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
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/28—Heterocyclic compounds containing nitrogen in the ring

Definitions

• German silver is frequently used for household articles commonly washed in polyphospirate-built detergent compositions, it is evident that this is a serious problem.
• polyphosphate and detergent compositions are provided containing a tarnish inhibitor which compositions will not tarnish copper, and nickel and copper alloys such as German silver.
• a tarnish inhibitor which compositions will not tarnish copper, and nickel and copper alloys such as German silver.
• stituted guanamine (2,4-diamino-s-triazine) which is.described by the following formula:
• R is a hydrocarbon or hetero'cyclic radical and can be selected from the group consistingof aliphatic, aryl, mixed alkylene aryl, mixed phenylene heterocyclic and mixed alkyl'eneheterocyclic hydrocarbon radicals, and the other R radicals can be hydrogen or any of the radicals selectedfrom the above-mentioned:
• R is an aliphatic hydrocarbon group" it can have-either a straight or branched chain, and can be saturated or unsaturated.
• the number of carbon atoms in the R" groups is'ir'n-- portant. Form'oguanamine' is not effective. Good tarnish-inhibiting properties appear when at' least one" of R R R3, R1; or R is a' radical having three carbon atoms and theremaining R groups are hydrogen, but relatively large amounts of such guanamines may be necessary for complete protection.
• Tarnish-inhibiting ability materially improves as the' R groups increase further in molecular weight; and lesser amounts of guanamine can be used;
• Optimum tarnish-inhibiting properties are displayed by compounds; in which the sumof the R groups-is from seven to seventeen carbon atoms, especially compounds in which at least one'R has from seven to seventeencarbon atoms, and. invsuch compounds the number of carboniatoms in the remaining R groups is .not critical, .although the lower alkyl groups,
• the tarnish inhibitor of the invention is a sub-- '2 i. e., those having from one to about five carbon atoms, and hydrogen are preferred.
• R radicals are straight and branched chain methyl, ethyl, propyl, heptyl, octyl, nonyl, butyl, hexyl, decyl, undecyl, dodecyl, tri'decyl, tetradecyl, pentade'cyl, decenyl, heptylenyl, hexadecyl, heptadecyl, decynyl, dodecenyl, octa'de'cenyl, oct'adecadienyl, dodecynyl, the mixed alkyl radicals derived from fatty' oils such as palm oil, rapeseed oil, tall oil, linseed oil, etc., phenyl, benzyl, phenyl guanamyl, decylene guanamyl and octylene guanamyl
• the mixture of the nitrile, acid or ester and biguanide is heated at an elevated temperature, say 180 C., for several hours. Temperatures from 120 to 250 C. have been found satisfactory.
• the crude mixture which is obtained as a result of this reaction can be used without further purification and consists mainly of the substituted guanamide and, in the case of acid or ester reactants, of the amide of the acid or ester starting material in approximately equal amounts.
• the guanamine has been isolated and shown to be the principal antitarnishing constituent of the mixture.
• guanamines in accordance with the invention are nontoxic, sparingly water-soluble substances, but sufficiently water-soluble to permit their incorporation in polyphosphate and synthetic detergent solutions in the amounts required to impart tarnish inhibition thereto.
• guanamine An amount of the guanamine would be added to the polyphosphate and/or synthetic detergent composition suflicient to give tarnish inhibition when the composition is used in its normal way. Usually about 0.1% of the guanamine gives adequate tarnish inhibition, but larger amounts can be used if desired. From 0.1 to 5% is efiective under nearly all conditions and therefore is preferred. The maximum amount of guanamine 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 solution would not be used.
• the amount required will depend in part upon the tarnish-inhibiting properties of the particular guanamine in question, upon the tendency of the polyphosphate and/or synthetic detergent with which it is used to tarnish copper and nickel alloys and copper alloys, and upon the amounts of polyphosphate and synthetic detergent present.
• the guanamines of the invention are effective as tarnish inhibitors in both hard and soft water.
