Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/06—Phosphates, including polyphosphates
• • 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
  • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
• • 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/08—Silicates
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/395—Bleaching agents

Definitions

• a first aspect of this invention relates to solid cast detergent compositions which are particularly useful in home, industrial and institutional warewashing machines.
• a second aspect of this invention relates to methods for producing the detergent compositions.
• a third aspect of this invention relates to methods for using the detergent compositions.
• Warewashing compositions are typically available in liquid or granular form. While these forms have many advantages such as ease of manufacture, rapid dissolution rate and customer acceptance, they also have numerous drawbacks including stratification or settling of individual components, limits to the percent of active ingredients which may be incorporated, and instability of reactive components such as defoamers, surfactants, bleaches, etc. Further, liquid and granular warewashing compositions are easily spilled onto skin, clothing, etc. where they may cause injury and/or damage.
• a stable, substantially nonaqueous readily soluble, effective bleach-containing, solid cast warewashing detergent composition can be formed by combining hydratable, crystalline alkali metal silicate and water under conditions sufficient to cause substantially complete hydration of the silicate, and then combining an effective cleaning and glass protecting proportion of the hydrated silicate with an effective hardness sequestering proportion of a hydrated alkali metal condensed phosphate having sufficient water of hydration to allow the cast composition to solidify and an effective cleaning, bleaching and sanitizing proportion of a cellulose ether encapsulated bleaching source.
• the solid cast warewashing composition of this invention comprises water, hydratable, crystalline alkali metal silicate, alkali metal condensed phosphate, cellulose ether encapsulated bleach, and optionally, dye, perfume, surfactant, defoamer, an additional sequestering agent such as an alkali metal salt of a polyacrylic acid, a neutral soluble salt such as an alkali metal sulphate or an alkali metal chloride, and/or alkali compound.
• the solid cast warewashing composition contains about 20 to 55 wt-% hydratable, crystalline alkali metal silicate, preferably 20 to 40 wt-%.
• Alkali metal silicates are the reaction product of an alkali metal oxide (M2O) and silicon dioxide (SiO2) and have the general chemical formula (M2O) x :(SiO2) y wherein x and y indicate the molar ratio of alkali metal oxide to silicon dioxide.
• alkali metal silicates having various x:y mole ratios are well known as demonstrated by the general disclosure in Kirk-Othmar Encyclopedia of Chemical Technology, 2d Ed., Vol. 18, pp. 139-141.
• the desired properties and benefits of the solid cast warewashing composition described herein can be obtained using an alkali metal silicate having an x:y ratio of about 1:1 - 3:1, preferably 1:1.
• the alkali metal silicate has sufficient alkaline character to clean effectively and sufficient silicon dioxide to protect aluminum, china, glassware, etc. from the etchant effect of basic components in the composition.
• These silicates also have excellent solidification properties.
• the most preferred alkali metal silicate is sodium metasilicate having an Na2O:SiO2 ratio of about 1:1.
• the solid cast warewashing composition contains about 1 to 70 wt-% hydrated alkali metal condensed phosphate as a detergent builder and hardness sequestrant, preferably 15 to 40 wt-%.
• the service water commonly employed in cleaning baths contains substantial proportions of hardness ions most commonly calcium and magnesium ions, which can react with detergent components to decrease cleansing effectiveness and/or leave unsightly deposits upon the substrate being cleaned. Sequestrants act to prevent or delay crystal growth of calcium or magnesium compounds and thereby eliminate their reaction with other components and/or their precipitation.
• Condensed phosphate compositions useful in this invention include the water soluble alkali metal orthophosphates, polyphosphates, pyrophosphates and metaphosphates. It may be possible to employ some condensed phosphate in an anhydrous state and still have the cast composition solidify quickly. However, it has been found that the use of an anhydrous alkali metal tripolyphosphate results in a cast composition that takes over a day to solidify.
• the cast composition solidify as quickly as possible. If the cast composition takes too long to solidify, the encapsulated chlorine source, which is water soluble, breaks down releasing chlorine. Thus, the quicker the solidification of the cast composition, the higher the percentage of chlorine retained in the cast composition. A preferred time for solidification would be about 2 hours or less. It is preferable that if an alkali metal tripolyphosphate is used in this invention that it have a water of hydration greater than about 15 wt-% based upon the alkali metal tripolyphosphate composition in order for the cast composition to solidify quickly.
