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
  • C11D3/16—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
• • 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
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
• • 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
  • C11D3/3427—Organic compounds containing sulfur containing thiol, mercapto or sulfide groups, e.g. thioethers or mercaptales
• • 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
  • C11D3/3481—Organic compounds containing sulfur containing sulfur in a heterocyclic ring, e.g. sultones or sulfolanes

Definitions

• the said ring carbon atom bears as a" substituent a mercapto radical.
• Phenylbiguauidosalt of 2-mercapto- (1) (1) (2) benzothiazole. O-tolyl 'biguanidolsalt biz-memento beuzothiazole. O-biphenyl biguanirie salt of z mercap tobenzothiazoia' Zinc salt. otQ-rnercaptohenzothrazole Benzyl"hexamethylenetetramine salt oi2-nrezcaptohenzothiazole;g. i 6-au1ino-2-mercaptobenzothiazole 2-mercapto-4,5-dirnethylthiazole- Z-mercaptothlazoiine. 0;.
• Example I I Gert nan silver utensilsimmersed in a solution of the detergentcompositionwithout tarnish” inhibitor turned bluerblack under the conditions ofYthe abovetest.
• J Detergent solutionsuwere; formulated by dissolving 1.7 g, of active". component; 2.4 g; offtetrasodiurnm pyi'o phosphate; and 12.5 mg. of Z-me'rcaptothiazolinerin one Note: (1) indicates barely noticeablotarnlsh; (2) indicates slight tarnish; (3)) indicates moderate tarnish; (4) indicatesheavy tarnish; (5) indicates very heavy tarnish.
• Example II- Detergent compositions were. formulated by adding 0.015 to 0.50% by weightof the composition (0.03%
• the amount required for effective prevention of tarnishing depends in part, of course, upon the extent ;of protection afforded by the particular inhibitor used, and upon the particular phosphate and its concentration. An amount up to about 1% is satisfactory for tolylbiguanide and biphenylguanide.
• aromatic sulfonic acids such as thoseprepared by alkyla ting benzene or naphthalene with a kerosene fraction followed by sulfonation, aliphatic sulfonic acids, esters of sulfuric acid with aliphatic alcohols of 10 to 18 carbon atoms, particularly those derived bythe reduction of coconut oil, palm oil and like long-chain fatty acids; sulfonated castor oil, esters and ethers of isethionic acid,
• pyrophosphates A P O such as 'tetrasodinm pyrophosphate and tetrapotassium pyrophosphate, the hexameta- 'phosphates (APO -such as sodium hexametaphosphate and potassium hexameta'phosphate, and the tetrapolyphosphates A 1 0 such as hexasodium tetrapolyphosphate and hexapotassiumtetrapolyphosphate.
• APO hexameta- 'phosphates
• tetrapolyphosphates A 1 0 such as hexasodium tetrapolyphosphate and hexapotassiumtetrapolyphosphate.
• the anti-tarnishing agents in accordance with the invention may beincorporated in any compositions containing polyphosphates', they are of particular application to' synthetic detergent compositions which contain such phosphatesas builders, and which are formulated with either anionic-or nonionic detergents.
• Such. detergent compositions should contain conventional propor tions of active detergent withinlthe range between 15 and 40%, polyphosphate in an amountbetween -5 and 50%, based on the total compositionand the residue builders and inert materials.
• the tarnish inhibitors in accordance with the invention are useful with a wide range of anionic andnonionic synthetic detergents.
• anionic detergents the phenylpolypropylene sulfonates are particularly noteworthy. These sulfonates are characterized by th following structure;
• the invention is also applicable to water-soluble alkyl "1. to aqueous solutions containingpolyphosphates.
• the detergent composition may contain other supplemental builders in addition to the polyphosphate, including alkali metal and alkaline earth metal sulfates, chlorides, silicates, borates, carbonates,- metaphosphates, and orthophosphates, such assodium silicate, magnesium sulfate, sodium carbonate, sodium sulfate, trisodium phosphate, potassium carbonate, sodium orthophosphate, sodiummetaphosphate, calcium sulfate, calcium chloride; sodium chloride, sodium borate, potassium metaphos phate and magnesium chloride.
• alkali metal and alkaline earth metal sulfates such as sodium silicate, magnesium sulfate, sodium carbonate, sodium sulfate, trisodium phosphate, potassium carbonate, sodium orthophosphate, sodiummetaphosphate, calcium sulfate, calcium chloride; sodium chloride, sodium borate, potassium metaphos phate and magnesium chloride.
• the builder should but need not be water-soluble)
• organic materials such as starch, polyethylene glycols, polyvinyl alcohols and salts of car,- boxymethylcellulose may be used as builders. It has' been found that betweenabout 0.1 and 1% of an'alkali metal carboxymethylcellulose increasesdetergency and sudsing; i
• Thefbuilder mixture is so chosen among alkaline,
• the detergent composition is prepared by conventional mixturein a spray .or drum dryer at elevated tempera; tures- I pl"
• the tarnish inhibitorj may be added to the detergent composition at any stage of its manufacture, to the finished detergent composition, or to the detergent solution.
