Spinning preparations in the form of aqueous emulsions or aqueous solutions containing polymersSpinning preparations in the form of aqueous emulsions or aqueous solutions containing polymers هایلایت شده
Ulrich 45) Feb. 14, 1984 54 DISHWASHING COMPOST ON AND 4,115,308 9/1978 Guerry ................................ 252/135 METHOD Primary Examiner-P. E. Willis, Jr. (75) Inventor: Robert J. Ulrich, Taylors, S.C. Assistant Examiner-Robert A. Wax Attorney, Agent, or Firm-Bailey & Hardaway 73 Assignee: Texize, Division of MortonThiokol, Greenville, S.C. 57 ABSTRACT (21) Appl. No.: 309,016 Disclosed is a thixotropic automatic dishwasher compo 22) Filed: Oct. 6, 1981 sition having an aqueous solvent, a thickening agent, a source of chlorine, detergency levels of an anionic sur (51) Int. C. .......................... C11D 7/12: C11D 7/54 factant, builder salts and a buffer system to stabilize the 52 U.S. C. ........................................ 252/99; 252/94; chlorine source with the composition. The composition 252/95; 252/103; 252/109; 252/156; 252/173; is dispensed by shearing the gel form of the thixotropic 252/550 composition and thus having the composition develop (58 Field of Search ..................... 252/94, 95, 99, 103, the flow properties of a viscous liquid for the purpose of 252/109, 156, 173,550 depositing the composition within the detergent com (56) References Cited partment of an automatic dishwasher, but which : U.S. PATENT DOCUMENTS Re.29,473 11/1977 Fitzgerald, Jr. . 1,522,561 1/1925 Weber et al. 4,007,124 2/1977 Collier et al. ... 252/95 252/99 . . 252/109 quickly thereafter re-gels to acquire non-flowing prop erties unlike those of a liquid and substantially similar to the properties of a cohesive solid. 4,071,463 1/1978 Steinhauer ....... Ad 252/03 11 Claims, No Drawings 4,431,559 1. 2 storage. This problem is exacerbated by the tendency to DISHWASHING COMPOSITION AND METHOD store such dishwashing detergents in the highly moist environment beneath a kitchen sink. BACKGROUND OF THE INVENTION Attempts to overcome the shortcomings of granular This invention relates generally to the art of dish 5 products have been described in several prior art docu washing, and more particularly, to a composition for ments. Some attempts utilize a liquid medium rather use within a household automatic dishwasher. than a granular medium for the dishwashing detergent. Conventional household automatic dishwashers op There is, however, a distinct problem with liquid prod erate with various wash cycles, all of which require the ucts when it is attempted to dispense or retain the liquid release of a detergent at an appropriate time during the 10 within the detergent compartment of a household auto wash cycle. The detergent is conventionally released matic dishwasher. from a storage compartment within the door of the An additional problem associated with the use of a automatic dishwasher. The detergent compartment is liquid medium is the presence of several constituents normally defined by a spring loaded door which at the 15 within the liquid medium which have a tendency to appropriate time in the wash cycle opens to release the react with one another prior to the desired time of use detergent within the compartment to the working vol within the wash cycle. For example, the prior art has ume of the dishwasher. utilized several different liquid products on an institu The household automatic dishwashing detergents tional level wherein one liquid product is dispensed into which have been conventionally utilized are of granular 20 the wash cycle containing a surfactant and a separate or powderform and, to a large extent, extremely hygro distinct liquid product containing a source of chlorine is scopic. The property of being highly hygroscopic has released into the wash cycle. No such dishwashing led to many problems within the automatic dishwashing capability on a household scale, however, has permitted art, both within the wash cycle and during storage of the use of more than one liquid at a time. the detergent. The absorption and adsorption of mois There is described in U.S. Pat. No. 4,226,736 to Bush ture by a granular hygroscopic dishwashing detergent 25 et all a gelled dishwashing detergent containing a non tends to inactivate the chlorine-containing agents, and ionic surfactant. The product disclosed therein, how causes the individual granules to cake and coalesce into ever, requires a minimum yield point in order to main larger particles, making the product difficult to dispense tain the gelled product within the detergent compart and dissolve, frequently ineffective and, in some cases, ment of an automatic dishwasher. The product de deleterious to the dishwashing process. This dissolving scribed therein additionally contains no source of chlo problem is worsened by energy saving strategies which rine and thus would have to be utilized with the dual result in the lowering of water