CA2041902A1 - Nonaqueous liquid automatic dishwasher detergent composition - Google Patents

Abstract

PATENT

NONAQUEOUS LIQUID AUTOMATIC DISHWASHER DETERGENT COMPOSITION

ABSTRACT OF THE DISCLOSURE

ABSTRACT OF THE DISCLOSURE

The application is directed to a nonaqueous liquid automatic dishwasher detergent composition with improved anti-filming and anti-spotting properties and to a method of using the detergent composition. The detergent composition comprises a nonaqueous organic carrier liquid, silica, alumilla or titanium dioxide anti-filming agent, a water soluble polyacrylate anti-spotting agent, inorganic builder salts, bleach compound and detergent. The compositions provide reduced filming and spotting on dishware, glassware, china and the like, particularly in hard water. The nonaqueous liquid automatic dishwasher detergent compositions are stable in storage and are readily dispersible in water.

Description

~ ~ :r~ ~ 4 11~4q39 NONAQUEOUS LIQUID AUTOMATIC DISIIWASHER DETEr~GENT COMPOSITION

IIELATED APPLICATIONS
This application is reluted to applications Serial No. 323,138 filed March 13, 1989, Serial No. 323,126, filed March 10, 1989, now USP
4,889,653, Serial No. 323,134, filed March 13, 1989 and Serial No. 323,137, filed March 13, 1989 all of which are directed to aqueous automatic dishwasller detergent compositions containing an anti-filming agent or sn anti-filming and anti-spotting agent.
FIELD OF THE INVENTION
The present invention relates to an automatic dishwasher detergent composition having improved anti-~ilming and/or anti-spotting properties.
The present invention i8 particularly directed to 8 stable nonaqueous liquid di~hw~sher detergent composition containing an anti-filmirlg and/or nnti-spotting agent for use in an automatic di~hwa~her to clean dishware, glassware and the like.
The pre~ent invention more particularly relates to a nonaqueous liquid (lishwashing detergent composition with improved anti-filming and flnti-spotting properties and to a method of using the detergent compositioll to clean dishware, glassware, china and the like. The dishwashlng composition contains an anti-filmlng agent, or an anti-filming agent nnd poly acrylic scid polymer or salt nnti-spotting agent, inorganic builder salts, bleach compound and detergent.
The detergent dishwashing composition of the present invention reduce filming ~nd/or spotting on dishware, glasswQre, china and the like, particularly in hard water at low temperature.
More specifically, the invention relates to the use of a nonabrasive amount of smflll substantially water insoluble silica particles, as an ~ ~ "~ r;~

~nti-~iln)in~ ngcnt and polyacrylic ncid or sfllt polymer as an anti-sp(!tting ~gent in nonaqueous liquid dishwashing <letergent compositions to reduce filming and/or spotting.
The detergent comE)ositions do not require an added rinse aid, are stable in storage and are readily dispersible in the wAsh bath.
The present invention specifically relates to nonaqueous liquid automatic dishwashing detergent compositions having improved anti-filming properties, which are readily dispersible in the washing medium to provide effective cleaning of dishware, glassware, china and the like.
The preserlt invention al60 relates to an improved nonaqueous liquid composition and to Q method of u6ing the composition.
~ BRIEF DESCRIPTION OF TIIE INVENTION
The present invention i~ directed to a nonaqueous liquid automatic dishwasher detergent composition having improved unti-filming and/or anti-spotting properties for cleaning of dishware, gla~sware, china and the like. The detergent composition contains as an essentinl ingredient a nonnbrasive amount of smn]l 6ubstantinl1y wnter insoluble silica, nlumina or titnnium dioxide particles QS nn anti-fflming agent. The compositions can ~d~5itionAlly contain a polyacrylic acid polymer or salt as an ~nti-spotting agent .
The present invention specificAlly relates to nonaqueous liquid nutonl~tic dishwashing detel gent compositions having improved anti-rilming and/or anti-spotting properties for cleaning of dishware, glassware, china and the like.
The nonaqueous liquid compositions are stable in storage, do not settle, nre readily pOUI able and nre rerdily di~persed in water .
PRIOR ART
Commercially available household-machine dishwasher detergents provided in powder or liquid form have mnny disadvantages. Commercially available powder detergents h~ve the disndvantages of non-unifor m colnpo~ition; costly operntion~ necessary in their manufncture; tendency to cake in stor~ge at high humi(litie~, reflulting in the îormntion of IlJmp~
wllich are difficult to disperse; dustiness, n source of particular irritation to users whn suffer al]ergies; and ~endency to cake in the dishwasl1er machine dispenser.
In addition, the commercially av~ilable formulated powder detergents frequently require a separate step of hand towel wiping and drying of the dishware, glnssware, china and the like to avoid leaving undesirable traces or film. The use of ]iquid detergent compositions present other problems.
The builder salts æettle in storage and are not readily redispersed. The compositions al80 frequently become tllicker in storage and are not readily pourable .
l~or effective use, it i8 generally recommended thnt the automatic dishwashing detergent, hereinafter al60 designated ADD, contnin (1) sodium tripolyphosphate (NnTPP) to 60ften or tie up hard-water minerals and to emulsify and/or peptize soil; (2) sodium silicate to supE)ly the alkalinity necessary for effective (letergency and to provide protection îor dishware, such as fine china and protection against machine corrosion (3) sodium carbvnate, generally considered to be optional, to enhance alkalinity; (4) a chlorine-releasing agent to aid in cleaning; (5) a surractnnt and (fi) a defoamer to reduce fo~m, thereby enhallcing machlne efficiency. See, for example, SDA Detergents in Depth, "Formulations Aspects Of Machine Dishwashing," Thomas Oberle (1974). Cleansers npproximnting to the nfore-described compositions are mostly liquids or powders. Generally, such compnsition6 omit hypochlor~te blesch, since it tends to react with other chemically active ingredients, particularly surfactant, thereby impniring its effectivene6s.
U . S . Patent No . 3, 985, 668 describes abra6ive scouring cleaners of gel-like consistency containing (1) suspending agent, preferably the Smectite and attnpulgite types of clay; (2) abrasive, e.g. silica sand or ~ i ,"~

