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
  • C11D3/0073—Anticorrosion 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
  • C11D3/046—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
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/06—Phosphates, including polyphosphates

Definitions

• This invention relates to detergent compositions containing tarnish inhibitors and more particularly to polyphosphate compositions containing water-soluble stannous salts as tarnish inhibitors.
• compositions containing polyphosphates are now widely used for detergent and other purposes.
• Aqueous solutions of polyphosphates tend, when at certain pH values to tarnish copper, and nickel and copper alloys such as German silver (a nickel-zinc-copper alloy) to a variety of shades from yellow to bluish-black, especially if the solutions are at elevated temperatures and are allowed to remain in contact with the metal or alloy for several minutes. Since German silver is frequently used for household articles commonly washed in polyphosphatebuilt detergent compositions, it is evident that this is a serious problem.
• polyphosphate compositions are provided containing a tarnish inhibitor which compositions inhibit the formation of tarnish upon copper, and nickel and copper alloys such as German silver.
• the tarnish inhibitors of the invention are watersoluble inorganic and organic stannous salts, for example, stannous chloride, bromide, fluoride, tartrate, iodide, and sulfate.
• Stannic salts on the other hand are inefiective to inhibit the formation of tarnish.
• water-soluble stannous salt may be converted into a stannite or a soluble tin-polyphosphate complex.
• the tarnish inhibitors are referred to as water-soluble stannous salts, especially since on a production basis the tarnish inhibitors are added to the crutcher slurry of the detergent product in the form of water-soluble stannous salts.
• an amount of the water-soluble stannous salt is added to the polyphosphate composition which is sufiicient to give tarnish inhibition when the composition is used in. its normal way. It will be understood that the amount required will depend in part upon the tarnish inhibiting properties of the particular stannous salt in question, upon the tendency of the polyphosphate with which it is used to tarnish copper, and nickel and copper alloys, and upon the amount of polyphosphate present. In general, therefore, at least about 1.3% of the water-soluble stannous salt based on the weight of the polyphosphate present in the detergent composition will inhibit the formation of tarnish by the composition.
• the maximum amount of the stannous salt is not critical, but more than is necessary to give the desired effect will usually not be used, and of course an amount in excess of that soluble in an aqueous solution of the composition would not be used. In most cases, the maximum suggested would be about 6.7%.
• the tarnish inhibitors of the present invention are effective with water-soluble alkali metal polyphosphates It is believed that a minor proportion of the.
• the alkali metal polyphosphates may include, by way of example, pentasodium and pentapotassium tripolyphosphates, tetrasodium and tetrapotassium pyrophosphates, sodium and potassium hexametaphosphates, and hexasodium and hexapotassium tetrapolyphosphates.
• alkali metal polyphosphate There is no critical amount of alkali metal polyphosphate which need be employed in the compositions, the amount of polyphosphate in the compositions being dictated only by the optional presence of organic nonsoap detergents and builders which might be included in the detergent compositions.
• organic nonsoap detergents which may be either anionic, cationic, or nonionic detergents and builders, water, and inert materials.
• These detergent compositions may contain alkali metal polyphosphate in any amount, usually between 5% and conventional proportions of organic nonsoap detergent, usually within the range between 5% and 40%; at least about 1.3% of a watersoluble stannous salt based on the weight of the polyphosphate; and the balance builders and inert materials.
• the alkylaryl sulfonates are a class of anionic detergents which may be included in the detergent compositions.
• One example thereof is the sulfonated phenyl polypropylene alkanes, characterized by the branched chain structure of polypropylene and a tertiary alkyl carbon at the benzene ring, and having the following general structure:
• M is hydrogen, an alkali metal or an organic amine amidoalkane sulfonates which are characterized by the following structure:
• R-0 o-N-(oHnnsoaa Where A is hydrogen or alkali metal, i.e., ammonium, sodlum, or potassium, n is a small whole number from one to
• A is hydrogen or alkali metal, i.e., ammonium, sodlum, or potassium
• n is a small whole number from one to
• organic aliphatic aminosulfonic acid such as taurine, NH CH CH SO H
• N-substituted taurines such as N-methyl taurine, or aminopropane sulfonic
• Other water-soluble alkyl aromatic sulfonic acids may constitute optional components such as those prepared by alkylating benzene or naphthalene with a kerosene fraction followed by sulfonation of aliphatic sulfonic acids, esters of sulfuric acid with aliphatic alcohols of ten Patented Sept.
• R is a straight or branched chain saturated or unsaturated hydrocarbon group having from eight to eighteen carbon atoms or an aralkyl group having a straight or branched chain saturated or unsaturated hydrocarbon group of from eight to eighteen carbon atoms attached to the aryl nucleus, and attached to A through the aryl nucleus
