A cleaning composition is disclosed that is particularly suited for compaction into tablet form, and comprises a phosphate salt, an improved perborate salt mixture wherein the improvement comprises a combination of anhydrous perborate and monohydrate perborate in the amount of about 50% to about 70% by weight of the total cleansing composition, wherein the combination includes at least 20% by weight of the total cleansing composition of anhydrous perborate, said combination having a portion present in a compacted granulated mixture with from about 0.01% to about 0.70% by weight of said combination of a polymeric fluocarbon fluorocarbon, and a chelating or sequestering agent present in amounts greater than about 10% by weight up to about 50% by weight of the total composition, said cleansing composition being capable of cleansing stained surfaces and the like with a soaking time of five minutes or less when dissolved in aqueous solution and producing a marked improvement in clarity of solution upon disintegration and cleaning efficacy over the prior art.
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1. An improved effervescent cleansing composition in tablet form comprising:
(a) about 20% to about 45% by weight of the final composition of an alkali metal or alkaline earth metal phosphate salt; (b) an improved perborate salt mixture wherein the improvement comprises a combination of anhydrous perborate and monohydrate perborate in the amount of about 50% to about 70% by weight of the total cleansing composition, wherein the combination includes at least 20% by weight of the total cleansing composition of anhydrous perborate, wherein the proportion of anhydrous to monohydrate perborate is from about 1 to 3 to about 3 to 1, said combination having a portion present in a compacted, granulated mixture with from about 0.01% to about 0.70% by weight of said combination of a polymeric fluorocarbon, said cleansing composition being capable of thoroughly cleansing stained surfaces within a soaking time of five minutes or less when dissolved in aqueous solution; (c) a sequestering agent in amounts of greater than about 10% by weight up to about 50% by weight of the compositions, said sequestering agent being selected from the group consisting of phosphonic acid derivatives, carboxylic and derivatives and mixtures thereof.
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comprising the composition of claim 15. 20. An improved effervescent cleansing composition in tablet form comprising: (a) improved perborate salt mixture wherein the improvement comprises a combination of anhydrous perborate and monohydrate perborate in the amount of about 50% to about 70% of the total cleansing composition, wherein the combination includes at least 20% by weight of the total cleansing composition of anhydrous perborate, wherein the proportion of anhydrous to monohydrate perborate is from about 1 to 3 to about 3 to 1, said combination having a portion present in a compacted, granulated mixture with from about 0.01% to about 0.70% by weight of said combination of a polymeric fluorocarbon, said cleansing composition being capable of thoroughly cleansing stained surfaces within a soaking time of five minutes or less when dissolved in aqueous solution; (b) a sequestering agent in amounts of greater than about 10% by weight up to about 50% by weight of the total composition. 21. The composition of claim 20 wherein said perborate salt mixture comprises alkali metal and alkaline earth metal perborates. 22. The composition of claim 21 wherein said alkali metal perborate salt mixture comprises sodium perborate monohydrate and anhydrous sodium perborate. 23. The composition of claim 20 wherein said anhydrous perborate is present in an amount of from about 20% to about 25% by weight. 24. The composition of claim 23 wherein said anhydrous perborate comprises anhydrous sodium perborate. 25. The composition of claim 20 wherein said polymeric fluorocarbon includes at least one fluoroolefin. 26. The composition of claim 25 wherein said polymeric fluorocarbon comprises polytetrafluoroethylene. 27. The composition of claim 26 wherein said polymeric fluorocarbon is present in an amount from about 0.33% to about 0.66% by weight. 28. The composition of claim 20 further including at least one material selected from the following: builders, detergents, lubricants, perfumes, flavorings, excipients, disinfectants, and mixtures thereof. 29. The composition of claim 20 wherein said sequestering agent is present in amounts of about 25% to about 40% by weight of the total composition. 30. The composition of claim 20 wherein said sequestering agent is selected from the group consisting of phosphonic acid derivatives, carboxylic acid derivatives and mixtures thereof. 31. The composition of claim 30 wherein said sequestering agent is selected from the group consisting of amino carboxylate, hydroxycarboxylate and mixtures thereof. 