perlite: ~nd (3) filler comprising ;ight density E)owdered polymers, exp~ln-~e(l perlite nncl the like. The perlite h~ a bouynr~cy nnd thll~
stabi1iæing effect on the composition in addition to serving as a bullcing agellt, thereby replacing w~ter otherwise ~qvnilnble for undesired supernatant layer formation due to leaking and phase destabilization. The foregoing are the essential ingredients. Optional ingredients include hypochlorite bleach, bleach stable surfactant and buffer, e. g. silicates, carbonates, and monophosphates. Builders, such as N~TPP, cnn be included as further optional ingredients to supply or supplement building ~unctinn not provided by the buffer, the amount of such huilder not exceeding 596 of the total composition, according to the pntent. Maintenance of the desired (greater than) p~l 10 levels is achieved by the buffer/builder components. Iligh pH is said to minimize decomposition of chlorine bleach and undesired interaction between surfactant and bleach. When present, NaTPP is limited to 596, a8 stated. Foam killer is not disclosed.
V.S. Patent 4,511,487 dated April 1~), 1985 descrihes ~ low-foamillg detergent pnste for dishwashers. The composition i8 b~lsed on n mixture of finely divided hydrated sodium metasilicate, an active chlorine compound and a thickelling ~gent which is a foliated silicate of the hectorite type.
Smnll nmount of nonionic tenside6 and alkali metal cnrbonates and/or hydroxides may be used.
The Laitem et al USP 4,753,748 discloses a non~queous li(luid automatic dishwflshing detergent composition comprising a liquid nonionic surfactant containing a stable or readily redispersible suspension of a polyphosphate builder nnd/or citrnte salt and an Rlkylene glycol mono fllkyl ether anti-gel Rgent .
Scott V~P 4,438,014 discloses ~ owder formulation cont~ining a novel nonionic surfactant for automatic dishwasher detergent compositions. The nonionic surfactant consists of an alkyl group to which there i8 directly attnched fl propylene oxide polymer to which is attached an ethylene oxide-~ } 'i~ ~,J'~ ~J~

propylene oxide random copolymer. The nonionic ~urfactant is described fl8-novi~ling optimun) clenning ~nd goo~l spottirlg ~nd film results and good defoaming power.
AVYANTAGES OVER TI~E PRlOR ~RT
The nonaqueous liquid detergent compositions of the preæent invention overcome many of the prior art problems associated with powder aIld liquid detergents. Because of the addition of a small effective amount of a silicR, a]umina or titanium dioxide anti-filming agent or silica and polyacrylic acid polymer or salt anti-spotting flgent to the composition an added rinse aid is not required and towel wiping and drying are not requlred to obtain dry spnrklillg clean dishes, glasses, cups and eating utensils.
The nonaqueous liquid automatic dishwashing detergent compositions of the present invention have the advantages of being stable, nonsettling in storage, and non-gelling in storage, and are readily dispersible in the dishwashing machine. The liquid compositions of the present invention are easily pourable, e~sily measured and easily put into dishwaslling machines.
Eiurther, I>ecause the dishwashing machines as built and marketed hflve a built in volume ~pace in which the detergent is placed, the concentrated nature of the liquid detergent concentrate composition of the present lnvention a]lows placing in the dishwashing machine more nctive liquid detergent, e. g. more dispersed polyphosphate and other detergeIlt builders .
The nonaqueous liquid detergent compositions of the present invention with the exception of the anti-film agent, are refldily soluble in the wash water in the dishwashing machine.
OBJECTS OF THE PRESENT INVENTION
It is an object of the present invention to provide a nonnqueous liquid automatic dishwasher detergent composition that has improved anti-filming nnd/or anti-spotting properties.
It is anot}ler object of the invention to provide a nonnqueous liquid detergent composition which is stable in sto} age, does not degrade or decompose, is easily pourable, i8 readily dispersible and is readily soluble ill the dishwashing wflter.
A f~lrther object of the invention is to provide a method of washing dishware, glassware, china and the like in sn automatic dishw~shing mflchine using a nonaqueous liquid detergent composition in which a separate rinse aid is not added or needed.
A still further object of the invention is to provide a method of wflshing dishware, glassware, china and the like in an nutomutic washing mnchine using a nonaqueous liquid detergent composition by which method the dishware, glassware, china and the like are machine dried with reduced film arJcl/or spots.
It is a further object of this invention to provide fln improved nonnqueous liquid detergent composition, especially an automatic dishwasher (letergent composition, by incorporating in the compo.sition a smnll effective amount of a silica anti-filming agent or silica and polyacrylic acid polymer or salt flS anti-filming and ~nti-spotting agents.
DETAILED DESCRIPTION OF TIIE INVENTION
'rhese ancl other objects of the invention which will be(!(>me more r en(lily understood from the following detailed description of the invention nnd preferred embodiments thereof which are achieved by incorporating in n nonaqueous liquid detergent composition a small but effective amount of fl silica, alumina or titanium dioxide anti-filming agent or silica anti-filming agent and polyacrylic acid polymer or salt anti-spotting agent. More particulflrly, in R preferred and specific embodiment of the invention, there is provided a nonaqueous liquid automatic dishwasher detergent composition in which is incorporntcd from about O . 5 to IO96 of a silica anti-filming agent or silicn anti-filming agent and I to 30% of a water soluble polyacrylic acid polymer or salt flnti-spotting agent. The silica anti-filming agent has a pflrticle ~ize of flbout 0.1 to 10 microns. The water soluble polyacrylic acid or salt polymer has a molecular weight of about 1000 to 100, 000, ~ 2~

