CA1334389C - Machine dishwasher water spot control composition - Google Patents
Machine dishwasher water spot control compositionInfo
- Publication number
- CA1334389C CA1334389C CA 530579 CA530579A CA1334389C CA 1334389 C CA1334389 C CA 1334389C CA 530579 CA530579 CA 530579 CA 530579 A CA530579 A CA 530579A CA 1334389 C CA1334389 C CA 1334389C
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- detergent composition
- weight
- polyacrylate
- percent
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Classifications
-
- 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
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
-
- 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
- C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
-
- 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
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38609—Protease or amylase in solid compositions only
-
- 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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3942—Inorganic per-compounds
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
Water spot reduction compositions containing an oxygen bleach, a proteolytic enzyme, and a polyacrylate for use in cleaning dishes and the like in a machine dishwasher.
The compositions effectively reduce the presence of water spots which form on dish surfaces and the like during machine dishwashing operations.
The compositions effectively reduce the presence of water spots which form on dish surfaces and the like during machine dishwashing operations.
Description
1710.002 l 334389 MACHINE DISHWASHER WATER SPOT CONTROL COMPOSITION
FIELD OF THE INVENTION
The present invention relstes generally to cornpositions for use in machine dishwashers to facilitate the cleaning of dishes and the like. More particularly, the present invention relates to compositios which reduce water spot forrnation on articles cleaned in machine dishwashers.
BACKGROUND OF THE INVENTION
Machine dishwashers ~re widely used to clean soiled dishes, cooking utensils and other containers for serving and preparing food, such as plates, cups, glasses, silverware, pots, pans, etc., generically referred to as "dishes". While the construction and cornposition of these items vary widely, st usually have glossy, solid surfaces on which the presence of dried water spots is readily noticeable. These dried water spots are aesthetically unappealing and thus methods and compositions for reducing their number and size are of great concern to the detergent industry as well as to the consumer.
Typical machine dishwashers operate by subjecting food soiled dishes and the like to alternating wash and rinse cycles inside a closed washing chamber. Spray nozzles inside the charnber direct powerful streams of hot wash liquor and rinse water onto to the soiled dish surfaces. A consideraMe amount of food residue is thereby removed by the force exerted by these pressurized water streams. There is, however, a substantial amount of food residue which resists dislodgement by the water jets. It is known that by adding certain detergent compositions to the wash water, a much greater quantity of food soil can be removed from soiled article surfaces during the washing cycle. These machine or "automatic" dishwasher detergent compositions as they are known dramatically increase the ~le~ning efficiency of machine ~ hers primarily by alkaline ~ - - 1 334389 710.002 cleaning action and through the emulsification and dispersion of food residue which otherwise clings to dish surfacbs despite the action of wash water jets.
While food soils vary greatly in composition, generally food residue which remains on dish surfaces contains an organic component which often includes a mixture of various proteins. Since the make-up of typical food residue is known, detergent compositions are formulated such that their various c~onentC
are effective in breaking down food soils during the wash cycle of autanatic dishwashers. The emulsification of food soil is most often achieved through the use of surface active agents or "surfactantsn, as they are known. Surfactants not only help remove food residue by emulsification, they also provide cleaning power through wetting, foaming, dispersing and penetrating actions. It will be recognized by those skilled in the art that there are many dif ferent types of surfactants suitable for use in automatic dishwasher detergents and that low foaming, non-ionic surfactants are especially suited for use in these compositions. For example, low-foaming, fatty alcohol ethoxylates and ethylene oxide/propylene oxide block polymers are widely used` in the manufacture of machine dishwashing detergents.
Automatic dishwashing detergents also contain detergent builders such as complex phosphates, carbonates, sulfates and silicates which compliment the detersive action of sufactants. For example, by sequestering certain metallic ions which are present in most water sources, phosphates reduce hard water film formation caused by the deposition of metallic precipitates. Moreover, alkalinity builders provide alkaline cleaning power which is particularly important in automatic di~h..~shing compositions since, by its very nature, automatic di~l,..~shing does not provide the mechanical action of hand di~ hi~ Since physical contact with the wash liquor by the consumer does not occur when dishes are cleaned in a machine di~l,..~l.er, allcalinity builders are especially suitable for use in automatic ~h..~hing detergents.
Bleaches can be used in connection with these other du,h. ~hine detergent composition components to remove food residue by breaking down the 710.002 food residue to simpler components. However, the cleaning action of bleaches differs somewhst from most other dishwashing canposition com~onents in that bleaches clean by breaking chernical bonds within molecules rather than the physical bonds which exist between molecules. Although some bleaches are reducing agents, typical bleaches employed in dishwashing compositions are oxidizing agents. Basically, oxidizing bleaches cause the oxidation of chemical bonds, thereby reducing large molecules to smaller units. The smaller units can then be more easily removed during the dishwashing process. The most widely usedoxidizing bleaches, particularly in dishwashing compositions, are dry chlorine bleaches. Many cornpositions use such hypochlorite generators as sodium dichloroisocyanurate and chlorinated trisodium phosphate. Chlorine bleaches are strong oxidizing agents but their usefulness is limited by their tendency to cause unwanted oxidation of other wash cornpound components and by their brief shelf life. Chlorine bleaches are such strong oxidizing agents that great care must betaken to ensure that the other cornponents with which they are mixed are not adversely affected during storage and, moreover, during use. Due to these and other drawbacks inherent in the use of chlorine bleaches in dishwashing compositions, many formulators have instead proposed that oxygen bleaches be used as the principal oxidizing agent in dishwashing compositions. Oxygen bleaches not only possess greater potential cnpatibility with other d~. ~hir~
composition components, they exhibit much greater stability during storage. While the most frequent oxygen bleach proposed for use is sodium perborate, the use ofmany inorganic peroxides, such as sodium percarbonate, potassium nopersulfate, and hydrogen peroxide has also been proposed.
It is evident then that the process by which food residue is r~ ,ed from dish surfaces is the result of various physical and chemical interactions which take place during the washing and rinsing cycles inside the wash chamber. It is theorized that food particles which remain on dish surfaces after final rinse promote water droplet formation and, ultimately, form tro~hl~ dried water spots. These minute food particles serve to anchor droplets of water which would otherwise sheet off of dish surfaces. In particular it is thought that bits of 1 33438~
protein residue have a tendency to adhere to article surfaces such that water droplets ~ccum~ te around the particles. It follows that it is these protein-anchored water droplets which dry into unsightly water spots. It will be apparent to those skilled in the art that a droplet of water contains a number of minerals and other substances which, when the water evaporates, leaves a residue corresponding roughly in size and shape to the original water droplet. This dried residue causes light to diffract at the water spot in a manner different from that of the surrounding area, thus making the spot visible. It would according to theory, then, seem highly desirable to eliminate as many of these particulate protein masses as possible in order to reduce water droplet accum~ tions which are believed to be the source of unwanted water spotting of dishes and the like.
It is known in the art that certain proteolytic enzymes are capable of reducing the amount of particulate protein soil on dish surfaces during machine dishwashing operations. In particular, proteases are effective in the removal of protein food soil by virtue of their ability to catalyze the hydrolysis of protein peptide linkages. Proteins, which are very high molecular weight compounds, are thereby converted into smaller peptide units which are more easily removed from article surfaces during the cleaning process. Automatic dishwashing compositions have thus been formlll~tl~d in the past which contain proteases. Due to a long-held belief in the industry, however, that proteolytic enzymes are incompatible with bleaches in solution, these prior art attempts to utilize proteolytic enzymes in the breakdown of protein soil have generally not included the addition of a bleaching agent in the final composition. Thus, these known compositions have achieved no net reduction of water spotting. Any benefit produced by the protease is negated by the lack of bleach cleansing power in the composition.
