxylation of 1 to 6, having an alkali metal cation, preferably sodium.
The nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in the range from about 8 to 17, preferably from about 9.5 to 13.5, more preferably from about 10 to about 12.5. The hydrophobic moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance b0tween hydrophilic and hydrophobic elements.
3~ Examples of suitable nonionic surfactants include:
1. The polyethylene oxide condensates of alkyl phenol, e.g. the condensation products of alkyl phenols having an alkyl group containing from 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 3 to 30, preferably 5 to 14 moles of ethylene oxide per mole of alkyl phenol. The alkyl ~ubstituent in such compounds may be derived, - 16 - ~3~797 for example, from polymerised propylene, di-~30butylene, octene and nonene. Other exa~ples include dodecylphenol condensed with 9 moles of ethylene oxide per mole of phenol; dinonylphenol condensed with 11 moles of ethylene o~ide per mole of phenol;
nonylphenol and di-isooctylphenol condensed with 13 moles of ethylene oxide.
2. The condensation product of primary or secondary aliphatic alcohols having from 8 to 24 carbon atom~, in either straight chain or branched chain configuration, with from 2 to about 40 mole~, preferably 2 to about 9 moles of ethylene oxide per mole of alcohol. Preferably, the aliphatic alcohol comprises between 9 and 18 carbon atoms and i~ ethoxylated with between 2 and 9, desirably between 3 and 8 moles of ethylene oxide per mole of aliphatic alcohol. The preferred surfactants are prepared fro~
primary alcohols which are either linear (such as those derived from natural fats or, prepared by the Ziegler process from ethylene, e.g. myristyl, cetyl, stearyl alcohols), or partly branched such a~ the Lutensols, Dobanols and Neodols which have about 25% 2-methyl branching (Lutensol being a Trade Name of BASF, Dobanol and Neodol being Trade Names of Shell), or Synperonics, which are understood to have about 50~ 2-methyl branching (Synperonic is a Trade Name of I.C.I.) or the primary alcohols having more than 50% branched chain structure sold under the Trade Name Lial by Liquichimica. Specific examples of nonionic surfactants falling within the scope of the invention include Dobanol 45-4, Dobanol 45-7, Dobanol 45-9, Dobanol 91-2.5, Dobanol 91-3, Dobanol 91-4, Dobanol 91-6, Dobanol 91-8, Dobanol 23-6.5, Synperonic 6, Synperonic 14, the condensation products of coconut alcohol with an average of between 5 and 12 moles of ethylene oxide per mole of alcohol, the coconut alkyl portion having fro~
10 to 14 carbon atoms, and the condensation products of tallow alcohol with an average of between 7 and 12 moles of ethylene oxide per mole of alcohol, the tallow portion comprising essentially between 16 and 22 carbon atoms. Secondary linear alkyl ethoxylates are also suitable in the present compositions, especially those ethoxylates of the Tergitol series having from about 9 to 15 carbon atoms in the alkyl group and up to about 11, especially from about 3 to 9, ethoxy residues per molecule.

- 17 - ~3~)~97 The compounds formed by condensing ethylene oxide with a hydrophobic ba~e formed by the condensation of propylene oxide with propylene glycol. The molecular weight of the hydrophobic portion generally falls in the range of about lS00 to 1800. Such synthetic nonionic detergents are available on the market under the Trade Name of "Pluronic" supplied by Wyandotte Chemicalc Corporation.
Especially preferred nonionic ~urfactants for use herein are the Cg-Cl5 primary alcohol ethoxylates containing 3-8 mole~ of ethylene oxide per mole of alcohol, particularly the C12-C15 primary alcohols containing 6-8 moles of ethylene oxide per mole of alcohol.
Cationic surfactants suitable for use herein include quaternary ammonium surfactants and surfactants of a semi-pola~
nature, for example amine oxides.
Suitable surfactants of the amine oxide class have the general formula V

