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
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/02—Inorganic compounds
  • C11D7/04—Water-soluble compounds
  • C11D7/06—Hydroxides
• • 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
  • C11D3/3955—Organic bleaching agents
• • 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
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/02—Inorganic compounds
  • C11D7/04—Water-soluble compounds
  • C11D7/10—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
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/02—Inorganic compounds
  • C11D7/04—Water-soluble compounds
  • C11D7/10—Salts
  • C11D7/12—Carbonates bicarbonates
• • 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
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/02—Inorganic compounds
  • C11D7/04—Water-soluble compounds
  • C11D7/10—Salts
  • C11D7/14—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
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/02—Inorganic compounds
  • C11D7/04—Water-soluble compounds
  • C11D7/10—Salts
  • C11D7/16—Phosphates including polyphosphates

Definitions

• ABSTRACT OF THE DISCLOSURE Cleaning compositions inhibited against attack on glass and glazed ceramic and porcelain surfaces comprising essentially between about 80% and 99% by weight of at least one ingredient selected from the group consisting of caustic alkali, alkali metal carbonate, alkali metal phosphate, alkali metal silicate, alkali metal borate, alkali metal sulfate, alkali metal chlorinated cyanurate, chlorinated cyanuric acid and chlorinated trisodium phosphate, and between about 0.5% and 20% by weight of at least one alkali metal aluminum orthophosphate.
• the present invention is directed to improved cleaning compositions inhibited against deteriorative attack upon glass and glazed ceramic and porcelain surfaces, and a method of cleaning said glass and glazed ceramic and porcelain surfaces using said cleaning compositions in aqueous media.
• One object of this invention is to provide alkaline cleaning compositions having improved inhibition against attack on glass or glazed ceramic or porcelain surfaces.
• Another object is to provide a group of inorganic phosphorous compounds which inhibit to a very substantial degree the attack of automatic dishwasher detergent compositions and the like upon glazed china and earthenware.
• alkaline and acidic alkali metal aluminum orthophosphates may be incorporated in alkaline cleaning compositions to substantially reduce attack on glass and glazed surfaces.
• An unexpected and important finding is that the alkali metal aluminum orthophosphates are markedly superior for this purpose to sodium aluminate, the standard inhibitor used today in household detergent dishwashing compositions.
• the acidic orthophosphate inhibitors of the instant invention may be represented by the following empirical formula:
• M is an alkali metal, preferably sodium and/or potassium
• x is an integer between 1 and inclusive
• y is an integer between 2 and 4 inclusive
• z is an integer between 11 and 17 inclusive, with the sum of x+3y+z 3,410,804 Patented Nov. 12, 1968 ice numerically equal to the sum of the valences of the phosphate (PO 5) radicals, i.e., between 21 and 30.
• PO 5 phosphate
• alkaline orthophosphates which may be used in accordance with the present invention and their method of preparation are set forth in U.S. Patent 3,097,949, issued July 16, 1963.
• the alkaline sodium aluminum orthophosphate reaction products have the following approximate empirical composition:
• alkali metal aluminum orthophosphates or sodium aluminum orthophosphates is intended to include both the acidic and alkaline orthophosphates described hereinabove.
• the cleaning compositions of the instant invention are mixtures which may comprise, in addition to the inhibitors disclosed herein, a multiplicity of various well known ingredients but normally between about and 99% by weight of one or more of the following: a caustic alkali such as sodium hydroxide; an alkali metal salt such as alkali metal carbonates, phosphates, borates, silicates and sulfates; an organic or inorgnic active chlorine compound such as an alkali metal chlorinated cyanurate, chlorinated cyanuric acid, chlorinated trisodium phosphate or other nitrogen-containing halogenated compound, e.g., N-chloro succinarnide; and possibly a detergent or surface active compound, preferably a low or non-foamer, e.g., a nonionic alkyl aryl polyether such as Triton CF 10, a nonionic amine polyglycol condensate such as Triton CF 32, or an anionic sodium dodecyl