• 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:
• M M and M are hydrogen or an alkali metal, such as sodium, potassium and ammonium, and can be the same or different, and M is M and/ or M and/or M a is an integer of l or more, usually 1 to 4,
• I b is an integer of 1 or more, usually 1 or 2,
• x' is an integer of 1 or more, usually 1 to 6.
• polyphosphoric acids and their alkali metal salts coming within the invention are the polymetaphosphoric acids (HPO (a is 1, b is 1, x is more than 1), pyrophosphoric acid H P O (a is 2, b is 1, x is 1), triphosphoric acid H P O (a is 3, b is 2, x is 1), and tetraphosphoric acid H P O (a is 4, b is 3, x is 1).
• the guanamine tarnish inhibitors can be incorporated in compositions containing polyphosphates, and in compositions containing synthetic detergents, and are efiective to reduce tarnish due to polyphosphate or detergent in each of these types of compositions. They 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, cationic detergents, nonionic detergents, and mixtures thereof. In many instances they display an enhanced fifteen carbon atoms. whose preparation and properties are set forth in U. S.
• 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.
• guanamines are useful with a wide variety of anionic, cationic and nonionic synthetic detergents, with and without polyphosphates.
• alkyl aryl sulfonates are a class of detergents well known in the art under this name.
• One example thereof are the sulfonated phenylpolypropylene alkanes, charac- -terized by thebranched chain structure of polypropylene and a tertiary alkyl carbon at the benzene ring, and having the following general structure:
• R and R are alkyls, of the type formula C H and at least one R is a polypropylene group, the whole alkyl group containing preferably twelve to These are known compounds,
• Patent No. 2,477,383 to Lewis issued July 26, 1949; they are available in'commerce' under the trade names Oronite, Ultrawet and Neolene.
• amidoalkane sulfonates which are characterized: bythe following structure:
• A is hydrogen oran alkali metal, i. e., ammonium, I
• 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.
• These compounds are prepared by interacting the corresponding aliphatic acid anhydride or halide with an or- V ganic aliphatic aminosulfonic acid, such as taur'ine and the various N substituted taurines, such as N-methyl taurine, or aminopropane sulfonic acid;-NI-I (CH SOH.
• 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 frac- G and. thioether-andester.detergentshaving the following general formula:
• R-A-tcrn Hte-it-.cH-l- Hz n where 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 saturatedor 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 selectedfrom the group consisting ofethereal oxygen and-sulfur,jca'rboxylic esterand thiocarboxylicester groups and x is a. number'from eight to twenty.
• R can for examplebe 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.
• R is alkyl
• the detergent can be regarded as derived from an alcohol, mercaptan, oxy or thio fatty acid ofhighmolecular weight, by condensa'tion with ethylene oxide.
• Typical of this type of alkyl ether are the condensation-products of oleyl or 'dodecyl alcohol orrn'ercaptan .with from eight to seventeen 'zmoles of ethylene oxide, such -'as Emulfor ON, Nonic 218 and .SteroxI SE andSK.
• Typical alkyl 'esters are 61226 and R'enex (polyoxyethyleneester of tall oil acids), Sterox CD and Neutronyx 330 and 331 (higher fatty acid esters of polyethylene glycol).
• R is aralkyl
• 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 thiophenol with from eight to seventeen moles of ethylene oxide, available commercially under the trade names NIW, Antarox A-400, Igepal CA and CO, Triton X-100, Neutronyx 600 and Tergitol 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 metaphosphate, calcium sulfate, calcium chloride, sodium chloride, sodium borate and potassium metaphosphate.
• the builder should but need not be water-soluble.
• 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 al- -kali--metal carboxymethylcellulose increases detergency "and" sudsing.
• 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 7 or above. Preferably, its pH lies within the range from 7 8 for one-ha1f hour.
