CA1326803C - Thixotropic aqueous liquid automatic dishwashing detergent composition - Google Patents
Thixotropic aqueous liquid automatic dishwashing detergent compositionInfo
- Publication number
- CA1326803C CA1326803C CA000582266A CA582266A CA1326803C CA 1326803 C CA1326803 C CA 1326803C CA 000582266 A CA000582266 A CA 000582266A CA 582266 A CA582266 A CA 582266A CA 1326803 C CA1326803 C CA 1326803C
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- Prior art keywords
- composition
- thixotropic
- amount
- salt
- alumina
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
Abstract
THIXOTROPIC AQUEOUS LIQUID AUTOMATIC
DISHWASHING DETERGENT COMPOSITION
ABSTRACT OF THE DISCLOSURE
Thixotropic aqueous liquid automatic dishwashing detergent composition with improved anti-filming and anti-spotting properties and method of using the detergent composition. The detergent composition comprises alumina or titanium dioxide anti-filming agent, polyacrylate polymer builder, inorganic builder salts, chlorine bleach, bleach-stable detergent and a thixotropic thickener. The compositions provide reduced filming and spotting on dishware, glassware, china and the like, particularly in hard water, and remain stable against phase separation.
DISHWASHING DETERGENT COMPOSITION
ABSTRACT OF THE DISCLOSURE
Thixotropic aqueous liquid automatic dishwashing detergent composition with improved anti-filming and anti-spotting properties and method of using the detergent composition. The detergent composition comprises alumina or titanium dioxide anti-filming agent, polyacrylate polymer builder, inorganic builder salts, chlorine bleach, bleach-stable detergent and a thixotropic thickener. The compositions provide reduced filming and spotting on dishware, glassware, china and the like, particularly in hard water, and remain stable against phase separation.
Description
132~803 PATENT
4442(B) TIIIXOTROPIC AQUEOUS LIQUID AUTOMATIC
DISHWASHING DETERGENT COMPOSITION
FIELD OF THE INVENTION
_ .
The present invention relates to a thixotropic aqueous liquid automatic dishwashing detergent composition with improved anti-filming and anti-spotting properties and method of using the detergent composition to clean dishware, glassware, china and the like. The dishwashing composttion contains alumina or titanium dioxide, as the anti-filming agent, polyacrylic acid polymer builder inorganic builder salts, chlorine bleach, bleach stable detergent and a thixo~ropic thickener.
The detergent dishwash1ng composition of the present invention reduce8 filming and 8potting on dishware, glassware, china and the like, particularly in hard water, and remains stable against phase separation.
More specifically, the invention relates to the use of aluminum or titanium dioxide as an anti-filming agent and polyacrylic acid polymer builder in thixotropic aqueous liquid dishwashing detergent compositions to reduce ~llming and spotting.
The detergent compositions do no require an added rinse aid, are stable in storage, do not settle and are readily redispersible and are pourable .
The pre8ent invention al80 relates to thixotropic aqueous suspension with improved physical ~tability. The invention relates to the use of long chain fatty acids, metal salts of fatty acids and clay as thixotropic agents for forming stable gel-like liquid suspensions suitable for use as liquid automatic dishwasher detergent composition.
The present invention specifically relates to aqueous liquid automatic dishwashing detergent compositions having thixotropic properties, improved anti-filming and anti-spotting properties and improved physical stability 1326~03 properties, which are readily di6persible in the washing medium to provide effective cleaning of dishware, glassware, china and the like.
PRIOR ART
Commercially available household-machine dishwasher detergents provided in powder form have several disadvantages, e. g. non-uniform composition; costly operations necessary in their manufacture; tendency to cake in storage at high humidities, resulting in the formation of lumps which are difficult to disperse; dustiness, a source of particular irritation to users who suffer allergies; and tendency to cake in the dishwasher machine dispenser. Liquid forms of such compositions, however, generally cannot be used in automatic dishwashers due to high foam levels, unacceptably low viscosities and exceedingly high alkalinity.
In addit10n, the presently used formulated powder detergents frequently require a separate step of hand towel wiping and drying o~ the dishwarQ, glassware, china and the like to avoid leaving undesirable traces or film of precipitated calcium and magnesium salts. The use of liquid detergent compo~itions present other problems. The builder salts settle in storage and are not readily redispersed. The compositions also frequently become thicker in storage and are not readily pourable.
Recent research and development activity has focused on the gel or "thixotropic" form of such compositions, however, such compositions have generally proven to be insufficiently viscous to remain "anchored" in the dispenser cup of the dishwasher, and moreover yield spotty residues on dishware, glassware, china and the like. Ideally, thixotropic cleansing compositions should be highly viscous in a quiescent state, Bingham plastic in nature, and have relatively high yield values. When subjected to shear stresses, however, such as being ~haken in a container or squeezed through an orifice, they should quickly fluidize and, upon cessation of the applied shear stress, quickly revert to the high viscosity/Bingham plastic state. Stability is likewise of primary importance, i.e. there should be no significant evidence of phase separation or leaking after long standing.
For effective use, it is generally recommended that the automatic dishwashing detergent, hereinafter also designated ADD, contain (1) sodium tripolyphosphate (NaTPP) to soften or tie up hard-water minerals and to emulsify andlor peptize soil; (2) sodium silicate to supply the alkalinity necessary for effective detergency and to provide protection for fine china glaze and pattern; (3) sodium carbonate, generally considered to be optional, to enhance alkalinity; (4~ a chlorine-releasing agent to aid in the eliminution of soil specks which lead to water spotting; and (5) defoamer/surfactant to reduce foam, thereby enhsncing machine efficiency and supplying regui~ite detergency. See, for example, SDA Detergents in Depth, "Formulations Aspects of machine Dishwashing," Thomas Oberle (1974). Clean8ers approximating to the afore-described compositions are mostly liquid~ or powder~. Generally, su¢h compodtions omit hypochlorite bleach, since it tends to react with other chemically active ingredients, particularly surfactant, thereby degrading the suspending or thixotropic agent and impairing its effectiveness.
Thus, U.S. Patent No. 3,985,ff68 describes abrasive scouring cleaners of gel-like consistency contdning (1) suspending agent, preferably the Smectite and attapulgite types of clay; (2) abrasive, e.g. silica sand or perlite; and ( 3 ) filler comprising light density powdered polymers, expanded perlite and the like, which has a bouyancy and thus stabilizing effect on the composition in addition to serving as a bulking agent, thereby replacing water otherwise available 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, ~uch as NaTPP, can be included as further optional ingredients to supply or supplement building function not provided by the buffer, the amount of such builder not exceeding 5% of the total composition, according to the patent . Maintenance of the de~ired ( greater than) pH 10 levels is achieved by the buffer/builder components. High pH
is said to minimize decompo~ition of chlorine bleach and undesired S interaction between surfactant and bleach. When present, NaTPP is limited to 5%, as stated. Foam killer is not disclosed.
In U.K. Patent Application GB 2,116,199A and GB a,140,450A, both of which are assigned to Colgate-Palmolive, liquid ADD compositions are diselosed which have properties desirably charaeterizing thixotropic, gel-type strueture and wMeh inelude eaeh o~ the various ingredients neeessary for effective detergency with an automatie dishwasher. The normally gel-like aqueous automatlc dishwasher detergent composition having thlxotropie propert~e~ ineludes the following ingredients, on a weight basis:
(a) 5 to 3S% alkall metal tripolyphosphate;
(b) 2,5 to 20% sodium silieate;
(e) 0 to 9% alkali metal earbonate;
(d) 0.1 to 5% ehlorine bleaeh stable, water dispersible organie detergent aetive material;
(e) 0 to 5% chlorine bleaeh stable foam depressant;
(0 ehlorine bleach eompound in an amount to provide about 0.2 to 491 of available chlorine;
(g) thixotropie tMckener in an amount sumcient to provide the composition wlth thixotropy index of about 2.5 to 10; and (h) sodium hydroxide, as necessary, to adjust pH.
ADD compositions 80 formulated are low-foaming; are readily soluble in the washing medium and mo~t effective at pH values best conducive to improved eleaning performanee, viz, pH 10.5-13.5. The compositions are normally of gel consisteney, i.e. a highly viseous, op&~ue jelly-like material having Bingham plastic character and thus relatively high yield values.
Accordingly, a definite shear force is neeessary to initiate or increase flow, .~ , such as would obtaln wlthln the agltated dlspenser cup of an energlzed automatlc dlshwasher or a stream of water. Under such condltlons, the composltlon ls qulckly fluldlzed and easlly dlspensed. When the shear force ls dlscontlnued, the fluld composltlon ~ulckly reverts to a hlgh vlscoslty, Blngham plastlc state closely approxlmatlng lts prlor conslstency.
U.S. Patent 4,511,487 dated Aprll 16, 1985 descrlbes a low-foaming detergent paste for dlshwashers. The composltion ls based on a mlxture of flnely dlvlded hydrated sodlum meta-slllcate, an actlve chlorlne compound and a thlckenlng agent whlch ls a follated slllcate of the hectorlte type. Small amount of nonlonlc tensldes and alkall metal carbonates and/or hydroxldes may be used.
A related Canadlan patent appllcatlon ls Serlal No.
526,708, flled January 6th, 1987. The copendlng appllcatlon dlscloses thlxotroplc aqueous automatlc dlshwashlng detergent composltlon which contalns a long chaln fatty acld as a thlxo- ;
troplc thlckener agent.
Another related Canadlan patent appllcatlon 19 Serlal No. 550,065 flled October 23rd, 1987. Thls copendlng appllca-tlon dlscloses an aqueous llquld thixotroplc clay dlshwashlng detergent composltlon comprlslng a metal salt of a long chaln fatty acid and a polyacryllc acld polymer or salt stablllzlng agent.
ADVANTAGES OVER THE PRIOR ART
The thlxotroplc aqueous llquld detergent composltlons of the present lnventlon overcome many of the prlor art prob-lems assoclated wlth powder and llquld detergents. Because of the addltlon of a small effectlve amount of an alumlna or tlta-nlum dloxlde antl-fllmlng agent and polyacryllc acld polymer or salt bullder to the composltlon an added rinse ald 18 not re-qulred and towel wlplng and drylng are not requlred to obtaln dry sparkllng clean dlshes, glasses, cups and eatlng utenslls.
The thlxotroplc ' .
132~803 aqueous liquid detergent compo~ition has the additional advantages of being stable, non-settling in storage and readily redispersible. The liquid compositions of the present invention are easily pourable, easily measured and easily put into the dishwashing machines.
An additional and unexpected advantage of adding the alumina or titanium dioxide anti-filming agent to the detergent formulatlon is that the alumlnum or tltanlum dloxlde inhibits brown stain formation in the dishwashing machlne. The brown stain is formed by the deposltlon ln the dishwashlng machine of lron and/or manganese oxldes. The brown staln formatlon ls a particularly serlous problem ln areas havlng hard water. The alumlna or titanlum dioxide in the formulation acts on the iron and/or manganese ln the wash water to prevent thelr deposltion in the dishwashing machine as iron and/or manganese oxides.
ASPECTS OF THE PRESENT INVENTION
It 18 an aspect of the present lnventlon to provlde a thlxotropic aqueous llquld automatlc dishwasher detergent composition that has improved anti-filming and anti-spotting properties.
It is another aspect of the invention to provide a thlxotropic aqueous llquld detergent compositlon which is stable in storage, easily pourable and readlly dispersible in the dishwashing water.
A further aspect of the lnvention is to provide a method of washing dishware, glassware, china and the like in an automatic dishwashlng machlne using a thixotropic aqueous liquid detergent composition in which a separate rinse aid is not added or needed.
A still further aspect of the inventlon is to provide a method of washing dishware, glassware, china and the like in .. ; . .
an automatlc washing machine using an aqueous liquid detergent composltion by whlch method the dishware, glassware, china and the like are machine dried without leaving traces or a film.
It is a further aspect of this invention to provide stable aqueous thlxotropic aqueous liquid compositions, especially automatic dishwasher detergent compositions, by incorporating in the aqueous suspension a small effective amount of an alumina or titanium dioxide anti-filming agent and polyacrylic acid polymer or salt builder. There is also added a minor amount of a fatty acid, metal salt of a fatty acid and/or clay thixotroplc thickener effec~ive to inhibit the settling of the suspended particles and to prevent phase separation.
DE~AILED DESCRIPTION OF THE INVENTION
The invention will become more readily understood from the following detailed description of the lnvention and preferred embodiments thereof. The lnvention concerns the incorporatlon in an aqueous llquld detergent composition of a small but effective amount of an alumina or titanlum dloxide antl-filmlng agent and polyacrylic acld polymer or salt builder. The physical stability of the composition is improved by the additlon of a fatty acid, metal salt of a fatty acid and/or clay thixotropic thickener. The lnvention provides a gel-llke thixotropic aqueous liquid automatic dishwashing detergent composition comprislng water, at least one lngredient selected from the group conslsting of organic detergent, chlorine bleach, detergent builder, sequestering agent, foam lnhlbitor and mixtures thereof in which is incorporated from about 0.5 to 5% of an alumina or titanium dioxide partlcles as anti-filming agent and about 2 to 14% of a water soluble polyacrylic acid polymer or salt builder. The alumina or 1~ 2g 803 62301-1519 titanium dloxide anti-filming agent has a particle size of about 0.1 to 10 microns. The water polyacrylic acld or salt preferably has a molecular weight of about 500 to 100,000. The composition comprises a sufficient amount of a long chain fatty acid or metal salt of a long chain fatty acid, or elther of the foregoing in admixture with a clay thixotropic thickener to provide a thixotropic index of about 2.5 to 10 and to inhibit settllng of the suspended particles, such as alkali metal builder salts, etc.
