US2692236A - Nonsoap detergent compositions containing antitarnishing agents - Google Patents

Nonsoap detergent compositions containing antitarnishing agents Download PDF

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Publication number
US2692236A
US2692236A US215634A US21563451A US2692236A US 2692236 A US2692236 A US 2692236A US 215634 A US215634 A US 215634A US 21563451 A US21563451 A US 21563451A US 2692236 A US2692236 A US 2692236A
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United States
Prior art keywords
detergent
water
tarnishing
detergent composition
sodium
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US215634A
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English (en)
Inventor
Sweet Warren William
Mead William Jasper
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Colgate Palmolive Co
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Colgate Palmolive Co
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Publication date
Priority to BE509522D priority Critical patent/BE509522A/xx
Priority to NL75956D priority patent/NL75956C/xx
Application filed by Colgate Palmolive Co filed Critical Colgate Palmolive Co
Priority to US215634A priority patent/US2692236A/en
Priority to DEC4941A priority patent/DE928543C/de
Priority to GB27783/51A priority patent/GB704576A/en
Priority to CH307922D priority patent/CH307922A/de
Application granted granted Critical
Publication of US2692236A publication Critical patent/US2692236A/en
Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/20—Other heavy metals
    • 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
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea

Definitions

  • the present invention relates to novel detergent compositions and, more particularly, to detergent compositions having improved anti-tarnishing properties.
  • Certain detergent compositions have been known for many years and have been widely accepted since their lime resistance and other valuable properties make them advantageous for many uses, e. g., dishwashing, laundering, etc.
  • An unexpected difficulty has been noted in the cleansing of certain metallic surfaces, such as articles made of German silver or having a German silver base, by solutions of such detergent compositions, containing certain water-soluble polyphosphate compounds.
  • the Washed articles may exhibit tarnishing of the metallic surfaces.
  • the undesirable effects may range from a diminution or loss of luster of the highly polished metallic surfaces to a harsh discoloration or stain, or worse.
  • the tarnish film if it may be so called, is of such a nature that it is difiicult to analyze, even with microscopic or X-ray means.
  • the discoloration tarnishing effects appear to be particuanism by which these desired results are obtained larly objectionable in non-soap detergent compositions containing complex polyphosphates, usually in aqueous alkaline solutions of such detergent compositions.
  • Such adverse effects represent a significant problem from the standpoint of consumer appeal and in the cleansing and maintenance of such susceptible metals.
  • the present invention relates to detergent compositions consisting essentially of a non-soap water-soluble synthetic detergent, a water-soluble polyphosphate compound, and a minute amount (e. g. up to about 1 of a symmetrical N,N' dibutyl thiourea as a tarnish inhibitor.
  • a minute amount e. g. up to about 1 of a symmetrical N,N' dibutyl thiourea as a tarnish inhibitor.
  • the detergent composition may comprise water-soluble inorganic polyphosphate salts.
  • Thesesalts have the property of inhibiting precipitation of calcium material andrthe like in aqueous solution and may be considered as derived from orthophosphoric acid or the like by the removal of water, though any suitable means of manufacture may be employed ifdesired.
  • These molecularlydehydrated polyphosphate salts may be wholly or partially neutralized, such as the alkali metal or ammonium salts of tripolyphosphoric, tetraphosphoric, and pyrophosphoric acids.
  • Suitable examples are sodium tripolyphosphate (NasPsOio), potassium tripolyphosphate, tetrasodium pyrophosphate, hexasodium hexametaphosphate (Grahams salt), hexasodium tetraphosphate, etc.
  • novel compositions of the present invention may also contain as the active ingredient a water-soluble non-soap organic synthetic detergent either with or without admixture with the polyphosphates. It is preferred to use the anionic sulphated or sulphonated synthetic detergents (including suitable mixtures thereof). Included therein are the aliphatic sulphated or sulphonated detergents, such as the sulphated aliphatic compounds having about 12 to about 26 carbon atoms, and more particularly, the aliphatic acyl-containing compounds having an acyl radical of about 8 to 22 carbon atoms such as the aliphatic carboxylic ester detergents.