• the efiectiveness of the inhibitor is rated as follows:
• the detergent composition is prepared by conventional lowing f latio methods, as by blending the ingredients thereof in an percent aq u solution or slurry and then drymg the result- Sodium Oronite (active) (sodium phenylpolypromg mixture in a spray or drum dryer at elevated tempylene lf t p Tetrasodiurn pyrophosphate 30.0
• the tarnish inhibitor may be added to the polyphoss i tripolyphosphate 15 phate or detergent composition at any stage of its manu- Sodium carboxymethylcellulose 0.5 facture, to the finished polyphosphate or detergent coms di i1i 6,0 position, or to the polyphosphate or detergen solution.
• guanamines employed in the following examples s di ulfat and i 20,5 were prepared by heating mixtures of biguanide and the Water 7.0 corresponding nitrile at ISO-200 C. for about two to four hours. 1:1 molar ratios were taken of biguanide 10() and the nitrile. The crude product was used unless other- Wi in i Guanamine 1 0.02 to 5 2 33 212; g f i g f s P actlon of the composl' 1 0.044 to 11.1% based on the weight of the polyphosphates.
• guanamin'ewithout an-R' substituent is a guanamin'ewithout an-R' substituent,.is.-noteifective as a tarnishinhibitor.
• R is a higher alkyl group.
• compositions also were "evaluated for-their sud sing properties. This wasdoneusing the Terg-O-Tometer em-- ploy-ing thefollowingprocedurezl2.64 g. of thedetergent composition Without the tarnish inhibitor was weighed into:a 100 ml. beakerand 'the appropriateamount'of the tarnish inhibitor tobe testedwas added. "'Fifty mL of SO p.;p.-m. Waterwas'then added and the solids brought 'into solution with the aid of heat; The solution was-diluted to 1,000 ml. with 50 p. p..-m. water, brought to 120 F. and placed in the cup of a standard Terg-O-Tometer.
• Compositions containingv tarnish inhibitors of the-invention do not tarnish copper, nickel-copper-Zi'n-c alloys such as German silver, coinage nickel or brass, whichnorma'lly tarnish whenexposed to aqueous' solutions containing-polyphosphates and/ or synthetic detergents. It isnot possible atthis tim'e to explain whythe-compounds-of theinventhe weight of the-tarnish producin'g substance, i: e.',polyphosphate and/or detergent, unless otherwisestated.
• the-compounds-of theinventhe weight of the-tarnish producin'g substance i: e.',polyphosphate and/or detergent, unless otherwisestated.
• the weightsofguanamine are given as based'on the dry weightof the total composition.
• a detergent composition consisting essentially of a water-soluble substance selected from the group consisting of polyphosphates and synthetic organic nonsoap anionic and nonionic detergents 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 substance and having the general formula:
• N /NR4R5 where at least one R is an organic radical selected from the group consisting of hydrocarbon and guanamine radicals having at least three carbon atoms, and the remain ing R radicals are selected from the group consisting of hydrogen, hydrocarbon, and guanamine radicals.
• R is the mixed alkyl radicals derived from a naturally-occurring fatty oil.
• a detergent composition consisting essentially of 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:
• R is an organic radical selected from the group consisting of hydrocarbon and guanamine radicals having at least three carbon atoms, and the remaining R radicals are selected from the group consisting of hydrogen, hydrocarbon, and guanamine radicals.
• a detergent composition consisting essentially of a water-soluble synthetic organic nonsoap detergent selected from the group consisting of anionic and nonionic detergents 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 detergent and having the general formula:
• R is an organic radical selected from the group consisting of hydrocarbon and guanamine radicals having at least three carbon atoms, and the remaining R radicals are selected from the group consisting of hydrogen, hydrocarbon and guanamine radicals.

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• 0
  • BE BE539762D patent/BE539762A/xx unknown
• 1954
  • 1954-07-12 US US442895A patent/US2848420A/en not_active Expired - Lifetime
• 1955
  • 1955-07-11 FR FR1127340D patent/FR1127340A/fr not_active Expired
  • 1955-07-13 DE DEU3428A patent/DE969642C/de not_active Expired

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