temperatures within composition approach heretofore utilized on an institu household dwellings. tional basis as discussed above. Conventional household dishwashing detergent pow ders and granules generally require a water temperature 35 SUMMARY OF THE INVENTON of at least 130-140' F. in order to be dissolved for the washing process; thus setting an absolute minimum It is thus an object of this invention to provide a water temperature for such products to be useful. In an dishwasher. composition for use within an automatic non-granular automatic dishwasher, however, even with water at an appropriate temperature, automatic dishwashing deter- 40 a Itnon-granular is a further object of this invention to provide such product containing both detergency gents may cake within the detergent compartment prior levels of surfactants and a bleach. to release to the wash cycle. Such caking causes diffi It is a still further and more particular object of this culty in the formation of an aqueous solution which is invention necessary for detergent to occur and frequently results wherein a tosurfactant provide such a dishwashing composition and a source of chlorine maintain in deposition of granular and caked detergent particles stability during long periods of storage. i upon articles being washed and adverse reaction there It is a still further object of this invention to provide with. Spotting and actual pitting of silverware and alu a novel minum utensils can occur from the deposition of granu product. process of dispensing a dishwasher detergent lar products during the wash cycle. Household automatic dishwashing detergents con These as well as other objects are accomplished by a ventionally contain chlorine bleach in order to remove thixotropic composition having an aqueous solvent, a stains and break down proteinaceous matter. The mois thickening agent, a source of chlorine, detergency lev ture which causes caking also reduces the chlorine sta els of an anionic surfactant, builder salts and a buffer bility particularly if chlorinated cyanurates are utilized system to stabilize the chlorine source within the com in the granular detergent composition. Moisture thus 55 position. The product is dispensed by shearing the gel presents a double threat to the efficacy of a granular form of the thixotropic composition and thus having the detergent product. composition develop the flow properties of a viscous A further problem brought about by the hygroscopic liquid for the purpose of depositing the composition nature of granular dishwashing detergents is associated within the detergent compartment of an automatic dish with the storage and dispensing thereof. Due to the washer, but which quickly thereafter re-gels to acquire caking which can result upon exposure to moisture, it is non-flowing properties unlike those of a liquid and sub necessary that such hygroscopic detergents bestored in stantially similar to the properties of a cohesive solid. containers comprised of a barrier to moisture perme DETAILED DESCRIPTION ation. Such barrier packing materials are readily avail able, but complicate the packaging and dispensing 65 In accordance with this invention it has been found schemes. Even with the utilization of barrier material, that a thixotropic composition may be utilized as an however, moisture still contacts the packaged material automatic dishwashing detergent without the disadvan through the container opening, both during use and tages heretofore associated with prior art compositions. 4,431,559 3 4. It has additionally been found that such a composition and can be present in an amount of from about 45 to 60 may contain both detergency levels of an anionic sur percent by weight. factant and a chlorine source. Surprisingly and unex The key to the dispensing and retention of the com pectedly the chlorine source is stable in the presence of position of this invention within the storage compart an anionic surfactant within the the thixotropic compo- 5 ment of an automatic dishwasher is the utilization of a sition of this invention. The chlorine source within the thickening agent with functional electrolytes to bring automatic diswasher detergent composition of this in about the thixtropic properties of the overall composi vention aids in the breakdown of proteinaceous organic tion. The phenomenon of thixotropy is well known in material, helps remove food stains, aids in sanitizing, the ceramic and clay technology art, but has nothereto and aids in the prevention of water spotting. 