• A is selected from the group consisting of ethereal oxygen and sulfur, carboxylic ester and thiocarboxylic ester groups and x is a number from eight to twenty.
• R can, for example, be a straight or branched chain octyl, nonyl, decyl, lauryl, myristyl, cetyl or stearyl group, or an alkyl aryl group such as octylbenzene, nonylbenzene, decylbenzene, stearylbenzene, etc.
• M is hydrogen or an alkali metal or organic amine cation and x, A and R are as above.
• R is alkyl
• the detergent can be regarded as derived from an alcohol, mercaptan, oxy or thio fatty acid of high molecular weight, by condensation with ethylene oxide.
• Typical of this type of alkyl ether are the condensation products of oleyl or dodecyl alcohol or mercaptan with from eight to seventeen moles of ethylene oxide, such as Emulfor ON, Nonic 218 and Sterox SE and SK.
• Typical alkyl esters are G1226 and Renex (polyoxyethylene ester of tall oil acids), Sterox CD and Neutronyx 330 and 331 (higher fatty acid esters of polyethylene glycol).
• the detergent can be derived from an alkyl phenol or thiophenol.
• the ethoxynated alkyl phenols and thiophenols have the following general formula:
• R is a straight or branched chain saturated or unsaturated hydrocarbon group having at least eight carbon atoms up to approximately eighteen carbon atoms, A is oxygen or sulfur and x is a number from eight to twenty.
• R can, for example, be a straight or branched chain octyl, nonyl, decyl, lauryl, cetyl, myristyl or stearyl group.
• Typical are the condensation products of octyl and nonyl phenol and thiophenol with from eight to seventeen moles of ethylene oxide, available commercially under the trade names NIW, Antarox A400, Igepal CA and CO, Triton X-100, Neutronyx 600 and Tergitol NFX.
• the optional supplemental builders may be alkali metal inorganic salts, typical examples of which include sodium and potassium sulfates, sodium and potassium chlorides, sodium and potassium silicates, and sodium and potassium carbonates.
• organic materials such as sodium carboxymethyl cellulose can be used as builders.
• the builder mixture is so chosen among alkaline, neutral, and acidic salts that the composition obtained in an aqueous 0.14% washing solution has a pH of about 7 or above.
• its pH lies within the range of about 7 to about 11, since solutions which are more alkaline may be irritating to the skin and tend to weaken some fabrics, particularly woolens.
• the alkali metal carbonates are preferred agents for bringing the pH of the solution to a high alkaline value within the preferred range.
• the detergent compositions of the invention inhibit the formation of tarnish upon copper, and nickel and copper alloys such as German silver in either hard or soft water. It will be appreciated that the detergent compositions may exist in any dry form, such as drum-dried or spraydried detergent compositions, or may be in liquid form.
• the polyphosphate detergent compositions may be prepared by conventional methods, as by blending the ingredients thereof in an aqueous solution or slurry and then drying the resulting mixture in a spray or drum 170 F. to provide 2.25 grams of polyphosphate per quart of solution. A tarnish inhibitor was then added thereto in the form of a solution. More water was then added thereto to give a total volume of one quart. 300 mls. of the solution were placed in a beaker and the temperature adjusted to F. to F. A strip of metal, such as.
• German silver, six inches by one inch which had been cleaned with a metal polish and rinsed and dried was partially immersed in the solution and allowed to remain for one-half hour at 160 F. to 170 F.
• the metal strip was then removed, rinsed and dried with a cloth.
• the strip was visually examined for tarnish and the effectiveness of the tarnish inhibitor rated as follows:
• Examples 1-18 below show that at least about 3% of a water-soluble stannous salt based on the weight of polyphosphate inhibits the formation of tarnish by typical polyphosphates, such as pentasodium tripolyphosphate, tetrasodium pyrophosphate, sodium hexametaphosphate, and hexasodium tetrapolyphosphate.
• typical polyphosphates such as pentasodium tripolyphosphate, tetrasodium pyrophosphate, sodium hexametaphosphate, and hexasodium tetrapolyphosphate.
• the examples show that at least about 3% of stannous chloride based on the weight of polyphosphate is effective in inhibiting the formation of tarnish by pentasodium tripolyphosphate and tetrasodium pyrophosphate, while at least about 0.3% of stannous chloride is effective in inhibiting the formation of tarnish by sodium hexametaphosphate. and at least about 1% of stannous chloride is effective in inhibiting the formation of tarnish by hexasodium tetrapolyphosphate.
• This solution tarnished German silver only to grade 1 while an identical solution without the presence of the stannous chloride tarnished German silver to grade 6.
• Tetra sodium pyrophosphate was substituted in the same amount for the pentasodium tripolyphosphate in the above composition.
• a strip of German silver metal placed in the solution of the composition containing stannous chloride was tarnished only to grade 1, whereas a strip of German silver metal placed in the solution of the composition without the presence of the stannous chloride tarnished to grade 6.
• compositions X and Y the amounts of the various components are expressed in percent by Weight.
• composition X (Examples 23-28) 6 6 4 2 1 1 Grading (Composition Y) (Examples 29-34) 6 4 4 3 3 1
• Examples 23-34 show that at least about 1.3% of stannous chloride based on the weight of polyphosphate inhibits the formation of tarnish by polyphosphate coman organic nonsoap detergent as shown by Examples 19- positions containing an organic anionic nonsoap detergent