  • aliphatic anionic detergents may be found the sulphuric acid esters of polyhydric alcohols incompletely esterified with higher fatty acids, e. g. coconut oil mono-glyceride mono-sulphate, tallow di-glyceride monosulphate; the long chain pure or mixed higher alkyl sulphates, e. g. lauryl sulphate, cetyl sulphate, higher fatty alcohol sulphates derived from reduced coconut oil fatty acids; the hydroxy sulphonated higher fatty acid esters e. g.
  • higher fatty acid esters of 2,3 di-hydroxy propane sulphonic acid the higher fatty acid esters of low molecular weight alkylol sulphonic acids, e. g. oleic ester of isethionic acid; the higher fatty acid ethanolamide sulphates, the higher fatty acid amides of amino alkyl sulphonic acids, e. g. lauric amide of taurine, and the like.
  • alkyl aryl sulphonate detergents are also well known in the art. They may be monoor polynuclear in structure. More particularly, the aromatic nucleus may be derived from benzene, toluene, xylene, phenol, cresols, naphthalene, etc. The alkyl substituent on the aromatic nucleus may vary widely as long as the desired detergent power of such active ingredient is preserved.
  • alkyl aromatic sulphonate detergents are the higher alkyl aromatic sulphonates.
  • the higher alkyl substituent may vary widely. Thus, it may be branched or straight-chained in structure and comprise decyl, dodecyl, keryl, mixed long-chain alkyls from polymeric lower mono-olefins, etc.
  • Preferred examples of this class are the higher alkyl mononuclear aryl sulphonates wherein the alkyl groups is about 8 to about 22, and preferably about 12 to about 18 carbon atoms.
  • the higher alkyl benzene sulphonates wherein the higher alkyl group averages about 12 to about 16 carbon atoms
  • propylene may be polymerized to the tetramer and condensed with benzene in the presence of a Friedel-Crafts catalyst to yield essentially the dodecyl benzene derivative which is suitable for sulphonation to the desired sulphonate compounds.
  • these various anionic detergents are generally used in the form of the water-soluble salts, such as the alkali metal, alkaline earth metal, ammonium, amine, and alkylolamine salts. While the sodium, potassium, ammonium and alkylolamine (e. g. mono-, di, and triethanolamine) salts are preferred ordinarily, other salts such as the lithium, calcium, and magnesium salts may be used if desired. For general use, it is ordinarily preferred to use the sodium and potassium salts. For certain specialized uses, it may be preferred to select the ammonium and alkylolamine salts in view of their generally greater solubility in aqueous solution.
  • the sodium, potassium, ammonium and alkylolamine salts e. g. mono-, di, and triethanolamine
  • other salts such as the lithium, calcium, and magnesium salts may be used if desired.
  • non-ionic detergents may be present in the detergent composition and, if desired, in admixture with other compatible detergents such as suitable anionic sulphated or sulphonated ones described above.
  • these non-ionic agents are also well. known in the art and include the polyoxyethylene ethers of alkyl aromatic hydroxy bodies (e. g. the alkylatedpolyoxyethylene phenols) and the polyoxyethylene ethers of long chain aliphatic alcohols, etc. Long chain derivatives of polyhydroxy compounds such as the appropriate ethers of polyalkylene glycols may also be employed therein.
  • the tarnish inhibitor is a symmetrical N,N or 1.3 dibutyl thiourea com- 4 pound;
  • Such dibutyl thioureas as N,N' or 1,3 dibutyl thioureas having the structural formula O4H9NH-ONHC Hu are encompassed within the scope of the disclosure.
  • the butyl substituents may be either normal butyl, isobutyl, or secondary butyl in structure as each has been employed with marked success.
  • structurally related compounds such as symmetrical dimethyl and diisopropyl thiourea have been found generally unsatisfactory in the same relationship.
  • the amount of the indicated tarnish inhibitor in the detergent composition is generally extremely small and effective to produce the desired improvements in the tarnish inhibition or prevention. Generally, the amount'will be less than about 1% by weight of the composition,,and preferably a fraction of 1%, e. g. up to about 0.5%. While greater amounts, may be employed if desired it will usually be found that amounts less than about 1% are satisfactory with commercial detergent compositions, Naturally the specific amount of the tarnish inhibitor to be incorporated in a selected detergent composition will vary somewhat with the nature and concentration of the synthetic detergent and particularly of the polyphosphate builders and the contemplated field of application or manner of use. The appropriate amount of inhibitor to be employed however may readily be ascertained by means of relatively simple and standard tarnishing tests as indicated infra.