32. The composition of claim 31 wherein the sequestering agent comprises ethylenediamine tetraacetic acid or nitrilotriacetic acid and salts thereof. 33. The composition of claim 31 wherein the sequestrant is selected from the group consisting of gluconic acid, citric acid and salts thereof. 34. The composition of claim 33 wherein the sequestrant comprises a phosphonate salt, its alkali metal salts and mixtures thereof. 35. The composition of claim 34 wherein the sequestrant is selected from the group consisting of amino tri(methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine tetra (methylene phosphonic acid), hexamethylenediaminetetra-(methylenephosphonic acid), diethylene triamine penta(methylenephosphonic acid) and mixtures thereof. 36. A method of cleaning dentures comprising soaking the dentures in an aqueous solution formed by dissolving the tablet of claim 1 in water and thereafter removing the dentures from said aqueous solution. 37. A method of cleaning dentures comprising soaking the dentures in an aqueous solution formed by dissolving the tablet of claim 6 in water and thereafter removing the dentures from said aqueous solution. 38. A method of cleaning dentures comprising soaking the dentures in an aqueous solution formed by dissolving the tablet of claim 9 in water and thereafter removing the dentures from said aqueous solution. 39. A method of cleaning dentures comprising soaking the dentures in an aqueous solution formed by dissolving the tablet of claim 15 in water and thereafter removing the dentures from said aqueous solution. 40. A method of cleaning dentures comprising soaking the dentures in an aqueous solution formed by dissolving the tablet of claim 20 in water and thereafter removing the dentures from said aqueous solution. 41. A method of cleaning dentures comprising soaking the dentures in an aqueous solution formed by dissolving the tablet of claim 24 in water and thereafter removing the dentures from said aqueous solution. 42. A method of cleaning dentures comprising soaking the dentures in an aqueous solution formed by dissolving the tablet of claim 27 in water and thereafter removing the dentures from said aqueous solution. 43. A method of cleaning dentures comprising soaking the dentures in an aqueous solution formed by dissolving the tablet of claim 35 in water and thereafter removing the dentures from said aqueous solution. |
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The present application is a continuation-in-part of my copending application Ser. No. 487,489, filed Apr. 22, 1983 now U.S. Pat. No. 4,518,520.
The present invention relates generally to cleansing compositions, and more particularly to cleansing compositions that are prepared in tablet form for use.
Cleanser compositions, and in particular those compositions having utility for hard surface cleaning applications, have utilized oxidizing agents and bleaching agents in concert to remove visible stains, while at the same time providing the capability for the removable of scale or plaque buildup on the surfaces. Thus, a variety of cleansing compositions are known and have been prepared either with abrasive materials for use as scouring cleansers, or alone for purpose of mild surface cleaning applications such as passive dispersion in a liquid medium such as water, and for soaking applications, such as the cleaning of dentures. All of these compositions have employed a variety of sulfate salts, such as bisulfates, monopersulfates, and sulfates as detergents, oxidizers and the like, and have also utilized alkali metal and alkaline earth metal halides as bleaches. Such compositions have also included perborate, carbonate and phosphate salts in varying amounts, to provide effervescence and activation. Representative cleansing compositions covering these various applications are set forth in U.S. Pat. No. 3,337,466 to Puetzer et al., U.S. Pat. No. 3,704,227 to Hill, Applicant's U.S. Pat. No. 4,362,639 and Applicant's copending applications, Ser. Nos. 251,030, 380,157 and 380,104undr under agitation to form the desired particles, and may possess particle sizes ranging on the order of 30 mesh or greater. The exact details of the preparation of the compacted perborate salt particles is disclosed in my copending Application Ser. No. 380,164, the disclosure of which is incorporated herein by reference.
In addition to the ingredients set forth above, the present compositions may contain a variety of additional ingredients selected on the basis of desired end use. Thus, for example, the compositions may include detergent compounds, such as organic and inorganic detergents, including non-ionic detergents such as the various polyoxyethylene ethers of aromatic and aliphatic alcohols, as well as the polyoxyethylene ethers of hydrophobic propylene oxide polymers. These compounds assist in maintaining a foaming action, in the instance where the cleansing compositions are placed in aqueous solution.
