Патент USA US3085992код для вставки
United States Patent O?ce 3,085,982 Patented Apr. 16, 1963 1 2 3,085,982 the need for solvent and/ or special surface active agents (alkylolamide or alkylglyceryl ether sulfonate) in a ho LIQUID DETERGENT COMPOSITION David C. Steer and Norman R. Smith, Cincinnati, Ohio, assiguors to The Procter & Gamble Company, Cin cinnati, Ohio, a corporation of Ohio No Drawing. Filed Apr. 22, 1959, Ser. No. 808,022 8 Claims. (Cl. 252-437) mogeneous built liquid detergent; the object of an aspect of the invention is to do so when silicate is present. These and other objects are accomplished by a deter gent formulation containing: (I) from about 3% to about 10% of an aliphatic tertiary amine oxide; (2) from about 3% to about 15% of a non~soap synthetic detergent of the sulfated or sulfonated type; (.3) from about 3% to about 10% of a soluble hydrotrope; and (4) from about 10% to about 30% of a soluble pyrophosphate salt. This invention relates to liquid detergents of medium duty and heavy-duty, sudsing type. More particularly, it relates to improved liquid detergents which contain a tertiary amine oxide surface active agent. In recent years built liquid detergents have been gaining favor for washing soiled clothing, for washing dishes and for other purposes requiring an effective detergent. A built detergent is one which contains, in addition to the surface active agent, a soluble salt capable of sequester ing calcium and magnesium ions of hard water and also These ingredients are dissolved in an aqueous vehicle. When the use of the formulation makes a corrosion in hibitor desirable, ‘from about 3.5% to about 6% of alkali metal silicate solids are dissolved in the same solution. In the following more complete disclosure of the inven tion, percentages refer to weight percent of the total for mula unless otherwise indicated. It will be appreciated capable of increasing the level of detergent effectiveness that in an aqueous system it is for the most part immaterial of the surface active agent. Built liquid detergents have, 20 by which ionic salts a particular ion is introduced; for to some extent, replaced granular built detergents for in the aqueous product there will be substantially com various reasons. These reasons include: complete free plete and continuous exchange of ions. dom from dustiness, compact package, convenience in Amine oxides are compounds of the general formula pouring and measuring, and simpli?cation of manufacture. R1R2R3N->O. The arrow is a conventional representa The problems which have to be overcome in formulat 25 tion of a semipolar bond. They are generally prepared ing built detergents in clear homogeneous liquid form are by the direct oxidation of the appropriate tertiary amine. mainly the problems of incorporating suf?cient surface When R1 is a much longer chain than R2 and R3, amine active agent and builder into the same solution. In cur oxides have surface activity. For the purpose of this rent practice an anionic sulfated or sulfonated compound invention R1 is an alkyl radical of from about 10 to about is ordinarily used as surface active agent, and potassium 30 16 carbon atoms. Desirable surface active properties pyrophosphate is used as builder. Various surface active are lost if R1 is substantially less ‘than 10 carbon atoms, agents, hydrotropes and solvents are employed to increase and solubility in the present formulation is too low if R1 their compatibility. The fact that the builder may cor is greater than 16 carbon atoms. R2 and R3 are each rode non-ferrous metals such as aluminum, may, depend selected from the group consisting of methyl and ethyl ing on the use for which the product is intended, lead to 35 radicals. ‘Preferably R1 is a dodecyl radical or a mixture the inclusion of sodium silicate as a corrosion inhibitor. of dodecyl with de-cyl, tetradecyl and hexadecyl radicals, Its presence requires that special provisions be made to keep the ingredients compatible. Limitations on the pH of the formulation or the presence of agents designed to such that at least 50% of the radicals are dodecyl radicals. A convenient source of a preferred mixture is the middle cut of coconut fatty alcohol which has the approxi achieve compatibility is usually required. 40 mate chain length composition: 2%—Cm, 66%—C12, In U.S. Patent 2,859,182 a combination of alkali metal aryl sulfonate and at least one alkylolamide is disclosed 23%——C,4, and 9%——C1?. R2 and R3 are preferably solubilizing agent, for example triamylphosphate or potas invention. They complex the calcium and magnesium ions methyl radicals. The amine oxide is used at from about for making certain detergent compositions homogeneous. 