  • compositions consisting essentially of the indicated synthetic detergents and the polyphosphates. More particularly, it is preferred to use compositions consisting essentially of about 10 to about 50% and usually about 15 to about 40% synthetic detergents, preferably of an anionic sulphated or'sulphonated nature, and about 10 to about and usually about 20 to about 60% of these water soluble polyphosphates, preferably tripolyphosphate, the above percentages being by weight of total solids-of the detergent compositions. With such. compositions it has been found that amounts of inhibitor of less than about 1%, and preferably up'to about 0.5% e. g. .05-.5%, are usuallyhighly effective in achieving the desired tarnish inhibiting action on German silverand the'like.
  • critical pH'value appears to be within the range of about 7.5-8.5, and usually about 8. Above such values for aqueous solutions of the detergent composition, adverse eifects are most marked and the use of inhibitor yields optimum results.
  • a 2% or more aqueous solutions of position so that the tarnish inhibitor and detergent composition may be sold to the user as a unitary composition.
  • the additives may be incorporated at any point during the manufacturing process at which subsequent operations will not adversely modify the properties of the detergent compositions.
  • the various ingredients may be dry-mixed or wet-mixed in any suitable manner.
  • a procedure which is convenient, economical and productive of the best results with synthetic detergent compositions is the addition of the inhibitor in the form of an aqueous or alcoholic slurry to an aqueous slurry of the active detersive ingredients with vigorous stirring to form a relatively smooth, uniform and homogenous paste.
  • compositions may be prepared in the form of solutions, pastes or as dry or partially hydrated solid products, preferably in finely divided condition. Accordingly, the slurry of the detergent composition may be subjected to any suitable drying operation and converted to particle form. The mixture may thus be subjected to conventional spray-drying, rolldrying or drum-drying operations utilizing temperatures of above 212 to obtain heat-dried homogenous detersive particles.
  • the detergent compositions may include any of these substances embuilders are the various alkali metal phosphates (e. g. trisodium phosphate), the alkali metal silicates, sulphates, carbonates, etc. Suitable organic materials such as sodium carboxymethylcellulose, fatty acid amides, alcohols, esters may also be employed herein.
  • a detergent composition is prepared by compounding 35% sodium dodecyl benzene su1pho nate,40% sodium tripolyphosphate, 3% sodium N silicate, 0.8% carboxymethylcellulose and 0.06% optical bleach (Blancophor MVI) and the balance sodium sulphate.
  • An aqueous 1% solution of the foregoing detergent composition stains German silver as indicated by the following simple test which involves the immersion of metal strips in the detergent solution to be tested under selected time and temperature conditions: Approximately 20 milliliters of the 1% detergent solution is poured into a 30 milliliter beaker and placed on a hot water bath until a temperature of about 50 C. is reached. German silver strips (Whitehead metal, 14 BS it hard, approximately 18% nickel, 65% copper, 17% zinc) are cut to A x 2" size. Each strip is abraded using wet #320A Behr-Manning Durite abrasive paper.
  • the strips are thoroughly rinsed in running tap water using a toothbrush, then dipped in denatured ethyl alcohol and airdried on a clean towel.
  • the strips are then half immersed in the above-mentioned 1% detergent solution and after 30 minutes at 50 C. are removed and patted dry with a clean towel. This procedure produces a dark stain on the surface of the German silver.
  • a detergent composition is prepared by forming about a 57% solid slurry containing on a solids basis about.35% sodium dodecyl benzene asses 8B sulphonate (derived from a propylene tetramer) about 40% sodium tripolyphosphate, sodium sulphate, and the remainder minor amounts of sodium chloride, sodium hydroxide, sodium carboxymethylcellulose, etc. This slurry is agitated at about 140 F. in a conventional soap crutcher to form a relatively homogeneous mixture.
  • 1,3 din-.butyl thiourea in .an amount of 0.1% of total solids of the slurry is added in the form of an aqueous slurry to the detergent slurry which is further agitated to form a uniform mixture.
  • 'Iheslurry is then subjected to spray-drying with heated .air at a temperature of about 350 F. with a resultant moisture loss of about 40%.
  • the resultant composition is recovered in the form of beads and has a pH of about 9.5-8.7 in 0.5% aqueous solution. This composition gives effective inhibition of tarnishing of German silver also.
  • EXAMPLE III A detergent composition is prepared by the procedure of Example II with the modification that the organic detergent is sodium lauryl sulphate in concentration of solids, and a proportionately increased amount of sodium sulphate. The presence of 0.1% di-n-butyl thiourea gives similarly satisfactory results.
  • a detergent composition normally tending in water solution to cause tarnishing of a copper base alloy consisting essentially of water-soluble inorganic polyphosphate salt, and having incorporated therein a small amount of 'di-butyl'thiourea sufiicient to inhibit said tarnishing.