10 fore been utilized within an automatic dishwashing The composition of this invention being thixotropic composition to create the advantages possessed by the has the desirable attributes of a solid dishwashing deter composition of this invention. It is preferred to utilize gent without the shortcomings thereof and simulta conventional clays, silica, silicates and aluminosilicates neously has the advantages of a liquid dishwashing as thickening agents in combination with salts and phos detergent without the disadvantages thereof. These 15 phates described below to create the thixotropic prop advantages will become apparent from the following erties within the composition. The buffer system and description which will first describe the method of dis builder salt act as electrolytes to interact with the fine pensing and using the composition of this invention. clay or other particles and bring about the thixotropic The composition of this invention is stored in a con properties. As examples, montmorillonite and bentonite tainer in a gel form. At the time of use, the container 20 containing the gel is agitated or shaken so as to shear the clays may be utilized as well as colloidal silica and alu gel and cause the gel to have flow properties substan from about 2 toGenerally, minosilicates. 5 percent a thickening agent content of by weight of the overall com tially similar to the properties of a viscous liquid. The position is sufficient to produce composition is then dispensed into the detergent com ties rendering the composition ofthe thixotropic proper partment of an automatic dishwasher by dispensing in a 25 tially dispensible as a liquid, but withinvention this the substan tenacity of a manner similar to the dispensing of any liquid. The gel to maintain its presence within the detergent com composition within the compartment regels into a non partment of an automatic dishwasher. flowable state without the now undesirable flow prop The thickening agent in the composition of this in erties of a liquid. Having this property, the gel is re vention tained within the detergent compartment of the dish- 30 scribed inprovidesthe not only the desirable attributes de preceding paragraph but may also act as washer until it is introduced into the wash cycle. The a gentle abrasive to enhance gel possesses sufficient tenacity to be retained within the tics of the overall composition.the cleansing characteris closed detergent compartment without leakage during the parts of the wash cycle wherein the closed deter ofThe chlorine source utilized within the composition this invention adds significantly to the overall effi gent compartment is not utilized. 35 cacy of the dishwashing composition. The chlorine The gel, comprised to a large extent of an aqueous solution, does not require high temperature water to be source is desirably a hypochlorite and preferably an activated or dissolved for its intended function within alkali hypochlorite. Examples of chlorine sources utiliz the wash cycle. Additionally because the composition is able within this invention are sodium hypochlorite, to a large extent an aqueous solution, it is not adversely 40 lithium hypochlorite, calcium hypochlorite, and chlori nated trisodium phosphate. A problem with the prior affected by a moist environment. The composition of this invention is a colloidal dis art utilization of hypochlorites within a liquid solution persion having thixotropic properties. For purposes of has been the tendency for the hypochlorite to break this disclosure the composition is referred to as a sol down and form hypochlorous acid, HOCl, which is when it exhibits liquid like properties and a gel when it 45 unstable and will not survive the necessary period of exhibits solid like properties. time required for efficacy in an household dishwashing Having generally set forth the process of utilizing the detergent. In accordance with this invention, however, composition in accordance with this invention, the it has been found that such breakdown may be mini composition, itself, comprises a solvent, a thickening mized by the utilization of a buffer system. Generally agent, a chlorine source, an anionic surfactant, a builder 50 the chlorine source is present in an amount sufficient to salt to retain removed soil within the wash liquid, and a increase the efficacy of the dishwashing composition buffer system to stabilize the chlorine source within the and may be present in an amount from about 0.05 to composition. An unexpected advantage of the composi about 5 percent by weight of the overall composition. tion of this invention is that the buffer system and The buffer system in accordance with this invention builder salt perform not only their intended function but 55 is one which will maintain and establish a pH within the also act as electrolytes which interact with the thicken range of about 10 to 13 for the overall composition and ing agent and bring about the thixotropic properties of which is sufficient to prevent acidic additions from the overall composition. The various constituents of the forming significant quantities of hypochlorous acids and composition are discussed in detail in the description thus render the chlorine source ineffective. The buffer which follows. 