Also, the compositions may contain other adjuvant materials, that may be inorganic or organic in structure. Thus, inorganic water-soluble alkaline builders such as alkali and alkaline earth metal carbonates, hydroxides, and mixtures may be added.
The present compositions may optionally contain sequestrants for the purpose of maintaining solution clarity, in the instance where the compositions are placed in solution. The sequestrants may also assist in the inhibition of corrosion and tarnish of particles soaked in solution containing the present compositions. Useful sequestrants include ethylene diamine tetracetic acid (EDTA) and its corresponding alkali salts, as well as other polyfunctional organic acids, such as citric acid, maleic acid and their corresponding salts.
Those chelating or sequestering agents which are to be used in amounts greater than about 10% up to about 50% by weight are phosphonic acid and its derivatives, and carboxylic acid derivatives. Among those specific phosphonic acid derivatives are the salts of ethane-1-hydroxy-1,1-diphosphonic acid. For example, aminotri(methylene phosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine tetra(methylene phosphonic acid), ethylenediaminetetra(methylene phosphonic acid), hexamethylenediaminetetra(methylenephosphonic acid), diethylene triamine penta(methylenephosphonic acid), among others. The alkali metal salts and analogues of the above phosphonates are also useful.
Those carboxylic acid derivatives useful as chelating or sequestering agents include the hydroxycarboxylic acids and salts thereof, as well as amino carboxylates. For example, the hydroxycarboxylic acid compounds include gluconic acid and citric acid, among others known in the art. The amino carboxylates include nitriloacetic acid and ethylenediaminetetraacetic acid (EDTA). As previously mentioned, however, small amounts of EDTA are not effective in removal of calcium deposits from stained materials.
Mixtures of any or all of the chelating or sequestering agents is also contemplated.
Thus, the instant invention requires a critical combination of a phosphate salt, a pregranulated perborate salt mixture, and a chelating or sequestering agent in amounts greater than about 10% up to about 50% by weight of the composition. The pregranulation and method of tableting of the instant invention permit the high percentages of chelating or sequestering agents to be incorporated without experiencing cloudiness of solution or a significant change in tablet dissolution time.
In the instance where the compositions is to be prepared for use as a denture cleanser, other additives such as flavorings, colorants, perfumes and the like may be added in various amounts, as mentioned earlier. For example, the flavorings may include varieties of mint, oil of clove, artificial vanilla flavoring, and others. These materials may be included and blended in various combinations within the scope of the present invention. The choice of the required amounts is likewise within the skill of the art.
In the instance where the present cleansing compositions are formulated for use as denture cleansers, the colorants useful herein are those known as F.D. & C. & D. & C. dyes and lakes. These materials are certified by the Federal Food and Drug Administration as acceptable for use in food, drug and cosmetic applications, and drug and cosmetic colorings. The materials acceptable for the foregoing spectrum of use are preferably water-soluble, and include indigoid dye, known as F.D. & C. Blue No. 2, or its Lake which is the disodium salt of 5,5'-indigo-tindisulfonic acid. Similarly, the dye known as F.D. & C. Green No. 1, comprises a triphenylmethane dye or F.D. & C. Green #3 and is the monosodium salt of 4-[4-(N-ethyl-p-sulfobenzylamino)diphenylmethylene]-[1-(N-ethyl-N-p-sulfon iumbenzyl)-2,5-cyclohexadienimine] or F.D. & C. Green #3. A full recitation of all F.D. & C. and D. & C. and their corresponding chemical structures may be found in the Kirk-Othmer Encyclopedia of Chemical Technology, at Volume 5, pages 857-884, which text is accordingly incorporated herein by reference. Dyes and colorants will fade at different rates and may be chosen to provide specific end points.