  • a detergent composition in accordance with claim 1 which contains about 10 to about 50% of water-soluble organic detergent selected from the group consisting of the water-soluble organic sulfate, sulfonate and non-ionic detergents.
  • a detergent composition normally tending in water solution to cause tarnishing of a copper base alloy consisting essentially of water-soluble inorganic tripolyphosphate salt, and having incorporated therein a small amount of symmetrical di-butyl thiourea sufiicient to inhibit said tarnishing.
  • a detergent composition normally tending in water solution to cause tarnishing of a copper base alloy consisting essentially of water-soluble inorganic polyphosphate salt, and water-soluble organic detergent selected from the group consisting of the water-soluble organic sulfate, sulfonate and non-ionic detergents, and having incorporated therein a small amount of symmetrical di-butyl thiourea sufficient to inhibit said tarnishing.
  • a detergent composition consisting essentially 'of water-soluble inorganic polyphosphate salt and about .01-1% of N,N di-butyl thiourea.
  • a detergent composition consisting essentially of water-soluble inorganic tripolyphosphate salt and about .01-1% of N .N di-butyl thiourea.
  • a detergent composition in accordance with claim 6 which contains about 10 to about 50% of water-soluble organic detergent selected from the roup consisting of the water-soluble organic sulfate, sulfonate and non-ionic detergents.
  • a detergent composition normally tending in water solution to cause tarnishing of a copper base alloy consisting essentially of water-soluble organic detergent selected from the group consistin of the Water-soluble organic sulfate and sulfonate detergents, and having incorporated therein a small amount of symmetrical di-butyl thiourea sufficient to inhibit said tarnishing.
  • a detergent composition consisting essentially of water-soluble higher alkyl aryl sulfonate detergent and about ill-1% of di-butyl thiourea.
  • A. detergent composition normally tending in water solution to cause tarnishing of a copper base alloy consisting essentially of water-soluble higher alkyl benzene sulfonate detergent, and having incorporated therein N,N di-butyl thiourea in an amount up to about 1% and suificient to inhibit said tarnishing.
  • a detergent composition normally tending in Water solution to cause tarnishing of a copper base alloy consisting essentially of Water-soluble higher alkyl sulfate detergent, and having incorporated therein N,N' di-butyl thiourea in an amount up to about 1% and sufficient to inhibit said tarnishing.
  • a detergent composition normally tending in Water solution to cause tarnishing of a copper base alloy consisting essentially of Water-soluble higher fatty acid monoglyceride monosulfate detergent, and havin incorporated therein 1 l,N di-butyl thiourea in an amount up to about 1% and sufficient to inhibit said tarnishing.
  • detergent composition consisting essentially of Water-soluble organic detergent selected from the group consisting of the watensoluble organic sulfate, sulfonate and non-ionic detergents, about l080% of water-soluble inorganic polyphosphate selected from the group consisting of tripolyphosphate, pyrophosphate, hexainetaphosphate, tetraphosphate and mixtures thereof, and about 01 to about 1% of N,N di-butyl thiourea.
  • a heat-dried detergent composition in particulate form normally tending in water solution to cause tarnishing of a copper base alloy consisting essentially of water-soluble organic detergent selected from the group consisting of the Watersoluble organic sulfate, sulfonate and non-ionic detergents, and about 10% to 80% of watersoluble inorganic tripolyphosphate, and having incorporated therein a small amount of N,N' dibutyl thiourea sufiicient to inhibit said tarnishing.
  • a heat-dried detergent composition in particulate form normally tending in water solution to cause tarnishing of a copper base alloy consisting essentially of sodium higher aikyl mononuclear aryl sulfonate detergent and about 10% to about 80% sodium tripolyphosphate, and havincorporated therein N,N' di-butyl thiourea in an amount up to about 1% and sutficient to inhibit said tarnishing.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Detergent Compositions (AREA)
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US215634A 1951-03-14 1951-03-14 Nonsoap detergent compositions containing antitarnishing agents Expired - Lifetime US2692236A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BE509522D BE509522A (en(2012)) 1951-03-14
NL75956D NL75956C (en(2012)) 1951-03-14
US215634A US2692236A (en) 1951-03-14 1951-03-14 Nonsoap detergent compositions containing antitarnishing agents
DEC4941A DE928543C (de) 1951-03-14 1951-11-10 Reinigungsmittel
GB27783/51A GB704576A (en) 1951-03-14 1951-11-27 Detergent compositions
CH307922D CH307922A (de) 1951-03-14 1952-01-29 Reinigungsmittel.

