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
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0026—Low foaming or foam regulating 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/78—Neutral esters of acids of phosphorus
• • 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
  • C11D3/046—Salts
• • 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
  • C11D3/3951—Bleaching agents combined with specific additives

Definitions

• This invention relates to detergent compositions which are particularly suitable for use in automatic dishwashers.
• Such compositions are normally alkaline and contain detergency builder materials, relatively low levels of low sudsing surfactants and a source of available chlorine.
• This invention is based on modifications in conventional, automatic dishwasher detergent compositions that provide surprisingly effective cleaning and lessening of spotting and filming while requiring little or no pretreatment. While not limited thereto, granular compositions are especially preferred.
• the invention reiates to automatic dishwasher detergent compositions containing a chlorine bleach ingredient, a surfactant compatible with said bleach ingredient and a source of bromide ions which comprise:
• compositions of the invention contain from about 20% to about 95% , preferably from about 40% to about 90%, by weight of deter- g en cy builder component, or mixtures thereof, on an anhydrous basis.
• the detergency builder material can be any of the detergent builder materials known in the art which include trisodium phosphate, tetrasodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate, sodium silicates having SiO 2 :Na 2 O weight ratios of from about 1:1 to about 3.6:1, sodium carbonate, sodium hydroxide, sodium citrate, borax, sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium carboxymethyloxy- succinate, sodium carboxymethyloxymalonate, polyphosphonates, polymeric carboxylates such as polyacrylates, and mixtures thereof.
• monomeric organic detergency builder materials comprise not more than about 10% of the composition by weight.
• Preferred detergency builder materials have the ability to remove metal ions other than alkali metal ions from washing so- lu tions by sequestration, which as defined herein includes chelation, or by precipitation reactions.
• Sodium tripolyphosphate is a particularly preferred detergency builder material which is a sequestering agent.
• Sodium carbonate is a preferred precipitation detergency builder, particularly when it is desirable to reduce the total phosphorous level of the compositions of the invention.
• Chlorinated trisodium orthophosphate can act as both a chlorine bleach and a precipitation detergency builder material.
• silicates especially sodium silicates having SiO 2 :Na 2 O weight ratios of from about 1: 1 to about 3.6:1 is a particularly preferred embodiment of the invention.
• Such silicates are a source of alkalinity useful In the automatic dishwashing process and also act to inhibit the corrosion of aluminum, glassware and ceramic glazes.
• compositions of the invention contain from about 15% to about 50% sodium tripolyphosphate, from about 5% to about 40% of sodium silicate solids as described hereinbefore and from 0% to about 25% sodium carbonate by weight.
• compositions of the invention can contain a chlorine bleach ingredient to provide from about 0.1% to about 5%, preferably from about 0.5% to about 3%, of available chlorine based on the weight of the detergent composition.
• An inorganic chlorine bleach ingredient such as chlorinated trisodium phosphate can be utilized, but organic chlorine bleaches such as the chlorocyanurates are preferred. Water-soluble di- chlorocyanurates such as sodium or potassium dichloroisocyanurate dihydrate are particularly preferred.
• Available chlorine is the chlorine which can be liberated by acidification of a solution of hypochlorite ions (or a material that can form hypochlorite ions in solution) and at least a molar equivalent amount of chloride ions.
• a conventional analytical method of determining available chlorine is addition of an excess of an iodide salt and titration of the liberated free iodine with a reducing agent.
• compositions of the invention contain from about 0.1% to about 15%, preferably from about 1.5% to about 8%, most preferably from about 2% to about 6%, of a low-foaming nonionic surfactant, preferably one which is solid at 35°C (95°F), more preferably one which is solid at 25°C (77°F).
• a low-foaming nonionic surfactant preferably one which is solid at 35°C (95°F), more preferably one which is solid at 25°C (77°F).
• Reduced surfactant mobility is a consideration in stability of the bleach component.