R5 1+ (CH2)i 1 R6 V
O _ O
wherein R5 is a linear or branched alkyl or alkenyl group having 2~ 8 to 20 carbon atoms, each R6 is independently selected from Cl_4 alkyl and -(CnH2nO)mH where i i8 an integer from 1 to 6, j is 0 or 1, n is 2 or 3 and m is from 1 to 7, the sum total of CnH2nO groups in a molecule being no more than 7.
In a preferred embodiment R has from lO to 14 carbon atoms and each R6 i8 independently selected from methyl and -(CnH2nO)mH wherein m i8 from 1 to 3 and the sum total of C~H2nO groups in a molecule is no more than 5, preferably no more than 3. In a highly preferred embodiment, j i8 0 and each R6 i8 methyl, and R i8 C12-C14 alkyl-3~ Another suitable class of amine oxide species i9 represented by bis-amine oxides having the following substituents.

~ 3~7~7 R : tallow C16-C18 alkyl: palmityl; oleyl: stearyl R6: hydroxyethyl i : 2 or 3 A ~pecific example of this preferred clas~ of bis-amine oxide~
N-hydrogenated C16-C18 tallow alkyl-N,N',N'tri-~2-hydroxyethyl) -propylene-1,3-diamine oxide.
Suitable quaternary ammonium surfactants for use in the present composition can be defined by the general formula VI:

R7 h+ - - (CH2)i R8 l _ R8 z VI

wherein R i6 a linear or branched alkyl, alkenyl or alkaryl group having 8 to 16 carbon atoms and each R i6 Illdependently selected from Cl_4 alkyl, Cl_4 alkaryl and -(CnH2nO)m wherein i is an integer from 1 to S,-j i8 0 or 1, n is 2 or ~ and m i8 from 1 to 7, the sum total of CnH2nO groups in a molecule being no more than 7, and wherein Z represents counteranion in number to give electrical neutrality.
In a preferred embodiment, R7 has from 10 to 14 carbon atoms and each R~ is independently selected from methyl and (CnH2nO)mH wherein m is from 1 to 3 and the sum total of 2~ CnH2nO groups in a molecule is no more than 5, preferably no more than 3. In a highly preferred embodiment j is O, R~ i6 selected from methyl, hydroxyethyl and hydroxypropyl and R7 i 9 C12-C14 alkyl. Particularly preferred surfactants of this class include C12 alkyl trimethylammonium salts, C14 alkyltrimethylammonium salts, coconutalkyltrimethylammonium salts, coconutalkyldimethyl-hydroxyethylammonium salts, coconutalkyldimethylhydroxy-propylammonium salts, and C12 alkyldihydroxyethylmethyl ammonium salts.

- 19 ~.~3~'7~97 Another group of useful cationic compounds are the diammonium salt~ of formula VI in which j is 1, R is C12-C14 alkyl, each ~8 i~ methyl, hydroxyethyl or hydroxypropyl and i i~ 2 or 3. In a particularly preferred surfactant of this type, R i8 coconut alkyl, R8 i~ methyl and i is 3.
The detergent compositions of the invention al60 include a bleach system comprising an inorganic or organic peroxy bleaching agent, a heavy metal scavenging agent and in preferred compositions, an organic peroxy acid bleach precursor.
Suitable inorganic peroxygen bleaches i~clude sodium perborate mono- and tetrahydrate, sodium percarbonate, sodium persilicate and urea-hydrogen peroxide addition products and the clathrate 4Na2S04:2H202:1NaCl. Suitable orqanic bleaches include peroxylauric acid, peroxyoctanoic acid, peroxynonanoic acid, peroxydecanoic acid, diperoxydodecanedioic acid, diperoxyazelaic acid, mono- and diperoxyphthalic acid and mono-and diperoxyisophthalic acid. The bleaching agent is present-in the compositions of the invention at a level of from about 5~ to about 35% preferably from about 10% to about 25% by weight.
The heavy metal scavenging agent is preferably a water-soluble chelating agent. Preferred are aminopolyacids having four or more acidic protons per molecule. Suitable chelating agents include aminocarboxylate chelating agents such as ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid ~HEEDTA), dihydroxyethylethylenediaminediacetic acid ~DHEEDDA), diethylenetriaminepentaacetic acid ~DETPA), 1,2-diaminocyclohexane-N,N,N',N'-tetraacetic acid (~CTA) and water-soluble salts thereof, and aminopolyphosphonate chelating agents such as ethylenediaminetetra~methylenepho~phonic acid) ~EDTMP), diethylenetriaminepenta~ethylenephOsphoniC acid) ~DETPMP), nitrilotri~methylenephosphonic acid) ~NTMP), hexamethylenediaminetetramethylenephosphonic acid (HMTPM) and water-soluble salts thereof. The above water-soluble sequestrants are generally at a level of from about 0.05% to about 4%
preferably from about 0.1% to about 1.0% by weight. In any event the total content of phosphorus in the present compositions is preferably no more than about 1%, more preferably no more than about 0.1% by weight of total composition.