3% to about 10% of the total formula. Too little amine In these compositions the pH must be adjusted to about oxide adversely affects the performance of the formula 11.4 or above to keep silicate in solution. 45 tions and too much amine oxide interferes with achieving Different agents for solving the problem of making builder and detergent in sufficient amount in a homoge neous liquid. detergent, builder and silicate compatible, which are dis Soluble pyrophosphate salts are suitable builders in this closed in US. Patents 2,877,185 and 2,877,186, are: a sium benzene sulfonate; and an “assistant solubilizer," 50 of hard water; and, when the calcium ions of hard Water for example ethyl alcohol or diethyleneglycol monobutyl are present in excess, have an additional water softening ether; and a particular detergent, alkyl glyceryl ether sul fonate. The alkyl glyceryl ether sulfonate and the solubilizing agent are used together, and the assistant solubilizer is preferably included. 55 ‘ effect by precipitating calcium pyrophosphate. They also serve to increase the level of detergency obtainable with synthetic surface active agents. Potassium, sodium, eth anolammonium, diethanolammonium, and triethanolam Liquid detergents generally contain one or more agents, monium are suitable salts of the pyrophosphate anion in called suds builders, to increase their sudsing. Typical the practice of this invention; potassium pyrophosphate is especially preferred. The soluble salt of pyrophosphate is suds builders are coconut ethanolamide and lauryl al In addition to being one more ingredient to be cohol. employed at a level of from about 10% to about 30%. The pyrophosphate salts, like other sequestering agents, ‘ added to an already complicated formula, these suds 60 are corrosive towards aluminum. If the detergent solution ‘ builders may require, in certain formulations, a partic is to contact this metal for prolonged periods of time, es pecially at elevated temperatures, a corrosion inhibitor should be desirably included. In a product designed for colored for use in liquid products. They are not con 65 hand laundry of fine fabrics, it is unnecessary. Soluble sidered to serve the cleaning function of a detergent. silicates are highly effective inhibitors and can be added An object of this invention is to provide a homoge to the formulas of this invention without difficulty at levels neous built liquid detergent of improved sudsing charac of from about 3.5% to about 6%. Potassium, or prefer ular perfume to cover their odor. Amide-type suds builders, unless puri?ed, are often undesirably highly teristics and good detergent effectiveness. ably sodium silicates haviug a weight ratio of Slog/M20 A further object of this invention is to eliminate suds 70 of from about 1.0 to about 2.16 and preferably from about builders from a high sudsing liquid detergent formulation. 1.6 to about 2.6 can be used. “M” in this ratio refers to An additional object of this invention is to eliminate sodium or potassium. Less than about 3.5% sodium sili 3,085,982 3 4 cate solids, although useable in the present compositions, does not provide protection against corrosion at typical fonate and alkyl sulfate are therefore especially preferred anionic detergents. Preferred formulas of this invention use conditions, and more than about 6% sodium silicate include those in which two anionic detergents are used in solids is difficult to incorporate into a homogeneous liquid. combination with the amine oxide. For example, C12 alkyl benzene sulfonate, coconut alkyl sulfate and dimeth Suitable hydrotropes to increase the compatibility of the ingredients of the formulations of this invention are the aryl sulfonates disclosed in the hercinbefore cited patents. More speci?cally they are soluble salts of the hydrotrope anions. Preferred hydrotrope anions are benzene sulfon ate, xylene sulfonate and toluene sulfonate. They are used 10 yldodecylarnine oxide in approximately equal quantities in a detergent combination which gives superior sudsing. good mildness to the skin and relatively low cost and is especially preferred in the practice of this invention. Slight variations from equal quantities of the amine oxide and the anionic detergents permits ?ne adjustment of the prop erties of the formulas. If more of one detergent is used, ammonium, and triethanolammonium and especially as preferably less of another is used. To maintain the ho the alkali metal, potassium, or sodium, salts. Sodium or mogeneous character of the product, the sum of anionic potassium toluene sulfonate is especially preferred. The