In accordance with this aspect, the present invention also provides a normally gel-like aqueous llquid automatic dishwasher detergent composition having thixotropic properties whlch includes, on a weight basis.
(a) 5 to 35% of detergent bullder, such aæ alkali metal tripolyphosphate;
(b) 2.5 to 40% sodium silicate;
(c) 0.5 to 5% alumlna or titanium dioxlde anti-filmlng aqent having a particle slze of about 0.1 to 10 mlcrons;
(d) 2 to 14% polyacryllc acid polymer or salt bullder havlng a molecular welght of about 1,000 to 100,000;
(e) 0 to 9~ alkall metal carbonate;
(f) 0.1 to 5% chlorine bleach stable, water dispersible organlc detergent actlve materlal;
(g) 0 to 5% chlorine bleach stable foam depressant;
(h) chlorlne bleach compound ln an amount to provide about 0.2 to 4% of avallable chlorlne;
(1) thlxotroplc thlckener in an amount sufficlent to provlde a thlxotroplc index of about 2.5 to 10;
(;) 0 to 8% sodium hydroxide; and (k) balance water.
.~ -j , . . , :
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`- 1326803 62301-lS19 Also related to this specific aspect, the invention provides a method for cleaning dishware in an automatic dlshwashlng machine with an aqueous wash bath containing an effective amount of the liquid automatic dishwasher detergent (LADD) composition as described above. According to this aspect of the invention, the LADD composition can be readily poured into the dispensing cup of the automatic dishwashing machlne and will, within just a few seconds, promptly thicken to its normal gel-like or pa#ty state to remain securely within the dispensing cup untll shear forces are again applied thereto, such as by the water spray from the di~hwa~hing machine.
The invention will now be descrlbed in greater detall by way of specific embodiments thereof.
The LADD products of for example the prlor dlsclosure ln the aforementioned GB 2,116,199A and GB 2,140,450A exhibit rheologlcal 8a D
properties as evaluated by testing product viscosity a8 a function of shear rate. The compositions exhibited higher viscosity at a low shear rate and lower viscosity at a high shear rate, the data indicating efficient fluidization and gellation well within the shear rates extant within the standard dishwasher machine. In practical term6, this means improved pouring and processing characteristics as well as less leaking in the machine dispenser-cup, compared to prior liquid or gel ADD products. For applied shear rates corresponding to 3 to 30 rpm, viscosities (Brookfield) correspondlngly ranged from about 10,000 to 30,000 cps to about 3,000 to 7,000 cps, as measured at room temperature by means of ~n LVT Brookfield viscometer sfter 3 minutes using a No. 4 spindle. A shear rate of 7.4 sec 1 corresponds to a spindle rpm of about 3. An approximate 10-fdd increase in shear rate produceo about a 3- to 9-fold reduction in viscosity.
The compositions of the assignee's prior invention thus exhibit threshold nutdizsttons at lower shear rates and of s1gniflcantly greater extent in terms ot in¢remental increases 1n shear rate versus incremental decrease in viscosity. This property of the LADD produ¢ts of the prior invention i8 summarized in terms of a thixotropi¢ index (TI) which is the ratio of the apparent viscosity at 3 rpm and st 30 rpm. The prior compositions have a TI of from 2 to 10. The LADD compositions should exhibit substantial and quick return to prior quiescent state consistency when the shear force is discontinued.
In terms of apparent viscosity, it has been ascertained that 80 long as the viscosity at room temperature (22+1C) measured ln a Brookfield Viscosimeter HATD, using a number 4 spindle at 20 rpm, is less than about 20,000 cps, the composition can be readily shaken so that a thixotropic composition can be easily "fluidized" or "liquefied" to allow the product to be dispensed through a conventional squeeze tube bottle or other convenient dispenser.
- 1326803 : -The present invention is based upon the surprising dlscovery that substantially improved anti-fllming and anti-spottlng properties can be obtained by adding to the thixotropic aqueous liquid detergent composition a smal}
effective amount of a silica anti-filming agent and polyacrylic acid polymer or salt builder. The physical stability, i.e., resistance to phase separation, settling, etc. can be achieved by adding to the composition a small effective amount of a thixotropic thickener and stabilizing agent.
_NTI-FILHING AGENTS
The alumina or titanium dioxlde anti-filming agent materials that can be uged are readily commercially available.
The alumlna material that can be used as an anti-filming agent is insoluble in water and has the formula Al203. Suitable materlal~ are available under the trademarks Alumlnum Oxide C, Degussa and Catapal D, Vista. A preferred alumina material i~
Alumlnumoxld C~.
The particle slze of the alumlna and titanlum dloxlde material that 1~ used iæ important in achieving the desired anti-filming properties.
The alumina or titanlum dloxlde particles that are used are finely dlvided and can have a particle size of about 0.10 to 10 mlcron~, preferably 0.50 to 8 mlcrons and more preferably about 1.0 to 5.0 mlcrons. The llica particles of this size and ln the amount used herein are not abrasive.
The finely divided alumina or titanium dioxide materlal partlcles ln the dishwashing wash act to coagulate proteinaceous particulate soils and keeps them in suspenslon and with the polyacrylic acid polymer or salt acts as an anti-redeposition agent to prevent them from depositing on the cleanglass and dishware.
~Trade-mark 10 , ... . . . , . . . ~ , - .
1 3 2 g~3 62301-1519 Without intending to limit the invention in any way it is theorized that the alumina and tltanium dioxide anti-fllmlng agents function in the following manner. The glass surface of vitreous glassware contain negative charges on their surface through the Si-0 bonds. Usually the oxygen atoms carry these charges. It is postulated that these negatively charged lons will B .~! lOa attract pos~tively charged particles snd thereby will form sn "artificial soil"
layer. This protective layer will then repel the regular food 80il and will increase the anti-redeposition property of the automatic dishwushing detergent. The ~umina and titanium dioxide particles, respectively, will generate poslti~rely charged p-rticles which will bond themselves to the glssswsre surfsce to form the artificial soil layer which will prevent the formation of film.
The amount of alumins or titanium dioxtde anti-fflming agent that can be used to achieve tho dedred improvement in fflming and spotting will depend on the hsrdness ot the wster, detergent active compound, inorganic salt~ and other ADD ingredients. The aluminum or titanlum dioxide anti-fllming ~gent is partlculsrly eftective in hard wssh water of, for examplo, 300 ppm hsrdness or more.
The smount ot alumina or titsntum dioxide snti-fllm sgent thst is used can b~ bout 0.5 to 5~, pre-erabb about 1 to ~% and moro preferably sbout 1.S to 3~ by wdght b-sed on tho welght ot the entire compodtlon.
The alumina snd tltsnlum dloxide csn e~ch be used alone or csn be used mixed together snd/or mixed with 8 si1ica snti-~llming sgent. When the antt-filmtng agents sre used mlxed together the wdght percent amounts ; 20 mentloned sbove are the totsl for the ingredients in the mixture.
POLYACRYLIC ACID POLYMPRS ~ND SALTS THEREOP
The polyscrylic scld polymers snd sslts thereof thst can be used sre generslly comm-rcially svaihble Imd sre brietly described a8 follows.
The polyscrylic scid polymers snd salts thereof that can be used comprise wster soluble low moleculsr weight polymers havlng the îormula I-IRl 12 ~. _ - lC - I - _ R3 COOM n wherein the Rl, R2 and R3 can be the same or different and can be hydrogen, Cl-C4 lower alkyl, or combinations thereof. The value of n is 5 to 1000, preferably, 10 to 500, snd more preferably 20 to 100. M
represents hydrogen, or an alkali metal such as sodium or potassium. The pre&rred substituent for M is sodium.
The preferred Rl, R2 and R3 groups are hydrogen, methyl, ethyl and propyl. Preferred acrylic acid monomer i8 one where 1~1 to R3 are hydrogen, e. g. acrylic acid, or where R1 and R3 are hydrogen and R2 is methyl, e.g. methyl acrylic acid monomer.
The degree of polymerization, i . e. the value of n, i9 generally determined by the limit compatible with the solubility of the polymer in water. The terminal or end groups of the polymer are not critical and can be H, OH, CH3 or a low molecular weighe hydrocarbon.
The poly~crylic acid polymers and salts thereof can have a molecular weight of 500 or 1,000 to 100,000, preferably 1,500 to 50,000 and especially preierably 2,000 to 10,000.
r ~ SpeclNc polyacrylic acid polymers which can be used include the A Acrysol~LMW acrylic acid polymers from Rohm snd Haas, such as the Acrysol LMW-45NX, a neutralized sodium salt, which has a molecular weight of about 4,500 and Acrysol LMW-20NX, a neutralized sodium salt, which hss a molecular weight of about 2, 000 . The low molecular weight acrylic acid polymers can, for example, have a molecular weight of about I, 000 to 10, 000 . Another polyacrylic acid polymer that can be used is Alcosperse~
110 (from Alco) which is a sodium salt of an organic polycarboxylate and 2S which has a molecular weight of about 100,000.
The above polyacrylic acid polymers and salts thereof can be made using procedures known in the art, see for example U.S. Patent 4,203,858.
The amount of polyacrylic acid polymer or salt builder that can be used to achieve the desired improvement in anti-filming and anti-spotting 1~26803 62301-1519 properties will depend on the hardness of the water, detergent active compound, inorganic salts and other ADD ingredients.
The polyacrylic acid or salt builder is particularly effective in reducing spotting in hard water of, for example, 300 ppm hardness or more.
Generally, the amounts of the polyacrylic acid polymer or salt that can be used are in the range of from about 2.0 to 14%, preferably from about 3.0 to 12%, especially preferably about 4 to 10~.
THIXOTROPIC THICKENERS
The thixotropic thickeners or suspending agents that can be used ln accordance wlth the present inventlon to provide the aqueous medlum wlth thlxotropic properties may be organic, for example, fatty acid or fatty acld polyvalent metal salt~ or inorganlc collold forming clay materials. The thixotropic thickeners ~hould be stable to high alkalinity and stable to chlorine bleach compounds such as sodium hypochlorite. The preferred thixotropic thlckeners comprlse the fatty aclds, the fatty acld polyvalent metal salts and the lnorganlc, collold-formlng clays of smectlte and/or attapulglte types. The amountof the thlxotroplc thlckener used wlll depend on the particular thickener used, but sufficlent thlckener 1B added to the formulatlon to provlde the compo~ltion with a thixotropy index of about 2.5 to 10.
The preferred fatty acld thixotropic thickeners are the higher allphatlc fatty monocarboxylic acids having from about 8 to about 22 carbon atoms, more preferably from about 10 to 20 carbon atoms, and especially preferably from about 12 to 18 or 16 to 20 carbon atoms, lnclusive of the carbon atom of the carboxyl group of the fatty acid. The aliphatic radical may be saturated or unsaturated and may be straight or branched. Straight chain saturated fatty acids are preferred.
Mixtures of fatty acids may be used, such as those derived from natural sources, such as tallow fatty acid, coco fatty 13a . , ~ .
:~ 1326803 62301-1519 acld, soya fatty acid, etc., or from synthetlc sources avall-able from lndustrial manufacturlng processes.
Thus, examples of the fatty aclds whlch can be used as thlckeners lnclude, for example, decanolc acld, laurlc acld, dodecanolc acld, palmltlc acld, myrlstlc acld, stearlc acld, olelc acld, elcosanolc acld, tallow fatty acld, coco fatty acld, soya fatty acld and mlxtures of these aclds. Stearlc acld and mlxed fatty aclds, e.g. coco fatty acld, are pre-ferred.
The amount of the fatty acld thlckener to achleve the deslred values of thlxotropy and physlcal stablllty wlll depend on such factors as the nature of the fatty acld, detergent actlve compound, lnorganlc salts, especlally TPP, other LADD
lngredlents, as well as the antlclpated storage and shlpplng condltlons.
Generally, however, amounts of the fatty acld thlxo-troplc agent that can be used are ln the range of from about 0.03 to 0.5%, preferably from about 0.03 to 0.2%, especlally preferably from about 0.05 to 0.15%, provlde the de~lred long term stablllty and absence of phase separatlon.
The polyvalent metal ~alts of the above fatty aclds can also be used ln the present lnventlon as thlxotroplc thlck-ener agents. Sultable metal salt thlxotroplc thlckeners are dlsclosed ln Canadlan appllcatlon Serlal No. 546,121 flled September 4, 1987.
The preferred metals are the polyvalent metals such as magneslum, calclum, alumlnum and zlnc.
Generally, the metals may be present ln the dlvalent to pentavalent state. Preferably, the metal salts are used ln thelr hlgher oxldatlon states. Naturally, for LADD composl-tlons, as well as any other appllcatlons where the lnventlon composltlon wlll or may come lnto contact wlth artlcles used for the handllng, storage or servlng of food products or whlch otherwlse may come lnto contact wlth or be consumed by people or anlmals, the metal salt should be selected by taklng lnto conslderatlon the toxlclty of the , 1~6803 metal. Por this purpose, the calcium and magnesium salts are especially highly preferred as generally safe food additives.