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US215634A US2692236A (en) 1951-03-14 1951-03-14 Nonsoap detergent compositions containing antitarnishing agents

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US2692236A true US2692236A (en) 1954-10-19

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BE (1) BE509522A (en(2012))
CH (1) CH307922A (en(2012))
DE (1) DE928543C (en(2012))
GB (1) GB704576A (en(2012))
NL (1) NL75956C (en(2012))

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2813831A (en) * 1954-04-21 1957-11-19 Lever Brothers Ltd Detergent compositions containing acyl dicyandiamide tarnish inhibitors

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2209464A (en) * 1936-11-02 1940-07-30 Standard Oil Co Lubricant
US2238651A (en) * 1937-05-21 1941-04-15 Du Pont Inhibition of corrosion
US2618603A (en) * 1949-02-04 1952-11-18 Procter & Gamble Detergent compositions containing metal discoloration inhibitors

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2374187A (en) * 1945-04-24 Detergent composition
US2374544A (en) * 1945-04-24 Detergent composition
NL64498C (en(2012)) * 1943-08-28
US2494580A (en) * 1947-05-24 1950-01-17 Procter & Gamble Detergent composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2209464A (en) * 1936-11-02 1940-07-30 Standard Oil Co Lubricant
US2238651A (en) * 1937-05-21 1941-04-15 Du Pont Inhibition of corrosion
US2618603A (en) * 1949-02-04 1952-11-18 Procter & Gamble Detergent compositions containing metal discoloration inhibitors

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2813831A (en) * 1954-04-21 1957-11-19 Lever Brothers Ltd Detergent compositions containing acyl dicyandiamide tarnish inhibitors

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GB704576A (en) 1954-02-24
NL75956C (en(2012))
DE928543C (de) 1955-06-02
CH307922A (de) 1955-06-30
BE509522A (en(2012))

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