The foregoing colorants may be blended with each other in a variety of combinations. It is particularly desirable that the colorants be chosen so that the composition when initially dissolved will present a deep hue. This is important in the instance where the composition serves as a denture cleanser, as the fading phenonmenon embodied in denture cleansers can be more easily observed by the end user.
The use of F.D. & C. Blue #1 Lake is particularly important in that the tablet color is blue without adversely affecting the color of the solution.
The present invention includes a method for the preparation of salts containing the hydrogen peroxide by crystallization of the hydrated and non-hydrated salts, which comprises preparing at least a portion of the combination of at least two of the perborate salts components, said combination comprising an anhydrous and a monohydrate perborate salt as a first pregranulation (pregranulation A) including the polymeric fluorocarbon, and compacting this first mixture to form a plurality of particles thereof. In a similar manner a second type of pregranulation can be formed (pregranulation B) comprising at least a portion of the phosphate, the chelating or sequestering agent, a detergent and the polymeric fluorocarbon, and compacting the second mixture to form a plurality of particles thereof. The pregranulation mixtures, A and B, should be in combination. The remainder of the ingredients, including the phosphates purchased or prepared with a particle size within the aforementioned ranges, are then combined to form a final mixture which may be prepared in tablet form, in the instance, for example, where the present compositions are to be utilized as denture cleansers. The present invention relates to the said cleansing composition as a fast acting denture cleanser and a method of preparation of a superior denture cleanser which results in an improved clarity of solution when dissolved in water and a process for producing the same in a solid dosage form
The use of finely divided polytetrafluoroethylene and a high foaming surfactant results in improved aesthetics. This is due to the fact that the majority of the Polytetrafluoroethylene becomes trapped in the foam layer thereby aggregating at the surface of the aqueous solution and leaving the volume of the solution clear of particles. The polytetrafluoroethylene in combination with the perborate combination described above are believed primarily responsible for the improved properties of the instant compositions.
It is preferable to prepare the present compositions in tablet form in such instance, as it is easier to achieve the uniformity of quantity and distribution of the ingredients of the compositions that is necessary to assure the corresponding uniformity of performance of the cleanser. Thus, cleanser tablets have been found to exhibit uniformity of color reaction, distintegration and fade time, in cleaning ability on a tablet-to-tablet basis.
In accordance with the present invention, the compositions may be prepared in tablet form without the need for increased addition of ingredients such as excipients, tableting agents and the like. While such ingredients may be added, the amounts of these ingredients may be reduced, due to the favorable effect exerted by the polymeric fluorocarbon present in the compacted granules of the perborate salt. Naturally, minor additional quantities of ingredients such as the polymeric fluorocarbon, may be made for their stated purpose, such as for lubrication and the like, however such additions and their respective amounts are not critical and do not form a part of the present invention.
A fuller understanding of the present invention will be gained from a review of the following illustrative examples. Unless specified otherwise, all amounts expressed as percent, are intended to be a percent by weight of the total composition. These examples are not intended to limit the effective scope of the invention.
A series of cleanser compositions were prepared having the ingredients set forth in Table I, below.
The compositions of each of Examples I-IV were prepared as follows. Initially, a quantity of anhydrous sodium perborate, in the form of a fluffy powder, and sodium perborate monohydrate was combined in a container with a quantity of polytetrafluorothylene powder identified as Grade F5A by Allied Chemical Corp. The polytetrafluoroethylene was added in the amounts based upon the weight of the perborate, as indicated with respect to each of the examples, above. Blending was performed for about 3 minutes, after which the mixture was compressed by passing through a tablet slugging machine having 27/32" dies. The slugs were then passed through an oscillating granulator having a 16 mesh screen, to form the granules of the anhydrous perborate/polytetrafluoroethylene/sodium perborate monohydrate mixture.