Many of these metal salts are commercially available. For example, the aluminum salts are available in the triacid form, e. g. ~luminum steurate as S aluminum tristearate, Al((~l7-H35C00)3. The monoacid ~alts, e.g. aluminum mono8tearate, Al(OH)2(C17H35C00) snd diacid salts, e.g. aluminum distearate, Al(OH)C17H35C00)2, and mixtures of two or three of the mono-, di- snd tri-acid salts can be used for those metals, e. g. Al, with valences of +3, and mixtures of the mono- and di-acid salts can be used for those metals, e.g. Zn, with valences of +2. It is more preferred that the diacids of the +2 valent metals and the trlacids of the +3 valent metals, the tetraacid~ of the +4 metals, and the pentacids of the +5 valent metals, be used in predom1nant amounts. For example, at least 309~, preferably at least S0%, especially preferably from 80 to 100% of the total metal salt should be in the h1ghest po~otble oxidation state, i.e. ea¢h of the possible valence sites is occupied by a fatty acid residue.
The metal salts, as mentioned above, are generally commercially avdlabb but can be eadly produced by, for example, saponification of a fatty acid , e . g. animal at , stearic acid , etc ., or the corresponding i'atty acid ester, followed by treatment with an hydroxide or oxide of the polyvalent metal, for exsmple, in the case of the aluminum salt, with alum, alumina, etc.
Calcium stearate, i . e . calcium distearate, magnesium stearate, i . e .
magnesium distearate, aluminum stearate, i.e. aluminum tristearate, and zinc steflrate, i.e. zinc distearate, are the preferred polyvalent fatty acid salt stabilizers. Mixed fatty acid metal salts, such as the naturally occurring acids, e. g. coco acid, as well as mixed fatty acids resulting from the commercial manufacturing process sre also advantageously used a~ an inexpensive but effective source of the long chain fatty acid.
The amount of the fatty acid salt stabilizers to achieve the desired enhancement of physical stability will depend on such factors as the nature of the fatty acid sslt, the nature ~nd amount of the thixotropic agent, detergent active compound, inorgsnic salts, especislly TPP, other LADD
ingredients, as well as the anticipsted storsge and shipping conditions.
Generally, however, amounts of the polyvalent metal fatty acid salt stabilizing agents in the rsnge of from sbout 0.02 to 1%, preferably from about 0 . 06 to 0 . 896, especially prefersbly from about 0 . 08 to 0 . 4%, provide the long term stsbility snd absence of phase separation upon standing or during transport at both low and elevated temperatures as are required for a commercially acceptable product.
There may also be used in the present invention the conventional inorganic thixotropic clay thickeners. The clay thickeners may be used in small amounts in combination with the fatty acid thickeners or in combination wtth fatty acid polyvalent metal salt thlckener8. The clay thickener8, however, may be used by themselves as the thixotropic thickeners.
The preferred clay thickeners comprise the inorganic, colloid forming clay8 of smectite and/or attapulgite types.
Smectite clays include montmorillonite (bentonite), hectorite, attapulgite, smectite, saponite, and the like. Montmorillonite clays are preferred and are available under tradenames such as Thixogel (Registered Trademark) No. 1 and Celwhite (Registered Trademark) GP, H, etc., from Georgia Kaolin Company; and Eccagum (Registered Trsdemark) GP, H, etc., from Luthern Clay Products. Attapulgite clays include the msterials .~ commercially available under the~ittagel (Registered Trademark), i. e . Attagel 40, Attagel 50 and Attagel 150 from Engelhard Minerals and Chemicals Corporation. Mixtures of smectite and attapulgite types in weight ratios of 4:1 to 1:5 nre also useful herein. Thickening or suspending sgents of the foregoing types are well known in the art, being described, 13268~3 for example, in V.S. Patent No. 3,985,668 referred to above. Abrasives or polishing agents should be avoided in the LADD compositions as they may mar the surface of fine dishware, crystal and the like.
When used in combination with the fatty acids or the fatty acid polyvalent metal salts, the clsy thixotropic thickeners are used in amounts of 0.1 to 3%, preferably 0.1 to 2.5% and more preferably in amounts of 0.1 to296.
When the clay thixotropic thickeners are used alone as the thixotropic thi¢kener agent they can be used in amounts of about 1,5 to 8%, preferably 2 to 5% by weight of the formulstion.
Generally, LADD effectiveness is directly related to (a) available chlorine levels; (b) alkalinity; (c) solubility in washing medlum; and (d) foam inhibltlon. It is preferred herein that the pH of the LADD composition be st least about 9, S, more preferably from about 10 . 5 to 13 . S and most preferably at least about 11,5. At the relatlvely lower pH values, the LADD product is too viscous, i.e. 801id-like, and thus not readily fluidized under the shear-for¢e levels created within the dispenser cup under normal machine operating conditions. Addition of NaOH is thus often needed to increase the pH to withln the above range8, and to increase flowability properties. The presence of carbonate is also often needed herein, since it acts as a buffer helping to maintain the desired pH level. Excess carbonate is to be avoided, however, since it may cause the formation of needle-like crystals of carbonate, thereby impairing the stability, thixotropy and/or detergency of the LADD product, as well as impairing the dispensibility of the product from, for example, squeeze tube bottles. Caustic soda (NaOH) serves the further function of neutralizing the phosphoric or phosphonic acid ester foam depressant when present. About 0.5 to 3 wt96 of NaOH and about 2 to 9 wt~ of sodium carbonate in the LADD composition are typical, although it should be noted that sufficient alkalinity may be provided by the NATPP and sodium silicate.
The NsTPP may be employed in the LADD composition in a range of about 8 to 35 wt%, prefer~bly about 20 to 30 wt%, and should preferably be free of heavy metal which tends to decompose or inactivate the preferred sodium hypochlorite and other chlorine bleach compounds. The NaTPP may be anhydrous or hydrated, including the stable hexahydrate with a degree Or hydration of 6 corresponding to about 18% by weight of water or more.
Actually, in view of the stabUity of the hexahydrate, the presence of some water of hydration is highly effective, serving it is thought to form seeds of the stable hexahydrate which expedites hydration and solubilization of the remaining NaTPP particles. If only the hexahydrate is used, the detergent product may be too liquid. Conversely, if only the anhydrous NaTPP is used, the product may, in some cases, be too thick and, therefore, unsuitable. Bepecially preferred LADD compositions are obtained, for exampb, when using a 0,5:1 to 2:1 we1ght ratio of anhydroua lS ¦ to hexahydrated NaTPP, values of about 1:1 being particularly preferred.
Poam inhibltion is important to increase dishwasher machine efficiency and mln1mize dostabilizing effects which might occur due to the presence of excess foam within the washer during use. Foam may be sufficiently reduced by suitable selection of the type andlor amount of detergent active material, 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 adjustment of the proportions of NaTPP which has a water softening effect may aid in providing the desired degree of foam inhibition.
However, it i8 generally preferred to include a chlorine bleach stable foam depressant or inhibitor. Particularly effective are the alkyl phosphonic acid esters o- the formula 1l HO--IP--R
OR
available for exsmple from BASF-Wyandotte (PCUK-PAE), and especially the alkyl acid phosphate esters of the formula O
HO--P--OR
OR
available, for example, from Hooker (SAP) snd Knapsack (LPKn-158), in which one or both R groups in each type of ester may repre~ent independently a Cl2_20 alkyl group. Mixture~ of the two type8, or any other chlorine bleach stable types, or mixtures of mono- and di-esters of the same type, may be employed . 13 specially preferred is a mixture of l mono- and di-C16 18 alkyl acid phosphate esters such as l monostearyl/distearyl acid phosphates 1.2/1 (Knapsack). When employed, proportions of 0,01 to 5 wt%, preferably 0.1 to 5 wt%, especially about 0.1 to 0.5 wt%, of foam depressant in the composition is typical, the weight ratio of detergent active component (d) to foam depressant (e) 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.
Although any chlorine bleach compound may be employed in the compositions of this invention, such as dichloro-isocyanurate, dichloro-dimethyl hydantoin, or chlorinated TSP, alkali metal, e.g.
potassium, lithium, magnesium and especiallr sodium hypochlorite is preferred. The composition should contain sufficient chlorine bleach compound to provide about O . 2 to 4 . 0% by weight of available chlorine, as determined, for example, by acidification of 100 parts of the composition with excess of hydrochloric acid . A solution containing about O . 2 to 9 . 0%
by weight of sodium hypochlorite contains or provides roughly the same percentage of available chlorine. A solution containing about 0.8 to 1.6% by weight sodium hypochlorite contains about 0.8 to 1.6% by weight of available chlorine and i8 especially preferred. For example, sodium hypochlorite 1~268~3 (NaOCI) solution of from about 11 to about 13% available chlorine in amounts of about 3 to 20%, preferably about 7 to 12%, can be advantageously used.
The sodium silicate, which provides alkalinity and protection of hard surfaces, such as fine china glaze and pattern, is employed in an amount ranging from about 2.5 to ~0 wt9~, preferably about 10 to 35 wt%, in the composition. At the higher levels specified herein for example at levels greater than about 10 wt% the silicate al80 provides increased antispotting action. The sodium silicate is generally added in the form of an aqueous solution, preferably having an Na20:SiO2 ratio of sbout 1:2.2 to 1:2.8, for example, 1:2.4. Most of the other components of the composition, especially NaOH, sodium hypochlorite and foam depressant may also be added in the ~orm o- an aqueous dispersion or solution.
Detergent active material useful herein must be stable in the presence of chlorine bleach, especially hypochlorite bleach, and those of the organic anionic, amine oxide, phosphine oxide, sulphoxide or betaine water dispersible surfactant types are pre-erred, the flrst mentioned anionics being most preferred. They are used in amounts ranging rom about 0.1 to 5% pre-erably about O . 3 to 2 . 0% . Particularly preferred surfactants herein are the Ihear or branched alkali metal mono- and/or di-(C8 14) alkyl diphenyl oxide mono andlor disulphates, commercially available for example as DOWFAX (Registered Trademark) 3B-2 and DOWFAX 2A-1.
In add1tion, the surfactant should be compatible with the other ingredients of the composition. Other suitable surfactants include the primary alkylsulphates, alkylsulphonates, alkylaryl-sulphonates and sec.-alkylsulphates. Examples include sodium C10_18 alkylsulphates such as sodium dodecylsulphate and sodium tallow alcoholsulphate; sodium C10 18 alkanesulphonates such as sodium hexadecyl-l-sulphonate and sodium C12 18 alkylbenzenesulphonates such as sodium dodecylbenzenesulphonates. The corresponding potassium salts may also be employed.
ZO
As other suitable surfactants or detergents, the amine oxide surfactants ~re typically of the structure R2RlNO, in which each R
represents a lower alkyl group, for instance, methyl, and Rl represents a long chain alkyl group having from 8 to 22 carbon atoms, for instance a lauryl, myristyl, palmityl or cetyl group. Instead of an amine oxide, a corresponding surractant phosphine oxide RaRlPO or sulphoxide RRlSO can be employed. Betaine surfactants are typically of the structure R2RlN -RnCOO, in which each R represents a lower alkylene group having from 1 to 5 carbon atoms. Specific examples of these surfactants are lauryl-dimethylamine oxide, myristyldimethylsmine oxide, the corresponding phosphine oxides snd sulphoxides, and the corresponding betaines, including dodecyldimethybmmonium scetate, tetrsdecyldiethylammonium pentanoato, hexsdecyl-dimethylsmmonium hexsnoste and the like. For biodegradability, the alkyl groups in these surfsctsnts should be linear, lg and su¢h compounds are preferred.
Sur~actants of the foregoing type, all well known ln the srt, are described, for example, in U. S . Patents 3 ,085 ,668 and 4, 271,030.
The amount o~ water contained in these compositions should, of course, be neither 80 hlgh a8 to produce unduly low visco~ity and fluidity, nor 80 low a8 to produce unduly high viscosity and low flowsbility, thixotropic properties in either case being diminished or destroyed. Such smount is readily determined by routine experimentation in any particular instsnce, generally ranging from about 25 to 75 wt%, pre(ersbly sbout 50 to 65 wt%.
The water should also be preferably deionized or softened. These amounts 2~ of water in the composition include the water added as parts of the liquid solutions of other ingredients, but do no include bound water, for example that in NaTPP hexahydrate.
Other conventional ingredients may be included in these compositions in small amounts, generally less than about 3 wt%, such as perfume, hydrotropic agents such as the sodium benzene, toluene, xylene and cumene ~ 1326803 sulphonate~, preservatives, dyestuffs and pigments and the like, all of course being stable to chlorine bleach compound snd high ~Ikalinity (properties of all the components). Especi~lly preferred for coloring are the chlorinated phthalocyanines and poiysulphides of aluminosilicate which provide, respectively, pleasing green and blue tints.
The liquid ADD compositions of this invention are readily employed in known manner for washing dishes, glssses, cups, esting utensils and the like in an automatic dishwasher, provided with a suitable detergent dispenser, in an aqueous wash bath contdning an effective amount of the 10 composition.
In a preferred embodiment of the inYention the aqueous liquid dishwsshing detergent composition is Çormulated using the below named ingredients.
l Component Weight Percent Alkali Metal Tripolypho~phate 10-25 Sodium Biltcate (47.5~) 15-40 Alumina or Titanium Dioxide Anti-filming Agent 1-4 Polyacrylic Acid Polymer or Salt 3-12 Alakli Metal Carbonate (anhydrous) 2-8 Chlorine Bleach Stable, Water Dispersible Organic Detergent Active Material 0.5-3 Chlorine Bleach Stable Foam Depressant 0.10-3 Chlorlne Bleach Compound 0.2-4 Fatty Acid Thixotropic Thickener 0.03-0.5 Sodium Hydroxide (50%) 2-6 Balance Water The thixotropic aqueous liquid automatic dishwashing detergent compositions of the present invention can contain conventional dishwashing detergent composition additives. The formulations can be prepared with commerclally available solid powder builders, and/or the ingredients can be mixed and the formulations ground to a desired particle size.
