CA2199817C

CA2199817C - Nonaqueous bleach-containing liquid detergent compositions

Info

Publication number: CA2199817C
Application number: CA002199817A
Authority: CA
Inventors: Kathleen Brenner Hunter; Josephine Ling Kong-Chan
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1994-09-26
Filing date: 1995-09-08
Publication date: 2000-07-25
Anticipated expiration: 2015-09-08
Also published as: CA2199817A1; DE69514818T2; US5872092A; MX9702315A; EP0783563A1; WO1996010073A1; AU3464295A; TW311933B; BR9509082A; PE17696A1; CN1166856A; JPH10506931A; TR199501167A2; DE69514818D1; EP0783563B1

Abstract

Disclosed are nonaqueous, bleach-containing liquid laundry detergent compositions which are in the form of a suspension of particulate material, including peroxygen bleaching agent and an alkyl sulfate anionic surfactant, dispersed in a liquid phase containing an alcohol ethoxylate nonionic surfactant and a nonaqueous, low-polarity organic solvent. Such compositions provide especially desirable cleaning and bleaching of fabrics laundered therewith and also exhibit especially desirable chemical and phase stability.

Description

~°~~9~17 WO 96!10073 PCT/(1S95/11257 NONAQUEOUS BLEACH-CONTAINING
LIQUID DETERGENT COMPOSITIONS
s FIELD OF THE INVENTION
to This invention relates to heavy duty liquid (HDL) laundry detergent products which are nonaqueous in nature and which contain a bleaching system based on peroxygen bleaching agents.
BACKGROUND OF THE INVENTION
15 Liquid detergent products are often considered to be more convenient to use than are dry powdered or particulate detergent products. Liquid detergents have therefore found substantial favor with consumers. Such liquid detergent products are readily measurable, speedily dissolved in the wash water, capable of being easily applied in concentrated solutions or dispersions to soiled areas on garments to be 20 laundered and are non-dusting. They also usually occupy less storage space than granular products. Additionally, liquid detergents may have incorporated in their formulations materials which could not withstand drying operations without deterioration, which operations are often employed in the manufacture of particulate or granular detergent products.
25 Although liquid detergents have a number of advantages over granular detergent products, they also inherently possess several disadvantages. In particular, detergent composition components which may be compatible with each other in granular products may tend to interact or react with each other in a liquid, and especially in an aqueous liquid, environment. Thus such components as enzymes, 3o surfactants, perfumes, brighteners, solvents and especially bleaches and bleach activators can be especially dif~~cult to incorporate into liquid detergent products which have an acceptable degree of chemical stability.
One approach for enhancing the chemical compatibility of detergent composition components in liquid detergent products has been to formulate 35 nonaqueous (or anhydrous) liquid detergent compositions. In such nonaqueous products, at least some of the normally solid detergent composition components tend to remain insoluble in the liquid product and hence are less reactive with each other WO 96/10073 ~ ~ PCT/US95/11257 than if they had been dissolved in the liquid matrix. Nonaqueous liquid detergent compositions, including those which contain reactive materials such as peroxygen bleaching agents, have been disclosed for example, in Hepworth et al., U.S.
Patent r 4,615,820, Issued October 17, 1986; 5chultz et al., U.S. Patent 4,929,380, Issued May 29, 1990; Schultz et al., U.S. Patent 5,008,031, Issued April 16, 1991;
Elder et ai., EP-A-03 V,U96, Pubiished June i0, i98i; Haii et ai., ~O
921~39678,~ub~ishe~i June 11, 1992 and Sanderson et al., EP-A-565,017, Published October 13, 1993.
Even though chemical compatibility of components may be enhanced in nonaqueous liquid detergent compositions, physical stability of such compositions to may become a problem. This is because there is a tendency for such products to phase separate as dispersed insoluble solid particulate material drops from suspension and settles at the bottom of the container holding the liquid detergent product. As one consequence of this type of problem, there can also be difficulties associated with incorporating enough of the right types and amounts of surfactant materials into nonaqueous liquid detergent products. Surfactant materials must, of course, be selected such that they are suitable for imparting acceptable fabric cleaning performance to such compositions but utilization of such materials must not lead to an unacceptable degree of composition phase separation.
Given the foregoing, there is clearly a continuing need to identify and provide liquid, bleach-containing detergent compositions in the form of nonaqueous liquid products that have a high degree of chemical, e.g., bleach and enzyme, stability along with commercially acceptable phase stability and detergent composition cleaning/
bleaching performance. Accordingly, it is an object of the present invention to provide nonaqueous, bleach-containing liquid detergent products which have such especially desirable chemical and physical stability characteristics as well as outstanding fabric laundering/bleaching performance characteristics.
SUMMARY OF THE INVENTION
The present invention provides nonaqueous liquid heavy-duty detergent 3o compositions comprising a stable suspension of solid, substantially insoluble particulate material dispersed within a nonaqueous liquid phase. The particulate material utilized comprises an inorganic peroxygen bleaching agent and a particular type of anionic surfactant. The liquid phase comprises a particular type of nonionic surfactant and a nonaqueous, low-polarity organic solvent.
Such compositions comprise A) from about 1% to 60% by weight of the composition of a nonionic surfactant component which comprises alcohol ethoxylates of the formula R1(OC2H4)nOH wherein R1 is a C6 - C16 alkyl group 2~9~17 WO 96!10073 PCT/US95/11257 and n is from about 1 to 80; B) from about 10% to 40% by weight of the composition of an anionic surfactant component which is substantially free of alkyl benzene sulfonate surfactant materials and which comprises sulfated anionic surfactants produced by the sulfation of higher Cg - C20 alcohols; C) from about 2%
to 30% by weight of the composition of particles of the peroxygen bleaching agent, which particles range in size from about 0.2 to 1,000 microns; and D) from about 1% to 60% by weight of the composition of the nonaqueous, low-polarity organic solvent component. Such compositions may also contain a wide variety of optional surfactants, builders and alkalinity sources, enzymes, bleach activators, chelating 1o agents, viscosity controVthickening agents, brighteners and perfumes.