The remaining ingredients of the composition were added to the perborate, the phosphate being added first, to form the second mixture, after which the mixture was formed into tablets by compression in a tablet slugging machine having a tablet die of 26/32". The tablets were performed to a hardness ranging from about 20 to about 30 S.C.U., and were thereafter cured in a hot air oven for 45 minutes at 95°C
After the preparation of the tablets was complete, representative tablets from each of the four formulations were tested for activity and efficacy, by placement in individual containers having approximately 120 milliliters of water at 45°C
Each of the compositions tested, exhibited a disintegration time of approximately 90 seconds or less, a pH ranging up to about 11.2, and a fade time of approximately 5 minutes. A reduced form tablet weight would fade in 12 minutes. It was determined that each of the compositions could thus be prepared into tablets for use as denture cleansers, with satisfactory activity and efficacy.
| TABLE I |
| ______________________________________ |
| Examples Percent Weight/ |
| Weight of the Total Composition |
| Ingredients I II III IV** |
| ______________________________________ |
| Sodium Bicarbonate |
| -- 14.0 -- Reduced |
| weight |
| Citric Acid -- 10.3 -- of |
| Example |
| Sodium Carbonate |
| -- 12.8 -- I 88% w/w |
| Colorant 0.2 0.1 0.25 0.18 |
| Oxone -- 39.5 -- -- |
| Ethylene Diamine |
| 3.4 1.25 2.7 3.00 |
| Tetraacetic Acid |
| Tetrasodium |
| Flavor and Fragrance |
| 0.5 1.0 0.53 0.44 |
| Detergent 0.5 0.65 0.17 0.44 |
| Magnesium Stearate |
| -- 0.2 0.02 -- |
| Sodium Perborate |
| 37.3* 12.5 33.7 32.80 |
| Monohydrate |
| Anhydrous Sodium |
| 22.85* -- 20.0* 20.10 |
| Perborate |
| Trisodium Phosphate |
| 33.8 -- 24.6 29.70 |
| Sodium Benzoate |
| 1.0 1.6 1.1 0.88 |
| Polytetrafluoro- |
| 0.45 -- 0.23 0.40 |
| ethylene |
| Filler -- 6.1 -- -- |
| Sodium Meta Silicate |
| -- -- 16.7 -- |
| ______________________________________ |
| *Includes approximately 0.45% by weight of total perborate |
| polytetrafluoroethylene prepared as a granulated mixture. |
| **This example is based on 88 grams total weight. |
Example I represents a preferred composition of the instant invention. Example II represents a typical composition of the prior art. Example III is nearly identical to Example I except that sodium meta silicate and magnesium stearate are added. As previously discussed above, magnesium stearate is used as a lubricant to facilitate preparation of the composition, making it easy to work and form. Sodium meta silicate is used in the prior art primarily as a cleanser. There are disadvantages to using silicates, particularly meta silicates, because they tend to increase the pH of the solution upon tablet dissolution. The increase in pH is believed to increase the darkness of the color of certain stains on dentures, thereby defeating the purpose of the product. Additionally, magnesium silicate contributes to tablet production problems by causing the formed tablet to adhere to the punches or dies. Thus, if the prior art compositions required the cleansing power of the silicate, it was advisable to have a lubricant, such as magnesium stearate, also present to prevent the production problems of adherence to dies or punches.
Example IV is identical in ingredients to Example I but the tablet is reduced in weight by 88%. The percents reported under this example are based on a total of 88 grams.
| TABLE II |
| ______________________________________ |
| % weight/weight of the |
| Total Composition |
| Ingredients V VI |
| ______________________________________ |
| Sodium Perborate Monohydrate |
| 36.3 36.3 |
| Sodium Perborate Anhydrous |
| 22.3 22.3 |
| Ethylenediaminetetraacetic Acid |
| 39.2 -- |
| Tetrasodium Salt Dihydrate |
| Ethylenediamine tetra (methylene |
| -- 39.2 |
| phosphonic acid) |
| Fragrance 0.7 0.7 |
| Surfactant 0.7 0.7 |
| Polytetrafluoroethylene Powder |
| 0.6 0.6 |
| Color 0.1 0.1 |
| Lubricating Aids 0.025 0.025 |
| ______________________________________ |
Examples V and VI represent composition of the instant invention which contain large amounts of the chelating agents ethylenediamine tetraacetic acid tetrasodium salt dihydrate and ethylene diamine tetra(methylene phosphonic acid). These agents were added in these amunts to demonstrate improved efficacy of cleaning and particularly the removal of calcium deposits on stained surfaces.