Proteolytic enzymes are themselves proteinaceous molecules.
Therefore, it has been generally held that when these enzymes are brought in contact with bleach, the enzymes are oxidized into simpler components, thus losing 1 33~3~
their ability to catalyze the breakdown of peptide bonds. That is, it has been thought that unless the proteolytic enzymes are protected somehow from oxidation by the bleach, they are unable to perform their catalytic function. This widely-held belief has resulted in numerous attempts to isolate bleaches from proteases both during storage of compositions containing both of these ingredients as well as during the wash cycle. For example, attempts have been made to microencapsulate bleach to delay its nxi~li7.ing action in the wash liquor until after the proteolytic enzymes have had an opportunity to catalytically break down protein soils.
I have discovered that despite the teachings of the prior art that bleaches and proteolytic enzymes are essenti~lly incompatible, a mixture coll~il~illg an oxygen bleach, a protease and a polyacrylate provides excellent reduction of water droplet formation on washed articles and thus prevents unwanted water spotting during the automatic dishwashing operation. Rather than producing an antagonistic reaction, I have observed that by combining an oxygen bleach, a protease and a polyacrylate along with standard detergent components, an unexpected synergistic action is produced which yields a high degree of water spot prevention. Also, I have discovered an automatic dishwashing detergent composition which contains both an oxygen bleach and a proteolytic enzyme that produces good water spot reduction when used in machine dishwashers.
SUMMARY OF THE INVENTION
In accordance with the present invention, a water spot reduction composition is provided which contains an oxygen bleach, a proteolytic enzyme, and a polyacrylate which, when used in combination with standard machine dishwashing detergent components such as phosphates, silicates and surfactants, reduces water spotting on washed article surfaces. A fully-built machine dishwasher detergent composition which contains both an oxygen bleach and a proteolytic en_yme is also disclosed that reduces the formation of water spots on article surfaces during the automatic dishwashing process.
" .~
. ~, -5-1710.002 It is therefore a primary object of the present invention to provide compositions which, when used in an automatic dishwasher, reduce the formation of water spots on dish surfaces and the like.
DETAILED DESCRIPTION OF THE IN~'ENTION
In accordance with the present invention, a water spot reduction composition is provided for use in a machine dishwasher which, when mixed with conventional automatic dishwasher components such as phosphates, silicates, surfactants and inorganic fillers to formulate an autornatic dishwasher detergent composition, reduces the presence of water spots on glassware during the machine dishwashing process. The water spot reduction composition comprises an oxygen bleach, a proteolytic enzyme and a polyacrylate. In the final autamatic dishwasher formulation, that is, when the water spot reduction composition is cornbined with phosphate builders, silicates, surfactants and the like to produce a fully built automatic dishwasher detergent composition, the oxygen bleach component of the present invention comprises from about .05% to 5% by weight, preferably from about .1% to 2% by weight, and most preferably fram about .25% to 1.0% by weight of available oxygen in the final built detergent.
By available oxygen, it is meant that the compound which is used as a source of oxygen in the present invention provides a certain amount of oxygen which is available to participate in oxidation reactions. It will be known to those skilled in the art that preferred sources of oxygen disclosed herein are typically sold with reference to their available oxygen content.
It will be known to those skilled in the art, that enzymes and in particular, proteolytic c.~y~es are sold with reference to their enzyme activity which is stated in various units depen~line on the individual manufacturer. I prefer to state my preferred concentration ranges of proteolytic enzyrne with reference to KNPU/g which is the enzyme activity expression used by Novo Industries of .. . .. .
~-- 1 3343~
1710.002 Copenhagen, Denmark. 1 KNPU is the amount of enzyme which hydrolyzes casein at standard reaction conditions at an initial rate such that colorimetric change of reaction with 2,4,6 - Trinitrobenzene-l-sulfonic acid corresponds to 1 millimol per glycine per minute. Standard reaction conditions are .05 Harnnerstein cssein, .05 molar borate buffer, P.H.9, 50 C with a reaction time of 20 minutes. In the final automatic dishwasher formulation, that is, when the water spot reduction composition of the present invention is combined with phosphate builders, silicates, surfactants and the like to produce a fully built automatic dishwasher detergent composition, the proteolytic enzyme component of the present invention provides from about 2 to 200 KNPU, preferably from 4 to 80 KNPU and most preferably from 10 to 40 KNPU per kilogram of the final built detergent.
The polyacrylate component of the present invention c~..y. ;ses from about .1% to 2096 by weight, and preferably frorn 1% to 10% by weight of the final built detergent composition. In other words, the water spot reduction composition of the present invention is comprised of an oxygen bleach as a source of available oxygen, a proteolytic enzyme which provides enzymatic activity and a polyacrylate.
Each of these three components are present in the water spot reduction composition in relative quantities which produce, respectively, available oxygen, enxyrnatic activity and polyacrylate in the percentage by weight ranges given with respect to the total weight of the final built detergent composition which includes phosphate builders, silicates, surfactants and the water spot reduction composition of the present invention.
Preferred oxygen bleaches for providing a source of available oxygen for use in the present invention include water soluble perc.. .l~! .ds such as alkaline metal perborates, percarbonates, persulfates and perphosphates as well as alkal;ne earth perphosphates, percarbonates and persulfates. Suitable alkali metal perborates include potassium perborate, sodium perborate tetrahydrate, and sodium perborate monohydrate. Most preferred oxygen bleaches for use in the present invention are the sodium perborates and in particular, sodium perborate r~ monohydrate. Other suitable canpounds which provide the necessary source of 1 3343~`9 710.002 available oxygen for use in this invention are hydrogen peroxide and its inorganic adducts which include the aforementioned alkali metal perborates, persulfates and percarbonates. In general, any organic peracid source of available oxygen is suitable for use in the present invention. Cornpatible mixtures of these oxygen bleaches rnay be suitable for use herein. It will also be apparent to those skilled in the art that oxygen bleach activators may be suitable for use in the practice of the present invention.
Suitable proteolytic enzymes for use in the present invention include trypsin, chyrnotrypsin, pepsin, papain, bromelin, carbo~cylase, collagenase, keratinase, elastase, amino peptidase, subtilisin, and aspergillopeptidase. The subtilisin enzymes derived from bacillus subtillis are especially preferred, such as Esperase 4.0T sold by Novo Industries which has a minimum enzyme activity of 4.0 KNPU/g. Proteolytic enzymes suited for use herein are active in a pH range of from about 4 to about 12 at a temperature of frcrn about 50 F to about 200 F.
Although suitable proteolytic enzymes can be obtained from many comnercial sources, trade formulations such as Alcalase, sold by Novo Industries of Copenhagen, Denrnark; Maxatase, sold by Koninklijke Gist-Brocades NV of Delft, Holland; Protease AP, sold by Schweizerische Ferment AG of Basel, Switzerland;
and, Esperase and Savinase, also sold by Novo Industries, are suitable for use in the present invention.
Suitable polyacrylates for use herein include polymers and copolymers of acrylic acid, methacrylic acid, esters o~ these acids or acrylonitrile. Preferred polymers of the above group are sodiurn polyacrylate and sodiurn polyhydroxyacrylate. It is preferred that the polyacrylates used in the present invention have a molecular weight of fr~ about 500 to about 200,000, and rnore preferably from about 1,000 to about 10,000. It is pennissible for use herein to use a mixture of the various preferred polyacrylates as the polyacrylate component of the present composition.