• compositions containing tarnish inhibitors of the invention do not tarnish copper, or nickel copper alloys such as German silver alloy, Monel metal, coinage nickel, or brass, whichnormally tarnish when exposed It' is not possible at this time to explain why the compounds' of the invention are effective tarnish inhibitors.
• a oerm n snver utensil is immersed for a'period in solution of the inhibitor and then immersed in a polyphosphate solu ⁇ tion not containing inhibitor only slight tarnishing re-" sults. This is taken as an indication that inhibitor is preferentially adsorbed by the metal, and that this is prevention, but of'course, such evidence .is not conclusive.
• the expression consisting essentially of as used arei essential to. the composition; namely, the tarnish inhibitor. and the alkali metal polyphosphate, and the expression does. not exclude other components from the composition whichdo not render it unsuitable for the desired purposes, such materials being, for instance, detergents, other builders, such as sodium silicate and sodium carbonate, carboxymethylcell'ulose, minor quantities of impurities, etc.
• a composition comprising a water-soluble polyphosphate which in aqueous solution tarnishes copper and copper and nickel alloys and a tarnish inhibitor in an amount to lessen the tarnishing action of the polyphosphate and having the general formula where Xis selected from the group consisting of oxygen and: sulfur and Z is a radicaltaken in sufiicient number to satisfy the free valences of the 4- and -ring carbon atoms and is selected from the group consisting of hydrogen, oxo oxygen, alkyl, arylzand saturated and unsaturated mono and polynuclear alicyclic and heterocyclic rings. condensed therewith. 1 i
• composition in accordance with claim 2 in which the tarnish inhibitor is 2-mercapto-4,5-dimethyl thiazole. 7'.
• composition in accordance with claim 3 in which the tarnish inhibitor 1s Z-mercaptothiazoline.
• composition in accordance with claim 4 in which the tarnish inhibitor is 2-mercaptobenzoxazole.
• composition in accordance with claim 5 in which the tarnish inhibitor is Z-mercaptooxazoline.
• a nonsoap detergent composition consisting essentially of an active organic detergent, a water-soluble polyphosphate which in aqueous solution tarnishes copper and copper and nickel alloys, and a tarnsh inhibitor in' an amount to lessen the tarnishing action of the polyphosphateand having the general formula where X is selectedfrom. the. group consisting of oxygen and sulfur and Z is a radical taken. in suflicient number to satisfy the free valences of the 4- and S-ring carbon atoms and; is selected from the group consisting, of-hy 13.
• a detergent composition in accordance with claim 10 in whic'liftlie' detergent is sodium phenyl polypropylene sulfonat'e'.
• a nonsoap detergent composition consisting essentially of 'a'n alkali metal alkyl aryl sulfonate detergent, a water-soluble polyphosphate which in aqueous-solution tarnishescopper and-copper and nickelalloys and a tarnish-inhibitorin-a-n amount to lessen the" tarnishing action of the-polyphosphate and having the general formula- 1 where X is selected from the group consisting of oxygen and sulfur and Z is a radical taken in suflicient number to satisfy the free valences of the 4- and S-ring carbon atoms and is slected from the group consisting of hydrogen, oxo oxygen, alkyl, aryl and saturated and unsaturated mono and polynuclear'alicyclic and heterocyclic rings condensed therewith.
• a detergent composition consisting essentially of an alkali metal phenyl polypropylene sulfonate detergent, pentasodium tripolyphosphate and a tarnish inhibitor in an amount to lessen the tarnishing action of the polyphosphate and having the general formula where X is selected from the group consisting of oxygen and sulfur and Z is a radical taken in sufficient number to satisfy the free valences of the 4- and S-ring carbon atoms and is selected from the group consisting of hydrogen, oxo oxygen, alkyl, aryl and saturated and unsaturated mono and polynuclear alicyclic and heterocyclic rings condensed therewith.

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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)
• Detergent Compositions (AREA)
• Preventing Corrosion Or Incrustation Of Metals (AREA)
• Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
• Anti-Oxidant Or Stabilizer Compositions (AREA)

Priority Applications (8)

Applications Claiming Priority (1)

Publications (1)

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Family Applications (1)

Country Status (7)

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Citations (8)

• 0
  • NL NL77796D patent/NL77796C/xx active
  • BE BE504343D patent/BE504343A/xx unknown
• 1950
  • 1950-07-08 US US172776A patent/US2861044A/en not_active Expired - Lifetime
• 1951
  • 1951-06-08 GB GB13612/51A patent/GB701168A/en not_active Expired
  • 1951-06-20 CH CH306236D patent/CH306236A/de unknown
  • 1951-06-20 CH CH300867D patent/CH300867A/de unknown
  • 1951-06-28 FR FR1039160D patent/FR1039160A/fr not_active Expired
  • 1951-07-05 DE DEL9489A patent/DE890252C/de not_active Expired

Patent Citations (8)

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