DETAILED DESCRIPTION OF TIIE INVENTION
The nonaqueous liquid detergent compositions of this invention comprise a nonionic surfactant - and low-polarity solvent-containing liquid phase having dispersed therein as a solid phase certain types of particulate materials. The essential and optional components of the liquid and solid phases of the detergent compositions herein, as well as composition form, preparation and use, are described in greater detail as follows: All concentrations and ratios are on a weight basis unless otherwise specified.
zo LIOUID PHASE
The liquid phase of the detergent compositions herein essentially contains certain types of nonionic surfactants and certain types of nonaqueous, low-polarity solvents.
(A) Nonionic Surfactant The liquid phase of the detergent compositions of this invention essentially comprises an ethoxylated fatty alcohol nonionic surfactant. Such a material corresponds to the general formula:
3o R1(OC2H4)nOH
wherein R1 is a C6 - C16 alkyl group and n ranges from about 1 to 80.
Preferably the R1 alkyl group, which may be primary or secondary, contains from about 9 to 15 carbon atoms, more preferably from about 10 to 14 carbon atoms. Preferably the ethoxylated fatty alcohol will contain from about 2 to 12 ethylene oxide moieties per' molecule, more preferably from about 3 to 10 ethylene oxide moieties per molecule.
The ethoxylated fatty alcohol nonionic surfactant will frequently have a hydrophilic-lipophilic balance (HI.B) which ranges from about 3 to 17. More -4~
preferably, the HLB of this material will range from about 6 to 15, most preferably from about 10 to 15.
Examples of fatty alcohol ethoxylates useful as the essential liquid nonionic surfactant in the compositions herein will include those which are made from 5 alcohol: of 12 to 15 carbon atoms and which contain about 7 moles of ethylene oxide. Such materials have been commercially marketed under the tradenames Neodol~'15-7 and Neodop23-6.5 by Shell Chemical Company. Other useful Neodol~' include Neodol#1-5, an ethoxylated fatty alcohol averaging 11 carbon atoms in its alkyl chsin with about 5 mole of ethylene oxide; Neodol~ 23-9, an etltoxylated to primary C 12 - C 13 alcohol having about 9 moles of ethylene oxide and Neodot~91-10, an ethoxylated Cg - C 11 primary alcohol having about 10 moles of ethylene oxide. Alcohol ethoxylates of this type have also been marketed by Shell Chemical Company under the Dobanotxvadename. Dobano~9l-5 is as ethoxylsted Cg-C 11 .
fatty alcohol with art avenge of S moles ethylene oxide and Dobanol~25-7 is an is ethoxylsted C 12-C 15 ~y ~oohol with an averagt of 7 moles of ethylene oxide per mole of fatty alcohol.
Other acamples of suitsbls ethoxylated s>colat nonionic sub inchide Te:gitol~i5-S-7 and Tergitol*15-S-9 both of which are linear secondary alcohol ethoxylues the have been conunercially marketed by Union Carbide Corporation.
2o The former is a mixed ethoxylation product of C 11 to C 15 linear seconduy alk>noi with 7 moles of ethylene oxide and tire latter is s sirnalar product but with 9 moles of ethylens oxide being reacted.
Otlur typo of alcohol ethoxylate nonionic: uteRrl in the present compositions am higher molecular waght noniordea, such as Neodol°'45-11, which aro simile 2s ethyimrs oxide condelt:uion products of highs fatty aicohols~ with the higher fatty alcohol being of 14.15 carbon storru and the rnunbes of ethylene oxide groups pa mots bang about 11. Such products have also bees connnercially marketed by Shell CI»l Compsay.
The alcohd ethoxylats nonionic which is ~sartiaUy utilized as part of the 30 liquid phase of the nonaqueous compoaitioru 1>aeirt will geners>ly be present to the extent of 8rom abort lye to 60'/~ by weight of ttte compootion. More preferably, the alcolroi etiroxylate nonionic will comprise from about 5~/~ to 35'/. by waght of the compositions herein. Most prefanbly, the esaentialty utilized alcohol ethoxylste nonionic will comprias from about 8°~ to 25'/~ by weight of the detergent 33 compositions heroin.
Trademarks _5. t (B) I~lona_au_enuc r_ow.polaritv Organic Solv A second essential component of the liquid phase of the detergent compositions herein comprises nonaqueous, low-polarity organic solvent(s). The term "solvent" is used herein to connote the non-surface active carrier or diluent portion of the liquid phase of the composition. While some of the essential and/or optional components of the compositions herein may actually dissolve in the "solvent"-containing liquid phase, other components will be present as particulate material dispersed within the "solvent"-containing liquid phase. Thus the term "solvent" is not meant to require that the solvent material be capable of actually to dissolving al! of the detergent composition components added thereto.
The nonaqueous organic materials which are employed as solrems herein are those which are liquids of low polarity. For purpose: of this invention, "tow polarity" liquids are those which have little, if any, tendency to dissolve the peroxygen bleach, e.g., sodium perborstei and optional bleach activators, -erg., is sodium nonanoyloxybenzene sulfonate (HOBS), which are present in the nonaqu~ compositions herein Thus relatively polar solvents such as etharroi and propsnediol should not be utilized. Suitable typee of low polarity solvents useful in .. the nonaqueov: liquid detergent compositions herein do include alkylene glycol mono lower alkyl ethers, lower molecular weight polyethylene glycols, lower 2o molecular weight mathyi esters and amides, and the like.
A proferrcd type of nonaquaou:, low.polarity solvent for ux herein comprises the mo-, di-, tri-, or tetra- CZ ~ C3 alkylene glycol mono CZ - C6. ~kyl Chas.
Spoci$c examples of such compaatds include diethyiene glycol monobutyi ether, t~a~hylent gly~l monob~yl et~, diProPohrate glyoOl monoeth~rl ether and ZS dipropy~ne gly~ool ntonobutyi ether. Diethyiene glycd monobutyl esltar and dipropylene glycol monobutyl ether are espeaall~r preferred. Compounds of this type haws been conanercialty marketed under the tradename: Dowano~
Carbitof~and Ce>losoiv~s~ ~.
Another preferred type of nonaqueous, lowpolarity organic solvent useful 3o heraiu comprises ttte lows molecular weight potyethyieae glycob (PEGS).
Such materials an those having molecular weights of a least about 150. PEGs of mole~u weight ranging from shout 200 to 600 ue most preferred.
Yet another prcfared type of non-polar, nonaqueous solvent comprises lower molecular waght methyl eaters. Such materials aro thoas of the general formula:
3s Rl-C(O~OCH3 when Rl ranges from 1 to about 18. F.xampia of suitable lower moleculsr weight methyl esters include methyl accrue, methyl propionate, methyl octanoste and methyl dodecanoue.
Trademarks ~~gg~~

