EP0003769B1 - Article contenant un détergent façonné et méthode pour sa préparation et son utilisation - Google Patents

Article contenant un détergent façonné et méthode pour sa préparation et son utilisation Download PDF

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Publication number
EP0003769B1
EP0003769B1 EP79100344A EP79100344A EP0003769B1 EP 0003769 B1 EP0003769 B1 EP 0003769B1 EP 79100344 A EP79100344 A EP 79100344A EP 79100344 A EP79100344 A EP 79100344A EP 0003769 B1 EP0003769 B1 EP 0003769B1
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EP
European Patent Office
Prior art keywords
detergent
article
cast
sodium
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP79100344A
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German (de)
English (en)
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EP0003769A1 (fr
Inventor
Peter J. Fernholz
James L. Copeland
Richard C. Penttila
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Ecolab Inc
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Economics Laboratory Inc
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Classifications

    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L15/00—Washing or rinsing machines for crockery or tableware
    • A47L15/42—Details
    • A47L15/44—Devices for adding cleaning agents; Devices for dispensing cleaning agents, rinsing aids or deodorants
    • A47L15/4436—Devices for adding cleaning agents; Devices for dispensing cleaning agents, rinsing aids or deodorants in the form of a detergent solution made by gradually dissolving a powder detergent cake or a solid detergent block
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0052—Cast detergent 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means

