US2813831A - Detergent compositions containing acyl dicyandiamide tarnish inhibitors - Google Patents

Detergent compositions containing acyl dicyandiamide tarnish inhibitors Download PDF

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Publication number
US2813831A
US2813831A US454841A US45484154A US2813831A US 2813831 A US2813831 A US 2813831A US 454841 A US454841 A US 454841A US 45484154 A US45484154 A US 45484154A US 2813831 A US2813831 A US 2813831A
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Prior art keywords
tarnish
dicyandiamide
detergent
copper
acyl
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Expired - Lifetime
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US454841A
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English (en)
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Scott Alan Dalton
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Lever Brothers Co
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Lever Brothers Co
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/32Amides; Substituted amides
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14Nitrogen-containing compounds
    • C23F11/146Nitrogen-containing compounds containing a multiple nitrogen-to-carbon bond

Definitions

  • This invention relates to cleaning compositions containing tarnish inhibitors and more particularly to polyphosphate and synthetic detergent compositions containing acyl dicyandiamides as tarnish inhibitors.
  • compositions containing polyphosphates and/or synthetic detergents are now widely used for detergent and other purposes.
  • Aqueous solutions of polyphosphates and some synthetic detergents 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 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 and detergent compositions are provided containing a tarnish inhibitor which compositions have a reduced tendency to tarnish copper, and nickel and copper alloys such as German silver.
  • the tarnish inhibitor of the invention is an acyl dicyandiamide which is described by the following general formula:
  • RtiiNH( J-NHON R is an aliphatic hydrocarbon group having either a straight or branched chain and can be saturated or unsaturated.
  • the number of carbon atoms in the R chain is not critical.
  • Optimum tarnish inhibiting properties are displayed by compounds in which R has from eleven to seventeen carbon atoms.
  • Typical R radicals having straight and branched chains are methyl, n-heptyl, n-octyl, tert-octyl, nonyl, decyl, undecyl, 2-ethyl decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, decynyl, dodecenyl, octa decenyl, octadecadienyl and dodecynyl.
  • acyl dicyandiamides are exemplary:
  • acyl dicyandiamide would be added to the polyphosphate and/or synthetic detergent composition sufiicient to give tarnish inhibition when the composition is used in its normal way, say, at a washing concentration. Usually about 0.5% of the acyl dicyandiamide gives adequate tarnish inhibition, but larger amounts can be used if desired. An amount of from 0.5 to 5% is effective under nearly all conditions and therefore is pre ferred.
  • the maximum amount of acyl dicyandiamide is not critical but more than is necessary to give the desired effect usually would not be used, and of course an amount in excess of that soluble in the use solution would not be used.
  • tarnish inhibitors of the invention are effective with water-soluble polyphosphates as a class at pH values where such polyphosphates tend to tarnish German silver (usually pH 6 or above) and particularly those polyphosphates identified by the following general formula from which it is seen that both the acids and their various salts are contemplated:
  • polyphosphoric acids and their alkali metal salts coming within the invention are the polymetaphosphoric acids (HPOa)x(a is l, b is 1, x is more than 1), pyrophosphoric acid H4P2O7 (a is 2, b is l, x is l), triphosphoric acid H5P301o (a is 3, b is 2, x is 1), and tetraphosphoric acid H6P4013 (a is 4, b is 3, x is l).
  • the tarnish inhibitors are particularly useful in synthetic detergent compositions which contain one or more polyphosphates as builders and one or more synthetic detergents, i. e., anionic detergents, nonionic detergents, and mixtures thereof. In many instances they display an enhanced tarnish-inhibiting action in the presence of both polyphosphate and detergent.
  • the polyphosphate-built detergent compositions should contain conventional proportions of active detergent, usually within the range between 5 to 40%, polyphosphate in any amount, usually between 5 to 50%, based on the total composition, and the residue builders and inert materials.
  • acyl dicyandiamides are not compatible with cationic detergents and display very poor tarnish-inhibiting action in their presence.
  • R1 and R2 are alkyl, of the type formula C I-I2,,+l, and at least one R is a polypropylene grou the whole alkyl group containing preferably twelve to fifteen carbon atoms.
  • A is hydrogen or an alkali metal, i. e., ammonium, sodium, or potassium
  • n is a small whole number from one to about five, preferably two or three
  • R is hydrogen, or an alkyl, aryl, or cycloaliphatic group, such as methyl
  • R is an alkyl or alkylene radical, such as myristyl, palmityl, oleyl and stearyl
  • Sodium palmitic tauride, sodiumpalmitic methyl tauride, sodium myristic methyl tauride, sodium palmitic-stearic methyl tauride and sodium palmitic methyl amidopropane sulfonate have been found to be particularly suitable for use in the compositions of the invention.
  • These compounds are prepared by interacting the corresponding aliphatic acid anhydride or halide with an or ganic aliphatic aminosulfonic acid, such as taurine, NHzCHzCHzSOsl-I, and the various N-substituted taurines, such as N-methyl taurine, or aminopropane sulfonic acid, NH2(CH2)3SO3H.
  • an or ganic aliphatic aminosulfonic acid such as taurine, NHzCHzCHzSOsl-I
  • the various N-substituted taurines such as N-methyl taurine, or aminopropane sulfonic acid, NH2(CH2)3SO3H.
  • the invention is also applicable to other water-soluble alkyl aromatic sulfonic acids, such as those prepared by alkylating benzene or naphthalene with a kerosene fraction followed by sulfonation to aliphatic sulfonic acids, esters of sulfuric acid with aliphatic alcohols of ten to eighteen carbon atoms, particularly those derived by the reduction of coconut oil, palm oil and like long-chain fatty acids, sulfonated castor oil, esters and 'ethers of isethionic acid, long-chain fatty acid esters and long-chain alkyl ethers of 1,2-dihydroxy propane-B-sulfonic acid and sulfuric acid esters of mono-glycerides and glycerol monoethers.
  • the salts of these acids are ordinarily employed.
  • tarnish inhibitors are also useful with nonionic detergents, such as, for example, dialkanolamidcs, and the alkyl oxyether and ester and thioether and ester detergents having the following general formula:
  • R is a straight orbranched chain saturated or unsaturated hydrocarbon group having from eight to eighteen carbon atoms or an aralkyl group having a straight or branched 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, st earyl benzene, etc.
  • the sulfated ethoxynated derivatives of the above also are useful anionic detergents:
  • M is hydrogen or an alkali metal or organic amine cation and x, A and R are as above.
  • 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, Sterox SE and Sterox SK.
  • Typical alkyl esters are 61226 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 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 thio-phenol with from eight to seventeen moles of ethylene oxide, available commercially under the trade names NlW, Antarox A-400, Igepal CA and CO, Triton X-lOD, Neutronyx 600 and fTergitol NFX.
  • the detergent composition can contain supplemental builders including alkali metal and alkaline earth metal sulfates, chlorides, silicates, borates, carbonates, metaphosphates, and orthophosphates, such as sodium silicate, magnesium sulfate, sodium tetraborate, sodium carbonate, sodium sulfate, trisodium phosphate, potassium carbonate, disodium orthophosphate, sodium rnetaphosphate, calcium sulfate, calcium chloride, sodium chloride, sodium borate and potassium metaphosphate.
  • supplemental builders including alkali metal and alkaline earth metal sulfates, chlorides, silicates, borates, carbonates, metaphosphates, and orthophosphates, such as sodium silicate, magnesium sulfate, sodium tetraborate, sodium carbonate, sodium sulfate, trisodium phosphate, potassium carbonate, disodium orthophosphate, sodium rnetaphosphate, calcium sulfate, calcium chloride, sodium chloride,
  • organic materials such as starch, polyethylene glycols, polyvinyl alcohols and salts of carboxymethylcellulose can be used as builders. It has been found that between about 0.1 and 1% of an alkali metal carboxymethylcellulose increases detergency and sudsing.
  • the builder mixture is so'chosen among alkaline, neutral andacidic salts that the composition obtained in an aqueous 0.14% solution has a pH of 7 or above.
  • its pH lies within the range from 7 to about 10 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 composition is 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 dryer at elevated temperatures.
  • the pure tarnish inhibitors may be added to the polyphosphate or detergent composition at any stage of its manufacture, to the finished polyphosphate or detergent composition, or to the polyphosphate or detergent solution.
  • a crude preparation is to be used, it is preferred to incorporate it direct in the solution, since processing, such as spray drying, may adversely affect the tarnish-inhibiting properties of such crude preparations.
  • Dicyandiamide 105 g. (1.25 moles) was mixed with 112 g. two moles) of potassium hydroxide in 900 cc. of acetone while the temperature was kept at 10 C. for one hour. To this solution there was slowly added 219 g. (one mole) of lauroyl chloride at a temperature below 10 C. The reaction mixture was diluted with 3 liters of water and then acidified with acetic acid. The precipitate of the crude acyl dicyandiamide was filtered and washed with acetone to remove the fatty acid. An aqueous washing removed the water-soluble impurities.
  • the myristoyl and stearoyl dicyandiamides were prepared in an identical manner, using the same molar proportions as employed in the preparation of the lauroyl dicyandiamide.
  • acyl dicyandiamides used in Examples 7 to 10 were crude products from a modified method of preparation in which water was substituted for the acetone and no attempt was made to purify the reaction product.
  • the myristoyl and stearoyl dicyandiamides are the most effective; the lauroyl dicyandiamide is elfective at a 0.79% concentration.
  • the myristoyl and stearoyl dicyandiamides are the most efiective of those tested.
  • the lauroyl dicyandiamide is elfective at higher concentrations.
  • the lauroyl .de rivative is the mo'st eifective.
  • Example 13 shows that lauroyl dicyandiamide is effective in overcoming the tarnishing etfect of the tetrasodium pyrophosphate (cf. Example 11).
  • compositions containing tarnish inhibitors of the invention have a reduced tendency to tarnish copper, nickelcopper zinc alloys such as German silver, coinage nickel or brassuwhich normally tarnish when exposed to aqueous solutions containing polyphosphates and/ or syntheticdetergents. It is not possible at .thistime to explain why the compounds of the invention are effective tarnishinhibitors. However, 'it has been observed thatwhen a German silver utensil is'immersed for a'period in an inhibitorand polyphosphate-containing detergent solution, and then immersed in a p0lyphosphatewontaining detergent solution not containing inhibitor, only slight tarnishing results. "This is taken as an indication thatthe inhibitor is preferentially adsorbed by the metal, and that this is important in tarnish prevention, but of course .such evidence is not conclusive.
  • A1 detergent composition consistingiessentially of a water 'soluble inorganic polyphosphatewhich in aqueous solution tarnishes copper and copper and nickel alloys and: a compound'having tarnishinhibitingproperties and defined byfthe general formula:
  • a nonsoap detergent composition consisting essentially of-an. active organic nonsoap detergent selected from*the group consisting of'anionic and nonionic synthetic detergents whichin aqueous 'solution tarnishes copper andv copper andnickel alloys and a compound having tarnish-inhibiting properties and defined by the general. formula:
  • R is an aliphatic hydrocarbon radical, the said compound being in an amount to-lessen thetarnishing action of the detergent.
  • Adeterge'nt composition inaccordance with claim 5 in whiclr'the tarnish inhibitor is stearoyl: dicyandiamide.
  • 9. -A detergentcomposition in accordance'with claim5 in"whieh' the detergent is sodium 'phenylpolypropylene sulfon'ate,
  • R is an aliphatic hydrocarbon radical
  • the said compound being-inian amount-.tolessen the tarnishing action of the polyphosphate.
  • a detergent composition in accordance with claim 11 in'which the tarnish inhibitor is lauroyl dicyandiamide.
  • a detergent composition consisting essentially of a Water-soluble"substance;selected from their, group cou- 9 sisting of inorganic polyphosphates and anionic and nonionic synthetic nonsoap detergents which in aqueous solution tarnish copper and copper and nickel alloys and a compound having tarnish inhibiting properties and defined by the general formula: 5
  • R is an aliphatic hydrocarbon radical, the said compound being in an amount to lessen the tarnishing 10 action of the substance.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Detergent Compositions (AREA)
US454841A 1954-04-21 1954-09-08 Detergent compositions containing acyl dicyandiamide tarnish inhibitors Expired - Lifetime US2813831A (en)