• a moderate or high foaming detergent may be used together with a foam depressant such as a silicone anti-foam compound.
• a foam depressant such as a silicone anti-foam compound.
• a germicidal quaternary ammonium compound, such as benzenethionium chloride is also commonly used in such cleaning compositions.
• these compositions are dissolved in water maintained at a suitable temperature (usually above 120 F.), the proportions of cleaning composition and water being such that the cleaning solutions formed are suitable for the intended industrial or household use.
• the cleaning composition is of the highly alkaline type (pH 12 or above) consisting normally of about 50% to by weight of caustic alkali (sodium hydroxide), 0% to 40% by weight of one or more materials selected from sodium carbonate, trisodium phosphate, tetrasodium pyrophosphate and sodium metasilicate, and 0.5 to 20% by weight of an etching inhibitor as described hereinbefore.
• caustic alkali sodium hydroxide
• 0% to 40% by weight of one or more materials selected from sodium carbonate, trisodium phosphate, tetrasodium pyrophosphate and sodium metasilicate 0.5 to 20% by weight of an etching inhibitor as described hereinbefore.
• the household dishwashing detergent compositions will comprise normally between about 20% and 80% of a condensed phosphate builder (sodium tripolyphosphate, tetrasodium pyrophosphate, potassium pyrophosphate, etc.), and between 5% and 65% by weight of one or more of the following: a sodium silicate (e.g., sodium metasilicate anhydrous or pentahydrate), preferably a detergent or surface active agent, and one or more specialized ingredients or fillers such as sodium chloride trisodium phosphate, sodium borate, chlorinated trisodium phosphate, chlorinated cyanuric acid derivatives, sodium sulfate, sodium carbonate, and a sanitizing agent.
• An organic water softening or chelating ingredient such as the salts of ethylenediamine tetracetic acid or nitrilo acetic acid and the like may also be used in place of part or all of the phosphate builder.
• Both the household and industrial cleaning compositions may be dissolved, preferably in water, and marketed in solution suspension or emulsion form to be later dissolved in a large volume of water for practical use. Accordingly, proportions given are on a dry weight basis and do not include any water or other solvent which may be used to convert the cleaning compositions to a liquid form. However, the usual practice is to prepare and market such compositions in powdered or granular form.
• a household dishwasher detergent may also contain borax (sodium tetraborate) and common salt (sodium chloride).
• Industrial cleaning compositions may in addition to the aforesaid ingredients contain sodium gluconate, sodium citrate or sodium tartrate.
• the alkali metal aluminum orthophosphates are effective in preventing attack at concentrations as low as about 0.5% and as high as 20% by weight of the dry ingredients.
• a preferred concentration in the dry industrial bottle washing formulations is between 2% and 15% by weight.
• a particularly preferred range for the inhibitor is between 2% and 6% by weight.
• Typical dishwashing compositions in accordance with the invention will preferably contain the following ingredients in the indicated proportions Ingredient: Parts by Weight Sodium tripolyphosphate 3060 Trisodium phosphate 30 Sodium metasilicate -50 Sodium carbonate 0-20 Detergent 0-4 Alkali metal aluminum orthophosphate 26 In the above formulation, the trisodium phosphate may be chlorinated.
• a typical dishwashing formulation according to this invention containing a chlorinated isocyanurate has the following ingredients Ingredient: Parts by weight Sodium tripolyphosphate 40 Trisodium phosphate 10 Sodium metasilicate, anhydrous 35 Sodium carbonate 9 Surfactant (Triton CF-lO) 1 Potassium dichloroisocyanurate 1 Alkali metal aluminum orthophosphate 4 TABLE I.TEST FORMULATION Ingredient: Parts by Weight Sodium tripolyphosphate 40 Trisodium phosphate 10 Sodium metasilicate, anhydrous 35 Sodium carbonate 10 Surfactant (Triton CF-10) 1 Inhibitor 4 RESULTS Retardation of China Glaze Attack [10-hour immersion time: 212i1 F.]