The nonaqueous, low-polarity organic solvents) employed should, of course, be compatible and non-reactive with other composition components, e.g., bleach and/or activators, used in the liquid detergent compositions herein. Such a solvent component will generally be utilized in an amount of from about 1% to 60% by weight of the composition. More preferably, the nonaqueous, low-polarity organic solvent will comprise from about 15% to 45% by weight of the composition, most preferably from about 20% to 45% by weight of the composition.
SOLn7 PHASE
1o The nonaqueous detergent compositions herein also essentially comprise a solid phase of particulate material which is dispersed and suspended within the liquid phase. The two essential components of the solid phase are A) a peroxygen compound bleaching agent, and B) a certain type of anionic surfactant. Each of these essential components is described in greater detail as follows:
(A) Peroxvr~en Bleaching Agent With Optional Bleach Activators One essential component of the solid phase of the detergent compositions herein comprises particles of a peroxygen bleaching agent. Such peroxygen bleaching agents may be organic or inorganic in nature. Inorganic peroxygen 2o bleaching agents are frequently utilized in combination with a bleach activator.
Useful organic peroxygen bleaching agents include percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, Issued November 20, 1984; European Patent Application EP-A-133,354, Banks et al., Published February 20, 1985; and U.S. Patent 4,412,934, Chung et al., Issued November 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-oxoperoxycaproic acid (NAPAA) as described in U.S. Patent 4,634,551, Issued 3o January 6, 1987 to Burns et al.
Inorganic peroxygen bleaching agents may also be used in particulate form in the detergent compositions herein. Inorganic bleaching agents are in fact preferred.
Such inorganic peroxygen compounds include alkali metal perborate and percarbonate materials. For example, sodium perborate (e.g. mono- or tetra-hydrate) can be used. Suitable inorganic bleaching agents can also include sodium or potassium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
Persulfate bleach (e.g., OXON~; manufactured commercially by DuPont) can also be used.
Frequently inorganic peroxygen bleaches will be coated with silicate, borate, sulfate or water-soluble surfactants. For example, coated percarbonate particles are available from various commercial sources such as FMC, Solvay Interox, Toksi s Denka and Degussa.
Inorganic peroxygen bleaching agents, e.g., the perborates, the percarbonates, etc., are preferably combined with bleach activators, which lead to the in sire production in aqueous solution (i.e., during use of the compositions herein for fabric laundering/bleaching) of the peroxy acid corresponding to the bleach activator.
Various non-limiting examples of activators arc disclosed in U.S. Patent 4,915,854, Issued April 10, 1990 to Mao et al.; and U.S. Patent 4,412,934 Issued November 1, 1983 to Chung et al. The nonanoyioxybenzate sulfonste (NOES) and tetraacetyi ethylene diamine (TAED) activators sro typical and preferred. qua thereof can also be used. See also the hereinbefoce referenced U.S. 4,634,ss1 for other typical is bleaches and acsivstors useful herder.
Other useRrl amido-derived bleach activators are those of the formulae:
R1N(R5x(O)RZC(Ou. or R1C(O)N(RS)RZC(O~.
wherein RI is an alkyl group contsirong from about 6 to about 12 carbon atoms, is an aikyieaa containing from 1 to about 6 carbon atoms RS is H or alkyl, aryl, or 2o alluryl containing from about 1 to about 10 carbon atom:i and L is any suitable leaving group. A leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophiiic shack on the bleach activuor by the perhydrolyais arriort. A Preferred leaving group is Phenol avifonats.
Prefatred ~narp~ of blacir activators of the above forrrrulae include (6 ?s ocnnaarido~ca~Oyl~xybe~esulfona~ (6-nonanamidocaproyl) oxyber~enasultbru~, (6-decanamido-csproyl~xybenzeneatrlfonste and mixtures thereof as daa~d ie the i~reinbefore referenced U.s. Patent 4,634,ss 1.
Another claw of uaetirl bleach sctivstoa comprises the benzoxszin-type activate disclosed by Hodgs a al. in U.S. Patent 4,966, 723, Issued October 30, 30 1990, . ~ A highly prekrred aaivstor of the benzoxazin-typs is:
Still another class of useRrl bleach activators includes the acyl lactam activuon, especially acyl caprolsctams and aryl valeroltctsnrs of the formulae:
Trademark i i ~0 C-CH,-CH2 0 ~-CHI-CI~
R6-C N H~ R6-C N
\CH=--CFi~ NCH=--CHI
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms. I~i'rghly preferred lactam activaton include benzoyi caprolactam, octanoyl caprolactam, 3,S,S.trimethyihexanoyl caprolactam, nonanoyi s caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyi valerolactam, octanoyl valerolactam, decanoyl valerolutam, undecenoyi valerolactam, 3,5,5.
trimethylhexanoyi valerolactam and mixtures thereof See also U.S. Patent 4,545,784, Issued to Sanderson, October 8, 1985, which dixloses acyi caprolactams, including benzoyl caprolactam, adsodxd into to sodium perborate. .
Stil! another dass of useRrl bleach ac:ivators acs those which arc liquid in form at room tempaatirre and can be added as liquids to the nonaqueovs liquid phase of the detergent compositions herein. One such squid bleach activator is acetyl triethyi citrate (ATC). Other examples include gtyc~rol triacetue and non:noyi is valerotactartx.
The paoxygen bleaching agent partides, and activator particles for those ac:ivstors which aro solids, should have an average particle size which ranges from about 0.2 to 1,000 microns, moro preferably Som about 1 to 800. microns.
Preferably, no moro than about 10'iG by weight of the bleaching agent and/or 2o acsivator partidas will be smaller than about 1 micron and no moro than about 10~/°
by weight of suds particles wit! be larger than about 500 microru. Both peroxygen bladdng agee~ and bleach ac:ivstor if a solid activator is utilized, should be in the form of which aro substarroauy insoluble in the nonaqueoua liquid phase of the present compositions.
2s Peroxygan bleaching agent will ga~ally comprise from about 2% to 30% by weight of the composition. Moro profe<ably, peroxygen bleaching agent will comprise 6rom about 2'~L to 20'iG by weight of the compo:ation. Moat preferably, paoxygan bleaddng agent will be present to the actent of from about 3'/° to 15% by weight of the composition. If utilized, bleach activuors can comprise from about 30 2% to 10% by weight of the composition. Frequ~tly, activators aro employed such that the rrmtar ratio of bleadting sgeru to activator ranges from about 1:1 to 10:1, more preferably from about 1.5:1 to 5:1.