- 20 ~ 97 The heavy metal scavenging agent herein can also be represented by water-soluble smeCtite-type clay~ selected from saponites, hectorites and sodium and calcium montmorillorites (sodium and calcium here designating the principal inorganic cation of the clay).
While any of the above smectite-type clays can be incorporated in the compositions of the invention, particularly preferred smectite-tyPe clays have ion-e~change capacities of at least 50 meq/lOOg clay, more preferably at least 70 meq/lOOg (meacured, for instance, as described in "The Chemistry and Physics of Clays", p.p. 264-265, Interscience (1979)). Especially preferred materials are as follows:-Sodium Montmorillonite Brock Volclay BC
Gelwhite GP
Thixo-Jel Ben-A-Gel Imvite Sodium Hectorite Veegum F
Laponite SP

Sodium Saponite Barasym NAS 100 Calcium Montmorillonite Soft Clark Gelwhite L

Lithium Hectorite Barasym LIH 200 ~3~

When pre~ent, the above clay~ are generally added at a level of from about 1% to about 20~, more preferably from about 2% ~o about 10% by weight of composition. Such clays also provide a fabric softening benefit to the compo~ition~.
Another suitable heavy metal scavenging agent is water-insoluble, preferably colloidal magne~ium silicate or a water-soluble magnesium salt forming magnesium silicate in the aqueous slurry crutcher mix prior to spray-drying. The magnesium silicate or salt is generally added at a level in the range from 1~ about 0.015% to about 0.2%, preferably from about 0.03% to about 0.15%, more preferably from about 0.05% to about 0.12% by weight (maqnesium basis). Suitable magne~ium salts include magnesium sulfate, magnesium sulfate hepatydrate, magnesium chloride and magnesium chloride hexahydrate.
The compositions of the invention preferably also contain_an organic peroxy acid bleach precursor at a level of from about 0.5%
to about 10%, preferably from about 1~ to about 6% by weight.
Suitable bleach precursors are disclosed in UK-A-2040983, and include for example, the peracetic acid bleach precursors such as tetraacetylethylenediamine, tetraacetylmethylenediamine, tetraacetylhexylenediamine, sodium p-acetoxybenzene sulphonate, tetraacetylglycouril, pentaacetylglucose, octaacetyllactose, and methyl o-acetoxy benzoate. Highly preferred bleach precursors, however, have the general formula IV