Definitions

  • This invention relates to a novel solid cast detergent-containing article which is particularly useful in institutional dishwashing machines and industrial washing machines. Another aspect of this invention relates to a method for producing the detergent-containing article. Another aspect of this invention relates to a method for using the detergent-containing article. Still another aspect of this invention relates to a method for isolating reactive and incompatible components within a solid cast detergent to minimize interaction between them during manufacture, storage, and dispensing.
  • higher performance solid detergents generally means higher alkalinity (e.g. greater concentrations of sodium hydroxide)-higher even to the point of posing safety hazards to the user.
  • detergents used for warewashing have been relatively low in alkalinity.
  • the extensive use of aluminum trays and utensils, the presence of soft metals in wash pump impellors and other factors generally prevented the use of high alkalinity detergents.
  • the aforementioned increased standards and shorter wash times (usually ten seconds or less) required by the increased volume of business in eating establishments have created a demand for these higher performance products.
  • alkali metal hydroxides e.g. sodium hydroxide
  • chemicals used in high performance products, particularly for hard surface cleaning include phosphates, silicates, chlorine containing-compounds, defoamers and organic polyelectrolyte polymers.
  • alkali metal hydroxides e.g. sodium hydroxide
  • chemicals used in high performance products, particularly for hard surface cleaning include phosphates, silicates, chlorine containing-compounds, defoamers and organic polyelectrolyte polymers.
  • Another problem may exist with a powdered detergent if its components are of different particle sizes and densities. Variations in particle size and density between components may lead to segregation during manufacturing, shipping, and handling. Even when uniform distribution can be achieved during manufacturing, handling and shipping may cause segregation: Segregation leads to non-uniformity in the composition of the detergent when it is withdrawn from the container. Agglomeration of the components has been used to minimize the segregation problem. However, the use of agglomeration usually requires recycling of any particles which are too large or too small, which can be a significant percentage of the product.
  • liquid detergents it is relatively easy to provide an automatic dispensing system and method. For example, liquid detergents can simply be pumped into the wash tank or reservoir directly from their shipping containers.
  • Solid detergents (which can be in briquette, or, most typically, in powdered form) present much more complicated automatic dispensing problems.
  • Several approaches have been devised for attacking these problems-that is, for utilizing solid phase detergents without losing the benefits of automatic dispensing.
  • detergents used in large conveyor type machines are dispensed directly from their shipping containers by means of a dispensing system similar to that described in U.S. Patent No. 3,595,438, issued July 27, 1971 (Daley, et al).
  • the shipping container is inverted and placed over a detergent dispenser reservoir and a water spray is used to dissolve the detergent from the drum as needed.
  • a system for dissolving powdered detergent from a five to ten gallon capacity shipping pail is also known, see U.S.
  • Patent No. 4,020,865 issued May 3, 1977 (Moffat, et al).
  • the solid powdered detergent in the shipping container is not in a form which normally would be introduced directly into the wash tank of the washing machine, it is generally preferred in the. art to convert the powder into a liquid, e.g. by dissolving the powder with water in a special apparatus designed to carry out the dissolving step.
  • the dissolving apparatus need not be physically remote from the washing machine. Indeed, it is a common practice to mount dissolving/dispensing devices directly above-or on the side wall of-the wash tank of the machine.
  • One typically used type of machine-mounted dispenser is the so-called water-in-reservoir type.
  • the water-in-reservoir approach is not limited to machine-mounted dispensers, however; in machine-mounted applications, the water-in-reservoir dispenser is generally used in a single tank warewashing machine).
  • the water-in-reservoir type of dispenser makes up a concentrated solution of detergent from the powder in the reservoir by means of swirling action or agitation provided by incoming water.
  • the concentrated solution is delivered directly to the wash tank by gravity or through a delivery tube.
  • the concentration of the detergent in the wash tank can be maintained at a preset level by means of a conductivity sensing controller similar to that described in U.S. Patent No. 3,680,070, issued July 25, 1972 (Nystuen).
  • powdered detergent dispensers which hold from four to six pounds of detergent.
  • the hopper of such dispensers can be filled from detergent-containing drums by means of a scoop or by the use of small individual (i.e. two pound) pouches of detergent.
  • Dispensing systems for washing systems consisting of multiple hoppers which are filled with different chemicals or mixtures of chemicals are also known.
  • Dispensing systems for dispensing briquettes of detergent are also known in the art (U.S. Patent No. 2,382,163, 2,382,164, 2,382,165 all issued August 14, 1945 and U.S. Patent No. 2,412,819, issued Dec. 17, 1946, all to MacMahon, and FR-A-1 368 126).
  • the detergent briquettes are made by casting and are dispensed from a modified water-in-reservoir round pot-shaped dispenser.
  • the briquettes (usually three) are held in a mesh basket which forms a slot about 1 1/4 inches wide across the diameter of the pot.
  • the dissolving action is provided by a stream of water directed against the lower-most briquette and from the swirling action of water around the submerged portion of the lower-most briquette.
  • water is left standing in the reservoir. This type of system has the advantage of making it visually possible to determine when the detergent dispenser reservoir needs replenishing.