(B) Essential Anionic Surfactant Another essential component of the solid phase of the detergent compositions ~ herein comprises a primary or secondary alkyl sulfate anionic surfactant.
Such surfactants are those produced by the sulfation of higher Cg - C20 fatty alcohols.
Conventional primary alkyl sulfate surfactants have the general formula ROS03-M+
wherein R is typically a linear Cg - C20 hydrocarbyl group, which may be straight to chain or branched chain, and M is a water-solubilizing cation. Preferably R
is a C10 - C 14 alkyl, and M is alkali metal. Most preferably R is about C 12 and M is sodium.
Conventional secondary alkyl sulfates may also be utilized as the essential anionic surfactant component of the solid phase of the compositions herein.
Conventional secondary alkyl sulfate surfactants are those materials which have the 15 sulfate moiety distributed randomly along the hydrocarbyl "backbone" of the molecule. Such materials may be depicted by the structure CH3(CH2)n(CHOS03'M+) (CH2)mCH3 wherein m and n are integers of 2 or greater and the sum of m + n is typically about 9 to 15, and M is a water-solubilizing cation.
2o Especially preferred types of secondary alkyl sulfates are the (2,3) alkyl sulfate surfactants which can be represented by structures of formulas A and B
(A) CH3(CH2)X(CHOS03-M+) CH3 and (B) CH3(CH2)y(CHOS03-M+) CH2CH3 for the 2-sulfate and 3-sulfate, respectively. In formulas A and B, x and (y+1) are, 25 respectively, integers of at least about 6, and can range from about 7 to about 20, preferably about 10 to about 16. M is a cation, such as an alkali metal, alkaline earth metal, or the like. Sodium is typical for use as M to prepare the water-soluble (2,3) alkyl sulfates, but potassium, and the like, can also be used.
The alkyl sulfate surfactants essentially utilized herein do not generally dissolve 3o in the liquid phase and will hence be dispersed throughout the liquid phase as discrete particles. Such particles will typically range in size from about 0.2 to 1,000 microns, more preferably from about 1 to 800 microns.
The requisite alkyl sulfate anionic surfactant should be used in relatively high concentrations in order to provide suitable soiUstain removal performance and in 35 order to provide suspension phase stability for the nonaqueous detergent compositions herein. The alkyl sulfate surfactant will generally range from about 10% to 40% by weight of the compositions herein. More preferably, alkyl sulfate will be utilized to the extent of from about 16% to 30% by weight of the composition. Frequently, alkyl sulfate surfactant will be employed in amounts suf~tcient to provide a liquid phase to alkyl sulfate anionic weight ratio of from about 1:1 to 5:1, more preferably from about 1.5:1 to 3.5:1.
s OPTIONAL COMPOSITION COMPONENTc In addition to the essential composition liquid and solid phase components as hereinbefore described, the detergent compositions herein can, and preferably will, contain various optional components. Such optional components may be in either io liquid or solid form. The solid form optional components may either dissolve in the liquid phase or may be dispersed within the liquid phase in fine particulate form. as part of the solid phase of the composition Some of the materials which may optionally be utilized in the compositions heron are described in greater detail as follows:
~s (~) ~is:niLSlufat~
Besides the es:eMia1>y utilized alcohol ethox~rlatea and alkyl suifue surfactants, the dcompositions herein may also contain other types of surfactant msteriala, provided such additional surfactants are comestible with other 2o composition components and do not substantially adversely affect composition stability or performance: Optional surfactant: can be of the anionic, nonionic, cationic, and/or amphoteric type. If employed, optional surfactants will generally comprise from about lx to 20'iG by weight of the compositions herein, more pre~abhr 8rom about 3x to 10'X° by weight of the compoaitiona herein.
a Ons pre~rrad type of optional nonionic ~aa~ comprises surfutsnts which an ethyi~ o~ddt (EO) - propylene oxide (PO) block polymer. Materials of this type ors well known nonionic . surfuxsn<s which have been muketed under the trada:urne Pturoroc. These material are formed by adding blocks of ethylene oxide moieties to the ends of poiypropylerte glycol chairs to adjust the s<rrface active 3o properties of tM rosulang blocfc polymer. EO-PO btoclc polymer nonionics of this type are dexribed in detail in Dsvidsohn and M~lwidsky, p~,gfl~~,; Longman Saentifc and Technical (198'n at pp. 34-36 and pp.
189.191 and in U.S. Patents 2,674,619 and 2,677,700.
These Pturonid'' type nonionic s~rrfactants are 33 believed to Rrnction a effective suspending agents for the particulste material which is dispersed in the liquid phase of the detergent compositions herein.
# Trademark One common type of anionic surfactant which should not be utilized in the compositions herein comprises the sulfonated anionics which are alkyl benzene sulfonates. Such non-bleach activating sulfonated anionic surfactants, like linear alkylbenzene sulfonate (LAS), tend not to provide acceptable phase properties for the nonaqueous liquid detergent compositions of this invention. Accordingly, such compositions should generally be substantially free of alkyl benzene sulfonate anionic surfactant materials.
(B) OprtionalOrQani 1o The desergent compositions herein may also optionally contain an organic . detergent builder muerial which serves to counteract the effa~s of cataum, or other ion, water hardness encountered during laundering/blesching ux of the compositions herein. Examples of such materials include the alkali metal, citrates, succinates, maleness, fatty acids, cuboxymethyi succinues, carboxyiues, polycarboxyiues~
arid is polyacetyl carboxylstes. Specific examples include sodium, potassium and 4thwm salts of oxydiauccinic acid, melLtic sad, berrzare polysarboxytic acids and citric acid.
Other examples aro organic phosphonsts type sequestering agents such as those ,. which hsve been sold by Mon:artto under the D~qu~~hradename and alkanehydroxy phosphonates. Citrate salts are highly prel~red.
Zo Other suitable organic builders include the highx molecule weight polymers and copotymen known to have builder properties. For example, such muerials i>icluds spprop~ats polyaaylic sad, polyrt>alac acid, and polyacryiidpolyn>sleic scid copolyn~ and that salts" such as those sold by BASF under the Sokalan ~
tradarnrk.
?3 If utiliixd; organic builder materials wiU ge~aUy comprise from about 1'~ to 60'x, mots pre~bly from about 3'/a to SO'h, moat preferably from abort 3x to 20'~i, by waght of the compoait;oro heroin.
(C) iL,B~Ci~illitY.~~
3o Ths dcompositions heron may ado optionally contain a material which serves to reruder aqueow wsshiry solutions formed from such compositions Ba~nUy alkaline in nadan. Such materials may or may not also act as detergart builders, i.a, as m~is~ which counteract the adverts ~ of water h:rdttas on detergency performar~
3s Examples of suitable alkalinity sources include watar.solubls alkali metal carbonates, bicarbonues, berates, silicates and metuilicuea. Although not preferred for ecological reasons, water-soluble phosphate salts may also be utilized as Trademark ~~9~7__ alkalinity sources. These include alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates. Of all of these alkalinity sources, alkali metal carbonates such as sodium carbonate are the most preferred.
The alkalinity source, if in the form of a hydratable salt, may also serve as a desiccant in the nonaqueous liquid detergent compositions herein. The presence of an alkalinity source which is also a desiccant may provide benefits in terms of chemically stabilizing those composition components such as the peroxygen bleaching agent which are susceptible to deactivation by water.
If utilized, the alkalinity source will generally comprise from about S% to 30%
to by weight of the compositions herein. More preferably, the alkalinity source can comprise from about 5% to 20% by weight of the composition. Such materials, while water-soluble, will generally be insoluble in the nonaqueous detergent compositions herein. Thus such materials will generally be dispersed in the nonaqueous liquid phase in the form of discrete particles.
(D) Optional Chelating Agents The detergent compositions herein may also optionally contain a chelating agent which serves to chelate metal ions, e.g., iron and/or manganese, within the nonaqueous detergent compositions herein. Such chelating agents thus serve to 2o form complexes with metal impurities in the composition which would otherwise tend to deactivate composition components such as the peroxygen bleaching agent.
Useful chelating agents can include amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof.
Amino carboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetrapropionates, triethylenetetra aminehexacetates, diethylenetriaminepentaacetates, ethylenediaminedisuccinates and ethanoldiglycines. The alkali metal salts of these materials are preferred.
Amino phosphonates are also suitable for use as chelating agents in the 3o compositions of this invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylene-phosphonates) as DEQUEST. Preferably, these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
Preferred chelating agents include diethylene triamine penta acetic acid (DTPA), ethylenediamine disuccinic acid (EDDS) and dipicolinic acid (DPA) and salts thereof. The chelating agent may, of course, also act as a detergent builder during use of the compositions herein for fabric laundering/bleaching. The chelating agent, if employed, can comprise from about 0.1% to 4% by weight of the compositions herein. More preferably, the chelating agent will comprise from about 0.2% to 2% by weight of the detergent compositions herein.
r 5 (E) Optional Enz~rmes The detergent compositions herein may also optionally contain one or more types of detergent enzymes. Such enzymes can include proteases, amylases, cellulases and lipases. Such materials are known in the art and are commercially available. They may be incorporated into the nonaqueous liquid detergent io compositions herein in the form of suspensions, "marumes" or "prills".
Enzymes added to the compositions herein in the form of conventional enzyme prills are especially preferred for use herein. Such prills will generally range in size from about 100 to 1,000 microns, more preferably from about 200 to 800 microns and will be suspended throughout the nonaqueous liquid phase of the composition.
~5 Prills in the compositions of the present invention have been found, in comparison with other enzyme forms, to exhibit especially desirable enzyme stability in terms of retention of enzymatic activity over time. Thus, compositions which utilize enzyme prills need not contain conventional enzyme stabilizing such as must frequently be used when enzymes are incorporated into aqueous liquid detergents.
2o If employed, enzymes will normally be incorporated into the nonaqueous liquid compositions herein at levels sufficient to provide up to about 10 mg by weight, more typically from about 0.01 mg to about S mg, of active enzyme per gram of the composition. Stated otherwise, the nonaqueous liquid detergent compositions herein will typically comprise from about 0.001% to 5%, preferably from about 0.01%
to 25 1% by weight, of a commercial enzyme preparation. Protease enzymes, for example, are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (ALn of activity per gram of composition.
(F) Optional Thickening Viscosit~Control and/or Dispersing Agents 30 The detergent compositions herein may also optionally contain a polymeric material which serves to enhance the ability of the composition to maintain its solid particulate components in suspension. Such materials may thus act as thickeners, viscosity control agents and/or dispersing agents. Such materials are frequently polymeric polycarboxylates but can include other polymeric materials such as 35 polyvinylpyrrolidone (PVP).
Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form.