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US (1) US2813831A (cs)
BE (1) BE537528A (cs)
CH (1) CH339308A (cs)
DE (1) DE1012018B (cs)
FR (1) FR1131946A (cs)
GB (1) GB772493A (cs)
NL (1) NL84040C (cs)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2618605A (en) * 1949-02-04 1952-11-18 Procter & Gamble Detergent compositions containing metal discoloration inhibitors
US2618606A (en) * 1949-02-04 1952-11-18 Procter & Gamble Detergent compositions containing metal discoloration inhibitors
US2692236A (en) * 1951-03-14 1954-10-19 Colgate Palmolive Co Nonsoap detergent compositions containing antitarnishing agents
US2698302A (en) * 1951-05-02 1954-12-28 Colgate Palmolive Co Detergent compositions containing metal discoloration inhibitors

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL77796C (cs) * 1950-07-08
US2618608A (en) * 1952-09-12 1952-11-18 Procter & Gamble Detergent compositions containing metal discoloration inhibitors

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2618605A (en) * 1949-02-04 1952-11-18 Procter & Gamble Detergent compositions containing metal discoloration inhibitors
US2618606A (en) * 1949-02-04 1952-11-18 Procter & Gamble Detergent compositions containing metal discoloration inhibitors
US2692236A (en) * 1951-03-14 1954-10-19 Colgate Palmolive Co Nonsoap detergent compositions containing antitarnishing agents
US2698302A (en) * 1951-05-02 1954-12-28 Colgate Palmolive Co Detergent compositions containing metal discoloration inhibitors

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NL84040C (cs) 1957-02-15
FR1131946A (fr) 1957-03-01
BE537528A (cs) 1955-10-20
DE1012018B (de) 1957-07-11
NL196631B (cs) 1956-04-16
GB772493A (en) 1957-04-17
CH339308A (de) 1959-06-30

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