  • the MacMahon patents also disclose detergent briquette compositions and methods of manufacturing the briquettes.
  • the briquette compositions and the methods of manufacture which are disclosed appear to require the presence of a silicate and trisodium polyphosphate or sodium carbonate.
  • Detergent bars or cakes comprising a significant level of an organic detergent and tripolyphosphates are also known. See U.S. Patent No. 3,639,286, issued Feb. 1, 1972 (Ballestra, et al).
  • Compressed tablets containing detergents are also known, see U.S. Patent No. 2,738,323, issued Mar. 14, 1956 (Tepas, Jr.) and U.S. Patent No. 3,417,024, issued Dec. 7, 1968 (Goldwasser).
  • the present invention involves a detergent-containing receptacle adapted for use in association with a washing machine such that detergent is dispensed from the receptacle by impinging a flow of aqueous liquid upon an exposed s..rface of the detergent, which receptacle is characterized in that the detergent is cast and solidified in ,ie receptacle.
  • the detergent comprises at least two solid components, at least one of said solid components comprising an alkaline hydratable chemical which is hydratable chemical is capable of absorbing or combining with water to form both discrete and continuous states of hydration, and comprises at least 30% of said detergent.
  • the detergent composition is normally formed by mixing and heating the components in an aqueous solution, allowing the solution to cool and thicken as hydration of the hydratable component or components occur, pouring the solution into a mold and allowing the mixture to solidify.
  • the aforementioned preformed plugs or cores of additional components can be inserted in the mixture after it has been added to a mold and before it has solidified.
  • the cast detergent composition is left in the disposable mold in which it was cast and is used by placing the mold in a detergent dispensing apparatus where the detergent is dissolved from the mold through the open portion of the mold by the use of a liquid spray.
  • hydratable chemical includes chemicals forming both discrete and continuous states of hydration and thus means a chemical which is capable of absorbing or combining with water (e.g. 0.2-20 moles of water per mole of chemical) to form either type or state of hydration.
  • the hydratable chemical will normally be alkaline, that is, a one weight-percent aqueous solution of the chemical will have a pH of greater than 7.0 at 23°C. Since the detergent compositions . used in this invention are highly alkaline, it is preferred that the hydratable component of the composition be alkaline in nature.
  • Hydratable chemicals useful in the practice of this invention include alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide; silicates, such as sodium metasilicate; phosphates, particularly phosphates of the formula MO-(-P0 3 M-) n - or the corresponding cyclic compounds wherein M is an alkali metal and n is a number ranging from 1 to about 60, typical examples of such phosphates being sodium or potassium orthophosphate and alkaline condensed phosphates such as sodium or potassium pyrophosphate, sodium tripolyphosphate, etc.; carbonates, such as sodium or potassium carbonate; borates, such as sodium borate; zeolites, etc. Combinations of two hydratable chemicals for example, sodium hydroxide and sodium tripolyphosphate, have been found to work particularly well in the practice of this invention.
  • a second necessary component of the detergent composition of this invention is water.
  • Water is used to form a solution containing the detergent components; the solution being cast into a mold and solidifying as the hydratable chemical or chemicals form a hydrate with the water.
  • Water may be added as a separate ingredient or in combination with one of the other components, for example as an aqueous solution of 50% sodium hydroxide.
  • detergent components and fillers can be included.
  • a source of available chlorine and a defoamer can be used including chlorinated isocyanurates, such as sodium dichloroisocyanurate dihydrate, and hypochlorites, such as sodium and lithium hypochlorite.
  • chlorinated isocyanurates such as sodium dichloroisocyanurate dihydrate
  • hypochlorites such as sodium and lithium hypochlorite.
  • an available chlorine containing component when included in the composition of this invention it is preferably incorporated in the composition as a preformed plug or core.
  • Defoamers are also normally included in detergent compositions.
  • a "defoamer" is a chemical compound with a hydrophobe/hydrophile balance suitable to reducing the stability of foam.
  • the hydrophobicity can be provided by an oleophilic portion of the molecule (e.g. an aromatic alkyl or aralkyl group; an oxypropylene unit or oxypropylene chain, or other oxyalkylene functional groups other than oxyethylene, e.g. tetramethylene oxide).
  • the hydrophilicity can be provided with oxyethylene units or chains or blocks and/or ester groups (e.g. organo-phosphate esters), salt-type groups, or salt-forming groups.
  • defoamers are nonionic organic surface-active polymers having hydrophobic groups or blocks or chains and hydrophilic ester-groups, blocks, units, or chains, but anionic, cationic, and amphoteric defoamers are known.
  • nonionic defoaming surfactants see U.S. Patent No. 3,048,548, issued Aug. 7, 1962 (Martin, et al), U.S. Patent No. 3,334,147, issued Aug. 1, 1967 (Brunelle, et al), and U.S. Patent No. 3,444,242, issued- May 13, 1969 (Rue, et al).
  • Phosphate esters are also suitable, e.g.
  • esters of the formula RO ⁇ ( ⁇ PO 3 M ⁇ ) n ⁇ R wherein n is as defined previously and R is an organic group or M (as defined previously), at least one R being an organic group such as an oxyalkylene chain.
  • R is an organic group or M (as defined previously)
  • R being an organic group such as an oxyalkylene chain.
  • a defoamer may be included as a preformed plug or core, as more fully described hereinafter. If it is included as a preformed core or plug it must be a solid, or be capable of being combined with other components to form a solid, at room temperature. Wax-like materials can be used to further isolate the chlorine source or defoamer in the core from the surrounding cast article.
  • the detergent composition is a mixture of the detergent composition