• Preferred surfactant compositions with relatively low solubility can be incorporated in compositions containing alkali metal dichtorocyanurates or other organic chlorine bleaches without an interaction that results in loss of available chlorine. The nature of this problem is disclosed in U.S. Patent 4,309,299 issued January 5, 1982 to Rapisarda et al and in U.S. Patent 3,359,207, issued December 19, 1967, to
• the surfactant is an ethoxylated surfactant derived from the reaction of a monohydroxy alcohol or alkylphenol containing from about 8 to about 20 carbon atoms, excluding cyclic carbon atoms, with from about 6 to about 15 moles of ethylene oxide per mole of alcohol or alkylphenol on an average basis.
• a particularly preferred ethoxylated nonionic surfactant is derived from a straight chain fatty alcohol containing from about 16 to about 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol, condensed with an average of from about 6 to about 15 moles, preferably from about 7 to about 12 moles, and most preferably from about 8 to about 9 moles of ethylene oxide per mole of alcohol.
• the ethoxylated nonionic surfactant so derived has a narrow ethoxylate distribution relative to the average.
• the ethoxylated nonionic surfactant can optionally contain propylene oxide in an amount up to about 15% by weight of the surfactant and retain the advantages hereinafter described.
• Preferred surfactants of the invention can be prepared by the processes described in U.S. Patent 4,223,163, issued September 16, 1980, Guilloty, incorporated herein by reference.
• the most preferred composition contains the ethoxylated monohydroxyalcohol or alkyl phenol and additionally comprises a polyoxyethylene, polyoxypropylene block polymeric compound; the ethoxylated monohydroxy alcohol or alkyl phenol nonionic surfactant comprising from about 20% to about 80%, preferably from about 30% to about 70%, of the total surfactant composition by weight.
• Suitable block polyoxyethylene-polyoxypropylene polymeric compounds that meet the requirements described hereinbefore include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane and ethylenediamine as the initiator reactive hydrogen compound.
• Certain of the block polymer surfactant compounds designated Pturonicw R and Tetronice by the BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable in the surfactant compositions of the invention.
• the compounds suitable for use in the surfactant compositions of the invention have relatively low cloud points. Cloud points of 1% solutions in water are typically below about 32°C and preferably from about 15°C to about 30°C for optimum control of sudsing throughout a full range of water temperatures and water hardnesses.
• the preferred surfactants of the invention in combination with the other components of the composition provide excellent cleaning and outstanding performance from the standpoints of residual spotting and filming.
• the preferred surfactants of the invention provide generally superior performance relative to ethoxylated nonionic surfactants with hydrophobic groups other than monohydroxy alcohols and alkylphenols, for example, polypropylene oxide or polypropylene oxide in combination with diols, triols and other polyglycols or diamines.
• compositions of the invention can optionally contain up to about 50%, preferably from about 2% to about 20%, based on the weight of ethoxylated nonionic surfactant of alkyl phosphate ester or mixtures thereof.
• Suitable alkyl phosphate esters are disclosed in U.S. Patent 3,314,891, issued April 18, 1967, to Schmolka et al, incorporated herein by reference.
• the preferred alkyl phosphate esters contain from 16-20 carbon atoms. Highly preferred alkyl phosphate esters are monostearyl acid phosphate and monooleyl acid phosphate, or salts thereof, particularly alkali metal salts, or mixtures thereof.
• the alkyl phosphate esters of the invention have been used to reduce the sudsing of detergent compositions suitable for use in automatic dishwashing machines.
• the esters are particularly effective for reducing the sudsing of compositions comprising nonionic surfactants which are heteric ethoxylated-propoxylated or block polymers of ethylene oxide and propylene oxide.
• compositions of the invention contain a water-soluble or water-solubilizable material capable of releasing from about 0.1 mole to about 10 moles, preferably from about 0.3 mole to about 3 moles, of bromide ions in aqueous solution per mole of available chlorine.
• Useful water-soluble bromide containing materials include alkali metal bromides, alkaline earth metal bromides, organic salts such as bromoacetamide, or bromamine; and inorganic salts such as CuBr or ZnBr 2"
• alkali metal bromides and alkaline earth metal bromides are preferred; sodium bromide, calcium bromide, and mixtures thereof are especially preferred.
• compositions of the invention are improved spotting and filming performance.