In another embodirnent of the present invention, a rnachine dishwashing *Trademark 1 33~3~
~ ., 710.002 detergent composition is provided which effectively reduces water spot formationover prior art compositions which comprises a phosphate builder, a silicate, a surfactant, an oxygen bleach, a proteolytic enzyme, optionally, a sulfste c~oundJ
and optionally, a carbonate compound. In this embodiment, suitable phosphates include the polyphosphates, specific exarnples of which include sodiurn tripolyphosphate, potassium tripolyphosphate, tetrasodium monol.ydl o~en tripolyphosphate, and trisodium dihydrogen tripolyphosphate. Expecially perferred for use herein is hydrated sodiurn tripolyphosphate. Phosphate builder comprisesfrom about 0% to about 80% by weight and preferably fram about 20% to about 40% by weight of the final composition.
Suitable silicates for use in practice of the present invention include alkali metal silicates such as sodium and potassium silicates. Sodium silicates which have a SiO2 to Na2O ratio of fran .5:1 to 4:1 are preferred for use herein.
Silicates comprise from about 5% to about 40% by weight of the detergent cornposition of the present invention.
Useful surfactants include thosse products formed by condensing one or more alkylene oxides of from 2 to 4 carbon atoms, such as ethylene or propylene oxide, with a reactive hydrophobic compound such as a fatty acid, fatty alcohol, glycol, a sterol, a fatty arnine or a fatty glyceride. Expecially preferred are the low-foaming fatty alcohol ethoxylstes and ethylene oxide/propylene oxide block polyrners. A surfactant comprises from sbout .5% to about 10% by weight of the composition herein.
This embodiment of the invenffon, as stated, may also optionally include inorganic fillers of which the alkali metal sulfates and carbonates are representative. We prefer to use fran about 0% to 50% by weight sodium carbonate and from about 0% to 50% by weight sodium sulfate.
Oxygen bleaches which are suitable for use in this embodiment of the invention include compounds which provide available oxygen in a quantity of from _ 9_ 1 33438~
1~10.002 about .05% by weight to 5% by weight avsilable oxygen, preferably from sbout .1%to sbout 2% svsilsble oxygen by weight and most preferbly, from sbout .25% to sbout 1% by weight svsilsble oxygen. By svailable ox-ygen~ it is meant that the oxygen content is messured by that smount which is available to psrticipate in oxidation reactions. Oxygen blesches preferred for use in this ~.~di,l.e,.t of the invention are wster soluble percornpounds including alksli metsl perborates, percarbonates, persulfates and perphosphates. Also suitsble for use herein sre the alksline esrth metsl perphosphstes, percarbonstes snd persulfstes. Specific alksli metsl perborstes which sre useful for the prsctice of the present invention include cslcium perborste, potsssium perborste, sodium perborste tetrshydrste, bsrium perborste; and sodium perborate monohydrate. Most preferred are the sodium perborates. Also suitable is hydrogen peroxide and its inorgsnic adducts.
Virtually any organic perscid source of svsilable oxygen will work in the ptesent invention.
Proteolytic er ~yllles which can be used in this ~.~i,..~:..t of the invention include those listed previously; that is, trypsin, chyll~tr~sill~ pepsin, papain, bromelin, carboxylsse, collagensse, keratinsse, elsstase, amino peptidsse, subtilisin and aspergillopeptidsse. Especislly preferred are subtilisin enzymes derived from bacillus subtillis. Those proteolytic enzymes which are suitsble for use in this embodiment of the invention are active in a pH range of from 4 to 12 at a temperature of from about 50 to 200. Espersse 4.0T, which has a ~ n~l enzyme sctivity of 4 KNPU/g, which is a trsdensme for a proteolytic enzyme sold by Novo Industries, is parffcularly preferred for use herein. In this ~ d;, ~ ~t of the invention the machine dishwsshing detergent composition contains a quantity of proteolytic enzyme which yields from about 2 KNPU to about 200 KNPU, preferably from about 4 KNPU to about 80 KNPU and most preferably from about 10 KNPU to about 40 KNPU per kilogram of the final composition.
In use, the polyacrylate-based watet spot reduction composition of the present invenffon is added to a typical automatic dishwasher composition cont~inine standard components such as alkalinity builders, surfactsnts, and silicates and ~ fr a~ k -lo-, . . . .
- 1710.002 appro~mately 60 grams of this mixture is placed in an automatic dishwasher alongwith the food soiled dishes. The dishwasher is then run through its wash and rinse cycles during which time the standard machine dishwasher composition and the water spot control composition are dispersed in the wash liquor. The wash liquoris then repeatedly circulated through the spray nozzles whereupon it is brought in contact with soiled dish surfaces. The water temperature may vary but is usuallyin the range of 100 F to 140 F. Typically, automatic dishwashers have two separate receptacles for dishwashing canpositions to be added sequentially during the wash cycles. For exarnple, a model manufactured by the Hobart Corporation, t Kitchen-Aid Energy Saver V Superba, operates with two consecutive wash cycles.
, . .
The first wash cycle lasts for three minutes, forty seconds and the second wash cycle lasts for four minutes, forty-five seconds. Each dishwashing composition receptacle holds approximately 30 grams. The first receptacle dispenses its contents at the beginning of the f irst wash cycle and the second receptacle dispenses its contents at the beginninE of the second wash cycle.
In use, the ernbodiment of the present invention which co"~. u,es a fully-built machine dishwasher detergent composition is placed in the dishwashing composition receptacles inside a machine dishwasher in the manner previously described to be dispensed at the beginning of the first wash cycle and then at the bçginr ing of the second wash cycle. Soiled dishes are of course placed inside the dishwasher and the washing process specified above is co~nen~ ed. For most machine dishwashers, 60 grams of the detergent composition will adequately clean and reduce spotting with a fu~l load of soiled dishes.
Of course, by re",oving the oxygen bleach and proteolytic enzyme fran the ~ ent of this invention which comprises a fully-built machine dishwasher detergent composition, and adding the water spot reduction cnposition to the r~naining composition, a fully-built detergent could be constructed which cont~in~
an oxygen bleach, a proteolytic enzyme and a polyacrylate, so long as the preferred concentrations of all components set forth herein were ob~e.~ed. Such is conternplated to be within the scope of the present invention.
~ rr~ h~
.. . . .. .
~ 334389 All percentages s-tated herein are by weight unless otherwise indicated.
A further understanding of the present invention will be obtained from the ~ollowin8 specific examples which are intended to illustrate the invention but not to limit the scope thereo~, parts and percentage~ being by weight unless otherwise indicated.
In all Or the following examples, the test procedure generally fo]lows that set forth in CSMA, designation DCC-05, published April of 1974. The dishwasher used wa~ a Kitchen-Aid Energy Saver V S~lperba manllfactured by t;he Hobart Corporation.
For each of the examples, the heavy wash cycle was used. This dishwa~her contains two detereent cups which open in two consecutive wash cycles. The first wash cycle lasts for three minutes, ~orty seconds and the second lasts Por four minutes, forty-five seconds. The water temperature was held at 120 F.
The water hardness used in the tests wa~ 18 grains per gallon.
In Examples I-III approximately 30 grams o~ dishwashing composition, including the water spot control composition, was added to each deter8ent cup. That is, a total of 60 grams of detergent composition including the water ~pot control composition was used to wash the test articles. In examples IV-VI, a total of 60 grams of the fully-built automatic dishwashing detergent composition of the present invention was to wash the test articles.
In these examples, the specific proteolytic enzyme used was Esperase 4.0T, manu~actured by Novo Industries of Denmark.
Experase 4.OT has a specified minimum enzyme activity of 4.0 KNPU/g. In these test examples, sodiùm perborate monohydrate was used as the oxygen bleach.
For those examples containing sodium polyacrylate, the sodium polyacrylate used was an approximate 5000 molecular weight sodium polyacry1ate.