The invention may be put into practice in various ways and a number of specific embodiments will be described to illustrate the invention with reference to the accompanying exdmples.
All amounts and proportions referred to herein are percent by weight of the composition unless otherwise Indicated.
The present invention is further illu~trated by the ~ollowing examples.
ExamPle 1 A thixotropic aqueous liquid automatic dishwashing detergent composition is formulated from the following ingredients in the amounts specified.
Component Weiqht Percent Deionized Water 31.04 Knapsack LPKN-158 Foam Depressan~(l) 0.16 Sodium Hydroxide (50%) 2.34 Sodium Carbonate (anhydrous)4.88 Sodium Tripolyphosphate (anhydrous) 11.70 Sodium Tripolyphosphate (hexahydrate) 11.70 Alumina Anti-fllming Agent(2)2.5 Sodium polyacrylate polymer builder(3) (A.I.) 8.00 Gel White H Clay 1.22 Alumlnum Stearate Thlxotropic Thickener 0.09 Dowfax 3B-2 Surfactant(4) 0.78 Sodium Hypochlorite (11%) 8.78 Sodlum Sillcate (1/2.23 - 43.5%) 16.81 Graphtol Green Color 0.002 100.002 (1) Mixture of mono and distearyl (C16-C18) alkyl esters of phosphoric acid, mole ratio 1.1.3.
(2) Aluminumoxid C (Degussa) has a particle s~ze of about 4 microns and is available from Degussa Corporation.
4442(B) TIIIXOTROPIC AQUEOUS LIQUID AUTOMATIC
DISHWASHING DETERGENT COMPOSITION
FIELD OF THE INVENTION
_ .
The present invention relates to a thixotropic aqueous liquid automatic dishwashing detergent composition with improved anti-filming and anti-spotting properties and method of using the detergent composition to clean dishware, glassware, china and the like. The dishwashing composttion contains alumina or titanium dioxide, as the anti-filming agent, polyacrylic acid polymer builder inorganic builder salts, chlorine bleach, bleach stable detergent and a thixo~ropic thickener.
The detergent dishwash1ng composition of the present invention reduce8 filming and 8potting on dishware, glassware, china and the like, particularly in hard water, and remains stable against phase separation.
More specifically, the invention relates to the use of aluminum or titanium dioxide as an anti-filming agent and polyacrylic acid polymer builder in thixotropic aqueous liquid dishwashing detergent compositions to reduce ~llming and spotting.
The detergent compositions do no require an added rinse aid, are stable in storage, do not settle and are readily redispersible and are pourable .
The pre8ent invention al80 relates to thixotropic aqueous suspension with improved physical ~tability. The invention relates to the use of long chain fatty acids, metal salts of fatty acids and clay as thixotropic agents for forming stable gel-like liquid suspensions suitable for use as liquid automatic dishwasher detergent composition.
The present invention specifically relates to aqueous liquid automatic dishwashing detergent compositions having thixotropic properties, improved anti-filming and anti-spotting properties and improved physical stability 1326~03 properties, which are readily di6persible in the washing medium to provide effective cleaning of dishware, glassware, china and the like.
PRIOR ART
Commercially available household-machine dishwasher detergents provided in powder form have several disadvantages, e. g. non-uniform composition; costly operations necessary in their manufacture; tendency to cake in storage at high humidities, resulting in the formation of lumps which are difficult to disperse; dustiness, a source of particular irritation to users who suffer allergies; and tendency to cake in the dishwasher machine dispenser. Liquid forms of such compositions, however, generally cannot be used in automatic dishwashers due to high foam levels, unacceptably low viscosities and exceedingly high alkalinity.
In addit10n, the presently used formulated powder detergents frequently require a separate step of hand towel wiping and drying o~ the dishwarQ, glassware, china and the like to avoid leaving undesirable traces or film of precipitated calcium and magnesium salts. The use of liquid detergent compo~itions present other problems. The builder salts settle in storage and are not readily redispersed. The compositions also frequently become thicker in storage and are not readily pourable.
Recent research and development activity has focused on the gel or "thixotropic" form of such compositions, however, such compositions have generally proven to be insufficiently viscous to remain "anchored" in the dispenser cup of the dishwasher, and moreover yield spotty residues on dishware, glassware, china and the like. Ideally, thixotropic cleansing compositions should be highly viscous in a quiescent state, Bingham plastic in nature, and have relatively high yield values. When subjected to shear stresses, however, such as being ~haken in a container or squeezed through an orifice, they should quickly fluidize and, upon cessation of the applied shear stress, quickly revert to the high viscosity/Bingham plastic state. Stability is likewise of primary importance, i.e. there should be no significant evidence of phase separation or leaking after long standing.
For effective use, it is generally recommended that the automatic dishwashing detergent, hereinafter also designated ADD, contain (1) sodium tripolyphosphate (NaTPP) to soften or tie up hard-water minerals and to emulsify andlor peptize soil; (2) sodium silicate to supply the alkalinity necessary for effective detergency and to provide protection for fine china glaze and pattern; (3) sodium carbonate, generally considered to be optional, to enhance alkalinity; (4~ a chlorine-releasing agent to aid in the eliminution of soil specks which lead to water spotting; and (5) defoamer/surfactant to reduce foam, thereby enhsncing machine efficiency and supplying regui~ite detergency. See, for example, SDA Detergents in Depth, "Formulations Aspects of machine Dishwashing," Thomas Oberle (1974). Clean8ers approximating to the afore-described compositions are mostly liquid~ or powder~. Generally, su¢h compodtions omit hypochlorite bleach, since it tends to react with other chemically active ingredients, particularly surfactant, thereby degrading the suspending or thixotropic agent and impairing its effectiveness.
Thus, U.S. Patent No. 3,985,ff68 describes abrasive scouring cleaners of gel-like consistency contdning (1) suspending agent, preferably the Smectite and attapulgite types of clay; (2) abrasive, e.g. silica sand or perlite; and ( 3 ) filler comprising light density powdered polymers, expanded perlite and the like, which has a bouyancy and thus stabilizing effect on the composition in addition to serving as a bulking agent, thereby replacing water otherwise available 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, ~uch as NaTPP, can be included as further optional ingredients to supply or supplement building function not provided by the buffer, the amount of such builder not exceeding 5% of the total composition, according to the patent . Maintenance of the de~ired ( greater than) pH 10 levels is achieved by the buffer/builder components. High pH
is said to minimize decompo~ition of chlorine bleach and undesired S interaction between surfactant and bleach. When present, NaTPP is limited to 5%, as stated. Foam killer is not disclosed.
In U.K. Patent Application GB 2,116,199A and GB a,140,450A, both of which are assigned to Colgate-Palmolive, liquid ADD compositions are diselosed which have properties desirably charaeterizing thixotropic, gel-type strueture and wMeh inelude eaeh o~ the various ingredients neeessary for effective detergency with an automatie dishwasher. The normally gel-like aqueous automatlc dishwasher detergent composition having thlxotropie propert~e~ ineludes the following ingredients, on a weight basis:
(a) 5 to 3S% alkall metal tripolyphosphate;
(b) 2,5 to 20% sodium silieate;
(e) 0 to 9% alkali metal earbonate;
(d) 0.1 to 5% ehlorine bleaeh stable, water dispersible organie detergent aetive material;
(e) 0 to 5% chlorine bleaeh stable foam depressant;
(0 ehlorine bleach eompound in an amount to provide about 0.2 to 491 of available chlorine;
(g) thixotropie tMckener in an amount sumcient to provide the composition wlth thixotropy index of about 2.5 to 10; and (h) sodium hydroxide, as necessary, to adjust pH.
ADD compositions 80 formulated are low-foaming; are readily soluble in the washing medium and mo~t effective at pH values best conducive to improved eleaning performanee, viz, pH 10.5-13.5. The compositions are normally of gel consisteney, i.e. a highly viseous, op&~ue jelly-like material having Bingham plastic character and thus relatively high yield values.
Accordingly, a definite shear force is neeessary to initiate or increase flow, .~ , such as would obtaln wlthln the agltated dlspenser cup of an energlzed automatlc dlshwasher or a stream of water. Under such condltlons, the composltlon ls qulckly fluldlzed and easlly dlspensed. When the shear force ls dlscontlnued, the fluld composltlon ~ulckly reverts to a hlgh vlscoslty, Blngham plastlc state closely approxlmatlng lts prlor conslstency.
U.S. Patent 4,511,487 dated Aprll 16, 1985 descrlbes a low-foaming detergent paste for dlshwashers. The composltion ls based on a mlxture of flnely dlvlded hydrated sodlum meta-slllcate, an actlve chlorlne compound and a thlckenlng agent whlch ls a follated slllcate of the hectorlte type. Small amount of nonlonlc tensldes and alkall metal carbonates and/or hydroxldes may be used.
A related Canadlan patent appllcatlon ls Serlal No.
526,708, flled January 6th, 1987. The copendlng appllcatlon dlscloses thlxotroplc aqueous automatlc dlshwashlng detergent composltlon which contalns a long chaln fatty acld as a thlxo- ;
troplc thlckener agent.
Another related Canadlan patent appllcatlon 19 Serlal No. 550,065 flled October 23rd, 1987. Thls copendlng appllca-tlon dlscloses an aqueous llquld thixotroplc clay dlshwashlng detergent composltlon comprlslng a metal salt of a long chaln fatty acid and a polyacryllc acld polymer or salt stablllzlng agent.
ADVANTAGES OVER THE PRIOR ART
The thlxotroplc aqueous llquld detergent composltlons of the present lnventlon overcome many of the prlor art prob-lems assoclated wlth powder and llquld detergents. Because of the addltlon of a small effectlve amount of an alumlna or tlta-nlum dloxlde antl-fllmlng agent and polyacryllc acld polymer or salt bullder to the composltlon an added rinse ald 18 not re-qulred and towel wlplng and drylng are not requlred to obtaln dry sparkllng clean dlshes, glasses, cups and eatlng utenslls.
The thlxotroplc ' .
132~803 aqueous liquid detergent compo~ition has the additional advantages of being stable, non-settling in storage and readily redispersible. The liquid compositions of the present invention are easily pourable, easily measured and easily put into the dishwashing machines.
An additional and unexpected advantage of adding the alumina or titanium dioxide anti-filming agent to the detergent formulatlon is that the alumlnum or tltanlum dloxlde inhibits brown stain formation in the dishwashing machlne. The brown stain is formed by the deposltlon ln the dishwashlng machine of lron and/or manganese oxldes. The brown staln formatlon ls a particularly serlous problem ln areas havlng hard water. The alumlna or titanlum dioxide in the formulation acts on the iron and/or manganese ln the wash water to prevent thelr deposltion in the dishwashing machine as iron and/or manganese oxides.
ASPECTS OF THE PRESENT INVENTION
It 18 an aspect of the present lnventlon to provlde a thlxotropic aqueous llquld automatlc dishwasher detergent composition that has improved anti-filming and anti-spotting properties.
It is another aspect of the invention to provide a thlxotropic aqueous llquld detergent compositlon which is stable in storage, easily pourable and readlly dispersible in the dishwashing water.
A further aspect of the lnvention is to provide a method of washing dishware, glassware, china and the like in an automatic dishwashlng machlne using a thixotropic aqueous liquid detergent composition in which a separate rinse aid is not added or needed.
A still further aspect of the inventlon is to provide a method of washing dishware, glassware, china and the like in .. ; . .
an automatlc washing machine using an aqueous liquid detergent composltion by whlch method the dishware, glassware, china and the like are machine dried without leaving traces or a film.
It is a further aspect of this invention to provide stable aqueous thlxotropic aqueous liquid compositions, especially automatic dishwasher detergent compositions, by incorporating in the aqueous suspension a small effective amount of an alumina or titanium dioxide anti-filming agent and polyacrylic acid polymer or salt builder. There is also added a minor amount of a fatty acid, metal salt of a fatty acid and/or clay thixotroplc thickener effec~ive to inhibit the settling of the suspended particles and to prevent phase separation.
DE~AILED DESCRIPTION OF THE INVENTION
The invention will become more readily understood from the following detailed description of the lnvention and preferred embodiments thereof. The lnvention concerns the incorporatlon in an aqueous llquld detergent composition of a small but effective amount of an alumina or titanlum dloxide antl-filmlng agent and polyacrylic acld polymer or salt builder. The physical stability of the composition is improved by the additlon of a fatty acid, metal salt of a fatty acid and/or clay thixotropic thickener. The lnvention provides a gel-llke thixotropic aqueous liquid automatic dishwashing detergent composition comprislng water, at least one lngredient selected from the group conslsting of organic detergent, chlorine bleach, detergent builder, sequestering agent, foam lnhlbitor and mixtures thereof in which is incorporated from about 0.5 to 5% of an alumina or titanium dioxide partlcles as anti-filming agent and about 2 to 14% of a water soluble polyacrylic acid polymer or salt builder. The alumina or 1~ 2g 803 62301-1519 titanium dloxide anti-filming agent has a particle size of about 0.1 to 10 microns. The water polyacrylic acld or salt preferably has a molecular weight of about 500 to 100,000. The composition comprises a sufficient amount of a long chain fatty acid or metal salt of a long chain fatty acid, or elther of the foregoing in admixture with a clay thixotropic thickener to provide a thixotropic index of about 2.5 to 10 and to inhibit settllng of the suspended particles, such as alkali metal builder salts, etc.