• the compound having the formula Na Al I-I (PO -2.5H O and its method of preparation are not previously disclosed in the art.
• This compound may be prepared as follows: To 10 moles of H PO acid) is added 1.35 moles of Na CO and the mixture is heated to 80 C. Then 1.15 moles of Al O -3H O is added and the mixture heated to C. The reaction mixture is held under reflux at 90 C. until considerable precipitate forms. The mixture is subsequently filtered; the collected sodium aluminum phosphate crystals are washed with cold water, then ethanol and finally dried at C.
• the compound corresponds to the formula Na Al H (PO -2.5H O with an X-ray diffraction pattern showing lines of major intensity at 3.07, 4.00 and 8.10 angstroms. It is soluble to the extent of 4 g. per 100 ml. H O with some decomposition and exhibits a pH of 3.0 in a 1% solution.
• the compound exhibits endotherms at 210 C. (about 6 moles of H 0 loss), 240-255 C. (an additional 1.5 moles H O loss), 320 C. (an additional 1.5 moles H O loss) and 430 C. (an additional 1 mole H O loss).
• the crystals by microscopic examination appear to be rhombohedral with oblique extinction under cross-Nichols.
• Example 1 Dishwashing detergent compositions were formulated and tested in accordance with the CSMA standard procedure mentioned supra.
• Inhibitor Sodium alu-minate (standard) [Solution pH: Initial12.5, final-12.02] Time (brs.): Observations Bright glosspattern intense.
• water marks refers to very fine lines which appear in the glazed dish surface. Since these lines are produced by attack of the glaze by alkali, they cannot be removed by washing, rubbing or ordinary after-treatment of the dishes.
• Treated saucer showed no water marks or fading when compared to untreated saucer.
• Formulation Ingredient Parts by weight Sodium tripolyphosphate 45 Sodium metasilicate pentahydrate 20 Sodium carbonate 10 Chlorinated trisodium phosphate 20 Surfactant (Triton CF-lO) l Inhibitor 4 The results of these tests are summarized in the following data:
• Example 3 An industrial bottle washing solution is prepared by dissolving 48 parts caustic soda and 7 parts inhibitor in 1,450 parts by weight of water. Into this solution, maintained at a temperature of 185i5 F., are placed new glass bottles weighing approximately 400 g. After exposing the bottles to this solution for a period of six days, the bottles are removed from the solution and weighed to determine the weight loss after exposure. By the above procedure, the acidic and alkaline sodium aluminum phosphates are found to inhibit attack on the glass bottles to a substantial degree.
• a cleaning composition inhibited against attack on glass and glazed ceramic and porcelain surfaces consisting essentially of between about 80% and 99% by weight of at least one ingredient selected from the group consisting of caustic alkali, alkali metal carbonate, alkali metal phosphate, alkali metal silicate, alkali metal borate, alkali metal sulfate, alkali metal chlorinated cyanurate, chlorinated cyanuric acid, and chlorinated trisodium phosphate, and between about 0.5% and by weight of at least one alkali metal aluminum orthophosphate of the formulae:
• M A1 H (PO4) 7 m wherein M is an alkali metal, x is an integer between 1 and 5 inclusive, y is an integer between 2 and 4 inclusive, and z is an integer between 11 and 17 inclusive, with the sum of x+3y+z numerically equal to the sum of the valences of the phosphate (PO radicals; and
• x is a number of from 6 to 15
• y is a number from 1.5 to 4.5
• z is a number from 4 to 40.
• composition of claim 1 wherein said composition consists essentially of between 50% and 95% by weight of caustic alkali and between 2% and 15% by weight of at least one sodium aluminum orthophosphate.
• An alkaline water soluble organic anionic or nonionic automatic dishwashing composition inhibited against attack on glass and glazed ceramic and porcelain surfaces consisting essentially of between 20% and by weight of a condensed phosphate builder; and between 0.5% and 20% by weight of at least one sodium aluminum orthophosphate of the formulae:
• M is an alkali metal
• x is an integer between 1 and 5 inclusive
• y is an integer between 2 and 4 inclusive
• z is an integer between 11 and 17 inclusive, with the sum of x+3 y+z numerically equal to the sum of the valenecs of the phosphate (PO radicals;