*Trademark . 1 334389 1710.002 EXAMPI E I
To a typical machine dishwsshing detergent composition containing sodium tripolyphosphate, a non-ionic surfactant, sodium sulfate, and sodium silicate, there was added a quantity of sodium perborate monohydrate to achieve a final concentration in the mixture of .75% by weight available oxygen, a quantity of sodium polyacrylate to achieve 8 final concentration in the mixture of 2.5% by weight sodium polyacrylate, and a quantity of Esperase 4.0T to achieve a final concentration of .75% Esperase in the mixture. The glassware so washed and dried was then evaluated using the ratings set forth in the aforementioned CSMA
standard; that is, Rating Spotting Glass Spotless 2 Spots at Random 3 One-Follrth of Glass Covered with Spots 4 One-Half of Glass Covered with Spots S Glass Cornpletely Covered with Spots This comparison rating was ernployed for all of the examples. The glassware was examined, the rating for each piece of glassware tabulated and the results averAged. The average glassware spotting of glassware washed with this forrnation was 1.125.
EXAMPLE II
In accordance with the procedure set forth in the introduction to these examples, detergent fonnulation of sodium tripolyphosphate he~cahydrate, non-ioT~ic surfactant, sodium sulfate, and sodium silicate was combined with quantities of sodiurn perborate, sodiurn polyaceylate, and Esperase 4.0T such that the final concertration of available oxygen was .375%, by weight. The final concentration of sodium polyacrylate was 5.096 by weight and the final concentration of Experase was 1.125% by weight.
*Tra dema rk ç~ ;
1 33438q 1710.002 The glassware so washed and dried was observed and rated in accordance with the aforementioned spotting scale. The glassware was dete~nined to have an average spotting rating of 1Ø
EXAMPLE III
In this exarnple, the standard machine dish~...sl,ing detergent set forth in the previous example was cornbined with sodiurn perborate, sodium polyacrylate and esperase 4.0T to achieve final concentrations of .375% by weight available oxygen, t`,q ~
2.5% by weight sodium polyacrytate and a final concentration of Esperase 4.0T of 1.125% by weight.
After the glassware was washed and dired in accordance with the CSMA
Test Standard, the glasware was inspected and found to have an average glassware spotting of lØ
EXAMPLE IV
In this example, the autornatic dishwashing canposition of the present invention was prepared as follows:
Ingredient % by Weight Sodium Tripolyphosphate Hexahydrate 76.76 Sodium Metasilicate Pentahydrate 19.9 Non-ionic Surfactant 1.3 Sodium P~rborate Monohyd~dte 1.79 Esperase 4.0T .25 The canposition was used to wash glassware in accordance with the aforementioned standard and the glassware so washed was found to have an average glassware spotting of 1.24.
~rcec~ ar7 .~
1 33~
1710.002 EXAMPLE V
In this example, the automatic dishwashing canposition of the present invention was prepared as follows:
Ingredient % by welght Sodium Tripolyphosphate Hexahydrate 74.55 Sodium Metasilicate Pentahydrate 19.9 Non-ionic Surfactant 1.3 Sodium P~rborate Monohydrate 3.75 . ~, ~' Esperase''4.0T .5 The composition was used to wash glassware in accordance with the aforementioned standard and the glassware so washed was found to have an average glassware spotting of 1.07.
FIELD OF THE INVENTION
The present invention relstes generally to cornpositions for use in machine dishwashers to facilitate the cleaning of dishes and the like. More particularly, the present invention relates to compositios which reduce water spot forrnation on articles cleaned in machine dishwashers.
BACKGROUND OF THE INVENTION
Machine dishwashers ~re widely used to clean soiled dishes, cooking utensils and other containers for serving and preparing food, such as plates, cups, glasses, silverware, pots, pans, etc., generically referred to as "dishes". While the construction and cornposition of these items vary widely, st usually have glossy, solid surfaces on which the presence of dried water spots is readily noticeable. These dried water spots are aesthetically unappealing and thus methods and compositions for reducing their number and size are of great concern to the detergent industry as well as to the consumer.
Typical machine dishwashers operate by subjecting food soiled dishes and the like to alternating wash and rinse cycles inside a closed washing chamber. Spray nozzles inside the charnber direct powerful streams of hot wash liquor and rinse water onto to the soiled dish surfaces. A consideraMe amount of food residue is thereby removed by the force exerted by these pressurized water streams. There is, however, a substantial amount of food residue which resists dislodgement by the water jets. It is known that by adding certain detergent compositions to the wash water, a much greater quantity of food soil can be removed from soiled article surfaces during the washing cycle. These machine or "automatic" dishwasher detergent compositions as they are known dramatically increase the ~le~ning efficiency of machine ~ hers primarily by alkaline ~ - - 1 334389 710.002 cleaning action and through the emulsification and dispersion of food residue which otherwise clings to dish surfacbs despite the action of wash water jets.
While food soils vary greatly in composition, generally food residue which remains on dish surfaces contains an organic component which often includes a mixture of various proteins. Since the make-up of typical food residue is known, detergent compositions are formulated such that their various c~onentC
are effective in breaking down food soils during the wash cycle of autanatic dishwashers. The emulsification of food soil is most often achieved through the use of surface active agents or "surfactantsn, as they are known. Surfactants not only help remove food residue by emulsification, they also provide cleaning power through wetting, foaming, dispersing and penetrating actions. It will be recognized by those skilled in the art that there are many dif ferent types of surfactants suitable for use in automatic dishwasher detergents and that low foaming, non-ionic surfactants are especially suited for use in these compositions. For example, low-foaming, fatty alcohol ethoxylates and ethylene oxide/propylene oxide block polymers are widely used` in the manufacture of machine dishwashing detergents.
Automatic dishwashing detergents also contain detergent builders such as complex phosphates, carbonates, sulfates and silicates which compliment the detersive action of sufactants. For example, by sequestering certain metallic ions which are present in most water sources, phosphates reduce hard water film formation caused by the deposition of metallic precipitates. Moreover, alkalinity builders provide alkaline cleaning power which is particularly important in automatic di~h..~shing compositions since, by its very nature, automatic di~l,..~shing does not provide the mechanical action of hand di~ hi~ Since physical contact with the wash liquor by the consumer does not occur when dishes are cleaned in a machine di~l,..~l.er, allcalinity builders are especially suitable for use in automatic ~h..~hing detergents.
Bleaches can be used in connection with these other du,h. ~hine detergent composition components to remove food residue by breaking down the 710.002 food residue to simpler components. However, the cleaning action of bleaches differs somewhst from most other dishwashing canposition com~onents in that bleaches clean by breaking chernical bonds within molecules rather than the physical bonds which exist between molecules. Although some bleaches are reducing agents, typical bleaches employed in dishwashing compositions are oxidizing agents. Basically, oxidizing bleaches cause the oxidation of chemical bonds, thereby reducing large molecules to smaller units. The smaller units can then be more easily removed during the dishwashing process. The most widely usedoxidizing bleaches, particularly in dishwashing compositions, are dry chlorine bleaches. Many cornpositions use such hypochlorite generators as sodium dichloroisocyanurate and chlorinated trisodium phosphate. Chlorine bleaches are strong oxidizing agents but their usefulness is limited by their tendency to cause unwanted oxidation of other wash cornpound components and by their brief shelf life. Chlorine bleaches are such strong oxidizing agents that great care must betaken to ensure that the other cornponents with which they are mixed are not adversely affected during storage and, moreover, during use. Due to these and other drawbacks inherent in the use of chlorine bleaches in dishwashing compositions, many formulators have instead proposed that oxygen bleaches be used as the principal oxidizing agent in dishwashing compositions. Oxygen bleaches not only possess greater potential cnpatibility with other d~. ~hir~
composition components, they exhibit much greater stability during storage. While the most frequent oxygen bleach proposed for use is sodium perborate, the use ofmany inorganic peroxides, such as sodium percarbonate, potassium nopersulfate, and hydrogen peroxide has also been proposed.