• the preferred condensed phosphate composition is sodium tripolyphosphate having a water of hydration greater than about 15 wt-% prior to its addition to the other component. While both granular and powdered condensed phosphate compositions can be usefully employed in the present invention, granular condensed phosphates, having a particle size of about 10 to 40 U.S. Mesh, are preferred to reduce the product viscosity during processing.
• the solid cast warewashing composition of this invention contains about 0.1 to 20 wt-%, preferably 0.1 to 15 wt-%, of an encapsulated bleach.
• the bleach is coated with a first or inner coating of a separating water soluble compound and a second or outer coating of a cellulose ether.
• Bleaches suitable for use as the core component include any of the well known bleaching agents capable of removing stains from such substrates as dishes, flatware, pots and pans, textiles, countertops, appliances, flooring, etc. without significantly damaging the substrate.
• a nonlimiting list of such bleaches includes active halogen releasing bleaches such as hypochlorites, chlorites, chlorinated phosphates, chloroisocyanates, chloroamines etc.; and peroxide compounds such as hydrogen peroxide, perborates, percarbonates etc.
• Preferred bleaches include those bleaches which liberate an active halogen species such as Cl+, Br+, OCl ⁇ , or OBr ⁇ under conditions normally encountered in typical cleaning processes.
• the bleaching agent releases Cl+ or OCl ⁇ .
• a nonlimiting list of useful chlorine releasing bleaches includes calcium hypochlorite, lithium hypochlorite, chlorinated trisodium phosphate, sodium dichloroisocyanurate, potassium dichloroisocyanurate, [(monotrichloro)-tetra(monopotassium dichloro)] pentaisocyanurate, trichloromelamine, sulfondichloro-amide, 1,3-dichloro-5,5-dimethyl hydantoin, n-chlorosuccinimide, n,n′-dichloroazodicarbonimide, n,n-chloroacetyl urea, n,n′-­dichlorobiuret, chlorinated dicyanamide, trichlorocyanuric acid, and hydrates thereof.
• the most preferred bleaching agents are the alkali metal salts of chloroisocyanurates and the hydrates thereof.
• Compounds suitable for use as the inner coating component include any compound which is solid at those temperatures likely to be encountered during storage of the encapsulated bleach (i.e. -5° to 50°C), is chemically compatible with (i.e. does not react with) either the bleaching agent core or the water soluble cellulose ether outer coating, and is capable of separating the bleaching agent from the cellulose ether so as to prevent deactivation of the bleach by the cellulose ether.
• Useful separating compounds include specifically but not exclusively water insoluble compounds such as C 11 - 30 fatty acids, waxes and water soluble compounds such as alkyl sulfonates, alkyl sulfates, detergent builders and detergent fillers.
• the separating compound is an inorganic detergent builder or filler useful in the cleaning composition into which the bleach is to be employed.
• a nonlimiting list of such detergent builders and fillers includes inorganic compounds such as sodium sulfate, sodium chloride, tetrasodium pyrophosphate, alkali metal silicates, tetrapotassium pyrophosphate, pentasodium tripolyphosphate, pentapotassium tripolyphosphate, sodium sequicarbonate, potassium sequicarbonate, phytates, etc.
• the inner coating compound preferably comprises a mixture of sodium sulfate and a tripolyphosphate.
• Cellulose is a linear polymer of anhydroglucose units held together by glucosidic linkages. Each anhydroglucose unit contains three hydroxyl groups - one primary and two secondary. Cellulose derivatives such as cellulose ethers are formed by reaction of the cellulose with a chemical reagent at these hydroxyl groups.
• hydroxyethylcellulose can be prepared by the reaction of alkali cellulose with ethylene oxide in the presence of isopropanol, tert-butanol or acetone in accordance with the following equation:
• Cellulose derivatives useful as the outer coating component in the present invention are the water soluble cellulose ethers selected from the group consisting of (C1 ⁇ 4) alkyl cellulose, carboxy (C1 ⁇ 4) alkyl cellulose, hydroxy (C1 ⁇ 4) alkyl cellulose, di(C1 ⁇ 4) alkyl carboxy (C1 ⁇ 4) hydroxy (C1 ⁇ 4) cellulose, (C1 ⁇ 4) alkyl hydroxy (C1 ⁇ 4) alkyl cellulose and mixtures thereof.