R4-l-L IV

wherein R4 is an alkyl group containing from 6 to 12 carbon atoms wherein the longest linear alkyl chain extending from and including the carboxyl carbon contains from 5 to 10 carbon atoms and L is a leaving group, the conjugate acid of which has a pK
3~ in the range from 6 to 13.
The alkyl group, R4, can be either linear or branched and, in preferred embodiments, it contains from 7 to 9 carbon atoms.
Preferred leaving groups L have a PKa in the range from about 7 to about 11, more preferably from about 8 to about 10. Examples of leaving groups are those having the formula ~;~3~

a ) ~ 2 ) xY
0~

and b) ~2 wherein Z is ~, R or halogen, R is an alkyl group having from 1 to 4 carbon atoms, x is O or an integer of from 1 to 4 and Y is selected from SO3M, OSO3M, C02M, N (R )3Q and N (R )2- wherein M i8 H, alkali metal, al~aline earth metal, ammonium or substituted ammonium, and Q is halide or methosulfate.
The preferred leaving group L has the formula (a) in which Z
1~ is H, x is O and Y is sulfonate, carboxylate or dimethylamine oxide radicai. Highly preferred materials are sodium 3,5,5,-trimethylhexanoyloxybenzene sulfonate, sodium 3,5,5-trimethylhexanoyloxybenzoate, sodium 2-ethylhexanoyl oxybenzenesulfonate, sodium nonanoyl oxybenzene sulfonate and sodium octanoyl oxybenzene9ulfonate, the acyloxy group in each instance pref~rably being p-substituted.
The bleach activator herein will normally be added in the form of particles comprising ~inely-divided bleach activator and a binder The binder is generally selected from nonionic 2~ surfactants such as the ethoxylated tallow alcohols, polyethylene glycols, anionic surfactants, film forming polymers, fatty acids and mixtures thereof. Highly preferred are nonionic surfactant binders, the bleach activator being admixed with the binder and extruded in the form of elongated particles through a radial extruder as described in European Patent Application No. 62523, published October 13, 1982.

i~, ,.~ , .

~ '~3 C9'797 The compositiona of the invention can be supplemented by all manner of detergent and laundering components, inclusive of suds suppres~ors, enzymes, fluorescers, photoactivators, bleach catalysts, soil suspending agents, anti-caking agents, pigment~, perfumes, fabric conditioning agents etc.
Suds suppressors are represented by materials of the silicone, wax, vegetable and hydrocarbon oil and phosphate ester varieties. Suitable silicone suds controlling agents~lnclude polydimethylsiloxanes having a molecular weight in the ranga from 1~ about 200 to about 200,000 and a kinematic viscosity in the range from about 20 to about 2,000,000 mm /8, preferably from about 3000 to about 30,000 ~m2/s, and mixtures of siloxanes and hydrophobic silanated (preferably trimethylsilanated) silica having a particle size in the range from about 10 millimicron~ to about 20 millimicrons and a specific surface area above about 50 m2/g. Suitable waxes include microcrystalline waxes having a melting point in the range from about 65 C to about 100C, a molecular weight in the range from about 400-1000, and a penetration value of at lea~t 6, measured at 77 F by ASTM-D1321, 2~ and also paraffin waxes, synthetic waxes and natural waxes.
Suitable phosphate esters include mono- and/or di-C16-C22 alXyl or alkenyl phosphate esters, and the corresponding mono-and/or di alkyl or alkenyl ether phosphates containing up to 6 ethoxy groups per molecule.
Enzymes suitable 40r use herein include those discussed in US-A-3,519,570 and US-A-3,533,139 to McCarty and McCarty et al issued July 7, 1970 and Januar~ 5, 1971, respectlvely. Suitable fluorescers include Blan~opho~ aBH ~Bayer AG) and Tinopal~CBS and EM ~ ~Ciba Gelgy). Photoactlvators are discu8~ed in EP-A-57088, 3~ published August 4, 1982, highly preferred materials being z.lnc phthalocya-nine tri- and tetra-sulfonates. Suitable fabric conditioning agents i.nclude di-C12-C24 alkyl or aLkenyl amines and ammonium and quaternary an ~ nium salts. Suitable bleach catalysts are discussed in European Patent Application No. 72166, published February 16, 19~3 and Europear- ;
Patent Appli.cation No. 124,341, published November 7, 1984.