wo 9s/1oo73 Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, malefic acid (or malefic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and , methylenemalonic acid. The presence in the polymeric polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, ,_ -« styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight of the polymer.
Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water-soluble to salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000, and most preferably from about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, Diehl, U.S.
Patent 3,308,067, issued March 7, 1967. Such materials .may also perform a builder function.
If utilized, the optional thickening, viscosity control and/or dispersing agents should be present in the compositions herein to the extent of from about 0.1 %
to 4%
2o by weight. More preferably, such materials can comprise from about 0.5% to 2% by weight of the detergents compositions herein.
(G) Optional Brighteners. Suds Suppressors and/or Perfumes The detergent compositions herein may also optionally contain conventional brighteners, suds suppressors andlor perfume materials. Such brighteners, suds suppressors and perfumes must, of course, be compatible and non-reactive with the other composition components in a nonaqueous environment. If present, brighteners suds suppressors and/or perfumes will typically comprise from about 0.1 % to 2% by weight of the compositions herein.
COMPOSITION FORM
As indicated, the nonaqueous liquid detergent compositions herein are in the ~oTrn of bleaching agent and other materials in particulate form as a solid phase suspended in and dispersed throughout a nonaqueous liquid phase. Generally, the nonaqueous liquid phase will comprise from about 30% to 70% by weight of the composition with the dispersed solid phase comprising from about 30% to 70% by weight of the composition. Generally, size of the solid, insoluble particulate material -l5-{other than enryme prills) dispersed in the liquid phase will range from about 0.2 to 1,000 microns, more preferably from about 1 to 800 microns.
The bleach-containing liquid detergent compositions of this invention are substantially nonaqueous (or anhydrous) in character. While very small amounts of s water may be incorporated into such compositions as an impurity in the essential or optional components, the amount of water should in no event exceed about 5% by weight of the compositions heran. More preferably, water content of the nonaqueous detergent compositions herein will comprise less than about 2% by weight.
io The bleach-containing nonaqueous liquid detergent compositions herein will be relatively viscous and phase stable under conditions of cortunnaciat marketing and use of such compositions. Generally viscosity of the compositions herein will range from about 300 to 5,000 cps, more preferably from about 500 to 3,000 cps. For purposes of this invention, viscosity is measured with a Broolcseld ~scomaer using 13 a RV ~5 spindle at 50 rpm.
. The nonaqueoua liquid detergent compositions herein can be prepared by combining the esaauial and optional components thereof in any comrenient order and 20 by mixing, e.g., agnsting, the resulting componssnt combination to form the phase stabls compositions heroin. In a prsferrod process for preparing such compositions, Gsaerroai and emtain prefs:red optional components will be eombinmd is a partiexrl:r ordsc Such a procea is described in detail in the conarrraatly filed pataa application of Kuhteen B. Hunter and Josephine L. Kong-Chin, ?3 Canadian Patent Application No. 2,199,816.
Ia such s preferred preparation process, a liquid mstroc is foamed containing at least a major proportion, and preferably sub:taruiaUy a11, of the liquid components, a.g., the essauial alcohol ethoxylats nonionic s~ufrctant and the nonaqueous, low-polarity organic solvent, with the liquid comporamts being thoroughly admixed by 3o imparting shear agitation to this liquid combination. For example, rspid sowing with a mechanical stirrer may usefully be employed.
While shear agitstion is maintained, assentisUy aU of the sllcyl sulfate anionic surfactara, e.g., sodium tsuryi can be added is the foam of particles ranging in sits from about 0.2 to 1,000 microns. After addidoa of the alkyl sulfste particles, 33 particles of substantially aU of an alkalinity source, e.g., sodium carbonus, caa be added while continuing to maintain this admixture of composition components under shear agitation. Other solid form optional ingredients can be added to the composition at this point. Agitation of the mixture is continued, and if necessary, can be increased at this point to form a uniform dispersion of insoluble solid phase particulates within the liquid phase.
After some or all of the optional solid materials have been added to this agitated mixture, the particles of the requisite peroxygen bleaching agent can be added to the composition, again while the mixture is maintained under shear agitation. By adding the peroxygen bleaching agent material last, or after all or most of the other components, and especially after the alkalinity source particles, have been added, desirable stability benefits for the peroxygen bleach can be realized. If 1o enzyme prills are incorporated, they are preferably added to the nonaqueous liquid matrix last.
After addition of the bleaching agent particles, agitation of the mixture is continued for a period of time sufficient to form compositions having the requisite viscosity and phase stability characteristics. Frequently this will involve agitation for a period of from about 30 to 60 minutes.
As a variation of the composition preparation procedure hereinbefore described, one or more of the solid components may be added to the agitated mixture as a slurry of particles premixed with a minor portion of one or more of the liquid components. Thus a premix of a small fraction of the nonionic surfactant and/or nonaqueous, low-polarity solvent with particles of the alkyl sulfate surfactant andlor the particles of the alkalinity source and/or particles of a bleach activator may be separately formed and added as a slurry to the agitated mixture of composition components. Addition of such slurry premixes should precede addition of peroxygen bleaching agent particles which may themselves be part of a premix slurry formed in analogous fashion.
The compositions of this invention, prepared as hereinbefore described, can be used to form aqueous washing solutions for use in the laundering and bleaching of fabrics. Generally, an effective amount of such compositions is added to water, preferably in a conventional fabric laundering automatic washing machine, to form 3o such aqueous laundering/bleaching solutions. The aqueous washing/bleaching solution so formed is then contacted, preferably under agitation, with the fabrics to be laundered and bleached therewith.
An effective amount of the liquid detergent compositions herein added to water to form aqueous laundering/bleaching solutions can comprise amounts sufficient to form from about 500 to 7,000 ppm of composition in aqueous solution. More preferably, from about 1,000 to 3,000 ppm of the detergent compositions herein will be provided in aqueous washing/bleaching solution.