In accordance with this aspect, the present invention also provides a normally gel-like aqueous llquid automatic dishwasher detergent composition having thixotropic properties whlch includes, on a weight basis.
(a) 5 to 35% of detergent bullder, such aæ alkali metal tripolyphosphate;
(b) 2.5 to 40% sodium silicate;
(c) 0.5 to 5% alumlna or titanium dioxlde anti-filmlng aqent having a particle slze of about 0.1 to 10 mlcrons;
(d) 2 to 14% polyacryllc acid polymer or salt bullder havlng a molecular welght of about 1,000 to 100,000;
(e) 0 to 9~ alkall metal carbonate;
(f) 0.1 to 5% chlorine bleach stable, water dispersible organlc detergent actlve materlal;
(g) 0 to 5% chlorine bleach stable foam depressant;
(h) chlorlne bleach compound ln an amount to provide about 0.2 to 4% of avallable chlorlne;
(1) thlxotroplc thlckener in an amount sufficlent to provlde a thlxotroplc index of about 2.5 to 10;
(;) 0 to 8% sodium hydroxide; and (k) balance water.
.~ -j , . . , :
.
- ~
`- 1326803 62301-lS19 Also related to this specific aspect, the invention provides a method for cleaning dishware in an automatic dlshwashlng machine with an aqueous wash bath containing an effective amount of the liquid automatic dishwasher detergent (LADD) composition as described above. According to this aspect of the invention, the LADD composition can be readily poured into the dispensing cup of the automatic dishwashing machlne and will, within just a few seconds, promptly thicken to its normal gel-like or pa#ty state to remain securely within the dispensing cup untll shear forces are again applied thereto, such as by the water spray from the di~hwa~hing machine.
The invention will now be descrlbed in greater detall by way of specific embodiments thereof.
The LADD products of for example the prlor dlsclosure ln the aforementioned GB 2,116,199A and GB 2,140,450A exhibit rheologlcal 8a D
properties as evaluated by testing product viscosity a8 a function of shear rate. The compositions exhibited higher viscosity at a low shear rate and lower viscosity at a high shear rate, the data indicating efficient fluidization and gellation well within the shear rates extant within the standard dishwasher machine. In practical term6, this means improved pouring and processing characteristics as well as less leaking in the machine dispenser-cup, compared to prior liquid or gel ADD products. For applied shear rates corresponding to 3 to 30 rpm, viscosities (Brookfield) correspondlngly ranged from about 10,000 to 30,000 cps to about 3,000 to 7,000 cps, as measured at room temperature by means of ~n LVT Brookfield viscometer sfter 3 minutes using a No. 4 spindle. A shear rate of 7.4 sec 1 corresponds to a spindle rpm of about 3. An approximate 10-fdd increase in shear rate produceo about a 3- to 9-fold reduction in viscosity.
The compositions of the assignee's prior invention thus exhibit threshold nutdizsttons at lower shear rates and of s1gniflcantly greater extent in terms ot in¢remental increases 1n shear rate versus incremental decrease in viscosity. This property of the LADD produ¢ts of the prior invention i8 summarized in terms of a thixotropi¢ index (TI) which is the ratio of the apparent viscosity at 3 rpm and st 30 rpm. The prior compositions have a TI of from 2 to 10. The LADD compositions should exhibit substantial and quick return to prior quiescent state consistency when the shear force is discontinued.
In terms of apparent viscosity, it has been ascertained that 80 long as the viscosity at room temperature (22+1C) measured ln a Brookfield Viscosimeter HATD, using a number 4 spindle at 20 rpm, is less than about 20,000 cps, the composition can be readily shaken so that a thixotropic composition can be easily "fluidized" or "liquefied" to allow the product to be dispensed through a conventional squeeze tube bottle or other convenient dispenser.
- 1326803 : -The present invention is based upon the surprising dlscovery that substantially improved anti-fllming and anti-spottlng properties can be obtained by adding to the thixotropic aqueous liquid detergent composition a smal}
effective amount of a silica anti-filming agent and polyacrylic acid polymer or salt builder. The physical stability, i.e., resistance to phase separation, settling, etc. can be achieved by adding to the composition a small effective amount of a thixotropic thickener and stabilizing agent.
_NTI-FILHING AGENTS
The alumina or titanium dioxlde anti-filming agent materials that can be uged are readily commercially available.
The alumlna material that can be used as an anti-filming agent is insoluble in water and has the formula Al203. Suitable materlal~ are available under the trademarks Alumlnum Oxide C, Degussa and Catapal D, Vista. A preferred alumina material i~
Alumlnumoxld C~.
The particle slze of the alumlna and titanlum dloxlde material that 1~ used iæ important in achieving the desired anti-filming properties.
The alumina or titanlum dloxlde particles that are used are finely dlvided and can have a particle size of about 0.10 to 10 mlcron~, preferably 0.50 to 8 mlcrons and more preferably about 1.0 to 5.0 mlcrons. The llica particles of this size and ln the amount used herein are not abrasive.
The finely divided alumina or titanium dioxide materlal partlcles ln the dishwashing wash act to coagulate proteinaceous particulate soils and keeps them in suspenslon and with the polyacrylic acid polymer or salt acts as an anti-redeposition agent to prevent them from depositing on the cleanglass and dishware.
~Trade-mark 10 , ... . . . , . . . ~ , - .
1 3 2 g~3 62301-1519 Without intending to limit the invention in any way it is theorized that the alumina and tltanium dioxide anti-fllmlng agents function in the following manner. The glass surface of vitreous glassware contain negative charges on their surface through the Si-0 bonds. Usually the oxygen atoms carry these charges. It is postulated that these negatively charged lons will B .~! lOa attract pos~tively charged particles snd thereby will form sn "artificial soil"
layer. This protective layer will then repel the regular food 80il and will increase the anti-redeposition property of the automatic dishwushing detergent. The ~umina and titanium dioxide particles, respectively, will generate poslti~rely charged p-rticles which will bond themselves to the glssswsre surfsce to form the artificial soil layer which will prevent the formation of film.
The amount of alumins or titanium dioxtde anti-fflming agent that can be used to achieve tho dedred improvement in fflming and spotting will depend on the hsrdness ot the wster, detergent active compound, inorganic salt~ and other ADD ingredients. The aluminum or titanlum dioxide anti-fllming ~gent is partlculsrly eftective in hard wssh water of, for examplo, 300 ppm hsrdness or more.
The smount ot alumina or titsntum dioxide snti-fllm sgent thst is used can b~ bout 0.5 to 5~, pre-erabb about 1 to ~% and moro preferably sbout 1.S to 3~ by wdght b-sed on tho welght ot the entire compodtlon.
The alumina snd tltsnlum dloxide csn e~ch be used alone or csn be used mixed together snd/or mixed with 8 si1ica snti-~llming sgent. When the antt-filmtng agents sre used mlxed together the wdght percent amounts ; 20 mentloned sbove are the totsl for the ingredients in the mixture.
POLYACRYLIC ACID POLYMPRS ~ND SALTS THEREOP
The polyscrylic scld polymers snd sslts thereof thst can be used sre generslly comm-rcially svaihble Imd sre brietly described a8 follows.
The polyscrylic scid polymers snd salts thereof that can be used comprise wster soluble low moleculsr weight polymers havlng the îormula I-IRl 12 ~. _ - lC - I - _ R3 COOM n wherein the Rl, R2 and R3 can be the same or different and can be hydrogen, Cl-C4 lower alkyl, or combinations thereof. The value of n is 5 to 1000, preferably, 10 to 500, snd more preferably 20 to 100. M
represents hydrogen, or an alkali metal such as sodium or potassium. The pre&rred substituent for M is sodium.
The preferred Rl, R2 and R3 groups are hydrogen, methyl, ethyl and propyl. Preferred acrylic acid monomer i8 one where 1~1 to R3 are hydrogen, e. g. acrylic acid, or where R1 and R3 are hydrogen and R2 is methyl, e.g. methyl acrylic acid monomer.
The degree of polymerization, i . e. the value of n, i9 generally determined by the limit compatible with the solubility of the polymer in water. The terminal or end groups of the polymer are not critical and can be H, OH, CH3 or a low molecular weighe hydrocarbon.
The poly~crylic acid polymers and salts thereof can have a molecular weight of 500 or 1,000 to 100,000, preferably 1,500 to 50,000 and especially preierably 2,000 to 10,000.
r ~ SpeclNc polyacrylic acid polymers which can be used include the A Acrysol~LMW acrylic acid polymers from Rohm snd Haas, such as the Acrysol LMW-45NX, a neutralized sodium salt, which has a molecular weight of about 4,500 and Acrysol LMW-20NX, a neutralized sodium salt, which hss a molecular weight of about 2, 000 . The low molecular weight acrylic acid polymers can, for example, have a molecular weight of about I, 000 to 10, 000 . Another polyacrylic acid polymer that can be used is Alcosperse~
110 (from Alco) which is a sodium salt of an organic polycarboxylate and 2S which has a molecular weight of about 100,000.
The above polyacrylic acid polymers and salts thereof can be made using procedures known in the art, see for example U.S. Patent 4,203,858.
The amount of polyacrylic acid polymer or salt builder that can be used to achieve the desired improvement in anti-filming and anti-spotting 1~26803 62301-1519 properties will depend on the hardness of the water, detergent active compound, inorganic salts and other ADD ingredients.
The polyacrylic acid or salt builder is particularly effective in reducing spotting in hard water of, for example, 300 ppm hardness or more.
Generally, the amounts of the polyacrylic acid polymer or salt that can be used are in the range of from about 2.0 to 14%, preferably from about 3.0 to 12%, especially preferably about 4 to 10~.
THIXOTROPIC THICKENERS
The thixotropic thickeners or suspending agents that can be used ln accordance wlth the present inventlon to provide the aqueous medlum wlth thlxotropic properties may be organic, for example, fatty acid or fatty acld polyvalent metal salt~ or inorganlc collold forming clay materials. The thixotropic thickeners ~hould be stable to high alkalinity and stable to chlorine bleach compounds such as sodium hypochlorite. The preferred thixotropic thlckeners comprlse the fatty aclds, the fatty acld polyvalent metal salts and the lnorganlc, collold-formlng clays of smectlte and/or attapulglte types. The amountof the thlxotroplc thlckener used wlll depend on the particular thickener used, but sufficlent thlckener 1B added to the formulatlon to provlde the compo~ltion with a thixotropy index of about 2.5 to 10.
The preferred fatty acld thixotropic thickeners are the higher allphatlc fatty monocarboxylic acids having from about 8 to about 22 carbon atoms, more preferably from about 10 to 20 carbon atoms, and especially preferably from about 12 to 18 or 16 to 20 carbon atoms, lnclusive of the carbon atom of the carboxyl group of the fatty acid. The aliphatic radical may be saturated or unsaturated and may be straight or branched. Straight chain saturated fatty acids are preferred.
Mixtures of fatty acids may be used, such as those derived from natural sources, such as tallow fatty acid, coco fatty 13a . , ~ .
:~ 1326803 62301-1519 acld, soya fatty acid, etc., or from synthetlc sources avall-able from lndustrial manufacturlng processes.
Thus, examples of the fatty aclds whlch can be used as thlckeners lnclude, for example, decanolc acld, laurlc acld, dodecanolc acld, palmltlc acld, myrlstlc acld, stearlc acld, olelc acld, elcosanolc acld, tallow fatty acld, coco fatty acld, soya fatty acld and mlxtures of these aclds. Stearlc acld and mlxed fatty aclds, e.g. coco fatty acld, are pre-ferred.
The amount of the fatty acld thlckener to achleve the deslred values of thlxotropy and physlcal stablllty wlll depend on such factors as the nature of the fatty acld, detergent actlve compound, lnorganlc salts, especlally TPP, other LADD
lngredlents, as well as the antlclpated storage and shlpplng condltlons.
Generally, however, amounts of the fatty acld thlxo-troplc agent that can be used are ln the range of from about 0.03 to 0.5%, preferably from about 0.03 to 0.2%, especlally preferably from about 0.05 to 0.15%, provlde the de~lred long term stablllty and absence of phase separatlon.
The polyvalent metal ~alts of the above fatty aclds can also be used ln the present lnventlon as thlxotroplc thlck-ener agents. Sultable metal salt thlxotroplc thlckeners are dlsclosed ln Canadlan appllcatlon Serlal No. 546,121 flled September 4, 1987.
The preferred metals are the polyvalent metals such as magneslum, calclum, alumlnum and zlnc.
Generally, the metals may be present ln the dlvalent to pentavalent state. Preferably, the metal salts are used ln thelr hlgher oxldatlon states. Naturally, for LADD composl-tlons, as well as any other appllcatlons where the lnventlon composltlon wlll or may come lnto contact wlth artlcles used for the handllng, storage or servlng of food products or whlch otherwlse may come lnto contact wlth or be consumed by people or anlmals, the metal salt should be selected by taklng lnto conslderatlon the toxlclty of the , 1~6803 metal. Por this purpose, the calcium and magnesium salts are especially highly preferred as generally safe food additives.