• China protecting agents including soluble zinc and aluminum salts, aluminosilicates, aluminates, etc., can be present in amounts of from about 0.1% to about 5%, preferably from about 0.5% to about 2%.
• Filler materials can also be present including sucrose, sucrose esters, sodium chloride, sodium sulfate, etc., in amounts from about 0.001% to about 60%, preferably from about 5% to about 30%.
• Hydrotrope materials such as sodium benzene sulfonate, sodium toluene sulfonate, sodium cumene sulfonate, etc., can be present in minor amounts.
• Dyes, perfumes, crystal modifiers and the like can also be added in minor amounts.
• compositions of the invention are not restricted as to manner of preparation.
• the preferred compositions can be prepared in any manner, including dry mixing, that results in formation of a granular product form.
• the process described in U.S. Patent 2,895,916 issued July 21, 1959, to Milenkevich et al, and variations thereof, are particularly suitable. Also particularly suitable is the process described in U.S. Patent 4,427,417, issued January 24, 1984 to Porasik. Both of these patents are incorporated herein by reference.
• A. 33.2 Parts sodium tripolyphosphate is metered into a Schugi blender-agglomerator and wetted with a metered atomized feed of 10 parts water, 4.2 parts of a mix consisting of 2 parts polyoxyalkylene nonionic surfactant (condensation product of C 18 alcohol with average of 7.9 moles ethylene oxide), 2 parts polyether polyol nonionic surfactant, and 0.2 parts monostearyl acid phosphate, forming small particle size agglomerates which are discharged into a closed container and continuously stirred for 15 minutes residence to effect hydration of the hydratable salts.
• polyoxyalkylene nonionic surfactant condensation product of C 18 alcohol with average of 7.9 moles ethylene oxide
• polyether polyol nonionic surfactant 2 parts polyether polyol nonionic surfactant
• monostearyl acid phosphate monostearyl acid phosphate
• the hydrated agglomerates are discharged through a grinder and then fed to a second Schugi blender-agglomerator concurrently with 20 parts of sodium carbonate, 17.2 parts sodium sulfate and 22.46 parts of an aqueous sodium silicate solution containing 47.3% solids and a Si0 2 :Na 2 0 weight ratio of 2.4 added as an atomized spray. Minor amounts of perfume and dye are also added to the silicate solution. The agglomerates of perfume and dye are also added to the silicate solution.
• the agglomerates formed in the second blender-agglomerator are fed into a fluid-bed dryer and 2.5 parts sodium dichloroisocyanurate dihydrate is added. The agglomerates are then contacted with heated air from blowers and held for 10 minutes residence to accomplish drying.
• the dried agglomerates are discharged from the fluid bed and sized.
• compositions were evaluated at a concentration of 0.3% in a Tergotometer with city water (Cincinnati - 6.5 grains hardness/gallon), at a temperature of 120°F (48.9°C).
• the soils were baked onto stainless steel coupons, except for the spaghetti starch which was baked onto a Pyrex coupon.
• the coupons were agitated at 65 rpm for 10 minutes and soil removal efficiency was then measured gravimetrically.
• compositions of the invention consistently out performed the control on all soils.
• Example III The compositions of Example III were evaluated on spaghetti starch under the standard testing conditions. The temperature was varied. Soil removal efficiency was measured after 10 minutes.
• compositions were evaluated for soil removal efficiency in a Tergotometer at a concentration of 0.3% in city water (Cincinnati - 6.5 grains hardness/gallon) at a temperature of 150°F (65.5°C).
• the soil (spaghetti starch) was baked onto a Pyrex® coupon and agitated for 8 minutes at 65 rpm.
• the following detergent compositions were tested for spot- ting/filming. The tests were run at 130°F (54.4°C) with 28.7 grains of product added to a Kenmore dishwasher. Water hardness was 7 grams per gallon. Eighteen grams of a combination Crisco/milk soil was added to the prewash. Four glasses were used for testing, glasses two and four were milk coated for each of the three cycles. There was a minimum cool down of two hours between cycles.
• the composition with the source of bromide ions outperformed an equivalent composition without bromide on spotting while performing equally on filming.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Detergent Compositions (AREA)

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Cited By (10)

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• 1985
  • 1985-12-05 EP EP85202020A patent/EP0186234A3/fr not_active Withdrawn
  • 1985-12-16 CA CA000497739A patent/CA1278235C/fr not_active Expired - Lifetime

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