- 17- t !r, RAMP .)ES
The following examples illustrate tTie compositions of the present invention, but are not necessarily meant to limit or otherwise define the scope of the invention herein.
A composition of the present invention is prepared by mixing together the ingredients listed in Table I in the proportions shown.
to Table I
_ Wc-~, Neodol 1-3 14.4 71.9 Liquid Noniooit;Liquid Sur~ot -Dipeopyiene Slyoot 29.6 14~.a Low Polarity Liquid Orpoir:

Solves Pl~u~cni~ lOR3 9.6 47.9 Optional NoniaaidLiquid g " Sodiuta Lauryl Sul6st ZO 99.i Anbaie Sut~t O.Z-130w Particles Sodium Citrats Dihydrue 4 20 Dederpat Huilda0.2.300 Putides Dietbylenatriamina. 1.6 8 Chelmt 5-3001r Paetides peanao~ic Add (D?PA) T'u~opelx'AMS.HX'' . 0.3 1.6 FWA 5-2001r Partjdes Sodium Carborarr 11 39.9 Alkalioipr 0.2-130w Soueos Sodiioohba~oa 3.3 26.4 BNacb A~tivatoe0.1-150w Panicles Sodiurst P~boeals 3 14.3 Hydn~a pe~odda30-330 Particles lNooo~ydrals ~

0. ,_ 300800u j, Prills Toot 100 300 ~cl t .ri.~wr.n.w wr s ..~. a.y :..gar.
nr..or. ot.~o~l. e.. ar u~

Hr~e~r r~... eat co,~..
ae.
erw c~..~.