Many of these metal salts are commercially available. For example, the aluminum salts are available in the triacid form, e. g. ~luminum steurate as S aluminum tristearate, Al((~l7-H35C00)3. The monoacid ~alts, e.g. aluminum mono8tearate, Al(OH)2(C17H35C00) snd diacid salts, e.g. aluminum distearate, Al(OH)C17H35C00)2, and mixtures of two or three of the mono-, di- snd tri-acid salts can be used for those metals, e. g. Al, with valences of +3, and mixtures of the mono- and di-acid salts can be used for those metals, e.g. Zn, with valences of +2. It is more preferred that the diacids of the +2 valent metals and the trlacids of the +3 valent metals, the tetraacid~ of the +4 metals, and the pentacids of the +5 valent metals, be used in predom1nant amounts. For example, at least 309~, preferably at least S0%, especially preferably from 80 to 100% of the total metal salt should be in the h1ghest po~otble oxidation state, i.e. ea¢h of the possible valence sites is occupied by a fatty acid residue.
The metal salts, as mentioned above, are generally commercially avdlabb but can be eadly produced by, for example, saponification of a fatty acid , e . g. animal at , stearic acid , etc ., or the corresponding i'atty acid ester, followed by treatment with an hydroxide or oxide of the polyvalent metal, for exsmple, in the case of the aluminum salt, with alum, alumina, etc.
Calcium stearate, i . e . calcium distearate, magnesium stearate, i . e .
magnesium distearate, aluminum stearate, i.e. aluminum tristearate, and zinc steflrate, i.e. zinc distearate, are the preferred polyvalent fatty acid salt stabilizers. Mixed fatty acid metal salts, such as the naturally occurring acids, e. g. coco acid, as well as mixed fatty acids resulting from the commercial manufacturing process sre also advantageously used a~ an inexpensive but effective source of the long chain fatty acid.
The amount of the fatty acid salt stabilizers to achieve the desired enhancement of physical stability will depend on such factors as the nature of the fatty acid sslt, the nature ~nd amount of the thixotropic agent, detergent active compound, inorgsnic salts, especislly TPP, other LADD
ingredients, as well as the anticipsted storsge and shipping conditions.
Generally, however, amounts of the polyvalent metal fatty acid salt stabilizing agents in the rsnge of from sbout 0.02 to 1%, preferably from about 0 . 06 to 0 . 896, especially prefersbly from about 0 . 08 to 0 . 4%, provide the long term stsbility snd absence of phase separation upon standing or during transport at both low and elevated temperatures as are required for a commercially acceptable product.
There may also be used in the present invention the conventional inorganic thixotropic clay thickeners. The clay thickeners may be used in small amounts in combination with the fatty acid thickeners or in combination wtth fatty acid polyvalent metal salt thlckener8. The clay thickener8, however, may be used by themselves as the thixotropic thickeners.
The preferred clay thickeners comprise the inorganic, colloid forming clay8 of smectite and/or attapulgite types.
Smectite clays include montmorillonite (bentonite), hectorite, attapulgite, smectite, saponite, and the like. Montmorillonite clays are preferred and are available under tradenames such as Thixogel (Registered Trademark) No. 1 and Celwhite (Registered Trademark) GP, H, etc., from Georgia Kaolin Company; and Eccagum (Registered Trsdemark) GP, H, etc., from Luthern Clay Products. Attapulgite clays include the msterials .~ commercially available under the~ittagel (Registered Trademark), i. e . Attagel 40, Attagel 50 and Attagel 150 from Engelhard Minerals and Chemicals Corporation. Mixtures of smectite and attapulgite types in weight ratios of 4:1 to 1:5 nre also useful herein. Thickening or suspending sgents of the foregoing types are well known in the art, being described, 13268~3 for example, in V.S. Patent No. 3,985,668 referred to above. Abrasives or polishing agents should be avoided in the LADD compositions as they may mar the surface of fine dishware, crystal and the like.
When used in combination with the fatty acids or the fatty acid polyvalent metal salts, the clsy thixotropic thickeners are used in amounts of 0.1 to 3%, preferably 0.1 to 2.5% and more preferably in amounts of 0.1 to296.
When the clay thixotropic thickeners are used alone as the thixotropic thi¢kener agent they can be used in amounts of about 1,5 to 8%, preferably 2 to 5% by weight of the formulstion.
Generally, LADD effectiveness is directly related to (a) available chlorine levels; (b) alkalinity; (c) solubility in washing medlum; and (d) foam inhibltlon. It is preferred herein that the pH of the LADD composition be st least about 9, S, more preferably from about 10 . 5 to 13 . S and most preferably at least about 11,5. At the relatlvely lower pH values, the LADD product is too viscous, i.e. 801id-like, and thus not readily fluidized under the shear-for¢e levels created within the dispenser cup under normal machine operating conditions. Addition of NaOH is thus often needed to increase the pH to withln the above range8, and to increase flowability properties. The presence of carbonate is also often needed herein, since it acts as a buffer helping to maintain the desired pH level. Excess carbonate is to be avoided, however, since it may cause the formation of needle-like crystals of carbonate, thereby impairing the stability, thixotropy and/or detergency of the LADD product, as well as impairing the dispensibility of the product from, for example, squeeze tube bottles. Caustic soda (NaOH) serves the further function of neutralizing the phosphoric or phosphonic acid ester foam depressant when present. About 0.5 to 3 wt96 of NaOH and about 2 to 9 wt~ of sodium carbonate in the LADD composition are typical, although it should be noted that sufficient alkalinity may be provided by the NATPP and sodium silicate.
The NsTPP may be employed in the LADD composition in a range of about 8 to 35 wt%, prefer~bly about 20 to 30 wt%, and should preferably be free of heavy metal which tends to decompose or inactivate the preferred sodium hypochlorite and other chlorine bleach compounds. The NaTPP may be anhydrous or hydrated, including the stable hexahydrate with a degree Or hydration of 6 corresponding to about 18% by weight of water or more.
Actually, in view of the stabUity of the hexahydrate, the presence of some water of hydration is highly effective, serving it is thought to form seeds of the stable hexahydrate which expedites hydration and solubilization of the remaining NaTPP particles. If only the hexahydrate is used, the detergent product may be too liquid. Conversely, if only the anhydrous NaTPP is used, the product may, in some cases, be too thick and, therefore, unsuitable. Bepecially preferred LADD compositions are obtained, for exampb, when using a 0,5:1 to 2:1 we1ght ratio of anhydroua lS ¦ to hexahydrated NaTPP, values of about 1:1 being particularly preferred.
Poam inhibltion is important to increase dishwasher machine efficiency and mln1mize dostabilizing effects which might occur due to the presence of excess foam within the washer during use. Foam may be sufficiently reduced by suitable selection of the type andlor amount of detergent active material, 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 adjustment of the proportions of NaTPP which has a water softening effect may aid in providing the desired degree of foam inhibition.
However, it i8 generally preferred to include a chlorine bleach stable foam depressant or inhibitor. Particularly effective are the alkyl phosphonic acid esters o- the formula 1l HO--IP--R
OR
available for exsmple from BASF-Wyandotte (PCUK-PAE), and especially the alkyl acid phosphate esters of the formula O
HO--P--OR
OR
available, for example, from Hooker (SAP) snd Knapsack (LPKn-158), in which one or both R groups in each type of ester may repre~ent independently a Cl2_20 alkyl group. Mixture~ of the two type8, or any other chlorine bleach stable types, or mixtures of mono- and di-esters of the same type, may be employed . 13 specially preferred is a mixture of l mono- and di-C16 18 alkyl acid phosphate esters such as l monostearyl/distearyl acid phosphates 1.2/1 (Knapsack). When employed, proportions of 0,01 to 5 wt%, preferably 0.1 to 5 wt%, especially about 0.1 to 0.5 wt%, of foam depressant in the composition is typical, the weight ratio of detergent active component (d) to foam depressant (e) 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.
Although any chlorine bleach compound may be employed in the compositions of this invention, such as dichloro-isocyanurate, dichloro-dimethyl hydantoin, or chlorinated TSP, alkali metal, e.g.
potassium, lithium, magnesium and especiallr sodium hypochlorite is preferred. The composition should contain sufficient chlorine bleach compound to provide about O . 2 to 4 . 0% by weight of available chlorine, as determined, for example, by acidification of 100 parts of the composition with excess of hydrochloric acid . A solution containing about O . 2 to 9 . 0%
by weight of sodium hypochlorite contains or provides roughly the same percentage of available chlorine. A solution containing about 0.8 to 1.6% by weight sodium hypochlorite contains about 0.8 to 1.6% by weight of available chlorine and i8 especially preferred. For example, sodium hypochlorite 1~268~3 (NaOCI) solution of from about 11 to about 13% available chlorine in amounts of about 3 to 20%, preferably about 7 to 12%, can be advantageously used.
The sodium silicate, which provides alkalinity and protection of hard surfaces, such as fine china glaze and pattern, is employed in an amount ranging from about 2.5 to ~0 wt9~, preferably about 10 to 35 wt%, in the composition. At the higher levels specified herein for example at levels greater than about 10 wt% the silicate al80 provides increased antispotting action. The sodium silicate is generally added in the form of an aqueous solution, preferably having an Na20:SiO2 ratio of sbout 1:2.2 to 1:2.8, for example, 1:2.4. Most of the other components of the composition, especially NaOH, sodium hypochlorite and foam depressant may also be added in the ~orm o- an aqueous dispersion or solution.
Detergent active material useful herein must be stable in the presence of chlorine bleach, especially hypochlorite bleach, and those of the organic anionic, amine oxide, phosphine oxide, sulphoxide or betaine water dispersible surfactant types are pre-erred, the flrst mentioned anionics being most preferred. They are used in amounts ranging rom about 0.1 to 5% pre-erably about O . 3 to 2 . 0% . Particularly preferred surfactants herein are the Ihear or branched alkali metal mono- and/or di-(C8 14) alkyl diphenyl oxide mono andlor disulphates, commercially available for example as DOWFAX (Registered Trademark) 3B-2 and DOWFAX 2A-1.
In add1tion, the surfactant should be compatible with the other ingredients of the composition. Other suitable surfactants include the primary alkylsulphates, alkylsulphonates, alkylaryl-sulphonates and sec.-alkylsulphates. Examples include sodium C10_18 alkylsulphates such as sodium dodecylsulphate and sodium tallow alcoholsulphate; sodium C10 18 alkanesulphonates such as sodium hexadecyl-l-sulphonate and sodium C12 18 alkylbenzenesulphonates such as sodium dodecylbenzenesulphonates. The corresponding potassium salts may also be employed.
ZO
As other suitable surfactants or detergents, the amine oxide surfactants ~re typically of the structure R2RlNO, in which each R
represents a lower alkyl group, for instance, methyl, and Rl represents a long chain alkyl group having from 8 to 22 carbon atoms, for instance a lauryl, myristyl, palmityl or cetyl group. Instead of an amine oxide, a corresponding surractant phosphine oxide RaRlPO or sulphoxide RRlSO can be employed. Betaine surfactants are typically of the structure R2RlN -RnCOO, in which each R represents a lower alkylene group having from 1 to 5 carbon atoms. Specific examples of these surfactants are lauryl-dimethylamine oxide, myristyldimethylsmine oxide, the corresponding phosphine oxides snd sulphoxides, and the corresponding betaines, including dodecyldimethybmmonium scetate, tetrsdecyldiethylammonium pentanoato, hexsdecyl-dimethylsmmonium hexsnoste and the like. For biodegradability, the alkyl groups in these surfsctsnts should be linear, lg and su¢h compounds are preferred.
Sur~actants of the foregoing type, all well known ln the srt, are described, for example, in U. S . Patents 3 ,085 ,668 and 4, 271,030.
The amount o~ water contained in these compositions should, of course, be neither 80 hlgh a8 to produce unduly low visco~ity and fluidity, nor 80 low a8 to produce unduly high viscosity and low flowsbility, thixotropic properties in either case being diminished or destroyed. Such smount is readily determined by routine experimentation in any particular instsnce, generally ranging from about 25 to 75 wt%, pre(ersbly sbout 50 to 65 wt%.
The water should also be preferably deionized or softened. These amounts 2~ of water in the composition include the water added as parts of the liquid solutions of other ingredients, but do no include bound water, for example that in NaTPP hexahydrate.
Other conventional ingredients may be included in these compositions in small amounts, generally less than about 3 wt%, such as perfume, hydrotropic agents such as the sodium benzene, toluene, xylene and cumene ~ 1326803 sulphonate~, preservatives, dyestuffs and pigments and the like, all of course being stable to chlorine bleach compound snd high ~Ikalinity (properties of all the components). Especi~lly preferred for coloring are the chlorinated phthalocyanines and poiysulphides of aluminosilicate which provide, respectively, pleasing green and blue tints.
The liquid ADD compositions of this invention are readily employed in known manner for washing dishes, glssses, cups, esting utensils and the like in an automatic dishwasher, provided with a suitable detergent dispenser, in an aqueous wash bath contdning an effective amount of the 10 composition.
In a preferred embodiment of the inYention the aqueous liquid dishwsshing detergent composition is Çormulated using the below named ingredients.
l Component Weight Percent Alkali Metal Tripolypho~phate 10-25 Sodium Biltcate (47.5~) 15-40 Alumina or Titanium Dioxide Anti-filming Agent 1-4 Polyacrylic Acid Polymer or Salt 3-12 Alakli Metal Carbonate (anhydrous) 2-8 Chlorine Bleach Stable, Water Dispersible Organic Detergent Active Material 0.5-3 Chlorine Bleach Stable Foam Depressant 0.10-3 Chlorlne Bleach Compound 0.2-4 Fatty Acid Thixotropic Thickener 0.03-0.5 Sodium Hydroxide (50%) 2-6 Balance Water The thixotropic aqueous liquid automatic dishwashing detergent compositions of the present invention can contain conventional dishwashing detergent composition additives. The formulations can be prepared with commerclally available solid powder builders, and/or the ingredients can be mixed and the formulations ground to a desired particle size.