3~

Antiredeposition and 80il suspen~ion agents suitable herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose.
Liquid detergent compositions of the invention can additionally be supplemented by pH regulators such as potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium hydroxide, sodium carbonate, sodium bicarbonate, and mono-, di-and triethanolamine; solventS such as ethyl alcohol, i~sopropanol, propylene glycol, propane-l, 2-diol, hexyleneglycol; ànd 1~ hydrotopes such as urea.
Granular detergent compositions of the invention are preferably prepared by spray-drying an aqueous slurry comprising the anionic surfactant and detergency builder. The aqueous slurry is mixed at a temperature in the range from about 70-90C and the water-content of the slurry adjusted to a range of about 25%
Spray drying is undertaken with a drying gas inlet temperature of from about 250-350C, preferably about 275-330C, providing a final moisture content in the range of from about 8~ to 14~ by weight.

2~ In the Examples which follow, the abbreviations used have the following designations:-C12LAS Sodium linear C12 benzene sulphonate TAS : Sodium tallow alcohol sulphate C12/14As : C12/l4 alcohol sulphate, sodium salt TAEn : Hardened tallow ~lcohol ethoxylated with n moles o~ ethylene oxide per mole of alcohol 3~ Cl2TMAB : C12 alkyl trimethyl ammonium bromide Dobanol 45E7 : A C14_15 primary alcohol condensed with 7 moles o~ ethylene oxide.
TAED : Tetraacetyl ethylene diamine PAG : Penta acetyl glucose AO~S : Sodium p-acetoxy benzene sulphonate - 25 - ~ ~307~7 NOBS : Sodium nonanoyl oxybenzenesulphonate INOBS : Sodium 3,5,5 trimethyl hexanoyl oxybenzene sulphonate INOBA : Sodium 3,5,5 trimethyl hexanoyl oxybenzoic acid EHOBS : Sodium 2-ethyl hexanoyl oxybenzene sulphonate Silicate : Sodium silicate having an SiO2:Na20 ratio of 1.6 Sulphate : Anhydrous sodium sulphate Carbonate : Anhydrous sodium carbonate CMC : Sodium carboxymethyl cellulose Silicone : Comprising 0.14 part6 by weight of an 85:15 by weight mixture of silanated silica and silicone, granulated with 1.3 parts of sodium tripolyphosphate, and 0.56 parts of tallow alcohol condensed with 25 molar proportions of ethylene oxide 2~ NTA : Sodium nitrllotriacetate PCl : Copolymer of 3:7 maleic/acrylic acid, average molecular weight about 70,000, as sodium salt PC2 : Copolymer of 1:20 maleic/acrylic acid, average molecular weight about 12,000, as sodium salt PC3 : Polyacrylic acid, molecular weight about 70,000, as sodium salt PC4 : Copolymer o~ 3s7 maleic/acrylic acid, 3~ ave~ag~ molecular weight about 15,500 as sodium salt PC5 : Polyacrylic acid, average molecular weight about 4,500, as sodium salt Perborate : Sodium perborate tetrahydrate of nominal formula NaB02.3H20.H202 Enzyme : Protease EDTA : Sodium ethylene diamine tetra acetate ~30'7~'7 -- ~6 --.
Brightener : Disodium 4,4'-bis(2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene-2:2'-disulphonate.
DETPMP : Diethylene triamine penta(methylene phosphonic acid), marketed by Monsanto under the Trade name Dequest 2060 ~DTMP : Ethylenediamine tetra ~methylene phosphonic acid), marketed by Monsanto, under the Trade name Dequest 2041 Clay : Sodium montmorillonite Examples I to VIII
Granular detergent compositions are prepared as follows. A
base powder composition is first prepared by mixing all components except DobanoI 45E7, bleach, bleach activator, enzyme and suds suppressor in a crutcher a~ an aqueous ~lurry at a temperature of about 80C and containing about 35~ water. The slurry i8 then spray dried at a gas inlet temperature of about 300~C to form baæe powder granules. The bleach activator, where present, i~ then admixed with TAE80 as binder and extruded in the form of elongate particles through a radial extruder as described in European Patent Application Number 62523. The bleach activator noodle-~, bleach, enzyme and suds suppressor are then dry-mixed with the base powder composition and finally Dobanol 45E7 is sprayed into the final mixture.