In eccordance with the present invention there is provided a nonnqueous liquid automatic dishwasher detergent composition which includes, on n weight b~sis;
(a) 20 to 60% orgMnic carrier liquid;
(b) 20 to 60% organic or inorganic builder salt;
(c) 5 to 30% sodium silicate;
(d) 3 to 1596 peroxygen bleach compound;
(e) 0 to 8Q6 bleach activator;
(f) 0.5 to 1096 silica anti-filming agent;
(g) 0 to 30% polyacrylic acid polymer or salt;
(h) 0 to 25% alkali metal carbonate;
(i) 0.1 to 12% water dispersible organic detergent active material: and (;) 0 to 6% foam depressant.
The present invention al80 provides a method for cleaning dishwRre, glassware, china and the like in an automatic dishwashing machine with an aqueous wnsh bath containing an effective amount of the nonaqueous liquid automatic di6hw~sher detergent (LADD) composition as described above.
According to this aspect of the invention, the LADD composition is stable in 8torRge, iB easily meQsured and can be readily poured into the automatic dishwashing machine.
The inventiorl will llOW be described in greater detail by way of specific embodiments thereof.
In accordance with the present invention an improved automatic dishwflsher detergent composition is prepared by incorporating small amounts of a silica anti-filming agent or silica anti-ilming agent and polyacrylic acid polymer or salt in a dishwasher composition.
The present invention is based upon the discovery that substantially improved anti-filming and/or anti-spotting properties can be obtained by eddin g to the nonaqueous liquid detergent composition a small effective ~moutlt of 8 silica anti-filming agent or 8illca anti-filming agent an(l pc)lyAcrylic acid polymer or snlt anti-spotting agent.
In accordance with an embodiment of the present invention a ~lonaqueous liquid automatic dishwashing detergent composition is prepared by dispersing a polyphosphate builder in an organic carrier liquid. The polyphosphate builder may be replaced in whole or in part by an organic builder .
In ~ddition other ingredien~s can be added to the composition such as anti-encrustation agents, anti-foam agents, optical brighteners, enzyme~s and perfume.
Organic Carrier Liquids The organic carrier liquids that can be used in accordance with the present invention are carrier liquids, diluents and solvent~ that are compatible with the composition ingredients. Suitable organic carrier liquids are polyethylene glycol M . W . 300, M . W . 400 and M . W . 4000, propylene glycol, propylene carbonate, polypropylene glycol M.W. 200 and M.W. 300, me~hoxy propylene glycol, Carbowax Ml'EG 350 (polyethylene glycol methyl ether), from Union Carbide, triethanol amine, Butyl Carbitol, from DuPont Co, Glyme (ethylene glycol dimethyl ether), Diglyme (diethylene glycol dimethyl ether).
There can also be used a8 organic carrier liquids the alkylene glycol monoalkyl ethers. The alkylene glycol mono alkyl ethers are low molecular weight nmphiphilic compounds, particularly a mono-, di- or tri lower (C2 to C~) alkylene glycol mono lower (Cl to C5) alkyl ether. Suitable examples of such additive amphiphilic compound~ are ethylene glycol monoethyl ether C2115-O-C112CH2OH, diethylene glycol monobutyl ether C41~9-O-(CH2CH2O)2H and dipropylene glycol monomethyl ether C~ o-(cH2cHo)2H-c~3 The al?ove di~cussed organic carrier liquidg can be used alone or in adn)ixture in orller to ob~in ~ cleflired YiSCosity and st~bility of the product liquid .
The compositions of the present invention have good viscosity and stability characteristics and remain stable and pourable at low temperatures.
Liquid Nonionic Surfactant Detergents The liquid nonionic surfactant detergents that can be used in the pr,actice of the pre~ent invention nre preferably the low foam poly-lower alkoxylated lipophiles.
Useful nonionics are represented by the low foam Plurafnc series from BAS~ Chemical Company whlch are the reaction product of a higher linear alcohol nnd a mixture of ethylene and propylene oxide6, containing a mixed chain of ethylene oxide and propylene oxide, terminated by a hydroxyl group. Examples include a C13-C15 fatty alcohol condensed with 6 moles ethylene oxide and 3 moles propylene oxide, a C13-C15 fatty alcohol condellsed with 7 moles propylene oxide and 4 moles ethylene oxide and a C13-C15 fatty alcohol condensed with 5 moles propylene oxide and 10 moles ethylene oxide.
Other useful surfactants are Neodol 25-7 and Neodol 23-6 . 5, which products are made by Shell Chemical Company, Inc. The former is a condensation product of a mixture of higher fatty alcohols averaging about 12 to 15 carbon atoms, with about 7 moles of ethylene oxide and the Intter is o corresponding mixture wherein the carbon atom content of the higher fatty alcohol is 12 to 13 and the number of ethylene oxide groups present averages about 6 . 5 . The hlgher alcohols are primary alkanols. Other ex~mples of such detergents include Tergitol 15-S-7 ~nd Tergitol 15-S-9 (registered trademarks), both of which are linear secondary alcohol ethoxylates made by Union Carbide Corp. The former is mixed ethoxylation product of 11 to 15 carbon atoms linear secondary alkanol with seven moles ~~

r J ~ 4 ~ q.J ~ rJ

of ethylene oxide and the latter is a sim;lar product but with nine mole6 of ethylene oxide being reacted.
~ nonionic surfactant that c~n be used is available from Union Cflrbide Corporntion under the trQdemark Tergitol MDS-42. This nonionic surfact~nt i8 a C12-C14 linear alcohol containing 55% by weight random distributed oxyalkyl groups of which 42% are ethoxy and 5896 propoxy groups.
l A preferred nonionic surfactant th~t can be used in accordance with ¦ the present invention has the following formula l R-o-(po)x-(Eolpo)Tl ¦ R is an alkyl group having 8 carbon atoms, PO is a propylene oxide polymer attached directly to the oxygen of the alkyl group, x is 8 to 9, EO/PO represent~ a copolymer of ethylenc oxide and propylene oxide in which the ethylene oxide and propylene oxide are randomly mixed. The molar ratio of EO/PO is about 2:1 to 5:1, e.g. about 3:1. The total number of EO and PO groups in the copolymer are such that the number of EO and PO groups are 5 to 8 and the cloud point of the nonionic surfactQnt is about 20 to 30C.
A method of mnking the nonionic surfactant and a more complete description of the nonionic surfcatant is given in the Scott USP 4,438,014 which is incorporated herein in its entirety.
Other useful nonionic surfQctants are the Poly-Tergent S-LF
surfactants availQble from Olin Corporation. These surfRctants are low foaming, biodegradQble linear fatty alcohols. Surfactants o~ this type are available under the tradenQmes Poly-Tergent S-LF 18, Poly-Tergent S-305-l,F, Poly-Tergent S-405-LF and Poly-Tergent CS-1.
Mixture~ of two or more of the liquid nonionic ~urfQctPint~ can be used and in some cases advantages can be obtained by thc use of such mixtures.
In ad(lition, the above discussed nonionic surf~ctunt~, nnionic surfactants can ll180 be used.

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Anionic Surfactants The anioIlic surfnctants that can be used are the linear or brnnched alk~li metal mono- nnd/or di-(C8 14) alkyl diphenyl oxide mono and/or disulphonates, commercially availnble for example aæ DOWEAX ( Registered Trademark~ 3B-2 and DOWFAX 2A-l, Other suitable surfnctants include the primary alkylsulphates, alkylsulphonates, alkylaryl-sulphates and sec. alkylsulphates. Examples include sodium CIO 18 alkylsulphates such as sodium dodecylsulphate and sodium tallow alcoholsulphate; sodium C10 18 alkanesulphonates such as sodium hexadecyl-I-sulphonate and sodium CIa 18 alkylbenzenesulphonates such as sodium dodecylbenzenesulphonates. The corresponding potassium salts may nlso be employed.
Surfactnnts of the foregoing type, all well known in the art, are described, for example, in U.S. Patents 3,985,668 and 9,271,030, which are incorporated herein by reference thereto.
The nonionic and anionic surfactants are used in amounts of 0.1 to 12%, preferably 0.5 to IO.O~, and more preferably about 1.0 to 8.0%, for example 2 to 796.
ANTI-FILMING ~GENTS
The anti-filming agent comprises a nonnbrnsive amount Or smnll substantially water insoluble silicH particles. There can also be used as anti-filming agents alumina and titsnium dioxide particles. The anti-filming ngent accordingly can be a member selected from the group consisting of silica, alumina and titanium dioxide and mixtures thereof.
_ilica l'he silica anti-fllming agent materials that can be used are fumed or precipitated 6ynthetic or natural ~ilica. The silica may be nmorphous or crystalline .