  • the hydratable chemical or combination of hydratable chemicals will normally comprise at least 30%, and preferably 60%, by weight of the cast detergent composition.
  • the water of hydration will normally comprise at least 15%, and preferably 25%, of the cast detergent composition.
  • Performance improving additives such as available chlorine producing components and defoamers will normally comprise minor amounts of the composition, that is, less than 5%.
  • Typical three-component compositions of this invention can be formulated from (1) a phosphate or other hardness-precipitating or hardness sequestering agent, (2) an alkali metal hydroxide, and (3) water.
  • Typical four or five component compositions would further include a defoamer and/or a neutral inorganic salt (alkali metal halides, sulfates, etc.) and/or a chlorine source and/or a thickening agent, thixotrope, suspending agent, or the like.
  • Typical detergent compositions of this invention employ a condensed alkali metal phosphate for the sequestering of hardness (Mg ++ and Ca ++ ions).
  • condensed phosphates are known; see, for example U.S. Patent No. 3,535,258, issued Oct. 20, 1970 (Sabatelli, et al), U.S. Patent No. 3,579,455, issued May 18, 1971 (Sabatelli, et al) U.S. Patent No. 3,700,599, issued Oct. 24, 1972 (Mizuno, et al), and U.S. Patent No. 3,899,436, issued Aug. 12, 1975 (Copeland, et al).
  • the solid, cast detergent-containing article of this invention includes a disposable container or mold into which base detergent was cast and allowed to solidify.
  • the article will normally include a lid or cover.
  • the lid or cover can be made of the same or similar material as used to make the mold. As will be explained subsequently, this material is ordinarily alkaline-resistant, non-breakable, and inexpensive. Expensive corrosion-resistant metals or plastics can be used, if provision can be made for their recycling, but "disposable" materials would normally be preferred for most institutional uses.
  • the cast detergent composition is surrounded by and in contact with the mold on all but the upper surface of the solid cast detergent.
  • the core material may be optionally encased in a film or material which would not react with the core material or the-deterrent base. This coating could be comprised of a natural wax, a synthetic wax, a phosphate ester, or the like.
  • Some active chlorine sources such as calcium hypochlorite have been found to react very slowly at the plug-base detergent interface and would.nof normally need to be encased in a film or the like.
  • other chlorine sources such as sodium dichloroisocyanurate dihydrate have been found to be more reactive, in which case a protective film would be beneficial.
  • the mold or container can be made of any alkali-resistant material which can withstand moderately elevated temperatures, e.g. 65°C, and which can be formed into and hold the desired shape. Since the mold is generally intended to be "disposable" (i.e. not intended for re-use as a mold), inexpensive materials are preferred such as thermoplastics, resin-impregnated heavy paper or cardboard, and the like. Inexpensive but fragile materials such as glass or ceramics are less preferred due to handling or shipping problems, relatively flexible materials being preferred. Molds made of plastic (e.g. inexpensive thermoplastics) have been found to be particularly useful.
  • A. particularly useful detergent composition of this invention is formed by heating about 50-75 parts by weight of a 50-75 weight percent aqueous solution of an alkali metal hydroxide, e.g. sodium hydroxide, to about 55° to 65°C. While other alkali metal hydroxides may be used, sodium hydroxide has been found to be particularly useful and the following method of manufacturing will be described with respect to it. Aqueous solutions of 50 weight percent sodium hydroxide are readily commercially available. Solutions containing higher weight percents of sodium hydroxide are also available (e.g.
  • An aqueous solution of sodium hydroxide can also be prepared by mixing water and anhydrous sodium hydroxide in the desired ratio.
  • aqueous solution of sodium hydroxide After the aqueous solution of sodium hydroxide reaches a temperature of about 55° to 65°C, 30 to 40 parts by weight of anhydrous sodium tripolyphosphate are added to the solution. Since the sodium tripolyphosphate will not normally completely dissolve, it is kept suspended by continuous mixing. After the sodium tripolyphosphate has been added other optional fillers and components may be added if desired. The solution is then allowed to cool with continuous mixing. After approximately ten to fifteen minutes the mixture will begin to thicken. As it begins to thicken, the mixture is poured into a receptacle-shaped mold to a level at least part way up the side molding surfaces. As the mixture continues to cool it will solidify to form a cast composition.
  • preformed cores or plugs may be added.
  • the base detergent is allowed to solidify around it and retain it in place. While any shape or size plug could be used, it is normally preferred that the plug extend to the entire depth of the base detergent. The plug should extend the depth of the solidified detergent so that a constant ratio of components can be maintained while the base detergent and the plug are dissolved during use.
  • An alternative method of including a separately formed plug or plugs could consist of using a mold comprising one or more smaller molds positioned within the larger mold.
  • the large mold would be filled with the cast detergent base while the smaller mold or molds would contain separate compositions such as a source of available chlorine or a defoamer.
  • the compositions could be cast into the smaller mold or preformed as a plug and "pressed" into the mold.
  • the solid, cast detergent-containing article of this invention is normally used in detergent dispensing apparatus which can be part of a conventional institutional or industrial washing machine.
  • the article including a base detergent, a preformed core, and the container is placed in an inverted position over a spray means which is connected to a water source.
  • the spray means causes water to impinge on the exposed surface of the detergent and the core.
  • the detergent and the core dissolve and flow through a pipe to the wash tank of the washing machine.