EXAMPLES

I II III IV V VI VII VIII

TAS - - 3 ~ 3 C12/14As 5 3 8 - 4 1 4 TAE80 0 5 0.6 0.8 0.3 0.5 0.8 0.2 TAEll - 0.6 - - 1 - _ 1 Dobanol 45E7 2 6 4 2 - 8 10 5 Cl2TMAB 2 - - - 3 2 2 INOBS - 4 - - - _ _ _ EXAMPLES (Contd) I~OBA - - . 5 _ _ _ _ _ PAG - - _ _ _ 4 _ _ AOBS
Perborate 25 18 10 24 20 18 24 28 EDTMP - 0.4 0.3 - - - 1.0 DETPMP 0.4 - - - 0.5 - - 0.1 EDTA 0.2 0.2 0.2 0.1 0.3 0.1 0.2 0.3 Clay - 6 - 4 Magnesium (ppm) - - 750 - - - - ~00 PCl 1.5 4 2 - 1 7 1 2 Zeolite A* 9 16 12 6 13 24 9 14 Soap 1 3 - 2 - 3 3 2 Carbonate 8 12 10 8 7 13 6 11 Silicate 6 4 7 3 7 5 8 3 Silicone 0.2 0.2 0.3 0.2 0.2 0.4 0.5 0.2 Enzyme 0.1 0.5 0.4 0.3 0.4 0.5 0.7 1.0 Brightener 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Sulphate, Moisture &
Miscellaneous -----------------To 100-------------------------* Zeolite A of 4 A pore size.

The above compogitiong are zero phosphate detergent compositions displaying excellent bleach stability, fabric care and detergency performance across the range of wash temperatures with particularly outstanding performance in the case of Example~
I to IV on greasy and particulate soils at low wash temperatures.

~3ai7~

Examples IX to XII

The following granular detergent compo~itions are prepared as described in Examples I to VIII above.

IX X XI XII

C12/14As 8 AE80 0.8 0.3 0.3 Dobanol 45E7 2 4 6 2 I~OBA - 5 - - _-TAED 0.5 - 2.5 PAG
AOBS - - - 0.8 Perborate 25 10 17 24 EDT M - 0.3 0.3 DETPMP 0.4 - _ 0.4 EDTA - 0.2 0.2 0.2 0.1 Clay - - - 6 Magnesium (ppm) - 800 750 PC5 2 1 1 0.5 Zeolite A (4 A pore size) 11 16 13 5 Zeolite X ~10 A pore size) - ~ - 15 Soap 1 - - 2 Carbonate 8 10 12 12 Silicate 6 5 4 8 Silicone 0.2 0.5 0.3 0.2 Enzyme 0.1 0.3 0.4 0.3 Brightener 0.2 0.2 0.2 0.2 Sulphate, Moisture &
Miscellaneous ----------To 100---~

~3~

The above compo8ltion8 are zero pho8phate detergent compositions displaying excellent bleach stability, fabric care and detergency performance across the range of wash temperatures with outstanding whiteness maintenance performance and low wash temperature detergency performance on greasy and particulate 80ils.

ExampIes XIII to XV
The following granular detergent ~omposition~ are prepared as described in Examples I to VIII above.