It is evident then that the process by which food residue is r~ ,ed from dish surfaces is the result of various physical and chemical interactions which take place during the washing and rinsing cycles inside the wash chamber. It is theorized that food particles which remain on dish surfaces after final rinse promote water droplet formation and, ultimately, form tro~hl~ dried water spots. These minute food particles serve to anchor droplets of water which would otherwise sheet off of dish surfaces. In particular it is thought that bits of 1 33438~
protein residue have a tendency to adhere to article surfaces such that water droplets ~ccum~ te around the particles. It follows that it is these protein-anchored water droplets which dry into unsightly water spots. It will be apparent to those skilled in the art that a droplet of water contains a number of minerals and other substances which, when the water evaporates, leaves a residue corresponding roughly in size and shape to the original water droplet. This dried residue causes light to diffract at the water spot in a manner different from that of the surrounding area, thus making the spot visible. It would according to theory, then, seem highly desirable to eliminate as many of these particulate protein masses as possible in order to reduce water droplet accum~ tions which are believed to be the source of unwanted water spotting of dishes and the like.
It is known in the art that certain proteolytic enzymes are capable of reducing the amount of particulate protein soil on dish surfaces during machine dishwashing operations. In particular, proteases are effective in the removal of protein food soil by virtue of their ability to catalyze the hydrolysis of protein peptide linkages. Proteins, which are very high molecular weight compounds, are thereby converted into smaller peptide units which are more easily removed from article surfaces during the cleaning process. Automatic dishwashing compositions have thus been formlll~tl~d in the past which contain proteases. Due to a long-held belief in the industry, however, that proteolytic enzymes are incompatible with bleaches in solution, these prior art attempts to utilize proteolytic enzymes in the breakdown of protein soil have generally not included the addition of a bleaching agent in the final composition. Thus, these known compositions have achieved no net reduction of water spotting. Any benefit produced by the protease is negated by the lack of bleach cleansing power in the composition.
Proteolytic enzymes are themselves proteinaceous molecules.
Therefore, it has been generally held that when these enzymes are brought in contact with bleach, the enzymes are oxidized into simpler components, thus losing 1 33~3~
their ability to catalyze the breakdown of peptide bonds. That is, it has been thought that unless the proteolytic enzymes are protected somehow from oxidation by the bleach, they are unable to perform their catalytic function. This widely-held belief has resulted in numerous attempts to isolate bleaches from proteases both during storage of compositions containing both of these ingredients as well as during the wash cycle. For example, attempts have been made to microencapsulate bleach to delay its nxi~li7.ing action in the wash liquor until after the proteolytic enzymes have had an opportunity to catalytically break down protein soils.
I have discovered that despite the teachings of the prior art that bleaches and proteolytic enzymes are essenti~lly incompatible, a mixture coll~il~illg an oxygen bleach, a protease and a polyacrylate provides excellent reduction of water droplet formation on washed articles and thus prevents unwanted water spotting during the automatic dishwashing operation. Rather than producing an antagonistic reaction, I have observed that by combining an oxygen bleach, a protease and a polyacrylate along with standard detergent components, an unexpected synergistic action is produced which yields a high degree of water spot prevention. Also, I have discovered an automatic dishwashing detergent composition which contains both an oxygen bleach and a proteolytic enzyme that produces good water spot reduction when used in machine dishwashers.
SUMMARY OF THE INVENTION
In accordance with the present invention, a water spot reduction composition is provided which contains an oxygen bleach, a proteolytic enzyme, and a polyacrylate which, when used in combination with standard machine dishwashing detergent components such as phosphates, silicates and surfactants, reduces water spotting on washed article surfaces. A fully-built machine dishwasher detergent composition which contains both an oxygen bleach and a proteolytic en_yme is also disclosed that reduces the formation of water spots on article surfaces during the automatic dishwashing process.
" .~
. ~, -5-1710.002 It is therefore a primary object of the present invention to provide compositions which, when used in an automatic dishwasher, reduce the formation of water spots on dish surfaces and the like.
DETAILED DESCRIPTION OF THE IN~'ENTION
In accordance with the present invention, a water spot reduction composition is provided for use in a machine dishwasher which, when mixed with conventional automatic dishwasher components such as phosphates, silicates, surfactants and inorganic fillers to formulate an autornatic dishwasher detergent composition, reduces the presence of water spots on glassware during the machine dishwashing process. The water spot reduction composition comprises an oxygen bleach, a proteolytic enzyme and a polyacrylate. In the final autamatic dishwasher formulation, that is, when the water spot reduction composition is cornbined with phosphate builders, silicates, surfactants and the like to produce a fully built automatic dishwasher detergent composition, the oxygen bleach component of the present invention comprises from about .05% to 5% by weight, preferably from about .1% to 2% by weight, and most preferably fram about .25% to 1.0% by weight of available oxygen in the final built detergent.
By available oxygen, it is meant that the compound which is used as a source of oxygen in the present invention provides a certain amount of oxygen which is available to participate in oxidation reactions. It will be known to those skilled in the art that preferred sources of oxygen disclosed herein are typically sold with reference to their available oxygen content.
It will be known to those skilled in the art, that enzymes and in particular, proteolytic c.~y~es are sold with reference to their enzyme activity which is stated in various units depen~line on the individual manufacturer. I prefer to state my preferred concentration ranges of proteolytic enzyrne with reference to KNPU/g which is the enzyme activity expression used by Novo Industries of .. . .. .
~-- 1 3343~
1710.002 Copenhagen, Denmark. 1 KNPU is the amount of enzyme which hydrolyzes casein at standard reaction conditions at an initial rate such that colorimetric change of reaction with 2,4,6 - Trinitrobenzene-l-sulfonic acid corresponds to 1 millimol per glycine per minute. Standard reaction conditions are .05 Harnnerstein cssein, .05 molar borate buffer, P.H.9, 50 C with a reaction time of 20 minutes. In the final automatic dishwasher formulation, that is, when the water spot reduction composition of the present invention is combined with phosphate builders, silicates, surfactants and the like to produce a fully built automatic dishwasher detergent composition, the proteolytic enzyme component of the present invention provides from about 2 to 200 KNPU, preferably from 4 to 80 KNPU and most preferably from 10 to 40 KNPU per kilogram of the final built detergent.
The polyacrylate component of the present invention c~..y. ;ses from about .1% to 2096 by weight, and preferably frorn 1% to 10% by weight of the final built detergent composition. In other words, the water spot reduction composition of the present invention is comprised of an oxygen bleach as a source of available oxygen, a proteolytic enzyme which provides enzymatic activity and a polyacrylate.
Each of these three components are present in the water spot reduction composition in relative quantities which produce, respectively, available oxygen, enxyrnatic activity and polyacrylate in the percentage by weight ranges given with respect to the total weight of the final built detergent composition which includes phosphate builders, silicates, surfactants and the water spot reduction composition of the present invention.
Preferred oxygen bleaches for providing a source of available oxygen for use in the present invention include water soluble perc.. .l~! .ds such as alkaline metal perborates, percarbonates, persulfates and perphosphates as well as alkal;ne earth perphosphates, percarbonates and persulfates. Suitable alkali metal perborates include potassium perborate, sodium perborate tetrahydrate, and sodium perborate monohydrate. Most preferred oxygen bleaches for use in the present invention are the sodium perborates and in particular, sodium perborate r~ monohydrate. Other suitable canpounds which provide the necessary source of 1 3343~`9 710.002 available oxygen for use in this invention are hydrogen peroxide and its inorganic adducts which include the aforementioned alkali metal perborates, persulfates and percarbonates. In general, any organic peracid source of available oxygen is suitable for use in the present invention. Cornpatible mixtures of these oxygen bleaches rnay be suitable for use herein. It will also be apparent to those skilled in the art that oxygen bleach activators may be suitable for use in the practice of the present invention.