  • Detergent base and preformed core can be formulated to dissolve at substantially the same rate and thus supply the tank with a consistent ratio of ingredients.
  • compositions, form and method of producing the solid, cast detergent-containing article of this invention are illustrative of the composition, form and method of producing the solid, cast detergent-containing article of this invention. It is to be understood that many variations of composition, form and method of producing the cast detergent would be apparent to those skilled in the art.
  • the following examples, wherein parts and percentages are by weight unless otherwise indicated, are only illustrative.
  • the tripolyphosphate did not completely dissolve but was held in suspension by mixing. Mixing was continued without heating until the solution began to thicken, which was approximately 10-15 minutes after the addition of the tripolyphosphate.
  • a receptacle-shaped mold consisting of a slightly tapered cylindrical plastic container measuring about 6 1/2 inches (about 16.5 cm) at the major diameter (the open end) and about 5 1/2 inches (about 14 cm) at the minor diameter and about 4 1/2 inches (about 11.5 cm) in depth. The mixture was allowed to harden in the mold which took approximately 5 minutes.
  • composition of the final cast product (in weight-%) was approximately:
  • the defoamer was added following the addition of the sodium tripolyphosphate and was kept uniformly dispersed by continuous mixing until the mixture was poured in the mold. At the time it was poured the mixture was sufficiently viscous so that a uniform dispersion was maintained.
  • composition of the final cast product (in weight-% was approximately:
  • a mixture was prepared according to the procedure described in Example 1. 53.57 parts of 50% sodium hydroxide, 8.77 parts of anhydrous sodium hydroxide, and 35.06 parts of anhydrous sodium tripolyphosphate were used. The mixture was then poured into the mold described in Example 1. Before the mixture completely solidified 2.6 parts of a preformed circular "plug" measuring about 1 inch in diameter (about 2.5 cm) and about 3 1/2 inches (about 9 cm) in length, comprising a source of available chlorine, was placed approximately in the center of the mold. The length of the plug was such that it extended from the bottom of the mold to the surface of the mixture. The mixture was then allowed to harden around the plug.
  • composition of the solidified cast detergent (in weight-% was:
  • the available chlorine containing plug was prepared by forming a composition consisting of:
  • Veegum is a trademark for inorganic suspending agents.
  • plugs measuring about 1 inch (about 2.5 cm) in diameter and about 3 1/2 inches (about 9 cm) in length, were made by filling an appropriate size cylindrical die with the composition and subjecting the die to about 2,000 psi in a hydraulic press.
  • Plugs containing available chlorine were produced following the same procedure from the two following compositions:
  • This example was designed to illustrate how a plug could be further isolated from the base detergent.
  • One plug was made from each of the following formulas by compression molding at about 2000 psi mold pressure.
  • Example 3 A mixture was prepared following the procedure described in Example 2. 52.57 parts of 50% sodium hydroxide, 8.77 parts of anhydrous sodium hydroxide, 35.06 parts of anhydrous sodium tripolyphosphate and 1 part defoamer were used. The mixture was then poured into the mold described in Example 1. Before the mixture completely solidified, 2.6 parts of a chlorine containing plug similar to those described in Example 3 was added as described in Example 3.
  • composition of the solidified cast detergent was:
  • a solid cast detergent of the same formula as that described in Example 5 was produced. However, instead of mixing the defoamer with the base detergent it was added in the form of a plug. Thus, two plugs were used, one comprising a defoamer and the other comprising a source of available chlorine. The two plugs were.placed near the center of the mold after the detergent was added, but before it solidified.
  • composition of the solidified cast detergent was:
  • the defoamer plug was prepared by heating together 60 parts of a viscous (at room temperature) polyoxyalkylene glycol and 40 parts of a solid mixture of mono- and di-alkyl phosphate esters until the phosphate esters melted and then mixing until the mixture was uniform. The solution was then poured into a cylindrical mold and allowed to cool and form a solid plug at room temperature.
  • a solid cast detergent was produced using the same formula and procedure as described in Example 2 except that the 1 part of defoamer was added as a plug similar to those described in Example 6.
  • a solid cast. detergent of this invention were prepared using the following procedure. 40 parts of anhydrous sodium metasilicate and 39 parts of a 10 weight percent aqueous solution of sodium hypochlorite were added to a laboratory mixer provided with a stirring means and a heating means. The solution was heated to approximately 55 0- 60 0 C. Twenty parts of anhydrous sodium tripolyphosphate were added to the solution and the solution mixed without heating until it began to thicken. After the mixture had thickened but while it was still pourable it was poured into a mold consisting of the dimensions described in Example 1. Before the mixture completely solidified, 1 part of a defoamer plug similar to those described in Example 6 was added following the previously described procedure.
  • composition of the solidified cast detergent was approximately:
  • This example was designed to illustrate that the sodium tripolyphosphate component of the previous examples can be formed in-situ by reacting sodium trimetaphosphate with sodium hydroxide via the following reaction:
  • chlorinated trisodium phosphate may be used as the chlorine source.
  • a solid cast detergent having the following composition was prepared:
  • the above mixture was prepared using the procedure as described for Example 2.