C12/14As 4 a TAS
AE80 0.3 0.3 0 4 Dobanol 45E7 6 2 TAED 0.5 - - 2 Perborate 18 10 6 EDTMP 0.3 DETPMP - 0.4 EDTA 0.2 0.2 0.2 Magnesium (ppm) 1000 PCl 2 0.5 PC5 1 0.5 Zeolite A (4 A pore size~ 16 25 15 Carbonate 18 8 10 Silicate 1 6 5 Silicone 0.2 0.5 0.3 Enzyme 0.1 0.3 0.4 Brightener 0.2 0.2 0.2 Sulphate, Moi~ture &
Miscellaneous -----------To 100-----------. . .
The above compositions are zero phosphate detergent compositions displaying excellent bleach ~tability, fabric care and detergency performance across the range of wash temperatures with outstanding whiteness maintenance performance and low wash temperature detergency performance on greasy and particulate soils.

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A detergent composition comprising a) from about 5% to about 60% of organic surfactant selected from anionic, nonionic, zwitterionic, ampholytic and cationic surfactants and mixtures thereof, b) from about 7% to about 80% of a detergency builder essentially free of phosphate having a calcium builder capacity at pH 10 and 25°C
of at least about 1.5 moles/kg and a magnesium:calcium selectivity factor of at least about 0.2 and comprising (i) from about 2% to about 30% of polycarboxylate polymer selected from compounds having the empirical formula I

wherein X is CH2, Y is a comonomer selected from the group consisting of ethylene oxide, maleic acid, citraconic acid, itaconic acid, masaconic acid and mixtures thereof, R1 and R2 are bleach and alkali-stable polymer-end groups, R3 is H, OH or C1-4 alkyl, M is H, alkali metal, alkaline earth metal, ammonium or substituted ammonium, p Is from 0 to 2, and n is at least 10, and mixtures thereof (ii) from about 5% to about 50% of a water insoluble ion-exchange material having the formula II

Mz[(AlO2)z (SiO2)y)] xH2O II

wherein M is a calcium-exchange cation, z and y are at least 6; the molar ratio of z to y is in the range from about 1.0 to about 0.5; and x is from about 10 to about 264; the aluminosilicate having a calcium ion exchange capacity of at least 200 milligrams equivalent of CaCO3/gram, a calcium ion exchange rate of at least about 2 grains of Ca2+/gallon/minute/gram/gallon, and a particule size diameter of from about 0.1 microns to about 10 microns, and c) a bleach system comprising (i) from about 5% to about 35% of inorganic or organic peroxy bleaching agent, (ii) from 0% to about 10% of organic peroxy acid bleach precursor, and (iii) a heavy metal scavenging agent selected from the group consisting of the aminocarboxylate chelating agents, the aminopolyphosphonate chelating agents, the water-soluble smectite-type clays selected from saponites, hectorites and sodium and calcium montmorillonites, water-insoluble magnesium silicate, and mixtures thereof.

2. A composition according to Claim 1 wherein in formula I, Y comprises monomer units having formula III

III

3. A composition according to Claim 2 wherein in formula I, R3 is H or 1-4 alkyl, p is from about 0.1 to about 1.9 and n averages from about 10 to about 1500.

4. A composition according to Claim 3 wherein in formula I, n averages from about 120 to about 400.

5. A composition according to Claim 2 wherein in formula I, R3 is OH, p is from 0 to about 0.1, and n averages from about 50 to about 1500.

6. A composition according to Claim 2 wherein in formula I, R3 is H or C1-4 alkyl, p is 0, and n averages from about 10 to about 1500.

7. A composition according to Claim 2 wherein in formula I, R3 is H or C1-4 alkyl, p is from about 0.01 to about 0.09, and n averages from about 10 to about 1500.

8. A composition according to Claim 1 comprising from about 3% to about 10% of polycarboxylate and from about 10% to about 25% of water-insoluble aluminosilicate.

9. A composition according to Claim 2 wherein the polycarboxylate polymer is a mixture comprising a high molecular weight component having an n value averaging at least 100, and a low molecular weight component having an n value averaging less than 100, the weight ratio of high molecular weight component to low molecular weight component being at least about 1:1.