• EXAMPLES 35-38 Sodium hexametaphosphate and hexasodium tetrapolyphosphate were each substituted for the same amount of tetrasodium pyrophosphate in composition X and the compositions tested in accordance with the test procedure.
• a stannous salt is also eifective as a tarnish inhibitor in polyphosphate compositions containing other organic anionic nonsoap detergents as well as supplemental builders as shown by Examples 39-42.
• the tarnish was reduced to grade 4 when 2.2% of stannous chloride based on the weight of polyphosphate was included in the composition containing the sodium salt of N-palmitoyl- N-methyl taurine, while the tarnish was reduced to grade 2 when 2.2% of stannous chloride based on the weight of polyphosphate was included in the composition containing sodium-3-dodecyloxy-Z-hydroxypropane sulfonate.
• a water-soluble stannous salt is also effective as a tarnish inhibitor in polyphosphate compositions containing either an organic cationic nonsoap detergent or an or-., ganic nonionic nonsoap detergent as well as supplemental" builders, as illustrated by Examples 43-46.
• EXAMPLES 43-46 I 18% of an organic cationic nonsoap detergent, name- 2 4 )a( 3 6 )b( 2 4 )c prepared by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene.
• composition X sodium 'dodecylbenzenesulfonate
• b is an integer selected from the group consisting of 26 to 30 and a plus 0 is an integer such that the molecule contains from 40% to 50% of ethylene oxide
• the amount of the organic nonsoap detergent present" in the polyphosphate composition may be varied within the range from about 5% to about 40% as noted above and as further illustrated by Examples 47-50.
• composition Percent by Weight Sodium Dodecylbenzenesulfonate- 40.0 Tetrasodium Pyrophosphate 45. Sodium Carbonate 3.0 Sodium Silicate 6.0 Sodium Carboxymethylceflulose 0. Water. 5. 5
• the water-soluble stannous salts are effective as tarnish inhibitors when incorporated in a detergent-poly phosphate slurry and the slurry drum-dried as shown by the following example.
• EXAMPLE 51 The composition shown below was prepared in the form of an aqueous slurry having a 30% water content and drum-dried. 5 grams of the drum-dried product per quart of distilled water tarnished German silver only to grade 1.
• Examples 52-53 illustrate the fact that the stannous salts are effective as tarnish inhibitors in polyphosphate compositions when the polyphosphate compositions are used in hard water. It will be noted that in all of the previous examples the water was soft water, i.e., distilled water.
• the process of cleaning articles formed of copper and copper and nickel alloys without imparting appreciable tarnish thereto which comprises washing said articles with a detergent composition consisting essentially of an alkali metal polyphosphate which in aqueous solution having a pH of from about 7 to about 11 tarnishes copper and copper and nickel alloys and a water soluble stannous salt in an amount to lessen the tarnishing action of the polyphosphate.
• a detergent composition consisting essentially of an alkali metal polyphosphate which in aqueous solution having a pH of from about 7 to about 11 tarnishes copper and copper and nickel alloys and a water soluble stannous salt in an amount to lessen the tarnishing action of the polyphosphate.
• alkali metal polyphosphate is sodium hexametaphosphate.
• alkali metal polyphosphate is hexasodium tetrapolyphosphate.
• alkali metal polyphosphate is pentasodium tripolyphosphate.
• the process of cleaning articles formed of copper and copper and nickel alloys without imparting appreciable tarnish thereto which comprises washing said articles with a detergent composition consisting essentially of from about 5% to about 50% of an alkali metal polyphosphate which in aqueous solution having a pH of from about 7 to about 11 tarnishes copper and copper and nickel alloys, from about 5% to about 40% of an organic nonsoap detergent, and a water-soluble stannous salt in an amount of at least about 1.3% based on the weight of the polyphosphate and suflicient to inhibit such tarnishing.
• a detergent composition consisting essentially of from about 5% to about 50% of an alkali metal polyphosphate which in aqueous solution having a pH of from about 7 to about 11 tarnishes copper and copper and nickel alloys, from about 5% to about 40% of an organic nonsoap detergent, and a water-soluble stannous salt in an amount of at least about 1.3% based on the weight of the polyphosphate and
• alkali metal polyphosphate is pentasodium tripolyphosphate.
• alkali metal polyphosphate is hexasodium tetrapolyphosphate.
• organic nonsoap detergent is an organic cationic nonsoap detergent.
• organic nonsoap detergent is an organic nonionic nonsoap detergent.
• organic nonsoap detergent is an organic anionic nonsoap detergent.

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• Chemical & Material Sciences (AREA)
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• Oil, Petroleum & Natural Gas (AREA)
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• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Detergent Compositions (AREA)

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Cited By (7)

Citations (6)

• 0
  • BE BE551379D patent/BE551379A/xx unknown
• 1955
  • 1955-08-16 US US528814A patent/US2903431A/en not_active Expired - Lifetime
• 1956
  • 1956-10-01 FR FR1158939D patent/FR1158939A/fr not_active Expired

Patent Citations (6)

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