  • the mixture was poured (about 2360 g) into the mold which had a removable 2 inch diameter cylinder placed in the center. After the mixture had solidified, the 2 inch diameter cylinder was removed leaving a hollow cylindrical cavity. This hollow cavity was filled with about 340 grams of molten chlorinated trisodium phosphate. The chlorinate trisodium phosphate solidified upon cooling below its melting point. Some reaction occurred at the interface of the plug.
  • this reaction may be reduced significantly by allowing the cast detergent to cool thoroughly before the chlorinated trisodium phosphate was poured and/or coating the cavity surface with an inert barrier such as, for example, paraffin wax or mixed mono and dialkyl esters of polyphosphoric acid or like materials.
  • an inert barrier such as, for example, paraffin wax or mixed mono and dialkyl esters of polyphosphoric acid or like materials.
  • This example was designed to illustrate the production of a non-phosphate solid, cast detergent. Forty parts of 50% aqueous sodium hydroxide was heated to 150°F (65.5°C) in a jacketed stainless steel beaker equipped with a stirrer. Twenty parts of anhydrous sodium hydroxide were added and the mixture was stirred until a molten solution was formed. Twenty-five parts of liquid silicate (RU silicate from Philadelphia Quartz) having an SiO . /na 2 o ratio of 2.54 was added and resulted in the temperature of the mixture increasing to about 200°F (93°C). The mixture was cooled to about 150°F (71 °C) and 15 parts of sodium polyacrylate were added slowly while stirring continued.
  • RU silicate liquid silicate
  • the mixture was poured into a plastic container where it solidified upon cooling.
  • the purpose of this example is to compare the consistency of available chlorine recovery from a cast detergent-containing article produced according to the instant invention and a conventional, prior art, powdered detergent.
  • the prior art formula used consisted of a mixture of sodium tripolyphosphate, sodium dichloroisocyanurate (a chlorine source), sodium metasilicate, and sodium hydroxide. Sodium dichloroisocyanurate comprised approximately 28% of the formula.
  • the cast detergent-containing article used was produced by the process and using the formula described in Example 5.
  • the chlorine source was present in the form of a plug situated approximately in the center of the cast base detergent.
  • the cast detergent containing article was dispensed from an apparatus as described previously.
  • the prior art formula was dispensed from a water-in-reservoir dispenser of the type illustrated in Figure 1 of U.S. Patent No. 3,680,070, issued July 25, 1972 (Nystuen).
  • the amount of detergent present in the effluent was determined by the alkalinity of the effluent.
  • the "chlorine recovered-percent of theoretical” (CRPT) was then calculated from the formula
  • the conventional powdered detergent used was the same as that described in Example 11. This powdered detergent is commonly packaged in two-pound packages. Seven two-pound packages from the same production batch were selected at random for analysis. Ideally each of the packages should contain the same percentage of each of the four ingredient.
  • the percentage of available chlorine varied from 1.53 to 2.00. This variation is in part due to segregation during mixing and packaging of the powdered detergent. This segregation is probably one factor leading to variation in chlorine delivery. ⁇
  • This example was designed to compare the chlorine stability of cast detergents of this invention containing a chlorine source directly in the base detergent with cast detergents of this invention which incorporate a chlorine source as a core or plug, such as those described in Example 3.
  • a chlorine source as a core or plug, such as those described in Example 3.
  • Three different chlorine sources were used: sodium dichloroisocyanurate dihydrate (NaDCC-2H 2 0), lithium hypochlorite (LiOCl), and calcium hypochlorite (C 8 (OC') 2 ). All of the compositions were produced following the procedure of Example 1 with the chlorine source being added directly to the mixture following the addition of the sodium tripolyphosphate in one case and the chlorine being added as a plug in the other.
  • the chlorine source plug was dipped in a paraffin wax (m.p.
  • the purpose of this example was to compare the uniformity of delivery of defoamer from: (A) a conventional powdered detergent (Scoretm, a commercial product of Economics Laboratory, Inc.); (B) a cast detergent (product of Example 5); and (C) a cast detergent incorporating the defoamer as a core or plug (product of Example 6). All three of the formulations contained 1 % by weight of defoamer.
  • The'(A) conventional detergent and (B) the product of Example 5 contained the same defoamer; (C) the product. of Example 6 contained the blend of two defoamers described in Example 6 (the blend was used to obtain a solid product which could be molded into a plug).
  • Defoamers are included in detergents for spray-wash machines to control foam created by food soils. Foam in a wash tank leads to entrapment of air in the wash solution being recirculated through the machine and results in a reduction in mass and kinetic energy and which leads to poor soil removal. Excess foam in a wash tank causes a loss in water pressure which can be measured by a manometer connected to the wash manifold up stream from the water pump. Egg is a common foam-causing food soil and was selected for use in this test.
  • the C-11 1 Dispenser (optimally holds about four pounds of powdered detergent and thus 1.82 kg of conventional detergent (A) were used in the test. Products (B) and (C) were approximately 2.75 kg each and were of the configuration described in Example 1.
  • the pressure (in cm of water) was recorded when the dispenser was freshly charged, when about one-half of the detergent had been dispensed, and when about four-fifths of the detergent had been dispensed. Manometer readings were taken on the freshly charged detergent: (1) with water alone, (2) after the detergent was added, (3) five minutes after 115 grams of egg were added, and (4) five minutes after an additional 100 grams of egg were added.
  • the fill valve was opened to deliver 7.67 I of water per minute for dilution to simulate normal dilution of the wash tank by rinse water which is diverted to the wash tank to freshen the wash water.
  • the conductivity controller dispensed detergent as required to maintain a 0.2% concentration of detergent in the wash tank.