The invention may be put into practice in various ways and a number of specific embodiments will be described to illustrate the invention with reference to the accompanying exdmples.
All amounts and proportions referred to herein are percent by weight of the composition unless otherwise Indicated.
The present invention is further illu~trated by the ~ollowing examples.
ExamPle 1 A thixotropic aqueous liquid automatic dishwashing detergent composition is formulated from the following ingredients in the amounts specified.
Component Weiqht Percent Deionized Water 31.04 Knapsack LPKN-158 Foam Depressan~(l) 0.16 Sodium Hydroxide (50%) 2.34 Sodium Carbonate (anhydrous)4.88 Sodium Tripolyphosphate (anhydrous) 11.70 Sodium Tripolyphosphate (hexahydrate) 11.70 Alumina Anti-fllming Agent(2)2.5 Sodium polyacrylate polymer builder(3) (A.I.) 8.00 Gel White H Clay 1.22 Alumlnum Stearate Thlxotropic Thickener 0.09 Dowfax 3B-2 Surfactant(4) 0.78 Sodium Hypochlorite (11%) 8.78 Sodlum Sillcate (1/2.23 - 43.5%) 16.81 Graphtol Green Color 0.002 100.002 (1) Mixture of mono and distearyl (C16-C18) alkyl esters of phosphoric acid, mole ratio 1.1.3.
(2) Aluminumoxid C (Degussa) has a particle s~ze of about 4 microns and is available from Degussa Corporation.
(3) Alcosperse 149, about 2000 mw, available as a 40%
solution.
solution.
(4) Na mono- and didecyl dlphenyl ether disulfonate (45~ solution).
3d The ingredients are mixed following the procedure of Canadlan patent appllcation Serial No. 546,121 filed September 4th, 1987.
(The ingredients are added to the water generally in the order listed and gently stirred until a homogeneous mixture is obtained). The formulation is tested by washing glassware and dishware at a temperature of ~ 13~`$~1~
¦ 120F in hard water (300 ppm hardness) in an sutomatic dishwushing ¦ machine and the clean and dried dishe~ are found to have no apparent film ¦ and very few apparent ~pot8.
¦ Example 2 ¦ In order to demonstrate the effect of adding the silica anti-filming agent, formulations are prepared with and without the silica anti-filming agent and are compsred to a commercially available powder detergent composition.
The compositions are formulated to contain the following ingredients.
A B C D E
Alumina Alumina Titanium Tltanium ~o Anti-film Poly- No Poly- Dioxide Dioxide Agent/
acrylate acrylate Poly- No Poly- Polyacrylate Component acrylate acrylate Deionized Water 31,04 39.04 31.04 39.04 33.54 Knapsa¢k LPKN-158 Poam Depreos~nt O.lB 0,16 0.1B 0,16 0.16 Sodium Hydroxide (50~) 2.34 2.34 2,34 2.34 2,34 Sodlum Carbonate (anhydrous) 4.88 4.88 4.88 4.88 4.88 Sodlum Trlpolyphosphate (anhydrous) 11.70 11.70 11.70 11.70 11.70 Sodium Tripolyphosphate (hexahydrate) 11.70 11.70 11.70 11.70 11.70 Anei-filming Agent 2.50 2.50 2.50 2.50 ---Sodium ~yacrylate Polymer (A.l.) 8.00 --- 8.00 --- 8.00 Cel White H Clay 1.22 1.22 1.22 1.22 1,22 Aluminum Stearate Thixotropic Thickener 0.09 0.09 0.09 0-09 0-09 Doxfnx 3B-2 Surfactant 0.78 0.78 0.78 0.78 0.78 Sodium Hypochlorite (11%) 8.78 8.78 8.78 8.78 8.78 Sodium Silicate (1/2.23 - 43.5%) 16.81 16.81 16.81 16.81 16.81 100.00 100.00 100.00 100.00 100.00 (1) Alcosperse 149.
¦ The Ingredlen~s ore mlxed In n conventlonnl manner or cnn be mixe l followlng the procedure of Canadian patent application ¦ Serial No. 546,121 filed September 4th, 1987.
¦ (The Ingredlents nre added to the water generolly In thc order llstcd ond genlly slirrecl untll a homogeneouY mlxlure 18 ol)tDIned. ) Tlle formulntlon i~ tested by waehlng glassware at 12~F In hard wnter (300 ppm hardnes~) .
I The three abolre formulatlon~ (A) (U) (C) ~D) and (E) wore tcstcd ¦ ond compared wllh o commerclQlly avalloble powder outomollc dlshwasher detergent formulallon F. The formulatlon~ were lesled In a Kenmore oulomalic dlshwosher uslng the procedure de~cribed In ASTMD ~56G-7~
except lhat only four cleanlng cyclee nre u~ed. The fllming and epotllng l are evalualed accordlng to lhe following sc~le~:
¦ Fllm natlng Scale .
l. ~eet no apparent film ¦ 2 FYlmlng slighl becomlng apparent ¦ J. Noticeflble film increasing ¦ 4. Continued Incrense of slgnlflcent film ¦ 5. Nlmlng becomlng exceeelve G Nlmlng hlE~h exces~Jve buildup ¦ 7. Continued increa~e of exces~ive film.
¦ Spot natlng Scule ¦ A UeHt - no epota 2S ¦ 1~. Very few spot~ apparent ¦ C. Dl~tlnct ¦ D. Slgnlflcant coverage approxlmately 50~.
The ree~ obtnined a re reported In lhe below Toble 1 .~ , . . .
~ - 132~803 ¦ Formulstion Performance Rating ¦ Spot Fqlm (A) Alumina/Polyacrylate B 1-2 l (B) Alumina/No Pdyacrylate B-C 2 ¦ (C) Titanium Dioxide/Polyacrylate B 2-3 (D) Titanium Dioxide/No Polyacrylate B-C 2-3 (E) No Anti-film Agent/Polyacrylate B-C 3-4 (F) Commercial Powder DetergentB-C 3-4 l The producte (A) and (C) left no spot on glasswares except onettwo 10 ¦ prong marks and were rated (B). The product (E) with no anti-film agent ¦ left ~ significant uniform film B-C, 3-4 on glasswares. However, significant ¦ spotting and filming improvement were obtained with the formulations .
¦ contdning both snti-filming agent and polyacrylate.
1 ~32~8~3 ¦ Example 3 ¦ A thixotropic aqueous liquid automatic dishwashing detergent ¦ composition i8 formulated from the following ingredients in the amounts ¦ specified.
¦ Component Weight Percent ¦ Deionlsed Water 26.8 ¦ Knap8ack LPKN-158 Foam Depressant0.16 ¦ Sodium Hydroxide (50%) 2.34 ¦ Sodium Carbonate (anhydrous) 4.88 ¦ Sodium Tripolyphosphate (anhydrous) 11.70 ¦ Sodium Tripolyphosphste (hexahydrste) 11.70 ¦ Alumina ~nt1-filming Agent 2.50 ¦ Stearic ~cid Thixotroplc Th~¢kener0.10 ¦ Sodium Polyacrylato (MW 2000) 6.00 ¦ Dow~ax 3B-2 Surfactant .~
¦ Sodium Hypochlorite (11%) 7.ô1 ¦ Sodium Silicste (1/2.4-47.5~) 25.B0 ¦ Graphitol Greon 0.01 1 100.00 l The ingrodient~ sre added to the water genersUy in the order listed 20 ¦ and gently st1rred until a homogeneous mixture is obtained.
¦ The formulstion is tested by washing glassware at 130F in hard water ¦ (300 ppm hardness) in an sutomstic dishwsshing mschine. The cleaned and ¦ dried glassware are found to have no apparent film and very few appsrent ¦ epots.
25 ¦ The thixotropic squeous liquid sutomstic dishwashing detergent ¦ compositions of the present invention provide improved film properties.
¦ The invention is not to be limited by the sbove disclosure and Exsmples which are given as illustrstlons only. The invention is to be interpreted in accordance with the below claims.
3d The ingredients are mixed following the procedure of Canadlan patent appllcation Serial No. 546,121 filed September 4th, 1987.
(The ingredients are added to the water generally in the order listed and gently stirred until a homogeneous mixture is obtained). The formulation is tested by washing glassware and dishware at a temperature of ~ 13~`$~1~
¦ 120F in hard water (300 ppm hardness) in an sutomatic dishwushing ¦ machine and the clean and dried dishe~ are found to have no apparent film ¦ and very few apparent ~pot8.
¦ Example 2 ¦ In order to demonstrate the effect of adding the silica anti-filming agent, formulations are prepared with and without the silica anti-filming agent and are compsred to a commercially available powder detergent composition.
The compositions are formulated to contain the following ingredients.
A B C D E
Alumina Alumina Titanium Tltanium ~o Anti-film Poly- No Poly- Dioxide Dioxide Agent/
acrylate acrylate Poly- No Poly- Polyacrylate Component acrylate acrylate Deionized Water 31,04 39.04 31.04 39.04 33.54 Knapsa¢k LPKN-158 Poam Depreos~nt O.lB 0,16 0.1B 0,16 0.16 Sodium Hydroxide (50~) 2.34 2.34 2,34 2.34 2,34 Sodlum Carbonate (anhydrous) 4.88 4.88 4.88 4.88 4.88 Sodlum Trlpolyphosphate (anhydrous) 11.70 11.70 11.70 11.70 11.70 Sodium Tripolyphosphate (hexahydrate) 11.70 11.70 11.70 11.70 11.70 Anei-filming Agent 2.50 2.50 2.50 2.50 ---Sodium ~yacrylate Polymer (A.l.) 8.00 --- 8.00 --- 8.00 Cel White H Clay 1.22 1.22 1.22 1.22 1,22 Aluminum Stearate Thixotropic Thickener 0.09 0.09 0.09 0-09 0-09 Doxfnx 3B-2 Surfactant 0.78 0.78 0.78 0.78 0.78 Sodium Hypochlorite (11%) 8.78 8.78 8.78 8.78 8.78 Sodium Silicate (1/2.23 - 43.5%) 16.81 16.81 16.81 16.81 16.81 100.00 100.00 100.00 100.00 100.00 (1) Alcosperse 149.
¦ The Ingredlen~s ore mlxed In n conventlonnl manner or cnn be mixe l followlng the procedure of Canadian patent application ¦ Serial No. 546,121 filed September 4th, 1987.
¦ (The Ingredlents nre added to the water generolly In thc order llstcd ond genlly slirrecl untll a homogeneouY mlxlure 18 ol)tDIned. ) Tlle formulntlon i~ tested by waehlng glassware at 12~F In hard wnter (300 ppm hardnes~) .
I The three abolre formulatlon~ (A) (U) (C) ~D) and (E) wore tcstcd ¦ ond compared wllh o commerclQlly avalloble powder outomollc dlshwasher detergent formulallon F. The formulatlon~ were lesled In a Kenmore oulomalic dlshwosher uslng the procedure de~cribed In ASTMD ~56G-7~
except lhat only four cleanlng cyclee nre u~ed. The fllming and epotllng l are evalualed accordlng to lhe following sc~le~:
¦ Fllm natlng Scale .
l. ~eet no apparent film ¦ 2 FYlmlng slighl becomlng apparent ¦ J. Noticeflble film increasing ¦ 4. Continued Incrense of slgnlflcent film ¦ 5. Nlmlng becomlng exceeelve G Nlmlng hlE~h exces~Jve buildup ¦ 7. Continued increa~e of exces~ive film.
¦ Spot natlng Scule ¦ A UeHt - no epota 2S ¦ 1~. Very few spot~ apparent ¦ C. Dl~tlnct ¦ D. Slgnlflcant coverage approxlmately 50~.
The ree~ obtnined a re reported In lhe below Toble 1 .~ , . . .
~ - 132~803 ¦ Formulstion Performance Rating ¦ Spot Fqlm (A) Alumina/Polyacrylate B 1-2 l (B) Alumina/No Pdyacrylate B-C 2 ¦ (C) Titanium Dioxide/Polyacrylate B 2-3 (D) Titanium Dioxide/No Polyacrylate B-C 2-3 (E) No Anti-film Agent/Polyacrylate B-C 3-4 (F) Commercial Powder DetergentB-C 3-4 l The producte (A) and (C) left no spot on glasswares except onettwo 10 ¦ prong marks and were rated (B). The product (E) with no anti-film agent ¦ left ~ significant uniform film B-C, 3-4 on glasswares. However, significant ¦ spotting and filming improvement were obtained with the formulations .
¦ contdning both snti-filming agent and polyacrylate.
1 ~32~8~3 ¦ Example 3 ¦ A thixotropic aqueous liquid automatic dishwashing detergent ¦ composition i8 formulated from the following ingredients in the amounts ¦ specified.
¦ Component Weight Percent ¦ Deionlsed Water 26.8 ¦ Knap8ack LPKN-158 Foam Depressant0.16 ¦ Sodium Hydroxide (50%) 2.34 ¦ Sodium Carbonate (anhydrous) 4.88 ¦ Sodium Tripolyphosphate (anhydrous) 11.70 ¦ Sodium Tripolyphosphste (hexahydrste) 11.70 ¦ Alumina ~nt1-filming Agent 2.50 ¦ Stearic ~cid Thixotroplc Th~¢kener0.10 ¦ Sodium Polyacrylato (MW 2000) 6.00 ¦ Dow~ax 3B-2 Surfactant .~
¦ Sodium Hypochlorite (11%) 7.ô1 ¦ Sodium Silicste (1/2.4-47.5~) 25.B0 ¦ Graphitol Greon 0.01 1 100.00 l The ingrodient~ sre added to the water genersUy in the order listed 20 ¦ and gently st1rred until a homogeneous mixture is obtained.