hydrotrope salt is added at levels of from about 3% to 15 detergent and amine oxide is preferably kept in the range of from about 10% to about 25%. about 10%. Levels of from about 4% to about 6% are The inorganic builder content is preferably raised as preferred. The upper limit of about 10% is set by in the total synthetic detergent content is lowered; so that creasing dilution of the product by an ingredient substan the sum of builder and detergent is kept from about 25% tially inert so far as sudsing and detergency are concerned. The lower limit is the amount required to achieve a 20 to about 40%. In this range of composition the product has particularly good performance and homogeneous homogeneous solution. It will be appreciated that it is character. As a rough generalization, when the total de necessary that the formulations of this invention should tcrgent is greater than the builder the product is of me be liquid at somewhat higher and at somewhat lower tem» dium-duty type and can be recommended for hand laun peratures than usual room temperature. The amount of hydrotrope salt used is preferably the minimum amount 25 dering of ?ne fabrics and dishwashing. When the deter gent level is lowcr or equal to the builder, the product is which will hold the ingredients in solution at the temper as the soluble salts such as: ethanolammonium, diethanol ature to which it is desired that the formula can be cooled of heavy-duty type especially adapted for laundry and gen without phase separation. eral purpose use. Silicate is particularly desirable in the Amine oxide is an effective detergent; however, in order to achieve the objects of this invention, a supplemental heavy-duty product. non-soap anionic synthetic detergent is added. From about 3% to about 15% anionic detergent is employed. be added in minor amounts materials which make the product more effective or more attractive. The following are mentioned by way of example. A soluble sodium carboxymethylcellulose may be added in amounts up to Preferred anionic detergents which can be included are: alkyl benzene sulfonate, alkyl ethylene oxide ether sulfate In a ?nished detergent formulation there will preferably wherein there are from 1 to 5 ethylene oxide residues per 35 about 2% to inhibit soil redeposition. A tarnish inhibitor such as benzotriazole or ethylenethiourea may be added alkyl and the mixtures formed when 1 to 5 ethylene oxides in amounts up to about Fluorescers, perfume, and are reacted with one mole of alcohol, and alkyl sulfate. color, while not essential in the compositions of the in These may be represented, respectively, as: vention, may be added in amounts less than about 1%. 40 All the constituents of these liquid detergent formula where x is an integer from 1 to 5, and R804. In these tions are dissolved in water with the possible exception of certain of the minor nonessential ingredients which are compounds the alkyl chain (R) will contain from about at least ?nely and homogeneously dispersed to give the 9 to about 16 carbon atoms and preferably about 12 car bon atoms. Mixtures of alkyl radicals of different chain lengths are preferably used since they are soluble and effect of a one—phase composition. A maximum water level of about 70% is set by the need to get enough active ingredient in the solution to hold the volume required per usage to an acceptable level. The minimum water level readily available from synthetic or natural sources, e.g., coconut alcohol and a mixture containing tri-, tetra-, and pentapolypropylene polymers and averaging about 12 car of about 45% is set by the requirement of having su?i cient water to dissolve the ingredients. bon atoms. These detergents are used as soluble salts; 50 The mole ratio of potassium (and any alkanolammo~ speci?cally, they are used as sodium, potassium, ethanol nium ions) to sodium is maintained above about 3:1 to ammonium, diethanolammonium and triethanolammo nium salts. Sodium and triethanolamine salts are pre ferred. Other non-soap anionic synthetic detergents, with alkyl radicals as speci?ed above, can be usefully employed if they have the following characteristics: their salts, as speci?ed above, are soluble to the extent of at least 3% in an aqueous solution of 3% dimethyldodecylamine oxide, 3% potassium toluene sulfonate and 10% potassium pyro phosphate; and they are stable against hydrolysis in alka line solution. An example is the potassium salt of the sulfated condensation product of four moles of ethylene oxide with a mole of nonyl phenol. The formulas of this invention, containing amine oxide, maintain the one-phase nature of the product and prefer ably is maintained above about 3.511. Example I The following compositions were prepared and exam ined. All were clear homogeneous pourable liquids at room temperature. Formulas B and C were cooled to lower temperatures and remained clear at 50° F. Dimethyldodccyl amino oxide percent _____________________ .. 