• x is a number of from 6 to 15
• y is a number from 1.5 to 4.5
• z is a number from 4 to 40.
• the alkaline dishwashing composition of claim 3 wherein said composition consists essentially of the following ingredients in the indicated proportions- Ingredient: Parts by weight Sodium tripolyphosphate 30-60 Trisodium phosphate 5-30 Sodium metasilicate 10-50 Sodium carbonate 0-20 Alkali metal aluminum orthophosphate 2-6 5.
• the alkaline dishwashing composition of claim 3 wherein said composition comprises essentially the following ingredients in the approximate indicated proportions- Ingredient: Parts by weight Sodium tripolyphosphate 40 Trisodium phosphate 10 Sodium metasilicate, anhydrous 35 Sodium carbonate 10 Sodium aluminum orthophosphate 4 6.
• the alkaline dishwashing composition of claim 3 wherein said composition comprises essentially the following ingredients in the approximate indicated proportions- Ingredient: Parts by weight Sodium tripolyphosphate 45 Sodium metasilicate 20 Sodium carbonate 10 Chlorinated trisodium phosphate 20 Sodium aluminum orthophosphate 4 7.
• the alkaline dishwashing composition of claim 3 wherein said composition comprises essentially the following ingredients in the approximate indicated proportions Ingredient: Parts by weight Sodium tripolyphosphate 40 Trisodium phosphate 10 Sodium metasilicate, anhydrous 35 Sodium carbonate 10 NaAl H (PO -4H O 4 8.
• the alkaline dishwashing composition of claim 3 wherein said composition comprises essentially the following ingredients in the approximate indicated proportions- Ingredient: Parts by weight Sodium tripolyphosphate 40 Trisodium phosphate 10 Sodium metasilicate, anhydrous 35 Sodium carbonate 10 Na A13H15(PO )92.5H O 4 9.
• the alkaline dishwashing composition of claim 3 wherein said composition comprises essentially the following ingredients in the approximate indicated proportions Ingredient: Parts by weight Sodium tripolyphosphate 40 Trisodium phosphate 10 Sodium metasilicate, anhydrous 35 Sodium carbonate 10 Na Al2H15(PO4) 4 10.
• the alkaline dishwashing composition of claim 3 wherein said composition comprises essentially the following ingredients in the approximate indicated proportions Ingredient: Parts by weight Sodium tripolyphosphate 45 Sodium metasilicate, pentahydrate 20 Sodium carbonate 10 Chlorinated trisodium phosphate 20 11.
• the alkaline dishwashing composition of claim 3 wherein said composition comprises essentially the following ingredients in the approximate indicated proportions- Ingredient: Parts by weight Sodium tripolyphosphate 45 Sodium metasilicate, pentahydrate 20 Sodium carbonate 10 Chlorinated trisodium phosphate 2O Na3A12H15(PO4)g.4H2O 4 12.
• the alkaline dishwashing composition of claim 3 wherein said composition comprises essentially the following ingredients in the approximate indicated proportions Ingredient: Parts by weight Sodium tripolyphosphate Trisodium phosphate 10 Sodium metasilicate 35 Sodium carbonate 9 Potassium dichloroisocyanurate 1 Sodium aluminum orthophosphate 4 13.
• a method for inhibiting the attack by an aqueous alkaline cleaning solution on glass and glazed ceramic and porcelain surfaces which comprises dissolving in said aqueous alkaline solution between 0.5% and 20% by dry weight of the cleaning ingredients therein of an alkali metal aluminum orthophosphate drying the glass, glazed ceramic and porcelain surfaces.
• the alkali metal aluminum orthophosphate is sodium aluminum orthophosphate, and the latter is present in an amount which comprises between 2% and 6% by dry weight of the ingredients in said aqueous alkaline cleaning solution.

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Cited By (10)

Citations (6)

• 1966
  • 1966-01-03 US US517896A patent/US3410804A/en not_active Expired - Lifetime
  • 1966-11-08 IL IL26825A patent/IL26825A/xx unknown
  • 1966-11-09 GB GB50234/66A patent/GB1148197A/en not_active Expired
  • 1966-11-26 DE DE19661617203 patent/DE1617203A1/de active Pending
  • 1966-12-15 CH CH1799766A patent/CH489595A/de not_active IP Right Cessation
  • 1966-12-29 FR FR89423A patent/FR1506967A/fr not_active Expired
• 1967
  • 1967-01-03 BE BE692128D patent/BE692128A/xx unknown
  • 1967-01-03 NL NL676700057A patent/NL146876B/xx unknown

Patent Citations (6)

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