• the preferred cellulose ethers are the hydroxy (C1 ⁇ 4) alkyl celluloses with the most preferred cellulose ethers being hydroxyethylcellulose and hydroxy-propylcellulose.
• DS degree of substitution
• MS is defined as the number of moles of reagent (i.e. ethylene oxide) combined per anhydroglucose unit.
• the ratio of DS to MS is an indication of the average length of the side chains developed.
• the DS, MS and ratio of DS to MS can affect the chemical properties of the cellulose derivative and only those cellulose ethers that have a DS, MS and DS:MS which result in a water soluble compound may be usefully employed in the present invention.
• the composition can comprise about 20 to 90 wt-%, preferably about 40 to 70 wt-% bleach core, about 5 to 60 wt-%, preferably about 10 to 50 wt-% separating compound inner coating and about 1 to 25 wt-%, preferably about 2 to 10 wt-% water soluble cellulose ether outer coating.
• the water soluble cellulose ethers described herein are capable of protecting a bleaching agent core from deactivation in an alkaline environment because the cellulose ethers are water insoluble when in the presence of at least about 10-50 wt-% inorganic salts such as sodium chloride, sodium sulphate, sodium perborate, etc. (i.e. those conditions typically encountered in solid detergents) and water soluble only when the wt-% of inorganic salt falls outside these levels (i.e. those conditions typically encountered during use of the detergent).
• inorganic salts such as sodium chloride, sodium sulphate, sodium perborate, etc.
• the bleach may be encapsulated in any convenient manner capable of ensuring complete coating of the bleach. Obtaining a complete protective coating with the cellulose ether is simplified by the tendency of cellulose ethers to naturally form a nonporous, evenly distributed coating on a particle.
• the bleach is preferably encapsulated in a fluidized bed as set forth in detail in the Examples. Briefly, the separating composition is dissolved in an appropriate solvent, such as water when water soluble, to form an inner coating solution; the water soluble cellulose ether dissolved in water to form an outer coating solution; the bleach particles fluidized in a fluidized bed apparatus, the inner coating solution sprayed onto the fluidized particles and dried, and the outer coating solution sprayed on the fluidized particles and dried.
• an appropriate solvent such as water when water soluble
• the solid cast warewashing composition contains about 8 to 60 wt-%, preferably 8 to 35 wt-% water in addition to the water of hydration in the hydrated alkali metal condensed phosphate and other components of the cast composition.
• the water is necessary to form a homogeneous mixture capable of being cast and solidified.
• water in reference to the cast composition refers to water added as free water and not water added as water of hydration unless otherwise specified.
• solid cast warewashing composition including a defoamer, a secondary sequestrant such as a polyacrylate, an alkali compound, a detergent builder or filler, a dye and perfume.
• a secondary sequestrant such as a polyacrylate, an alkali compound, a detergent builder or filler, a dye and perfume.
• a defoamer is a chemical compound with a hydrophobe/hydrophile balance suitable for reducing the stability of protein 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 by oxyethylene units, chains, blocks and/or ester groups; e.g., organophosphate esters; salt-type groups, or salt-forming groups.
• defoamers are nonionic organic surface-active polymers having hydrophobic groups, blocks or chains and hydrophilic ester groups, blocks, units or chains; but anionic, cationic, and amphoteric defoamers are known.
• anionic, cationic, and amphoteric defoamers are known.
• nonionic defoaming surfactants see U.S. Patent No. 3,048,548, issued August 7, 1962 (Martin et al), U.S. Patent No. 3,334,147, issued August 1, 1967 (Brunelle et al), and U.S. Patent No. 3,442,242, issued May 13, 1969 (Rue et al).
• Phosphate esters are also suitable, e.g.
• esters of the formula RO-­(PO3M)- n R wherein n is a number ranging from 1 to about 60, typically less than 10 for cyclic phosphates, M is an alkali metal and R is an organic group or M, with at least one R being an organic group such as an oxyalkylene chain.
• the solid cast warewashing composition of this invention can include about 0 to 15 wt-% of a defoamer.
• the solid cast warewashing composition can employ a polyelectrolyte such as the polyacrylates of molecular weight 1000-3000 as secondary chelating or sequestering agent.