~ ; 2 1 ~ tJ ~3 The silica mE~terinl that i8 used may cont~sin up to about 0.1 to 5%
alumina ~A1203) ~ usually up ~o nbout 0.5 to 3% and more usu811y nbout 1%
nlumina, bNsed on the weight of silicn.
A preferred æilicn material is Syloid 244 which i6 amorpllous ~silica, has n pnrticle size of about 4 microns and is provided by W . R . Grace Co .
Another suitab]e silicn material is Silox 15, also from W.R. Grace Co., which has a particle size of about g microns.
Another preferred silicn materiPI is Huber Zeo 49 which is amorphous silica and is provided by J.M. Iiuber Corporntion and contains about 1 alumina (A1203).
l'he particle slze of the silica material that is used is importnnt in achieving the de~ired anti-filming properties.
Tlle silica particles that are used are finely divided and can have a particle size of about 0 .10 to 10 microns, preferably 0 . 50 to 8 microns and more preferably about 1. 0 to 5 . 0 microns . The silica particles of this size and the amount used herein are not abrasive.
The finely divided silica material particles in the dishwnshing wash nct to coagulate proteinaceous particulate 80ilg and keeps them in suspension to prevent them from depositing on the clean glass and dishware to form a film .
Alumina The alumina material that can be used as nn anti-filming agent i8 commercin]ly availAble and is insoluble in water and has the formula A1203.
Suitable materials are available under the tradenames Alumina Oxide C, availnble from Degussa Company and Catapal ~, available from Vista Corp.
Preferred alumina materinls are fumed altlmina and a precipitated alumina.
Titnnium Dioxide The titanium dioxide material that can be used as an anti-filming agent i8 insoluble in water and l)a~ the formula TiO2. Suitable materials ure available under the tradellames Titanium Dioxide P25, available from Degussa ~ 2~

Co. ~referred titanium dioxide materials are fumed titanium dioxide and precil)it~ted titnrlium dioxi~le.
The particle si~e of the alumina and titanium dio~cide material that are USe(l i8 important in achievin g the desired anti-filming propertie~ .
The alumina or titanium dioxide particles that are used are finely (livided and c~n have a particle size of about 0 . 01 to 10 microns, preferably 0 . 01 to 8 microns and more preferably about 0, 020 to 4 . 0 microns . For exRmple, a æuitable particle size is flbout 0 . 01 to 0 . 50 microns . The alumina and titanium dioxide particles of this size and in the amount used herein nre not nbrasive.
The finely divided alumina or titanium dioxide material particles in the dishwashing wash act to coagulate proteinaceous particulate soils and keeps them in suspension to prevent them from depositing on the clean glass and dishware .
Without intending to limit the invention in anyway it is theorized that the fllllmina and titanium dioxide anti-filming agents function in the following manner. The surface of vitreous glns~ware contnins negntively chnrged sites through the Si-O bonds. Usually the oxygen atoms carry these charges. It is postulated that these neg~tively charged ions will nttract positively charged particles and thereby will form an "artificifll F.oil" layer.
Thi~ protective mono-lflyer will then repel tlle regular food soil and wlll increase the anti-redeposition property of the automatic dishwashing detergent. The alumina and titanium dioxide particles, respectively, will genernte positively charged particles which will bond themselve~ to the glassware surface to form the artificial soil layer which will prevent the formfltion of film.
Tlle amount of silicn, alumina or titnnium dioxide anti-filming agent that can be used to achieve the desired improvement in film will depend on the hardne3s of the water, detergent active compound, inorganic salts and other ADD ingredients. The silica, alumina or titanium dioxide antl-filming ~ U~ J'~

agerlts are particularly eIfective in hnrd wash water of, for example, 300 p~m hardne6s or more.
Tlle ~mount of each of the silicnt alumina or titanium dioxide anti-rllm agerlt thllt i8 used can be about O . 5 to 10%, preferably about 1 to 896 and more preferab]y ~bout 1. 5 to 6~ by weight based on the weight of the entire composition.
The silica, ~lumina and titanium dioxide can each be used nlone or one or more of them can be used mixed together. When the anti-filming agents are used mixed together the weight percent amounts mentione(l above nre the total for the anti-film agent ingredients used in the mixture.
ANTI-SPOTTING AGENTS
rolyacrylic Acid Polymers ~nd Salts Thereof The polyacrylic acid polymers and salts thereof anti-spotting agents thnt c~n be used are genernlly commercially available and are briefly clescribed as follows.
The polyacrylic acid polymers and salts thereof that can be used comprise water soluble low molecular weight polymers having the formula 1 1 1 a I
_ - C - C --R3 COOM n wherein the Rl, R2 ~nd R3 can be the same or different and can be hydrogen, C1-C4 lower alkyl, or combinations thereof. The value of n is 5 to 100(), prefernbly, 10 to 500, and more preferably 20 to 100. M
represents hydrogen, or an alkali metal such as sodium or potassium. The preferred ~ubstituent for M i8 sodium.
The preferred R1, R2 and R3 groups are hydrogen, met}lyl, ethyl and propyl. Preferred acrylic acid monomer is one where Rl to I13 are hydrogen, e . g. acrylic acid, or where R1 and R3 are hydrogen and R2 is methyl, e. g. methyl acrylic acid monomer.

i `~ 2 ~

The degree of polymerization, i. e. the vnlue of n, is generally ~e~el mirled hy the limit eonlpatible with the ~ol~bility of the polymer in water. The terminal or end group~ of the polymer are not critical and can be 1~, Oll, CH3 or fl IOW molecular weight hydroc~rbon.
The polyacrylic acid polymers and salt~ thereof can have a molecular weight of 500 or 1,000 to 100,000, preferably 1,500 to 80,000 and especially preferably 2,000 to 50, 000 .
Specific polyacrylic acid polymers which can be used include the Acrysol LMW acrylic acid polymer~ from Rollm and HaQs, such ns the Acrysol LMW-45N, a neutralize<l sodium salt, which ha~ a molecular weight of about 4, 500 and Acrysol LMW-20NX, D neutralized sodium sfllt, which has a molecular weight of about 2, 000 . Other polyacrylic acld polymers or salts thereof thnt can be used are: Alcosperse 199, molecular weight 2000, Alcosperse 123, molecular welght 4500, Alcosperse 107, molecular weight 3000, Alcosperse 12~, molecular weight 2000, and Alcosperse 602N molecular weight 9500, nll of which are available from Alco Chemicul (~OI'p. The low moleculnr weight acrylic acid polymers can, for example, have a moleculnr weight of about 1,000 to 10,000. Another polyacrylic acid polymer that can be used i8 Alcosperse 110 (from Alco) which is a sodium salt of an organic polycarboxylate and which ha~ a molecular weight of ~bout 100, 000 .
The above polyacrylic acid polymers and salts thereof can be mnde using procedures known in the art, see for example U.S. Patent q,203,858.
The amount of polyflcrylic acid polymer or salt that can be used to achievc the desired improvement in anti-filming and anti-spotting properties will depend on the hardness of the water, detergent active compound, inorganic salt~ flnd other ADD ingredients.
The polyacrylic acid or salt anti-spotting agent is particularly effective in reducing spotting in hard water of, for example, 300 ppm hardness or more .