Suitable proteolytic enzymes for use in the present invention include trypsin, chyrnotrypsin, pepsin, papain, bromelin, carbo~cylase, collagenase, keratinase, elastase, amino peptidase, subtilisin, and aspergillopeptidase. The subtilisin enzymes derived from bacillus subtillis are especially preferred, such as Esperase 4.0T sold by Novo Industries which has a minimum enzyme activity of 4.0 KNPU/g. Proteolytic enzymes suited for use herein are active in a pH range of from about 4 to about 12 at a temperature of frcrn about 50 F to about 200 F.
Although suitable proteolytic enzymes can be obtained from many comnercial sources, trade formulations such as Alcalase, sold by Novo Industries of Copenhagen, Denrnark; Maxatase, sold by Koninklijke Gist-Brocades NV of Delft, Holland; Protease AP, sold by Schweizerische Ferment AG of Basel, Switzerland;
and, Esperase and Savinase, also sold by Novo Industries, are suitable for use in the present invention.
Suitable polyacrylates for use herein include polymers and copolymers of acrylic acid, methacrylic acid, esters o~ these acids or acrylonitrile. Preferred polymers of the above group are sodiurn polyacrylate and sodiurn polyhydroxyacrylate. It is preferred that the polyacrylates used in the present invention have a molecular weight of fr~ about 500 to about 200,000, and rnore preferably from about 1,000 to about 10,000. It is pennissible for use herein to use a mixture of the various preferred polyacrylates as the polyacrylate component of the present composition.
In another embodirnent of the present invention, a rnachine dishwashing *Trademark 1 33~3~
~ ., 710.002 detergent composition is provided which effectively reduces water spot formationover prior art compositions which comprises a phosphate builder, a silicate, a surfactant, an oxygen bleach, a proteolytic enzyme, optionally, a sulfste c~oundJ
and optionally, a carbonate compound. In this embodiment, suitable phosphates include the polyphosphates, specific exarnples of which include sodiurn tripolyphosphate, potassium tripolyphosphate, tetrasodium monol.ydl o~en tripolyphosphate, and trisodium dihydrogen tripolyphosphate. Expecially perferred for use herein is hydrated sodiurn tripolyphosphate. Phosphate builder comprisesfrom about 0% to about 80% by weight and preferably fram about 20% to about 40% by weight of the final composition.
Suitable silicates for use in practice of the present invention include alkali metal silicates such as sodium and potassium silicates. Sodium silicates which have a SiO2 to Na2O ratio of fran .5:1 to 4:1 are preferred for use herein.
Silicates comprise from about 5% to about 40% by weight of the detergent cornposition of the present invention.
Useful surfactants include thosse products formed by condensing one or more alkylene oxides of from 2 to 4 carbon atoms, such as ethylene or propylene oxide, with a reactive hydrophobic compound such as a fatty acid, fatty alcohol, glycol, a sterol, a fatty arnine or a fatty glyceride. Expecially preferred are the low-foaming fatty alcohol ethoxylstes and ethylene oxide/propylene oxide block polyrners. A surfactant comprises from sbout .5% to about 10% by weight of the composition herein.
This embodiment of the invenffon, as stated, may also optionally include inorganic fillers of which the alkali metal sulfates and carbonates are representative. We prefer to use fran about 0% to 50% by weight sodium carbonate and from about 0% to 50% by weight sodium sulfate.
Oxygen bleaches which are suitable for use in this embodiment of the invention include compounds which provide available oxygen in a quantity of from _ 9_ 1 33438~
1~10.002 about .05% by weight to 5% by weight avsilable oxygen, preferably from sbout .1%to sbout 2% svsilsble oxygen by weight and most preferbly, from sbout .25% to sbout 1% by weight svsilsble oxygen. By svailable ox-ygen~ it is meant that the oxygen content is messured by that smount which is available to psrticipate in oxidation reactions. Oxygen blesches preferred for use in this ~.~di,l.e,.t of the invention are wster soluble percornpounds including alksli metsl perborates, percarbonates, persulfates and perphosphates. Also suitsble for use herein sre the alksline esrth metsl perphosphstes, percarbonstes snd persulfstes. Specific alksli metsl perborstes which sre useful for the prsctice of the present invention include cslcium perborste, potsssium perborste, sodium perborste tetrshydrste, bsrium perborste; and sodium perborate monohydrate. Most preferred are the sodium perborates. Also suitable is hydrogen peroxide and its inorgsnic adducts.
Virtually any organic perscid source of svsilable oxygen will work in the ptesent invention.
Proteolytic er ~yllles which can be used in this ~.~i,..~:..t of the invention include those listed previously; that is, trypsin, chyll~tr~sill~ pepsin, papain, bromelin, carboxylsse, collagensse, keratinsse, elsstase, amino peptidsse, subtilisin and aspergillopeptidsse. Especislly preferred are subtilisin enzymes derived from bacillus subtillis. Those proteolytic enzymes which are suitsble for use in this embodiment of the invention are active in a pH range of from 4 to 12 at a temperature of from about 50 to 200. Espersse 4.0T, which has a ~ n~l enzyme sctivity of 4 KNPU/g, which is a trsdensme for a proteolytic enzyme sold by Novo Industries, is parffcularly preferred for use herein. In this ~ d;, ~ ~t of the invention the machine dishwsshing detergent composition contains a quantity of proteolytic enzyme which yields from about 2 KNPU to about 200 KNPU, preferably from about 4 KNPU to about 80 KNPU and most preferably from about 10 KNPU to about 40 KNPU per kilogram of the final composition.
In use, the polyacrylate-based watet spot reduction composition of the present invenffon is added to a typical automatic dishwasher composition cont~inine standard components such as alkalinity builders, surfactsnts, and silicates and ~ fr a~ k -lo-, . . . .
- 1710.002 appro~mately 60 grams of this mixture is placed in an automatic dishwasher alongwith the food soiled dishes. The dishwasher is then run through its wash and rinse cycles during which time the standard machine dishwasher composition and the water spot control composition are dispersed in the wash liquor. The wash liquoris then repeatedly circulated through the spray nozzles whereupon it is brought in contact with soiled dish surfaces. The water temperature may vary but is usuallyin the range of 100 F to 140 F. Typically, automatic dishwashers have two separate receptacles for dishwashing canpositions to be added sequentially during the wash cycles. For exarnple, a model manufactured by the Hobart Corporation, t Kitchen-Aid Energy Saver V Superba, operates with two consecutive wash cycles.
, . .
The first wash cycle lasts for three minutes, forty seconds and the second wash cycle lasts for four minutes, forty-five seconds. Each dishwashing composition receptacle holds approximately 30 grams. The first receptacle dispenses its contents at the beginning of the f irst wash cycle and the second receptacle dispenses its contents at the beginninE of the second wash cycle.
In use, the ernbodiment of the present invention which co"~. u,es a fully-built machine dishwasher detergent composition is placed in the dishwashing composition receptacles inside a machine dishwasher in the manner previously described to be dispensed at the beginning of the first wash cycle and then at the bçginr ing of the second wash cycle. Soiled dishes are of course placed inside the dishwasher and the washing process specified above is co~nen~ ed. For most machine dishwashers, 60 grams of the detergent composition will adequately clean and reduce spotting with a fu~l load of soiled dishes.
Of course, by re",oving the oxygen bleach and proteolytic enzyme fran the ~ ent of this invention which comprises a fully-built machine dishwasher detergent composition, and adding the water spot reduction cnposition to the r~naining composition, a fully-built detergent could be constructed which cont~in~
an oxygen bleach, a proteolytic enzyme and a polyacrylate, so long as the preferred concentrations of all components set forth herein were ob~e.~ed. Such is conternplated to be within the scope of the present invention.