• a polyelectrolyte such as the polyacrylates of molecular weight 1000-3000 as secondary chelating or sequestering agent. See, for example, U.S. Patent No. 3,535,285, issued October 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 October 24, 1972 (Mizuno et al), and U.S. Patent No. 3,899,436, issued August 12, 1975 (Copeland et al).
• polyacrylates can function as thickeners in aqueous systems.
• Cast detergent compositions of this invention can contain up to 20% by weight of a secondary sequestering agent in combination with the alkali metal condensed phosphates.
• alkali compound may also be included in the solid cast warewashing composition of this invention.
• useful alkalis include but are not limited to alkali metal hydroxides, soluble alkali metal silicates with the formula (M2O) x :(SiO2) y wherein M is an alkali metal and the ratio of x:y is about 1.0:1.6 to 1.0:3.75, alkali metal carbonates, alkali metal bicarbonates, alkali metal sesquicarbonates, and alkali metal borates. Up to 30% of such alkali compounds may be included in the solid cast warewashing composition.
• the cast composition can contain 0-15 wt-% of a surfactant for cleaning purposes.
• a surfactant for cleaning purposes.
• surfactants which can be used include nonionic, anionic, cationic, and amphoteric surfactants, preferably nonionic surfactants.
• a neutral soluble salt may also be included in the warewashing composition.
• Neutral soluble salts are typically the reaction product of a strong acid and a strong base including sodium sulfate, sodium chloride and others. Up to 20 wt-% of a neutral soluble salt may be included in the warewashing composition.
• the cast composition may further comprise up to 10 wt-% of a dye and up to 10 wt-% of a perfume.
• a particularly useful detergent composition of this invention is formed by heating an aqueous composition comprising about 8.0 to 60 wt-%, preferably 8 to 35 wt-% water and about 20 to 55 wt-% alkali metal metasilicate in a reaction vessel to about 35 to 99°C., preferably 65 to 85°C. The composition is held at said temperature range for about 15 minutes to two hours to form an alkali metal metasilicate hydrate. The temperature of the composition is then allowed to fall below about 65°C. by cooling.
• About 1 to 70 wt-% of a hydrated alkali metal condensed phosphate having water of hydration sufficient to increase the rate of the solidification of the cast composition is added to the composition to form a suspension.
• the suspension is cooled to a temperature below about 55°C., preferably about 48 to 55°C.
• the suspension is cast in a mold with about 0.1 to 20 wt-% of the encapsulated bleaching source which is mixed into the suspension prior to casting or co-added while pouring the suspension into the mold.
• the composition is then cooled. As the mixture continues to cool, it solidifies to form a cast composition.
• the hydration of the metasilicate should be held at a high temperature.
• no interfacing ions should be present in the liquid metasilicate solution/slurry.
• the preparation of the cast composition is conducted in such a manner as to limit as much as possible the amount of condensed phosphate which dissolves and introduces itself into the crystallizing mass. A slurry of condensed phosphate is preferred.
• Optional components including a dye, a perfume, a surfactant, a defoamer, an additional sequestrant such as an alkali metal salt of a polyacrylic compound, a neutral soluble salt, an alkali, or mixtures thereof, can also be included in the composition before solidification.
• a dye can be added anytime after the hydration of the metasilicate.
• a perfume can be added at the same time as the encapsulate or just prior to casting, since excessive heat destroys perfumes.
• a surfactant can be added anytime after the hydration of the metasilicate.
• An additional sequestering agent such as an alkali metal salt of a polyacrylic acid compound can be added anytime after the hydration of the metasilicate, preferably prior to the addition of the encapsulate.
• a neutral soluble salt such as an alkali metal chloride or an alkali metal sulfate can be added anytime after the hydration of the metasilicate.
• a defoamer can be added anytime after the hydration of the metasilicate.
• An alkali metal compound selected from the group consisting of alkali metal hydroxides, soluble alkali metal silicates of the formula (M2O) x :(SiO2) y wherein M is an alkali metal and the ratio of x:y is about 1.0:1.6 to 1.0:3.75, alkali metal carbonates, alkali metal bicarbonates, alkali metal sesquicarbonates, alkali metal borates and mixtures thereof can be added anytime after the hydration of the metasilicate.
• the cast composition solidify quickly since the chlorine encapsulate coating can dissolve in the added water.