¦ The formulstion is tested by washing glassware at 130F in hard water ¦ (300 ppm hardness) in an sutomstic dishwsshing mschine. The cleaned and ¦ dried glassware are found to have no apparent film and very few appsrent ¦ epots.
25 ¦ The thixotropic squeous liquid sutomstic dishwashing detergent ¦ compositions of the present invention provide improved film properties.
¦ The invention is not to be limited by the sbove disclosure and Exsmples which are given as illustrstlons only. The invention is to be interpreted in accordance with the below claims.
Claims (22)
1. A gel-like thixotropic aqueous liquid automatic dishwashing detergent composition comprising water, at least one ingredient selected from the group consisting of organic detergent, chlorine bleach, detergent builder, sequestering agent, foam inhibitors, and mixtures thereof, from about 0.5 to 5% of alumina or titanium dioxide particles or mixture thereof having a particle size of about 0.1 to 10 microns as anti-filming agent and about 2 to 14% of a polyacrylic acid polymer or salt, and a sufficient amount of a thixotropic thickener to provide a thixotropic index of about 2.5 to 10.
2. The composition of claim 1 wherein the alumina or titanium dioxide anti-filming agent is in an amount of about 1 to 4% and the polyacrylic acid polymer or salt is in an amount of about 3 to 12%.
3. A thixotropic aqueous liquid automatic dishwasher composition comprising approximately by weight:
(a) 5 to 35% detergent builder;
(b) 2.5 to 40% sodium silicate;
(c) 0.5 to 5% of an alumina or titanium dioxide anti-filming agent having a particle size of about 0.1 to 10 microns;
(d) 2 to 14% polyacrylic acid polymer or salt builder having a molecular weight of 1,000 to 100,000;
(e) 0 to 9% alkali metal carbonate;
(f) 0.1 to 5% chlorine bleach stable, water-dispersible organic detergent active material;
(g) 0 to 5% chlorine bleach stable foam depressant;
(h) chlorine bleach compound in an amount to provide about 0.2 to 4% of available chlorine;
(i) a sufficient amount of a thixotropic thickener to provide a thixotropic index of about 2.5 to 10.
(j) 0 to 8% of sodium hydroxide;
29a (k) balance water.
(a) 5 to 35% detergent builder;
(b) 2.5 to 40% sodium silicate;
(c) 0.5 to 5% of an alumina or titanium dioxide anti-filming agent having a particle size of about 0.1 to 10 microns;
(d) 2 to 14% polyacrylic acid polymer or salt builder having a molecular weight of 1,000 to 100,000;
(e) 0 to 9% alkali metal carbonate;
(f) 0.1 to 5% chlorine bleach stable, water-dispersible organic detergent active material;
(g) 0 to 5% chlorine bleach stable foam depressant;
(h) chlorine bleach compound in an amount to provide about 0.2 to 4% of available chlorine;
(i) a sufficient amount of a thixotropic thickener to provide a thixotropic index of about 2.5 to 10.
(j) 0 to 8% of sodium hydroxide;
29a (k) balance water.
4. The composition of claim 3 wherein the polyacrylic acid polymer or salt has the formula wherein R1, R2 and R3 can be the same or different and can be hydrogen, C1-C4 lower alkyl, M represents hydrogen, or an alkali metal, n = 5 to 1000 and the polymer has a molecular weight of 1000 to 100,000.
5. The composition of claim 3 wherein the thixotropic thickener comprises a long chain fatty acid in an amount of about 0.03 to 0.5%.
6. The composition of claim 3 wherein the thixotropic thickener comprises a polyvalent metal salt of a long chain fatty acid in an amount of about 0.02 to 1.0%.
7. The composition of claim 5 additionally comprising a clay thixotropic thickener in an amount of about 0.1 to 3.0%
8. The composition of claim 6 additionally comprising a clay thixotropic thickener in an amount of about 0.1 to 3.0%.
9. The composition of claim 3 wherein the alumina or titanium dioxide anti-filming agent has a particle size of about 0.5 to 8.0 microns.
10. A thixotropic aqueous liquid automatic dishwasher composition comprising approximately by weight:
(a) 5 to 35% alkali metal tripolyphosphate;
(b) 2.5 to 40% sodium silicate;
(c) 1 to 4% alumina or titanium dioxide anti-filming agent having a particle size of about 0.5 to 8.0 microns;
(d) 3 to 12% polyacrylic acid polymer or salt builder;
(e) 0 to 9% alkali metal carbonate;
(f) 0.1 to 5% chlorine bleach stable, water dispersible organic detergent active material;
(g) 0 to 5% chlorine bleach stable foam depressant;
(h) chlorine bleach compound in an amount to provide about 0.2 to 4% of available chlorine;
(i) a sufficient amount of a thixotropic thickener to provide a thixotropic index of about 2.5 to 10.
(j) 0 to 8% of sodium hydroxide;
(k) balance water.
(a) 5 to 35% alkali metal tripolyphosphate;
(b) 2.5 to 40% sodium silicate;
(c) 1 to 4% alumina or titanium dioxide anti-filming agent having a particle size of about 0.5 to 8.0 microns;
(d) 3 to 12% polyacrylic acid polymer or salt builder;
(e) 0 to 9% alkali metal carbonate;
(f) 0.1 to 5% chlorine bleach stable, water dispersible organic detergent active material;
(g) 0 to 5% chlorine bleach stable foam depressant;
(h) chlorine bleach compound in an amount to provide about 0.2 to 4% of available chlorine;
(i) a sufficient amount of a thixotropic thickener to provide a thixotropic index of about 2.5 to 10.
(j) 0 to 8% of sodium hydroxide;
(k) balance water.
11. The composition of claim 10 wherein the polyacrylic acid polymer or salt 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.
represents hydrogen, sodium or potassium, n = 10 to 500 and the polymer has a molecular weight of 1500 to 50,000.
12. The composition of claim 10 wherein the polyacrylic acid polymer or salt has a molecular weight of about 2000.
13. The composition of claim 10 wherein the polyacrylic acid polymer or salt has a molecular weight of about 4500.
14. The composition of claim 10 wherein the alumina or titanium dioxide anti-filming agent contains about 0.1 to 5% of alumina, based on weight of silica.
15. The composition of claim 10 wherein the alumina or titanium dioxide has a particle size of about 1 to 5 microns.
16. The composition of claim 10 wherein the thixotropic thickener comprises a long chain fatty acid having C16 to C20 carbon atoms in an amount of about 0.03 to 0.20%.
17. The composition of claim 10 wherein the thixotropic thickener comprises a polyvalent metal salt of a long chain fatty acid having C16 to C20 carbon atoms in an amount of about 0.06 to 0.8%.
18. The composition of claim 17 wherein the polyvalent metal is one of aluminum, calcium, zinc and magnesium.
19. The composition of claim 16 additionally comprising a clay thixotropic thickener in an amount of about 0.1 to 2.5%.
20. The composition of claim 17 additionally comprising a clay thixotropic thickener in an amount of about 0.1 to 2.5%.
21. A method for cleaning, soiled glassware and dishware in an automatic dishwashing machine which comprises contacting the soiled dishware in an automatic dishwashing machine in an aqueous washbath having dispersed therein an effective amount of the composition of claim 3.
22. A method for cleaning soiled dishware in an automatic dishwashing machine which comprises contacting the soiled glassware and dishware in an automatic dishwashing machine in an aqueous washbath having dispersed therein an effective amount of the composition of claim 10.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11718487A | 1987-11-05 | 1987-11-05 | |
| US117,184 | 1987-11-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1326803C true CA1326803C (en) | 1994-02-08 |
Family
ID=22371382
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000582266A Expired - Fee Related CA1326803C (en) | 1987-11-05 | 1988-11-04 | Thixotropic aqueous liquid automatic dishwashing detergent composition |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0315024A3 (en) |
| JP (1) | JPH01230699A (en) |
| AU (1) | AU620050B2 (en) |
| BR (1) | BR8805765A (en) |
| CA (1) | CA1326803C (en) |
| DK (1) | DK618988A (en) |
| FI (1) | FI885113A (en) |
| IL (1) | IL88166A (en) |
| NO (1) | NO173612C (en) |
| NZ (1) | NZ226709A (en) |
| PT (1) | PT88929B (en) |
| ZA (1) | ZA888078B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5064553A (en) * | 1989-05-18 | 1991-11-12 | Colgate-Palmolive Co. | Linear-viscoelastic aqueous liquid automatic dishwasher detergent composition |
| ZA887068B (en) * | 1987-09-29 | 1990-05-30 | Colgate Palmolive Co | Thixotropic aqueous liquid automatic dishwashing detergent composition |
| US5209863A (en) * | 1987-11-05 | 1993-05-11 | Colgate-Palmolive Company | Linear viscoelastic aqueous liquid automatic dishwasher detergent composition having improved anti-filming properties |
| CA2031289A1 (en) * | 1989-12-01 | 1991-06-02 | Fahim U. Ahmed | Automatic dishwasher powder detergent composition |
| AU637902B2 (en) * | 1990-05-07 | 1993-06-10 | Colgate-Palmolive Company, The | Nonaqueous liquid automatic dishwasher detergent composition |
| GB9027372D0 (en) * | 1990-12-18 | 1991-02-06 | Cussons Int Ltd | Detergent composition |
| US5094771A (en) * | 1991-05-07 | 1992-03-10 | Colgate-Palmolive Co. | Nonaqueous liquid automatic dishwasher detergent composition |
| PT101284A (en) * | 1992-06-08 | 1994-12-30 | Colgate Palmolive Co | Aqueous polymeric viscose agent and polymeric solution containing the said agent |
| JP2006199723A (en) * | 2005-01-18 | 2006-08-03 | Diversey Ip Internatl Bv | Liquid detergent composition for automatic washer and washing method using the same |
| EP2125618A4 (en) * | 2007-02-08 | 2012-03-21 | Fontana Technology | Particle removal method and composition |
| JP6068846B2 (en) * | 2011-08-24 | 2017-01-25 | 花王株式会社 | Solid bleach composition |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4695394A (en) * | 1984-04-20 | 1987-09-22 | The Clorox Company | Thickened aqueous cleanser |
| DK347485A (en) * | 1984-08-13 | 1986-02-14 | Colgate Palmolive Co | DISHWASHER FOR AUTOMATIC DISHWASHER |
| IN165509B (en) * | 1984-12-24 | 1989-11-04 | Colgate Palmolive Co | |
| GB8616615D0 (en) * | 1986-07-08 | 1986-08-13 | Unilever Plc | Rinse aid |
| US4857226A (en) * | 1986-10-29 | 1989-08-15 | Colgate-Palmolive Company | Thixotropic clay aqueous suspensions containing polyacrylic acid polymer or copolymer stabilizers |
| GB8718219D0 (en) * | 1987-07-31 | 1987-09-09 | Unilever Plc | Liquid abrasive cleaning composition |
| NZ226708A (en) * | 1987-10-28 | 1990-09-26 | Colgate Palmolive Co | Thixotropic dishwshing composition with silica and polycrylic acid polymer/salt |
-
1988
- 1988-10-25 NZ NZ226709A patent/NZ226709A/en unknown
- 1988-10-25 EP EP19880117719 patent/EP0315024A3/en not_active Withdrawn
- 1988-10-26 IL IL88166A patent/IL88166A/en not_active IP Right Cessation
- 1988-10-27 ZA ZA888078A patent/ZA888078B/en unknown
- 1988-11-02 AU AU24618/88A patent/AU620050B2/en not_active Ceased
- 1988-11-03 PT PT88929A patent/PT88929B/en active IP Right Grant
- 1988-11-04 DK DK618988A patent/DK618988A/en not_active Application Discontinuation
- 1988-11-04 CA CA000582266A patent/CA1326803C/en not_active Expired - Fee Related
- 1988-11-04 BR BR888805765A patent/BR8805765A/en not_active Application Discontinuation
- 1988-11-04 JP JP63279217A patent/JPH01230699A/en active Pending
- 1988-11-04 NO NO884944A patent/NO173612C/en unknown
- 1988-11-04 FI FI885113A patent/FI885113A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| AU620050B2 (en) | 1992-02-13 |
| PT88929B (en) | 1993-01-29 |
| NO173612B (en) | 1993-09-27 |
| NO884944D0 (en) | 1988-11-04 |
| IL88166A (en) | 1992-06-21 |
| FI885113A0 (en) | 1988-11-04 |
| EP0315024A3 (en) | 1991-03-20 |
| FI885113A (en) | 1989-05-06 |
| IL88166A0 (en) | 1989-06-30 |
| BR8805765A (en) | 1989-07-25 |
| DK618988A (en) | 1989-05-06 |
| NO173612C (en) | 1994-01-05 |
| ZA888078B (en) | 1990-06-27 |
| DK618988D0 (en) | 1988-11-04 |
| AU2461888A (en) | 1989-05-11 |
| NZ226709A (en) | 1990-10-26 |
| NO884944L (en) | 1989-05-08 |
| JPH01230699A (en) | 1989-09-14 |
| EP0315024A2 (en) | 1989-05-10 |
| PT88929A (en) | 1988-12-01 |
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