60 system is preferably a mixture of an alkali metal hydrox Water is utilized to maintain in solution most active ide and a salt. In addition to the builders, examples of constituents of the composition with the exception of buffering systems utilizable within the scope of this the thickening agents. However, some components may invention are sodium hydroxide and sodium bicarbon be present as separate phases and still be within the ate or sodium hydroxide and sodium carbonate. Gener scope of this invention. For example, an antifoaming 65 ally equal molar percentages of the buffer system are agent may be a separate phase or a builder salt may be added and a general weight percentage range for each present in excess of saturation. The aqueous solvent constituent would be from approximately 1 to 4 percent comprises a major portion of the overall composition by weight of the overall composition. 5 4,431,559 6 A builder salt is included within the composition of EXAMPLE I this invention to maintain removed soil matter in sus pension within the washliquid. Such builder salt may be Long range chlorine stability of the composition was any of the prior art builder salts conventionally utilized. measured by monitoring the active chlorine content. Examples of salts within the scope of this invention are The results are listed below. trisodium phosphate and tetrapotassium pyrophos phate. Such builders may be present in an amount from Sample Age Percent Active Chlorine about 2 to about 40 percent by weight of the overall (months) 77 F. 100 F. composition. The builder salt also interacts with the buffer system and is actually a part thereof to maintain 10 O 2 1.09 0.87 1.09 0.65 a desirable pH and stabilize the chlorine source. 4. 0.68 0.40 It should again be emphasized that the buffer system 6 0.54 0.23 and builder salt fulfill not only their primary function 8 0.49 but act as electrolytes to interact with the thickening 10 12 0.47 0.36 agent and bring about the thixotropic properties. 15 The anionic surfactant utilized within the composi tion of this invention must be one which is compatible The composition after one year at 77 F. still retained with the chlorine source when the buffering system is more than sufficient chlorine to be efficacious in an utilized and which provides sufficient detergency for automatic dishwasher. It is thus seen that the composi cleansing within an automatic dishwasher. The surfac 20 tion of this invention retained greater than thirty-three tant must be an anionic surfactant such as an alkalimetal percent (33%) of its original active chlorine after one alkyl sulfate. The preferred anionic surfactant is sodium year at 77 degrees F. lauryl sulfate. Generally, a surfactant content from a 30 The efficacy of the composition and its method of use weight percent aqueous solution of sodium lauryl sul was evaluated by dispensing the above composition into fate of from 0.5 to 4 percent by weight provides suffi 25 a dishwasher by shaking the container and the gelled cient detergency for functioning in an automatic dish product resulting in the transformation of the gel to a washer environment. sol to permit liquid-like dispensing into the detergent While the essential components of the composition of compartment of the dishwasher. Immediately after dis this invention have been described above it should be pensing into the detergent compartment, the composi pointed out that the composition once formulated is 30 tion regelled to have substantially non-flowing proper essentially a liquid solution with the thickeners being ties. the only second phase. The thickeners create the thixo The automatic dishwasher contained dinner plates tropic properties which provide for the unique dispens with soil material thereon. The material was baked onto ing and use characteristics of this invention. Other in 35 the plate for 2 hours at 200 degrees F. (93.3 degrees gredients may, however, be utilized in the formulation C.). The soil material comprised: so long as such ingredients do not interfere with the efficacy of the surfactant, chlorine source and buffering Constituent Weight systems. Such other constituents for example may com Ground Beef 120 grams prise colorants and perfumes in order to enhance the 40 Shredded Cheddar Cheese 120 grams overall aesthetic appeal of the dishwashing composi Whole Homogenized Milk 120 grams tion. Granulated White Sugar 120 grams Having generally described the composition in accor Cherry Pie Filling Raw Egg (excluding shell) 120 grams 1 grams dance with this invention, the following specific exam All Purpose four 30 grams ple is put forth as further aid to the understanding 45 Tomato Juice 120 grams thereof. EXAMPLE 1. The material was blended in a kitchen blender for 4 Several batches of the following composition were minutes until uniform. The material was basically an prepared by mixing the components in the order listed SO adaptation of an oven cleaner test described in Federal below to a high degree of dispersion. Specification P-C-1947B. The