4 Sodium polypropylene benzene suds so well in the laundry and dishpan that no suds build sulfonate (a mixture. of tri-, er is required. Among the anionics, the alkyl sulfate tetrm, and peutapropylenit averaging about C12} percent" makes a particular contribution to sudsing in the formulas Sodium coconut 1sulfate._ .do_. Potassiutntoluencsulfunate _ , do. _ of this invention. Alkyl benzene sulfonate is particularly l’otassiumpyrophosphate_._ . ' lo. _ favored for this purpose because in most circumstances it Sodium silicate solids S5102: ' r "at," reduces the cost of the formula. A supplemental anionic 70 detergent can tend to improve the mildness of the formu Water ____________________ “do” 6 15 _,do _ lations, alkyl benzene sulfonate being particularly note worthy in this respect. The supplemental anionic deter gents also permit the achieving of higher levels of active ingredients in a homogeneous liquid. Alkyl benzene sul 75 _ K/Nu,approx_1nole rutio_._llo_. 5 7 5 8 6 4 ti 3 5 4 ‘2 3 4 4 8 7 G t‘, 6 (I 18 18 ltt 18 ____ -_; ____ __ ‘ as . _ _ _ __ (1) 4.1 as} as 0.1’) (1.15 til 4.2 (2? l o as _ _ _ _ _ as _ _ _ (5) i . _ _ l?) 5.0 is _ _ . . __ (“I d ‘J 1 Coconut refers to the alkyls of lllltltllt? cut coconut ult-ohul containing about 292-010. [iti‘lk-On, ?lmy-Cu ul1tl9‘;T;,.—~C1s. 2 Balance. 3,085,982 5 6 for the purposes for which medium-built liquid products An additional composition, G, was prepared as a dupli are intended. cate of F except the 8% sodium coconut sulfate was re In these compositions, methylethylcoconutamine oxide placed by 6% potassium salt of a sulfated condensation or diethylcoconutamine oxide can be substituted for di product of one mole coconut 1 alcohol with 3 moles of methylcoconutamine oxide without substantially adversely 1 Coconut refers to the alkyls of middle out coconut alcohol affecting the physical characteristics or performance of the containing about 2%——Cio, 66%—Ci2, 23%—'C14. and 9%—Cld. compositions. ethylene oxide. The K/ Na mole ratio in this product was What is claimed is: about 7.4. 1. A substantially clear, high-sudsing, concentrated Products A, C, D, and F proved to be superior in main liquid detergent composition consisting essentially of: taining suds during the washing of soiled dishes to com- 10 (a) from about 3% to about 10% of an aliphatic ter mercially available built liquid detergents tested under the same conditions. tiary amine oxide having the general formula R1R2R3N-> 0, where R; is an alkyl radical containing Products B and G proved to be good dishwashing products, being about equal to available built liquid products. Products B and C were also employed in washing soiled 15 clothes in a typical domestic washing machine. The suds in the ?rst load was higher than for commercial built liquid detergents tested under the same conditions. The sodium silicate can be omitted from these formulas methyl and ethyl radicals, at least about 50% of said amine oxide having R1 containing 12 carbon atoms; (b) from about 3% to about 15% of a non-soap de tergent selected from the salts of the group of de without substantially affecting appearance or performance 20 except for their corrosiveness to non-ferrous metals. Dodecyl radicals and coconut radicals are substantially equivalent, that is one can be substituted for the other in the ingredients of this example with no substantial change in appearance or performance of the product. Potassium 25 benzene sulfonate or potassium xylene sulfonate can be used to replace potassium toluene sulfonate without losing the homogeneous nature of the product or adversely affecting its performance. from about 10 to about 16 carbon atoms and R2 and R3 are each selected from the group consisting of 30 Example I] tergent anions consisting of R804“, R(OC2H4)xSO(, where x is an integer from 1 to 5 R being an alkyl radical containing about 9 to about 16 carbon atoms, and mixtures thereof; (0) from about 3% to about 10% of a salt of a hydro trope anion selected from the group consisting of toluene sulfonate, benzene sulfonate, and xylene sul fonate; (d) ‘from about 10% to about 30% of a salt of a The following composition was prepared. pyrophosphate anion; and the balance substantially (e) water; It was a clear homogeneous pourable liquid at room temperature. It remained clear at 30° F. the cations of the salts of the group of detergent anions, of 35 the salts of the hydrotrope anions, and of the salts of the Percent Dimethyldodecylamine oxide __________________ __ said pyrophosphate anion being selected from the group consisting of potassium, sodium, ethanolammonium, di ethanolammonium, and triethanolammonium, ‘and the 6 Triethanolamine salt of polypropylene benzene sulfo nate (a mixture of tri-, tetra-, and pentapropylene averaging about C12) _______________________ __ 6 40 mole ratio of the total of potassium and of alkanolarn monium cations to sodium cations being greater than about 3:1, said composition being substantially free from amide suds-builders. 