~5 I ~ 2 ~ ~r ~ 2 Generally, the amounts of the polyacryllc acid polymer or salt anti-spottillg agent thnt cnn be use(l are in the range of from ~hout 1. 0 to 30~, preferably from about 2 . û to 25~, especially preferably about 4 to 2096 BUILDER SALTS
Generally, ADD effectiveness i8 related to (a) oxygen bleach levels;
(b~ alknlirlity; (c) solubility in washing medium; and (d) foam inhibition.
It is preferred herein that the pH of the aqueous wash bath after addition of the liquid ADD compofiition be at least about 9 . 5, more preferably from about 10 . 5 to 13 . 5 and most preferably at least about 11, 5, The nmount of ~Ikali metal ~ilicate added and the amount of alkali metal TPP added can be used to obtain the desired alkalinity in the wnsh bath.
The sodium carbonate can be ad(led to act a~ a buffer to maintain the de~ired pl~ level in the wnsh bath. The sodium carbonate can be added in an amount of 0 to 25 wt . %, preferably 5 to 20 wt . % and typically about 5 to 15 wt . % of the detergent composition .
The compositions of the present invention can contain inorgnnic builder finlts such n~ NaTPP or organic builder snltæ such ns the alk~li metnl snlts of polycarboxylic acids.
A preferred solid builder salt is nn alkali metal polyphosphate such af3 ~odium tripolyphosphnte (TPP). In place of all or part of the alkali metnl polyphosphate one or more other detergent builder f3alts can be u~ed.
Suitable other builder salts are alkali metnl borates, phosphntes and bicarbonates .
Specific examples of such builders are ~odium tetraborate, sodium pyrophosphate, potassium pyrophosphate, 60dium bicarbonate, sodium hexumetaphosphate, ~odium sesquicarbonnte, sodium mono and diorthophosphate, potnsaium bicarbonate and sodium or potassium zeol~te~.
The detergent builder6, e. g. NaTPP mny be employed in the nonaqueous liqui~ ADD composition in a range of 20 to 60%, preferably about 20 to 55 wt . %, and more preferably about 20 to 45 wt . ~; . The Na'rPP

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may be anhydrous or hydrated, including the stable hexahydrate with a degr ee of hydrrltion of 6 corresponding to about 18% by weight of water or more. However, anhydrous NaTPP is preferred.
The NaTPP may be replaced in whole or in part by organic builder salts. Since the compositions of this invention are generally highly concentrated, and, therefore, may be used st relatively low dosages, it is desirable to .supplement any phosphate builder (such as sodium tripolyphosphate) with an auxiliary builder such as an alkali metal polycarboxylic acid. Suitable alkali metal polycarboxylic acids are alkali metnl salts of citric and tartaric acid, e . g. monosodium and disodium citrate (nnhydrous). The sodium salts of cltric ancl tnrtaric acids are preferred.
Foam Inhibitors Foam inhibition is important to increase dishwasher machine efficiency and minimize destabilizing effects which might occur due to the presence of excess foam within the wssher during use. Foam may be sufficiently red~lced by suitable selection of the type and/or amount of detergent active materifll, the main foam-producing component. The degree of foam is also somewhat dependent on the hardness of the wash water in the machine whereby suitable ad~ustment of the proportions of NaTPP which has a water softening effect may ald in providing the desired degree of foam inhibition.
~owever, it is generally preferred to include a foam depressant or inhibitor. Particularly effective are the nlkyl phosphonic acid esters of the formula 1l"
HO--P --R
OR
available, for example, from BASF-Wyandotte (PCUK-PAE), and especially the alkyl acid phosphate e6ters of the formula R
HO--P--OR

OR

. . . . .. .

~ r ~

availllble, for exnmple, îrom ~looker (S~Y) and Knapsnck (LPKN-158), in whiclI one or both R groups in each type of ester may represent independerltIy a C12 20 alkyl group. Mixtures of the two types or mixtures of mono- and di-esters of the same type, may be employed. Especially preferred i5 a mixture of mono- and di-C16 18 alkyl acid phosphate esters such QS monostearyl/distearyl acid phosphates 1.2/1 (Knapsack). When employed, proportions of 0 . 01 to 6 wt . %, preferably 0 .1 to 5 wt . %, especially about D . 5 to 4 . 5 wt . %, of foam depre~snnt in the composition is typical, the weight ratio of detergent active component to foam depressant generally ranging from about 10 :1 to 1:1 and preferably about 4 :1 to 1:1.
Other defoamers which may be used include, for example, the known silicones, such as Dow Corning 1400 and 1500, which are polysiloxanes mixed with disperYed silica.
Bleaching Agents The peroxygen bleach compounds are preferrably used in the compositiona of the present invention. The oxygen blesches nre well known and are represented by percompounds whicll liberate hydrogen peroxide in solution. Preferred examples include sodium and potRssium perborates, percnrbonstes, and perphosphates, and potassium monopersulfate. The perborates, particularly sodium perborate monohydrate, are preferred. The peroxygen compounds can be used In an amount of 3 to 15, preferably 4 to 12 and more preferably 4 to 8% by weight.
ï he peroxyFen compourld is prefcrably used in admixture with an activator therefor. Suitable activntors which can lower the effective operating temperature of tlle peroxide bleaching agent are used.
Polyacylated compounds are preferred activators; among these, compounds such as tetraacetyl ethylene diamine ( T~ED ) and pentaacetyl glucose are particularly preferred. The bleach activators can be used in an amount of ~ 2 ~ 2 O to 8, preferably 1 to 8 and more preferably 2 to 6 wt. percent, for example 2 to 4 wt. percent.
The ble~ch activators interact with the peroxygen compounds to form a peroxyncid bleaching ngent in the wash water.
Other ufieful activntors include, for example, acetylsalicylic acid derivatives, ethylidene benzoate acetate and its sRlts, ethylidene carboxylate ~cetate and it~ salts, alkyl and alkenyl succinic anhydride, tetraacetylglycouril (TAGU), and the derivatives of these.
The conventionally used dishwasher detergent composition chlorine blench compounds such as dichloro-isocyanurate, alkali metal, e. g.
pc-tassium and sodium, hypochlorite should not be used because they are un6tflble in the organic carrier liquids used in the compositiol~s of the present invention. That i8 compounds that contain hypochlorite or that generate hypochlorite in the product liquid should not be used. Compounds that are stable in the product liquid, but that develop hypochlorite ion in the dishwasher water can however be u6ed. For example, a combination of sodium chloride and Oxone (TM for potassium mono persulfate) which deve]op hypochlorite ion isl the dishwflsher water can be used.
Sodium Silicate The ~odium silicste, which provide~ fllkalinity and protection of hard surfnces, such as fine china, i6 employed in an amount rnngirlg frorn about 5 to 30 wt.%, preferably about 7 to 26 wt.%, and more preferably about 8 to 29 wt . %, in the composition . Iior example the compo~ition can contain 8 to 15% sodium silicate. The sodium silicRte al60 protects the washing machine from corro6ion. The sodium silicRte can have a Na20:SiO2 ratio of 1.6/1 to 1/3 . 2 . The 60dlum silicate C~Sl be added in the form of a dry powder or a6 a nonaqueous dispersion, preferably hnvillg an Na20:SiO2 ratio of from 1/1 to 1/2.8, for examE-]e, 1/2.4. Potassium silicotes of the snme ratios cnn also be used. The preferred alkflli metal silicates are anhydrou6 sodillm disilicnte and sodium meta~ilicate.