~ rr~ h~
.. . . .. .
~ 334389 All percentages s-tated herein are by weight unless otherwise indicated.
A further understanding of the present invention will be obtained from the ~ollowin8 specific examples which are intended to illustrate the invention but not to limit the scope thereo~, parts and percentage~ being by weight unless otherwise indicated.
In all Or the following examples, the test procedure generally fo]lows that set forth in CSMA, designation DCC-05, published April of 1974. The dishwasher used wa~ a Kitchen-Aid Energy Saver V S~lperba manllfactured by t;he Hobart Corporation.
For each of the examples, the heavy wash cycle was used. This dishwa~her contains two detereent cups which open in two consecutive wash cycles. The first wash cycle lasts for three minutes, ~orty seconds and the second lasts Por four minutes, forty-five seconds. The water temperature was held at 120 F.
The water hardness used in the tests wa~ 18 grains per gallon.
In Examples I-III approximately 30 grams o~ dishwashing composition, including the water spot control composition, was added to each deter8ent cup. That is, a total of 60 grams of detergent composition including the water ~pot control composition was used to wash the test articles. In examples IV-VI, a total of 60 grams of the fully-built automatic dishwashing detergent composition of the present invention was to wash the test articles.
In these examples, the specific proteolytic enzyme used was Esperase 4.0T, manu~actured by Novo Industries of Denmark.
Experase 4.OT has a specified minimum enzyme activity of 4.0 KNPU/g. In these test examples, sodiùm perborate monohydrate was used as the oxygen bleach.
For those examples containing sodium polyacrylate, the sodium polyacrylate used was an approximate 5000 molecular weight sodium polyacry1ate.
*Trademark . 1 334389 1710.002 EXAMPI E I
To a typical machine dishwsshing detergent composition containing sodium tripolyphosphate, a non-ionic surfactant, sodium sulfate, and sodium silicate, there was added a quantity of sodium perborate monohydrate to achieve a final concentration in the mixture of .75% by weight available oxygen, a quantity of sodium polyacrylate to achieve 8 final concentration in the mixture of 2.5% by weight sodium polyacrylate, and a quantity of Esperase 4.0T to achieve a final concentration of .75% Esperase in the mixture. The glassware so washed and dried was then evaluated using the ratings set forth in the aforementioned CSMA
standard; that is, Rating Spotting Glass Spotless 2 Spots at Random 3 One-Follrth of Glass Covered with Spots 4 One-Half of Glass Covered with Spots S Glass Cornpletely Covered with Spots This comparison rating was ernployed for all of the examples. The glassware was examined, the rating for each piece of glassware tabulated and the results averAged. The average glassware spotting of glassware washed with this forrnation was 1.125.
EXAMPLE II
In accordance with the procedure set forth in the introduction to these examples, detergent fonnulation of sodium tripolyphosphate he~cahydrate, non-ioT~ic surfactant, sodium sulfate, and sodium silicate was combined with quantities of sodiurn perborate, sodiurn polyaceylate, and Esperase 4.0T such that the final concertration of available oxygen was .375%, by weight. The final concentration of sodium polyacrylate was 5.096 by weight and the final concentration of Experase was 1.125% by weight.
*Tra dema rk ç~ ;
1 33438q 1710.002 The glassware so washed and dried was observed and rated in accordance with the aforementioned spotting scale. The glassware was dete~nined to have an average spotting rating of 1Ø
EXAMPLE III
In this exarnple, the standard machine dish~...sl,ing detergent set forth in the previous example was cornbined with sodiurn perborate, sodium polyacrylate and esperase 4.0T to achieve final concentrations of .375% by weight available oxygen, t`,q ~
2.5% by weight sodium polyacrytate and a final concentration of Esperase 4.0T of 1.125% by weight.
After the glassware was washed and dired in accordance with the CSMA
Test Standard, the glasware was inspected and found to have an average glassware spotting of lØ
EXAMPLE IV
In this example, the autornatic dishwashing canposition of the present invention was prepared as follows:
Ingredient % by Weight Sodium Tripolyphosphate Hexahydrate 76.76 Sodium Metasilicate Pentahydrate 19.9 Non-ionic Surfactant 1.3 Sodium P~rborate Monohyd~dte 1.79 Esperase 4.0T .25 The canposition was used to wash glassware in accordance with the aforementioned standard and the glassware so washed was found to have an average glassware spotting of 1.24.
~rcec~ ar7 .~
1 33~
1710.002 EXAMPLE V
In this example, the automatic dishwashing canposition of the present invention was prepared as follows:
Ingredient % by welght Sodium Tripolyphosphate Hexahydrate 74.55 Sodium Metasilicate Pentahydrate 19.9 Non-ionic Surfactant 1.3 Sodium P~rborate Monohydrate 3.75 . ~, ~' Esperase''4.0T .5 The composition was used to wash glassware in accordance with the aforementioned standard and the glassware so washed was found to have an average glassware spotting of 1.07.
Claims (5)
-
-
- What Is Claimed Is:
- An automatic dishwasher detergent composition comprising: from about 20 to about 80 percent by weight of a phosphate builder, based on anhydrous phosphate weight; from about .5 to about 10 percent by weight surfactant; from about
- 5 to about 40 percent by weight alkali metal silicate; a quantity of an oxygen bleach sufficient to provide from about .05 to about 5 percent by weight available oxygen; a quantity of proteolytic enzyme sufficient to provide from about 2 to about 200 KNPU
per kilogram of said detergent composition; and from about .1 to about 20 percent by weight polyacrylate; but excluding layered clay.
The detergent composition of claim 1 comprising: from about 20 to about 40 percent by weight of said phosphate builder; a quantity of said oxygen bleach sufficient to provide from about .1 to about 2 percent by weight available oxygen; a sufficient amount of said enzyme to provide from about 4 to about 80 KNPU per kilogram of said detergent composition; and from about 1 to about 10 percent by weight of said polyacrylate.
The detergent composition of claim 2 comprising: a sufficient quantity of said oxygen bleach to provide from about .25 to about 1 percent by weight available oxygen; a sufficient amount of said enzyme to provide from about 10 to about 40 KNPU per kilogram of said detergent composition; and from about 2.5 to about 5 percent by weight of said polyacrylate.
The detergent composition of claim 3 in which said polyacrylate has a molecular weight of from about 500 to about 200,000.
The detergent composition of claim 4 in which said polyacrylate has a molecular weight of from about 1,000 to about 10,000.
The detergent composition of claim 5 wherein said phosphate compound is a polyphosphate.
The detergent composition of claim 6 which additionally includes a filler.
The detergent composition of claim 7 in which said filler comprises sodium sulfate.
The detergent composition of claim 7 in which said filler comprises sodium carbonate.
The detergent composition of claim 2 in which said polyacrylate has a molecular weight of from about 1,000 to about 10,000.
The automatic dishwashing composition of claim 10 wherein said phosphate compound is a polyphosphate.
The detergent composition of claim 11 which additionally includes a filler.
The detergent composition of claim 1 in which said polyacrylate has a molecular weight of from about 1,000 to about 10,000.
The automatic dishwashing composition of claim 13 wherein said phosphate compound is a polyphosphate.
The detergent composition of claim 14 which additionally includes a filler.
The detergent composition of claim 1 which additionally includes a filler.
The detergent composition recited in claim 1 wherein said oxygen bleach is a water-soluble inorganic percompound selected from the group consisting of alkali and alkaline earth metal perborates, percarbonates, perphosphates and persulfates.