10. A composition according to Claim 2 wherein the high molecular weight component has an n value averaging at least about 120, and the low molecular weight component has an n value averaging from about 10 to about 90, and wherein the weight ratio of high molecular weight component to low molecular weight component is from about 1.1:1 to about 10:1.

11. A composition according to Claim 1 wherein the polycarboxylate polymer comprises a mixture of (i)a copolymeric polycarboxylate having the general formula I:
wherein Y is a maleic-acid derived unit, R1 and R2 are bleach and alkali stable polymer-end groups, R3 is H, M is H, alkali metal, alkaline earth metal, ammonium or substituted ammonium, p is from about 0.1 to about 1.9 and n averages from 120 to 400, and (ii) a homopolymeric polyacrylate having the general I
in which X, R1, R2, R3 and M are each as defined in (i) above, p is 0 and n averages from about 10 to about 90, the weight ratio of copolymeric polycarboxylate to homopolymeric polyacrylate being at least about 1:1.

12. A composition according to Claim 1 wherein the heavy metal scavenging agent is a chelating agent selected from water-soluble aminopolycarboxylates and aminopolyphosphonates having at least four acidic protons per molecule or a water-insoluble smectite-type clay selected from saponites, hectorites and sodium and calcium montmorillonites.

13. A composition according to any of Claim 1 wherein the organic peroxy acid bleach precursor has the general formula IV.

IV

wherein R4 is an alkyl group containing from about 6 to about 12 carbon atoms wherein the longest linear alkyl chain extending from and including the carboxyl carbon contains from about 5 to about 10 carbon atoms and L is a leaving group, the conjugate acid of which has a PKa in the range from about 6 to about 13.

14. A composition according to Claim 1 having a phosphorus content of no more than 1%, preferably no more than about 0.1%.

15. A detergent composition comprising a) from about 5% to about 60% on organic surfactant selected from anionic, nonionic, zwitterionic, ampholytic and cationic surfactants and mixtures thereof, b) from about 7% to about 80% of a detergency builder essentially free of phosphate having a calcium builder capacity at pH 10 and 25°C of at least about 1.5 moles/kg and a magnesium:calcium selectivity factor of at least about 0.2, and c) a bleach system comprising (i) from about 5% to about 35% of inorganic or organic peroxy bleaching agent, (ii) from about 0.5% to about 10% of organic peroxy acid bleach precursor having the general formula IV

IV

wherein R4 is an alkyl group containing from about 6 to about 12 carbon atoms wherein the longest linear alkyl chain extending from and including the carboxyl carbon contains from about 5 to about 10 carbon atoms and L is a leaving group, the conjugate acid of which has a PKa in the range from about 6 to about 13, and (iii) a heavy metal scavenging agent.

16. A detergent composition comprising (a) from about 5% to about 60% of organic surfactant selected from anionic, nonionic, zwitterionic, ampholytic and cationic surfacants and mixtures thereof, (b) from about 7% to about 80% of a detergency builder essentially free of phosphate having a calcium builder capacity at 25°C of at least about 1.5 moles/kg and a magnesium:calcium selectivity factor of at least about 0.2, wherein the builder comprises from about 2% to about 30% of a mixture of (i) a copolymeric polycarboxylate having the general formula I:
I

wherein X is CH2, Y is a maleic-acid derived unit, R1 and R2 are bleach and alkali stable polymer-end groups, R3 is H, M is H, alkali metal, alkaline earth metal, ammonium or substituted ammonium, p is from about 0.1 to about 1.9 and n averages from about 120 to about 400, and (ii) a homopolymeric polyacrylate having the general I in which X, R1, R2, R3 and M are each as defined in (i) above, p is 0 and n averages from about 10 to 90 and wherein the weight ratio of copolymeric polycarboxylate to homopolymeric polyacrylate is at least 1:1, and c) a bleach system comprising (i) from about 5% to about 35% of inorganic or organic peroxy bleaching agent, (ii) from 0% to about 10% of organic peroxy acid bleach precursor, and (iii) a heavy metal scavenging agent.