I\lost of the other components of the composition, for e~ample. foam depressant can be added in the form of dry powders or nonaqueou dispersions or solutions.
The detergent active materials used in the present invention can b~s either the nonionic or anionic detergents. The nonionic detergents are, however, preferred.
Various conYentîonal ingredient6 may be included in these compositions in smnll amounts, generally less than about 4 wt . %, e . g. 0 . 5 to 9% such as perfume, hydrotropic agents such as the sodium benzene, toluene, xylene and cumene sulphonates, preservatives, dyestuffs and pigments and the like. Especially preferred for coloring are the clllorinated phthalocyanines and polysulphides of flluminosilicate which provide, respectively, pleasing green and blue tints.
The nonaqueous liquid Al)D composition6 of this invention are readily employed in known manner for washing dishes, glasses, cups, eating utensils and the like in an aqueous wash bat}l~ in an automatic dishwasher, containing an effective amount of the composition.
The composition may also include conventional orgnnic or inorganic thiclcening agents in amounts sufficient to obtain a product consistency of a cream or a paste.
The thickening agents, i.e. thickeners or suspendlng agents which provide thickening propertie~, are known in the art and may be organic or inorganic, water 601uble or insoluble, dispersible or colloid-rorming, an(l monomeric or polymeric, and should of course be stable in these compositions, e . g. stable to alkalinity. The preferred thickeners generally comprise the inorganic, colloid-forming clays of smectite and/or attapulgite types. These materi~qls are generally used in amounts of about 1. 5 to 10, preferably Z to 5 wt%, to confer the desired thickening properties to the formulation .

Z~

~ 2 ~ 2 Smectite clnys incl-lde montmorillvnite (bentonite), hectorite, attr~pulgite, smectite, saponite, and the like. MontmorilloIlite clays nre preferred and are available under tradenames such as Thixogel (Registered Trndemark) No. 1 and Gelwhite (Registered Trndemark) (3P, ~, etc., from aeorgia Kaolin Company; and ECCA~UM (Registered Trademark) GP, ~, etc., from Luthern Clay ProductY. Attapulgite clays include the materials commercially available under the tradename Attagel (Registered Trademark), i . e . Attngel 4n ~ Attagel 50 and Attagel 150 from Engelhard Minerals and Chemicnls CorporFttion. Bentone 27 and Betone 38 from NL Chemicals can also be used. Mixtures of smectite and attapulgite types in weight ratios of 4 :1 to 1: 5 are also useful. Thickening or ~uspending agents of the foregoing types are well known in the art, being described, for example, in USP 3, 985, 668, which i8 incorporated herein by reference thereto .
The nonaqueous liquid ADD compositions of this invention are rendily employed in known manner for washing dishes, glasses, cups, cookware, eating utensils and the like in an automatic dishwasher, provided with a suitable detergent dispenser, in an aqueous wash bath containing an effective amount of the composition.
In F~n embodiment of the invention an automatic dishwashing detergent concentrate compo~ition is formulsted using the below named ingrediente.

. ~ J ~
Preferred Componellt Weight Percent Weight Percent Organic Carrier Liquid 20-60 30-95 Sodium Tripolyphosphate 20-60 20-45 Sodium Carbonate 0-25 5-15 Surfactant Detergent1-12 3-8 Sodium SilicRte 5-30 10-24 Anti-filming Agent 1-10 1. 5-6 Sodium Polyacrylate 1-3~ 4-20 Oxygen Bleach 4-12 4-8 Bleach Activator 1-8 2-6 Color, Perfume 0-4 to 3 . 0 0 .1-0 . 5 Moisture 0-3 . 0 0.1 to 0 . 5 The nonaqueous liquid dishwasher detergent compositions of the present invention can contain conventional dishwashing detergent composition additives. The formulations can be prepared with commercially ~v~ sble detergent builders, peroxygen bleach compounds and blesch activntors and surfactant compounds.
The formulations csn be prepsred using the conventional blending and mixing procedures used for the preparation of liquid deterges~t compositions as briefly de~cribed below.
Method Of Preparation of Liquid Composition The compositions of the present invention can be prepared in two stages. In the first stage silica, alumina or titsnium dioxide anti-film ~gent, powdered silicste and low moleculsr weight polyacrylate powder when used~ nre pr~mllled using h cer~mic boll mill. The premilled 2~

? 2~
mntel ials ure then mi~ed u~ing a standnrd rotary mixer . This mixed mnterinl is then transîerred to an attritor and milled for 30 mlnute.s nt 5rl0 rpm using 1/4 inch stealite grinding media.
In the second stage the orgnnic cnrrier liquid ~nd Neodol 25-~ . 5 (nonionic surfactant~ are mixed, and the defoamer and phosphate builder salt~ nre added. The premilled anti-film agent and polyacrylate (when used ) are then added to the organic carrier liquid and nonionic surfactant mixture followed by the addltion of sodium carbonate, oxygen bleach and bleach activator and the remaining ingredients. ~fter mixing the liquids so]ids mixture is vigorously stirred to obtnin n stable dispersion of the solids in the organic carrier liquid.
One or more of the ingredients can be omitted or additional ingredients such as perfume~ and nnti-foam agents cnn be added to the composition.
The term nonaqueous liquid compositions as used herein is intended to include compositions containing 0-8% water, typically 2-6% and more typically 1-2% water. The water cnn be present in the form of hydrated compounds, i . e . bound water, for exnmple, sodium tripolyphosphate hexullydrate, hydrated sodium carbonste, hydrated sodium sulfate, sodium perbornte monohydrate and/or in the form of moisture, i . e . unbound water . It is preferred, however, that the composition contain les.s than 1% moisture a8 unbound wnter.
1~11 amountfi nnd proportions referred to herein are percent by weight of the composition unless otherwise indicated.
The invention mny be put into practice in various ways nnd a number Or specific embodiments will be described to illustrate the invention witl roference the accomp~nying sxsmples.