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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)
  • Detergent Compositions (AREA)

Claims (21)

1. Un réservoir à détergent adapté poure être utilisé dans une machine à laver, le détergent étant distribué du réservoir par application d'un flux de liquide sur une surface exposée du détergent, caractérisé en ce que le détergent est contenu dans le réservoir sous forme moulée et solidifiée.
2. Le dispositif selon la revendication 1, dans lequel le détergent comprend au moins deux composantes solides dont au moins l'une comprend un produit alcalin hydratable qui, en tant que produit hydratable est capable d'absorber de l'eau ou de se mélanger à de l'eau pour former des états d'hydratation aussi bien discrets que continus et qui comprend au moins 30% du dit détergent.
3. Le dispositif selon la revendication 1, dans lequel le dit. dispositif comprend également un couvercle fixé au dit réservoir.
4. Le dispositif selon la revendication 1, dans lequel le dit dispositif comprend également au moins un noyau préformé enrobé par et en contact avec le dit détergent jusqu'à ce que au moins une surface du noyau est exposée avec la surface libre du détergent.
5. Le dispositif selon la revendication 4, dans lequel le noyau préformé comprend une source de chlore.
6. Le dispositif selon la revendication 4, dans lequel le noyau préformé comprend un produit démoussant.
7. Le dispositif selon la revendication 4, dans lequel le dit dispositif comprend au moins deux noyaux préformés dont au moins l'un comprend une source de chlore et dont au moins l'autre des deux noyaux comprend un produit démoussant.
8. Le dispositif selon la revendication 5, dans lequel le noyau préformé est revêtu d'un film de protection inerte qui est en contact avec le partie adjacente du détergent.
9. Le dispositif selon la revendication 1 comprenant comme premier produit alcalin hydratable de l'hydroxide alcalin métallique et, comme deuxième produit alcalin hydratable, un tripolyphosphate alcalin métallique.
10. Le dispositif selon la revendication 9, dans lequel le poids total des deux produits alcalins hydratables comprend au moins 30% du poids du détergent et dans lequel le dit détergent comprend de l'eau, même à l'état solide.
11. Le dispositif selon l'une des revendications 9 ou 10, dans lequel le détergent comprend en plus un épaississant ou du thixotrope.
12. Le dispositif selon les revendications 9, 10 ou 11, dans lequel ledit détergent comprend en plus une source de chlore stable vis-à-vis de l'alcali.
13. Le dispositif selon l'une des revendications 9 à 12, dans lequel ledit détergent comprend en plus un produit démoussant.
14. Un dispositif selon l'une des revendications 9 à 13, dans lequel de t'eau a été introduite dans le détergent sous forme d'une solution aqueuse de l'hydroxide alcalin métallique:
15. Un dispositif selon la revendication 14, dans lequel une partie de l'hydroxide alcalin métallique est introduite sous forme d'un hydroxide alcalin métallique anhydre mélangé à la solution aqueuse de l'hydroxide alcalin métallique.
16. Un dispositif selon l'une des revendications 2 à 15, dans lequel le produit alcalin hydratable est choisi parmi le groupe composé de phosphate de sodiùm ou de potassium.
17. Le dispositif selon l'une des revendications 9 à 15, dans lequel l'hydroxide alcalin métallique est de l'hydroxide de sodium.
18. Le dispositif selon l'une des revendications 9 à 17, dans lequel le deuxième produit alcalin hydratable est du tripolyphosphate de sodium.
19. Le dispositif selon l'une des revendications 2 à 18, dans lequel le produit alcalin hydratable est ajouté sous forme de polyphosphate de sodium.
20. Le dispositif selon l'une des revendications 2 à 19, dans lequel le produit alcalin hydratable est choisi parmi le groupe composé de trimétaphosphate de sodium ou de potassium.
21. Le dispositif selon l'une des revendications 2 à 20, dans lequel le produit comprend au moins un produit polyélectrolytique de traitement de l'eau.
EP79100344A 1978-02-07 1979-02-06 Article contenant un détergent façonné et méthode pour sa préparation et son utilisation Expired EP0003769B1 (fr)