difference from the Fed TABLE eral Specification was that flour was substituted for tapioca to cause the test material to adhere more readily Weight to the dishes. This material was selected in order to test Component Percentage the detergent composition on particularly difficult to Tap Water 58% 55 remove foods and stains. A household automatic dish Montmorillonite Clay 2% washer was utilized and the tests were conducted in Fumed Silica of submicron size 2% Calcium Hypochlorite (65% active) 2% triplicate. Under all tests the composition of this inven Tetrapotassium Pyrophosphate (anhydrous) 30% tion performed satisfactorily in removing this difficult Anhydrous Soda Ash (sodium carbonate) 2% to remove material. Sodium Lauryl Sulfate (30% aqueous solution) 2% Glassware spotting was evaluated using ASTM Sodium Hydroxide (25% aqueous solution) 2% D3556-76T procedure. The product of this invention performed satisfactorily in the prevention of water The composition as prepared above typically had a spots on glassware. relative viscosity, utilizing a Brookfield Viscometer It is thus seen that this invention provides a non with a helipath stand, T-Espindle, at 6 rpm of 16,000 to 65 granular composition for use within a household auto 75,000 centipoise was light yellow in color and had a matic dishwasher containing both detergency levels of density utilizing the pycnometer method of 1.31 grams surfactant and a chlorine bleach in a stable state. It is per cc. further seen that this invention provides not only a 4,431,559 7 8 novel composition for use within a household automatic dispensing said sol with generally liquid-like proper dishwasher, but additionally provides a novel process ties into an automatic dishwasher whereby said for dispensing and using a dishwasher detergent prod thixotropic composition regels within said dish uct. As many variations will be apparent to those skilled washer. in the art from a reading of the above specification, such 5 2. A process according to claim 1 wherein said thick variations are included within the scope of this inven ening agent is selected from the group consisting of tion as defined by the following appended claims. silicas, silicates, aluminosilicates and clays. That which is claimed is: 3. The process according to claim 1 wherein said 1. A process for dispensing a dishwashing detergent buffer system comprises an alkali metal base and an composition, comprising the steps of: O alkali metal salt. providing a thixotropic dishwashing composition 4. A process according to claim 3 wherein said alkali which comprises; metal base is sodium hydroxide and said alkali metal salt an aqueous solvent present in an amount of about is sodium carbonate. 45 to 60% by weight of said composition, 5. A process according to claim 1 wherein said ani a thickening agent, having functional electrolytes 15 onic surfactant is an alkali metal alkyl sulfate. in an amount sufficient to render said composi 6. The process according to claim 5 wherein said tion thixotropic, anionic surfactant is sodium lauryl sulfate. a chlorine source present in amount of from about 7. The process according to claim 1 wherein said 0.05 to about 5.9% (percent) by weight of said chlorine source is a member selected from the group composition, 20 consisting of sodium hypochlorite, lithium hypochlo a buffer system to stabilize said chlorine source rite, calcium hypochlorite and chlorinated trisodium within said composition and-to maintain a pH phosphate, within the range of about 10 to 13, 8. A process according to claim 1 wherein said an anionic surfactant present in an amount equiva builder salt is tetrapotassium pyrophosphate. lent to about at least 0.5% (percent) by weight of 25 9. The process according to claim 1 having sufficient said composition when added as a 30% (percent) stability to maintain greater than thirty-three percent aqueous solution, (33%) of its original active chlorine after one year stor a builder salt present in an amount of from about 2 age at 77 degrees F. to about 40 percent by weight of said composi 10. The process according to claim 1 comprising 0.05 tion, 30 to 5 weight percent of alkali metal hypochlorite as said said composition being formulated to be thixotro chlorine source. pic and to have sufficient chlorine stability to be 11. The process according to claim 10 having gener efficacious in an automatic dishwasher after one ally equal molar additions an alkalimetal hydroxide and year storage at 77 F., said composition being in an alkali metal salt so as to minimize the formation of the form of a gel when at rest; 35 hypochlorous acid and to maintain a PH within the shearing said composition to form a sol with gener range of 10 to 13. ally liquid-like properties; and
Spinning preparations in the form of aqueous emulsions or aqueous solutions containing polymersSpinning preparations in the form of aqueous emulsions or aqueous solutions containing polymers هایلایت شده