2 ~ 7 Example 1 In ~ccordnnce with the present invention an aqueous liquid Rutomatic ~ishwssher cletergent composition waE~ formulated using the below named ingredients in the amounts indicatecl and i8 compared with a prior art commercial powder detergent.

A B
Prior Art Invention CommerciaI
Ingredient Liqu d (Part~)Powder (Parts) Organic Carrier Liquid39.1 --Sodium Tripolyphospate22 . 8 35 . 3 Sodium Carbonate 9 . 5 20 . 0 Sodium Sulfate -- 18 . 0 Nonionic Surfactant ( 1 ) 2 . 8 3 . 5 Sodium Silicate (1:2,4)7.6 10.0 SilicA Anti-filming Agent 4, 8 --Sodium Perborate Monohydrnte 4 . 8 4 . 8 Bleach Activator( ) 2 . 4 2 . 4 Sodium Polyacrylste(3)6, 2 __ Moisture < 1 13 99,5 101.6 ( 1 ) Tergitol MDS-42, from Union Carbide Corporation .
(2) Tetraacetylethylene diamine (TAED).

(3) Alcosperse 1301~, from Alco Chemical6.
The two above formulations (A) and (B ) were tested and compared for fllm and spot formation. The formulations were tested in a Kenmore automatic dishwasher using the procedure clescribed in AS1'MD 3566-79, except that only four cleaning cycles are used. The filming and spotting were ovaluated according to the following scales~

Film Rating Scale 1. B est, no apparent film 2, Filmlng slight, becoming apparent 3. Noticeable iilm, increasing ~4 '~ 2 ~ f~ 7, 4. Continued incrense of significant film 5. Filming becoming excessiv~

6. Filming high, excessive buildup 7. Continued incrense of excessive film.
Spot Rating Scale A. Best - no spots B. Very few spots apparent C. Distinct D. Significant coverage apprnximately 50~,.
ï'lle above compositions were tested cleaning glass tumblers.
The ASTM Method D3556-79 for the deposition on glassware during mechanicnl dishwashing, as menticned above, was used to evaluate the buildup of spots and film on glassware. 42 grams of the invention nonaqueous liquid detergent composition (A) and 50 grams of the commercial powder detergent composition (B) are used in each test. All testing re~ol ted W8S done in Kenmore Model 587.1548581) and/or model 587.1546580 Automntic l)ishwasller. The water wash temperature iff 120F and the water hs~.s ~00 ppm hardneffs.
The results sre reported below.
Formulation Spot Film Invention Formulation (A) B 3 Commercial Formulation ( B ) B 4 The commercial powder gnve more film than the invention nonaqueous iquid ADD compo=ition. There wa= no dilference in ihe =pot 600re=.

~ 2 ~

Example 2 Fvllowin~ the teachings of the present invention, nonnqueou6 lic~uid nutomatic dishwnsheI detergent compositions were formlllated using the below named ingredients in the amounts indicated.
A B C D
Wt,% Wt.% Wt.% Wt.%
Organic Carrier Liquid( ~ 36.3 3~.S 41.0 39.1 NnTl'P / 41. 0 38 . 924 . 022 . 8 Sodium Carbonate ,~ 10 . 0 9 . 5 Sodium Silicate 13 . 7 12 . 9 8 . 0 7 . 6 Surfactant( ) 2.6 2.q 3.0 2.B
Silica Anti-filming Agent( ) - - -- 4 . 8 Sodium Polyacrylate(q) - 5.2 6.5 6.2 aching Agent(5) 4.3 9.0 5.0 4.8 Bleach Activator(6) 2,1 2.0 2.5 2.4 100. O 100. O100. O100. O
(Dose Size, Gram6) (~7) (49 6) (40) (92) (1) Methoxy polyethylene glycol (Cflrbowflx MPRG 350) fronl Union Carbicle.
(2) Tergitol MDS which i8 a nonionic surfactant from Unlon Carbicle.
( 3 ) Syloid 24 ~ .
(4) Alcosperse 130D, Alco.
(5) Sodium perborate monohydrnte (Interox).
(fi) Tetraacetylethylenediamine (TAED).
The sbove formulations A, B, C and D were tested following the test nnd evaluation proceclure of Exsmple 1. The tests were cnrried ouc at 120F with 100 ppm water hardness, or 120F with 300 ppm water hnrdness.
There were ten glass tun~blers u~ed in each test and the nverage values are reported. The te6t result performance profile nre reported in the below table.

Performance Profile 1. ~STM Test 100 ppm hard water, F
A B C D
Spot Film Spot Film Spot Film Spot Film ~ D 2 - AB 2 Il. ASTM Test 300 ppm hard water, 120F
A B C D
Cycle Spot Film Spot Film Spot Film Spot Film l - - B 4 AB 2,3 2 - - B 4,5 AB 2,3 3 - - B ~,5 AB 3 The Test 1 ( 100 ppm hardness, 120F) data show thnt the polyacrylate in the formulations B and C provides substantially improved ~pot performance as compared to the comparison formulation A without polyacrylate. The film performance for the formulations A, B and C were similar .
The Test Il (300 ppm hardness, 120F) ~how that the addition of silica nnti-film agellt to invention formulation D, which also contains polyacrylate, improves the spot and film performance a8 compared to the formulation C
which contains only the polyacrylate.
The Te~t I data show that the addition of polyacrylate to the formulation improves spot performance, and the Test 11 data show thnt the further addition of &ilica improves spot and film performance.

l ~ r J ~ 1 "
Example 3 A nonaqueous liquid automatic dishwashing detergent composition is formulated from the following ingredients in the amounts specified.
Invention Formulation Alumina Anti-film Agent Component ( 1 ) Wt . 96 Organic Carrier Liquid 38 . 00 NaTPP 27. 84 So(lium Carbollnte (Anhydrous) 10 . 00 Sodium Silicate (1/2.35 - 43.5%) 12.00 Poly Tergent SLF-18 1, 00 Alumina Anti-filming Agent( ) 2 . 00 Sodium Perborate Monohydrate 4 . 8 }3leach Activator 2 . 9 Knapsack LPKN-158 Foam Depressant 0,16 1~
(1) Organic Carrier Liquid is Polyethylene Glycol 300 (Union Carbide).
(2) Ethoxylated propoxylated fatty alcohol (Olin Chemical).
( 3 ) Aluminum oxide C has a particle size of 0 . 02 microns and is available from DeGussa Co.
(4) TAED.
The formulation i8 tested by washing glassware at 130F in hard water (300 ppm hardness) in a Kenmore automatic dishwasher to clean glass tumbler~ using the procedure described in ASTMD 3566-79, except that only four cleaning cycles are used. The spotting and filming are evaluated as in Example 1. The clean tumblers are found to have reduced film as compared o commorctal powder formulat(on- not oontnlning alumin= anti-film agent.