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Application Number Priority Date Filing Date Title
US87578478A 1978-02-07 1978-02-07
US875784 1978-02-07

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EP0003769A1 EP0003769A1 (fr) 1979-09-05
EP0003769B1 true EP0003769B1 (fr) 1982-09-29

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EP (1) EP0003769B1 (fr)
JP (1) JPS594480B2 (fr)
BE (1) BE904138A (fr)
CA (1) CA1125621A (fr)
DE (1) DE2963759D1 (fr)
HK (1) HK53986A (fr)
IT (1) IT1110274B (fr)

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DE3519354A1 (de) * 1985-05-30 1986-12-04 Henkel KGaA, 4000 Düsseldorf Schmelzblockfoermiges alkalihydroxidfreies mittel fuer das maschinelle reinigen von geschirr und verfahren zu seiner herstellung
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DE3541153A1 (de) * 1985-11-21 1987-05-27 Henkel Kgaa Mehrschichtige reinigungsmittel in schmelzblockform
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DE69630058T2 (de) * 1995-11-13 2004-04-08 JohnsonDiversey, Inc., Sturtevant Fester reinigungsmittelblock
WO2002006431A2 (fr) 2000-07-14 2002-01-24 Henkel Kommanditgesellschaft Auf Aktien Corps creux a compartiment
JP2002348594A (ja) * 2001-05-25 2002-12-04 Asahi Denka Kogyo Kk 固形ブロック洗浄剤組成物およびその製造方法
US7442679B2 (en) * 2004-04-15 2008-10-28 Ecolab Inc. Binding agent for solidification matrix comprising MGDA
ES2313436T3 (es) * 2004-10-18 2009-03-01 Ecolab, Inc. Dosificador de productos solidos y procedimiento y aparato para controlar el caudal de administracion de un producto solido con un cambio de temperatura.
JP6236315B2 (ja) * 2013-12-27 2017-11-22 株式会社ニイタカ カートリッジ洗浄剤
MX2016013463A (es) * 2014-04-15 2017-01-18 Ecolab Usa Inc Bloque solido novedoso que comprende uno o mas dominios de forma prismatica o cilindrica y produccion del mismo.
JP5801941B1 (ja) * 2014-11-21 2015-10-28 株式会社ニイタカ 洗浄剤組成物、食器洗浄方法、液体洗浄剤組成物用キット及びカートリッジ洗浄剤
JP5753962B1 (ja) * 2015-04-13 2015-07-22 株式会社ニイタカ カートリッジ洗浄剤
JP6695103B2 (ja) * 2015-06-25 2020-05-20 株式会社ニイタカ カートリッジ洗浄剤
JP2019049004A (ja) * 2018-11-21 2019-03-28 エコラボ ユーエスエー インコーポレイティド プリズム又は筒状の形状の一つ又は複数のドメインを含む新規な固体ブロック及びその製造

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Also Published As

Publication number Publication date
JPS54152007A (en) 1979-11-29
BE904138A (nl) 1986-05-15
JPS594480B2 (ja) 1984-01-30
IT7919942A0 (it) 1979-02-06
EP0003769A1 (fr) 1979-09-05
IT1110274B (it) 1985-12-23
CA1125621A (fr) 1982-06-15
HK53986A (en) 1986-07-25
DE2963759D1 (en) 1982-11-11

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