A,r Ia. Car~OwOr 13 The order in which the components are mixed plays no significant role in the achievement of the overall phase stability of the product. However, it is particularly convenient to proceed as follows in order to provide products of especially desirable bleach stability:
Into a 1 ~Gter vessel are charged all the liquid ingredients (alcohol ethoxylates, 20 organic solvent, Pltuonic). The mixwce is thoroughly mixed with a mechanical mixer (Lightnin mixer) operued at 350 rpm. With agitation continuing, the sodium citrate DTPA and FWA particles ara added next. The resulting mixture is then Trademark further processed by subjecting it to high shear dispersing in a Ultra~Turrax T50, IKA~Labortechnik dispenser operated at 3,000 min ~ 1.
The mixture is then returned to the Lightnin mixer and, with agitation at 500 rpm, the sodium lauryi sulfate is added. With continuous agitation, the sodium carbonate is added next, followed by the powdered bleach activator. The mixture is thoroughly mixed until all solid particles are wetted and nicely dispersed in the liquid matrix. The sodium perborata monohydrate is then added. Finally, the proteax grills are then added last with mixing continuing at 800 rpm.
. The finished product is an opaque, white, creamy liquid with suspended solids.
to The blue enzyme grills are visible and give the product a speckled appearance. The viscosity is 620 cps when measured on a Brookfield RV viscometer with a RV #5 spindle at 50 rpm. ARer 1 week at ambient temperature, the viscosity of the product reaches 1000 cps and remains relatively constant aftervvards. Approximately Set, separation (clew phase on top layer) is observed aRer 3 days a ambient tempersaire.
is The separated phases are dispersed readily, and the dispensing Properties of the prodtut aro good.' Chemical stability of this product is excellent. ARa 4 weeks at 100°F, >85'X of the original Available Oxygen is still retained.
,- EXAMPLES II . X
The compositions of this irrvention, as well as two comparative compositions, 2o are illustrated by the examples set forth in Table II. All amounts listed aro as weight percent of composition.
Tab le F~o~~ It I~ itIl Y Y~ YQ YQI Ix DC I~

LtQtT)~

Neodd 1-0 - 9.6 - 8.3 to to a.: to -Neodo191.10 - 18.4 - - - - ..
-N~odoi Z3-9 17 - - -. - - - - -Anoosmi ns = - - a s 1 s 1 - 51 ~ -DPNB ~ilyool Z3.b 26.6Z3.4 16.6 35 Ethtr Plue~i~ IOR3 9.3 9.6 E.3 10 - - 10.6 - 14 A'fC - 9.6 3.7 14 - - 10.6 - 14 SOL>~S
Sod~umCIZLAS, O.Z-130p - - - - - - - 16.7 -SodiumCl4SASØZ~130pt - - - - - 16.7 - - -Sodiunt Isuryl:~ll~t. 0.1-150 19.4 1a.5 1E.4 10.73 16.7 - II - -Sodium PC. 30~330N 3.3 # Trademark Sodium PB 1, 50-350w 2.9 -- 2.9 3.1 3.5 3.5 3.4 3.5 4.6 NaNOBS, 0.2-150 5.1 4.9 5.1 5.5 4.7 4.7 -- 4.7 8.1 Table II lCont'd.) Example No. II III IV V VI VII VIII IX X
DPA 5-30011 -- 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.3 DTPA 5-30011 1.6 -- -- -- -- -- -- -- --Sodium Carbonate, 0.2-150}1 11.6 11.1 11.1 8.3 13.3 13.3 8.8 13.3 11.7 Sodium Citrate, 0.2-30011 3.9 5.6 7.4 4.2 -- - 8.8 -- 11.7 Protease Prills, 200-80011 0.4 0.4 0.4 0.4 0.4 0.4 - 0.4 0.4 FWA, 5-200~t 0.3 0.3 0.2 0.2 0.2 0.2 0.2 0.2 0.3 Sodium C14SAS = Sodium C14 secondary alkyl sulfate from Shell Chemical Company Sodium C12LAS = Sodium C12 linear alkylbenzene sulfonate NaNOBS = Sodium Nonanoyloxybenzensulfonate Sodium PC = Sodium percarbonate Sodium PB 1 = Sodium Petiwrate Monohydrate DPNB Glycol Ether = Dipropylene glyco monobutyl ether from Dow Chemical Company ATC = Acetyhriethylcitrate Pluronic lORS = Polyoxypropylene-polyoxyethylene Block Copolymer from BASF
Corporation 1~ AlkoSurf 718 = Blended low molecular weight methyl esters from AlkoAmerica Corporation Neodols = ethoxylated alcohols from Shell Chemical Company FWA = Fluorescent Whitening Agent DPA = Dipicolinic Acid DTPA = Diethyienetriamintpentaacetic Acid 15 Example IX is outside the scope of the present invention by virtue of its use of the linear alkylbenzene sulfonate anionic surfactant instead of the requisite alkyl sulfate anionic surfactant.
Example X is outside the scope of the present invention by virtue of its failure to include the requisite alcohol ethoxylate nonionic surfactant and alkyl sulfate 20 anionic surfactant.
The observed phase properties for each of the Table II compositions are set forth in Table III.
Ta le III
Example No. II III IV V VI VII IX X
p~ prope,~y. S S S S S S S~ 70°hT
phase Ptnpetty, 4 wk ~ RT SI. Sep Sl. Sep SI. Sep Sl. Sep SI. Sep Sl. Sep S~
70%T
S = Single Phase, Pourable 2$ SI. Sep. - Slightly Separated S~ = Not liquid %T = % of composition which is clear liquid as Top layer From the Table III Phase Property summaries, it can be seen that Examples IX
and X, which are outside the scope of the present invention, exhibit unacceptable or WO 96/10073 ~ PCT/US95I11257 less suitable phase separation tendency than do the Examples II - VIII
compositions of this invention.