The detergent composition recited in claim 1 wherein said proteolytic enzyme is selected from the group consisting of trypsin, chymotrypsin, pepsin, papain, bromelin, carboxylase, collagenase, keratinase, elastase, amino peptidease, subtilisin and aspergillopeptidease.
The detergent composition recited in claim 1 wherein said polyacrylate has a molecular weight of from 500 to 200,000.
The detergent composition recited in claim 19 wherein said polyacrylate is selected from the group consisting of polymers and copolymers of acrylic acid, methacrylic acid, esters of these acids and acrylonitrile.
The automatic dishwashing composition of claim 1 wherein said phosphate compound is a polyphosphate.
The automatic dishwashing composition of claim 1 wherein said surfactant is selected from the group consisting of low-foaming fatty alcohol ethoxylates and ethylene oxide/propylene oxide block polymers.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US84440486A | 1986-03-26 | 1986-03-26 | |
| US844,404 | 1986-03-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1334389C true CA1334389C (en) | 1995-02-14 |
Family
ID=25292643
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 530579 Expired - Fee Related CA1334389C (en) | 1986-03-26 | 1987-02-25 | Machine dishwasher water spot control composition |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0239379A3 (en) |
| JP (2) | JP2531518B2 (en) |
| AU (1) | AU6966887A (en) |
| CA (1) | CA1334389C (en) |
| NZ (1) | NZ219637A (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4988452A (en) * | 1988-06-09 | 1991-01-29 | The Procter & Gamble Company | Liquid automatic dishwashing detergent compositions containing bleach-stable nonionic surfactant |
| US4859358A (en) * | 1988-06-09 | 1989-08-22 | The Procter & Gamble Company | Liquid automatic dishwashing compositions containing metal salts of hydroxy fatty acids providing silver protection |
| GB2219596A (en) * | 1988-06-09 | 1989-12-13 | Procter & Gamble | Liquid automatic dishwashing compositions having enhanced stability |
| GB8922179D0 (en) * | 1989-10-02 | 1989-11-15 | Rohm & Haas | Polymer-containing granulates |
| HUT64391A (en) * | 1990-11-14 | 1993-12-28 | Procter & Gamble | Nonphosphated dishwashing compositions with oxygen belach systems and method for producing them |
| DE4114956A1 (en) * | 1991-05-02 | 1992-11-05 | Dispo Kommerz Ag Huenenberg | GRANULAR PHOSPHATE-FREE AGENT FOR MACHINE DISHWASHER |
| US5213706A (en) * | 1991-11-08 | 1993-05-25 | Lever Brothers Company, Division Of Conopco, Inc. | Homogeneous detergent gel compositions for use in automatic dishwashers |
| EP0560519B1 (en) * | 1992-03-10 | 1998-08-05 | Rohm And Haas Company | Use of water-soluble polymers in cleaning compositions, and water-soluble polymers for such use |
| US5559089A (en) * | 1992-03-12 | 1996-09-24 | The Procter & Gamble Company | Low-dosage automatic dishwashing detergent with monopersulfate and enzymes |
| EP0630400A1 (en) * | 1992-03-12 | 1994-12-28 | The Procter & Gamble Company | Low-dosage automatic dishwashing detergent with monopersulfate and enzymes |
| WO1994025557A1 (en) * | 1993-04-27 | 1994-11-10 | The Procter & Gamble Company | Liquid or granular automatic dishwashing detergent compositions |
| WO1994025556A1 (en) * | 1993-04-27 | 1994-11-10 | The Procter & Gamble Company | Liquid or granular automatic dishwashing detergent compositions |
| EP0717102A1 (en) | 1994-12-09 | 1996-06-19 | The Procter & Gamble Company | Liquid automatic dishwashing detergent composition containing diacyl peroxides |
| PT796317E (en) * | 1994-12-09 | 2000-08-31 | Procter & Gamble | COMPOSITION FOR AUTOMATIC WASHING OF LOICA CONTAINING PARTICLES OF PEROXIDES OF DIACYL |
| AU713659B2 (en) * | 1995-04-17 | 1999-12-09 | Procter & Gamble Company, The | Preparation and use of composite particles containing diacyl peroxide |
| US5663133A (en) * | 1995-11-06 | 1997-09-02 | The Procter & Gamble Company | Process for making automatic dishwashing composition containing diacyl peroxide |
| WO1998003624A2 (en) | 1996-07-24 | 1998-01-29 | The Procter & Gamble Company | Sprayable, liquid or gel detergent compositions containing bleach |
| DE19730650C2 (en) * | 1997-07-17 | 1999-12-02 | Henkel Kgaa | Process for avoiding the deposition of heavy metal ions on textile fibers |
| DE102008038479A1 (en) * | 2008-08-20 | 2010-02-25 | Henkel Ag & Co. Kgaa | Detergents or cleaners with increased detergency |
| AU2010247013B2 (en) | 2009-05-12 | 2015-02-26 | Ecolab Usa Inc. | Fast drying and fast draining rinse aid |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3579455A (en) * | 1968-08-02 | 1971-05-18 | Grace W R & Co | Machine dishwashing compositions containing sodium polyacrylate |
| DE1906705A1 (en) * | 1969-02-11 | 1970-08-13 | Knapsack Ag | Process for the production of enzyme and perborate detergents |
| SU889689A1 (en) * | 1979-09-05 | 1981-12-15 | Всесоюзный научно-исследовательский и проектный институт химической промышленности | Detergent for laundering |
| CH651314A5 (en) * | 1981-12-23 | 1985-09-13 | Colgate Palmolive Co | DETERGENT COMPOSITION FOR DISHWASHER. |
| US4427417A (en) * | 1982-01-20 | 1984-01-24 | The Korex Company | Process for preparing detergent compositions containing hydrated inorganic salts |
| JPS6060199A (en) * | 1983-08-15 | 1985-04-06 | ユニリーバー ナームローゼ ベンノートシヤープ | Enzym-containing detergent composition for dish washer |
| GB8321923D0 (en) * | 1983-08-15 | 1983-09-14 | Unilever Plc | Machine-dishwashing compositions |
| JPS6060198A (en) * | 1983-08-15 | 1985-04-06 | ユニリーバー ナームローゼ ベンノートシヤープ | Detergent composition for dish washer |
| GB8328075D0 (en) * | 1983-10-20 | 1983-11-23 | Unilever Plc | Dishwashing compositions |
| DE3428834A1 (en) * | 1984-08-04 | 1986-02-13 | Henkel KGaA, 4000 Düsseldorf | DISHWASHER |
| JPS6169897A (en) * | 1984-09-14 | 1986-04-10 | 花王株式会社 | Production of high density detergent improved in flowability |
| JPS62253697A (en) * | 1986-04-02 | 1987-11-05 | 花王株式会社 | Bleaching composition |
-
1987
- 1987-02-25 CA CA 530579 patent/CA1334389C/en not_active Expired - Fee Related
- 1987-03-04 AU AU69668/87A patent/AU6966887A/en not_active Abandoned
- 1987-03-16 NZ NZ21963787A patent/NZ219637A/en unknown
- 1987-03-25 EP EP87302562A patent/EP0239379A3/en not_active Withdrawn
- 1987-03-26 JP JP62072942A patent/JP2531518B2/en not_active Expired - Lifetime
-
1995
- 1995-10-19 JP JP30633395A patent/JPH09111294A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| NZ219637A (en) | 1989-09-27 |
| AU6966887A (en) | 1987-10-01 |
| EP0239379A3 (en) | 1989-05-24 |
| EP0239379A2 (en) | 1987-09-30 |
| JPS62236899A (en) | 1987-10-16 |
| JP2531518B2 (en) | 1996-09-04 |
| JPH09111294A (en) | 1997-04-28 |
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| Date | Code | Title | Description |
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