In vitro tests were performed on stained tiles and each of the compositions in Examples I-IV in Table I and Examples V and VI of Table II were used in tablet form to compare efficacy of cleaning. The compositions were tested for removal of composite food, plaque stain and tobacco stain on denture tiles.
The composition of Example I, embodying the instant invention, was found to be equivalent to Example III in removal of food and stain from denture test tiles. This would be expected since there is very little variation of the compositions, and indicates that magnesium stearate and sodium meta silicate are not necessary to the instant compsition.
The composition of Example I was superior to Example II in removal of plaque and stain on tiles in a period of 5 minutes and was surprisingly superior in clarity upon completion of dissolution as well. The composition of the prior art (Example II) required 12 minutes to equal the efficacy and cleaning capability of Example I and yielded a less aesthetically pleasing and clear solution. The reduced weight composition of Example IV was found to be equivalent and sometimes superior to the composition of Example II when tested on stained tiles for 12 minutes. The significance of this relates to a considerable cost savings, since a lighter product can be made which has the same cleansing power and efficacy as the heavier tablet of the prior art in the same cleaning time; or a standard weight tablet can be made which cleans as well as the prior art in half the soaking time without cloudiness.
The preferred compositions of Examples V and VI, containing 39% of the chelating agents, were more effective at removing the plaque and stains and particularly the calcium deposits from the tiles than the composition of Example I. This demonstrates that the high percentages of chelating agents are effective at improving the cleaning ability of the instant compositions. No cloudiness or change in dissolution time was distinguishable between Examples I, V and VI.
The in vitro tests above indicate several facets of the instant invention. One such facet concerns the speed of cleaning of the instant compositions over the prior art while simultaneously producing an improved clarity of solution. Another facet concerns maintaining the cleansing speed and efficacy equivalent to or slightly better than the prior art, yet having substantially reduced tablet weight and size and ingredient amounts in accomplishing this.
Clinical tests were performed on forty visibly stained dentures obtained from subjects who had restricted their oral hygiene practices and exposed their dentures to exaggerated quantities of tea, coffee, blueberries, and grape juice. The dentures were constructed of ADA certified materials and subjects refrained from cleaning their dentures for a total period of eight days prior to test using a specified procedure for consuming the staining foods. One half of each denture, as determined randomly, was cleaned with the prior art composition, Example II, for 12 minutes by soaking in aqueous solution, and the other half of the denture was cleaned in the same manner using the instant composition, Example I, in aqueous solution for 5 minutes of soaking time. The dentures were then examined and rated by an expert panel to determine which half of the denture was cleaner. Following the overall examination, the cleanliness of specified interproximal spaces was evaluated. In order to establish intra-examiner reliability, the dentures were randomly rearranged and evaluated a second time. The judges were not aware of the treatment regimen and made their own independent observations and judgment. Statistical analysis was conducted on the clinical study. The study was designed so that each denture surface received a total of eight ratings (two evaluations per denture by each of the four judges).
The design of this study provided for an actual in-use denture staining and cleaning. Restricted oral hygiene practices by the test subjects as well as the exposure to exaggerated staining mediums produced a visible stain on the dentures which was subsequently cleaned with the prior art composition (Example II above) under controlled conditions of temperature and time.
The results of the study clearly showed that the instant compositions are equally efficacious in less than half the soaking time than the prior art compositions in the overall removal of composite food stains from denture surfaces and in removal of composite stains from interproximal spaces. More particularly, the above study showed the instant applications when formulated into tablet form are equal or better in efficacy in a 5 minute soaking time than a tablet of the prior art in a 12 minute soaking time.
This invention may be embodied in other forms or carried out in other ways without departing from the spirit or essential characteristics thereof. The present disclosure is therefore to be considered as in all respects illustrative and not restrictive, the scope of the invention being indicated by the appended claims and all changes which come within the meaning and range of equivalency are intended to be embraced therein.
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