Claims

What is claimed is:

1. A nonaqueous liquid heavy duty detergent composition in the form of a suspension of solid, substantially insoluble particulate material comprising a peroxygen bleaching agent and an anionic surfactant component, dispersed in a liquid phase comprising a nonionic surfactant component and a nonaqueous, low-polarity organic solvent component, wherein said composition is further characterized in that it comprises:

(a) from 1% to 60% by weight of the composition of said nonionic surfactant component which comprises alcohol ethoxylates of the formula R1(OC2H4), OH wherein R1 is a C6-C16 alkyl group and n is from 1 to 80;

(b) from 10% to 40% by weight of the composition of said anionic surfactant component which comprises sulfated C8-C20 alcohols and which is free of alkyl benzene sulfonate anionic surfactant materials;

(c) from 2% to 30% by weight of the composition of particles of said peroxygen bleaching agent, which particles range in size from 0.2 to 1,000 microns;

(d) from 16% to 60% by weight of the composition of said nonaqueous, low-polarity organic solvent component, wherein said solvent component is selected from the group consisting of low molecular weight methyl esters of the formula R1 - C(O)-OCH3, wherein R1 ranges from 1 to 18 carbon atoms.

2. A composition according to claim 1 wherein:

(a) said nonionic surfactant component comprises materials selected from alcohol ethoxylates containing from 9 to 15 carbon atoms and having from 2 to 12 ethylene oxide moieties per molecule;

(b) said nonaqueous low-polarity organic solvent is selected from the group consisting of methyl acetate, methyl propionate, methyl octanoate and methyl dodecanoate;
(c) said peroxygen bleaching agent is selected from percarboxylic acids and salts thereof and alkali metal perborates and percarbonates; and (d) said anionic surfactant component comprises materials selected from C10-C14 primary alkyl sulfates.

3. A composition according to claim 2 wherein:
(a) said nonionic surfactant component comprises from 5% to 35% by weight of the composition;
(b) said nonaqueous, low-polarity organic solvent comprises from 16% to 45% by weight of the composition;
(c) said peroxygen bleaching agent particles comprises from 2% to 20%
by weight of the composition and range in particle size from 1 to 800 microns; and (d) said anionic surfactant component comprises from 15% to 30% by weight of the composition.

4. A composition according to claim 3 wherein:
(a) said peroxygen bleaching agent is selected from alkali metal perborates and percarbonates; and (b) said composition further comprises from 2% to 10% by weight of the composition of particles of a bleach activator which can react with said peroxygen bleaching agent to form a peroxy acid, said bleach activator particles ranging in size from 0.2 to 1,000 microns.

5. A composition according to claim 4 which also contains from 1% to 20% by weight of the composition of an additional nonionic surfactant comprising ethylene oxide-propylene oxide block polymers.

6. A composition according to claim 4which additionally contains from 1% to 60% by weight of the composition of an organic detergent builder selected from alkali metal, citrates, succinates, malonates, carboxymethylsuccinates, carboxylates, polycarboxylates and polyacetylcarboxylates.

7. A composition according to claim 6 wherein said organic detergent builder is sodium citrate.

8. A composition according to claim 4 which additionally contains from 5% to 30% by weight of an alkalinity source selected from water-soluble alkali metal carbonates, bicarbonates, borates, silicates and metasilicates.

9. A composition according to claim 8 wherein said alkalinity source is sodium carbonate.

10. A composition according to claim 6 which additionally contains from 0.1%
to 4% by weight of the composition of a chelating agent selected from amino carboxylates, amino phosphonates, polyfunctional substituted aromatic chelating agents and combinations of these chelating agents.

11. A composition according to claim 10 wherein said chelating agent is selected from diethylene triamine pentaacetic acid, ethylene diamine disuccinic acid and dipicolinic acid and the salts of these chelating agents.

12. A composition according to claim 6 which additionally contains from 0.001%
to 5% by weight of the composition of enzyme prills wherein said prills range in size from 100 to 1,000 microns, and wherein said enzyme is selected from proteases, amylases, cellulases, and lipases.

13. A composition according to claim 6 which additionally contains"
(a) from 0.1 % to 4% by weight of the composition of a thickening, viscosity control and/or dispersing agent selected from acrylic acid-based polymers having a molecular weight ranging from 2,000 to 10,000; and/or (b) from 0.1 % to 2% by weight of a compatible brightener, suds suppressor and/or perfume.

14. A nonaqueous, bleach-containing liquid heavy-duty detergent composition which comprises:
(a) from 8% to 25% by weight of the composition of an ethoxylated alcohol liquid nonionic surfactant which contains from 10 to 14 carbon atoms and from 3 to 10 moles of ethylene oxide;
(b) from 20% to 45% by weight of the composition of a nonaqueous organic liquid solvent selected from low-molecular weight methyl esters of the formula R1 -C(O)-OCH3 wherein R1 ranges from 1 to 18 carbon atoms.

(c) from 16% to 30% by weight of the composition of particles of a C10-C14 alkyl sulfate anionic surfactant;
(d) from 3% to 15% by weight of the composition of particles of a peroxygen bleaching agent selected from sodium and potassium perborates and percarbonates;
(e) from 2% to 10% by weight of the composition of particles of a bleach activator selected from nonanoyloxybenzene sulfonate and tetraacetyl ethylene diamine;

(f) from 5% to 20% by weight of the composition of particles of alkali metal carbonate; and (g) from 0.01% to 1% by weight of the composition of enzyme prills comprising an enzyme selected from proteases, amylases, cellulases and lipases;
wherein said composition is free of alkyl benzene sulfonate anionic surfactants and wherein said composition is in the form of a suspension of particulate material comprising said particles and said prills, dispersed throughout said liquid nonionic surfactant and solvent components with said particulate material ranging in size from 1 to 800 microns.

15. A composition according to claim 14 which also contains from 5% to 10% by weight of the composition of an additional nonionic surfactant comprising ethylene oxide-propylene oxide bleach polymers.

16. A composition according to claim 14 which additionally contains from 3% to 20% by weight of the composition of an organic detergent builder selected from alkali metal citrates.

17. A composition according to claim 16 which additionally contains from 0.2%
to 2% by weight of the composition of a chelating agent selected from diethylene triamine pentaacetic acid, ethylene diamine disuccinic acid and dipicolinic acid and the salts of these chelating agents.

18. A composition according to claim 17 which additionally contains from 0.5%
to 2% by weight of the composition of a thickening, viscosity control and/or dispersing agent selected from acrylic acid-based polymers having molecular weight of from 2,000 to 10,000.

19. A composition according to claim 14 which has from 30% to 70% by weight of the composition of a liquid phase and from 30% to 70% by weight of the composition of a solid particulate phase.

20. A composition according to claim 19 which has a viscosity of from 500 to 3,000 cps.