• 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 composition comprised 115.18 total parts.
• the contents were then poured into a 0.1 liter container simultaneously with 2.5 wt-% of the encapsulated chlorine source.
• the encapsulated chlorine source was made in accordance with Example 9.
• the contents of the container were mixed in the container.
• the mixture was then solidified in the container in 45 minutes.
• the percentage of available chlorine present in the cast composition after 2 to 3 weeks at room temperature was 84.92%.
• bleach granular dichloroisocyanurate dihydrate
• the bleach was fluidized with air and the bed heated to 68 - 74° C.
• the entire amount of first coating solution was sprayed onto the bleach granules through a Gustav Schlick Nozzle, Model 941, at an atomized air pressure of 40 psig to form once coated bleach particles.
• the process yielded 23.15 kg of protectively encapsulated bleach particles comprising 60 wt-% core of dichloroisocyanurate monohydrate bleach, 35 wt-% first coat of a mixture of 75 wt-% sodium sulfate and 25 wt-% sodium tripolyphosphate hexahydrate and 5 wt-% second coat of KLUCEL J.
• bleach granular dichloroisocyanurate dihydrate
• the bleach was fluidized with air and the bed heated to 72 - 74° C.
• the entire amount of first coating solution was sprayed onto the bleach granules through a Gustav Schlick Nozzle, Model 941, at an atomized air pressure of 40 psig to form once bleach coated particles.
• KLUCEL J a hydroxypropylcellulose purchased from Hercules, Inc.
• 70.94 kg water a second coating solution.
• the bed temperature was adjusted to 69 - 71° C. and the entire amount of second coating solution sprayed onto the once coated bleach particles through the Gustav Schlick nozzle to form twice-coated, protectively encapsulated bleach particles.
• the bed temperature was then adjusted to 74° C. and the protectively encapsulated dichloroisocyanurate monohydrate bleach particles dried.
• the process yielded 20.13 kg of protectively encapsulated bleach particles comprising 55.0 wt-% core of bleach, 35 wt-% first coat of a mixture of 75 wt-% sodium sulfate and 25 wt-% sodium tripolyphosphate hexahydrate and 10 wt-% second coat of KLUCEL J.
• bleach granular dichloroisocyanurate dihydrate
• the bleach was fluidized with air and the bed heated to 63 - 71° C.
• the entire amount of first coating solution was sprayed onto the bleach granules through a Gustav Schlick Nozzle, Model 941, at an atomized air pressure of 40 psig to form once coated bleach particles.
• the process yielded 21.95 kg of protectively encapsulated bleach particles comprising about 50 wt-% core of dichloroisocyanurate monohydrate bleach, 45 wt-% first coat of a mixture of 71 wt-% sodium sulfate and 29 wt-% sodium tripolyphosphate hexahydrate and 5 wt-% second coat of KLUCEL J.
• bleach a granular dichloroisocyanurate dihydrate which can be purchased from a number of sources.
• the bleach was fluidized with air and the bed heated.
• n-octyl sulfonate 40 wt-% n-octyl sulfonate, 60 wt-% water
• This second coating solution was diluted with 9.88 parts of soft water. This solution was sprayed onto the heated bed of particles to form twice coated protectively encapsulated bleach particles.
• KLUCEL J a hydroxypropylcellulose purchased from Hercules, Inc.
• 63.00 parts water a third coating solution.
• the bed temperature was adjusted to 56 - 64° C. and the entire amount of third coating solution sprayed onto the twice coated bleach particles through the Gustav Schlick nozzle to form thrice coated, protectively encapsulated bleach particles.
• the bed temperature was then adjusted to 66° C. and the protectively encapsulated bleach particles dried.
• protectively encapsulated bleach particles comprising about 43 wt-% core of dichloroisocyanurate monohydrate bleach, 31 wt-% first coat of a mixture of 71 wt-% sodium sulfate and 29 wt-% sodium tripolyphosphate hexahydrate, a second coat of 18 wt-% sodium n-octyl sulfonate and 9 wt-% third coat of KLUCEL J.

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• 1988
  • 1988-04-14 AU AU14619/88A patent/AU605573B2/en not_active Expired
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  • 1988-07-04 JP JP63165200A patent/JPH07103399B2/ja not_active Expired - Lifetime
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