~ ~ 2 ~ J ~

Example 4 The above Example 3 i8 repeated with the difference that 2 . 00 wt . 9i titanium dioxide i9 sub6tituted for the alumina anti-filming flgent. The Iormulation is tested by washing glassware at 130F in hard water (300 ppm hardness) as before. The clean tumblers are found to have reduced film as compare(l to commercial powder formulations not containing titanium dioxide anti-film agent.
The nonaqueous liquid automatic dishwasher detergent composition6 of the present invention provide improved film snd/or improved spot properties on gl~qssware and di6hware.
The invention is not to be limited by the above disclosure and examp]es which are given a8 illustrations only. The invention is to be interpreted in accordaTIce with the below claims.

Claims (20)

1. A nonaqueous liquid automatic dishwashing detergent composition having improved film performance comprising a nonaqueous organic carrier liquid and at least one ingredient selected from the group consisting of organic detergent, detergent builder, foam inhibitor and mixtures thereof, and a member selected from the group consisting of a nonabrasive 0.5 to 10.0% amount of small substantially water insoluble particles of silica, alumina or titanium dioxide, or mixtures thereof, as an anti-filming agent.

2 . The composition of claim 1 containing a nonabrasive 1. 0 to 8%
amount of the anti-filming agent.

3. The composition of claim 1 containing 1 to 30% of a water soluble polyacrylic acid polymer or salt anti-spotting agent.

4. A nonaqueous liquid automatic dishwasher detergent composition comprising approximately by weight:
(a) 20 to 60% organic carrier liquid;
(b) 20 to 60% inorganic or organic detergent builder;
(c) 5 to 30% sodium silicate;
(d) 0 to 25% alkali metal carbonate;
(e) 0.1 to 12% water-dispersible organic detergent active material;
(f) 0 to 6% foam depressant (g) 3 to 15% peroxygen bleach compound;
(h) 0 to 8% bleach activator; and (i) a nonabrasive 0.5 to 10% amount of an anti-filming agent which is a member selected from the group consisting of silica, alumina, titanium dioxide and mixtures thereof having a particle size of 0 .01 to 10 microns .

5. The composition of claim 4 wherein the peroxygen bleach compound is a member selected from the group consisting of sodium perborate, potassium monopersulfate, sodium percarbonate and monoperoxyphthalate .

6. The composition of claim 4 additionally containing 2 to 25% of a water soluble polyacrylic acid polymer or salt anti-spotting agent.

7. A nonaqueous liquid automntic dishwasher detergent composition comprising approximately by weight:
(a) 25-55% organic carrier liquid;
(b) 20 to 55% alkali metal tripolyphosphate;
(c) 7 to 26% sodium silicate;
(d) 5 to 20% alkali metal carbonate;
(e) 0.5 to 10% water dispersible organic nonionic detergent active material;
(f) 0.1 to 5% foam depressant;
(g) 9 to 12% of a peroxygen bleach compound;
(h) 2 to 6% of a bleach activator; and (i) a nonabrasive 1 to 8% amount of an anti-filming agent which is a member selected from the group consisting of silica, alumina, titanium dioxide and mixtures thereof having a particle size of 0.01 to 8 microns .

8. The composition of claim 7 additionally containing 2 to 25% of a polyacrylic acid polymer or salt anti-spotting agent which hns the formula wherein R1, R2 and R3 can be the same or different and can be hydrogen, Cl-C4 lower alkyl, M represents llydrogen, or an alkali metal, n = 5 to 1000 and the polymer has a molecular weight of 1000 to 100, 000 .

9. The composition of claim 7 wherein the bleach activator is tetraacetylethylenediamine (TAED).

10. The composition of claim 7 wherein the anti-filming agent is silica.

11. The composition of claim 7 wherein the anti-filming agent is alumina.

12. The composition of claim 7 wherein the anti-filming agent is titanium dioxide.

13. A liquid nonaqueous automatic dishwasher detergent composition comprising approximately by weight:
(a) 30 to 45% organic carrier liquid;
(b) 20 to 45% alkali metal tripolyphosphate;
(c) 10 to 24% sodium silicate;
(d) 5 to 15% alkali metal carbonate;
(e) 0.5 to 4.5% foam depressant;
(f) 1 to 8% water dispersible organic nonionic detergent;
(g) 4 to 12% peroxygen bleach compound;
(h) a nonabrasive 1.5 to 6% amount of an anti-filming agent which is a member selected from the group consisting of silica, alumina, titanium dioxide and mixtures thereof having a particle size of 0.01 to 8.0 microns; and (i) 4 to 20% water soluble polyacrylic acid polymer or salt.

14. The composition of claim 13 wherein the water soluble polyacrylic acid polymer or salt anti-spotting agent has the formula wherein R1 and R3 are hydrogen, and R2 is hydrogen or methyl, M
represents hydrogen, sodium or potassium, n = 10 to 500 and the polymer has a molecular weight of 1500 to 50,000.

15. The composition of claim 13 wherein the polyncrylic acid polymer or salt has a molecular weight of about 2000.

16, The composition of claim 13 wherein the polyacrylic acid polymer or salt has a molecular weight of about 4500.

17, The composition of claim 13 wherein the silica anti-filming agent contains about 0.1 to 5% of alumina, based on weight of silica.

18. The composition of claim 13 wherein the anti-filming agent has a particle size of about 0.01 to 5 microns .

19. A method for cleaning soiled glassware and dishware which comprises contacting the glassware find dishware in an automatic dishwashing machine in an aqueous washbath having dispersed therein an effective amount of the composition of claim 1 to obtain clean glassware and dishwashing with reduced film and/or spot.

20, A method for cleaning soiled glassware and dishware which comprises contacting the soiled glassware and dishware in an automatic dishwashing machine in an aqueous wash bath having dispersed therein an effective amount of the composition of claim 7 to obtain clean glassware and dishware with improved film and/or spot