2. The liquid detergent composition of claim 1 wherein Sodium silicate solids, Si02 to NazO is 1.6 _______ __ 5 Water _________________________________ __ Balance in the tertiary amine oxide R3 and R3 are each methyl K-l-triethanolammonium/Na, approx. mole ratio ___ 5.5 45 radicals. 3. A substantially clear high sudsing concentrated liquid The suds during washing soiled dishes obtained from detergent composition consisting essentially of: Potassium pyrophosphate _____________________ __ 25 Potassium toluene sulfonate ___________________ -_ 8.5 this product were more stable than suds obtained from (a) from about 3% to about 10% of an aliphatic ter commercially available built liquid detergents. This prod tiary amine oxide having the general formula R1R2R3N->O where R1 is an alkyl radical containing uct showed good sudsing and cleaning characteristics in washing soiled clothing. Example 111 from about 10 to about 16 carbon atoms and R2 and R3 are each selected from the group consisting of methyl and ethyl radicals, at least about 50% of said amine oxide having R1 containing 12 carbon atoms; The following compositions were prepared. They were clear homogeneous pourable liquids at room temperature. After freezing at 40° F. they again became clear and (b) from about 3% to ‘about 15% of a non-soap de tergent selected from the salts of the group of de homogeneous on being warmed to room temperature. I A l B Dirnethyleoconut I amine oxide ................. __ 5.0 tergent anions consisting of R804", R(OC2H4)XSO4" where x is an integer from I to 5 60 6.0 Sodium coconut 1 ethylene oxide ether suit-ate R being an alkyl radical containing about 9 to about 16 carbon atoms, and mixtures thereof; (0) ‘from about 3% to about 10% of a salt of a hydro trope anion selected from the group consisting of (average of 3 ethylene oxide residues per mole cule) __________________________________________ _. 8. 5 Sodium coconut I alkyl sulfate ___________________ __ 2. 5 10.0 ________ ._ Sodium polypropylene benzene sullonate (a mix ture oitri-, tetra, and penta’propyleue averaging about C12) _____________________________________ __ Potassium pyrophosphate_..___ ___ _ Potassium toluene suli'onate _____ __ Color ________________ -_ 4.0 12 5 0.0013 4.0 12 5 (I. 02 toluene sulfonate, benzene sulfonate, and xylene sul fonate; 0 0013 Bonzotriazole _ 0. 02 Water _______________ _ . Balance Balance K/Na, approx. mole re 4. 2 4. S 1 i (‘oconut refers to the alkyls of middle out coconut alcohol containing about 2€’—G1t, 6651-012, 2370-014, and9%—Cm. These compositions gave good suds in washing dishes and in hand washing of ?ne fabrics. They are highly suitable (d) from about 3.5% to about 6% of silicate solids of 70 the composition SlOgIMgO their weight ratio being from about 1.6:1 to about 2.6:] and wherein the M of M20 is selected from the group consisting of sodium and potassium; (e) from about 10% to about 30% of a salt of a pyro phosphate anion; and the balance substantially 3,085,982 7 8 (f) water; said amine oxide having R1 containing 12 carbon atoms; the cations of the salts of the said detergent anions, of the salts of the said hydrotrope anions, and of the salts of the said pyrophosphate anion being selected from the group consisting of potassium, sodium, ethanolammonium, 5 and triethanolammonium, the mole ratio of the total of potassium and alkanolammonium cations to sodium ca (b) ‘from about 3% to about 15% of a sodium salt of a non-soap detergent anion selected from the group consisting of R804", R(OC2H4)XSO4" where x is an integer from 1 to 5 tions being greater than about 3:1, said composition being substantially free from amide suds-builders. 4. The liquid detergent composition of claim 3 ‘where 10 in the amine oxide R2 and R3 are each methyl radicals. 5. The liquid detergent of claim 3 wherein the detergent anion is 11%‘ “ >30, R being ‘an alkyl radical containing about 9 to about 16 carbon atoms, and mixtures thereof; (0) from about 3% to about 10% of potassium toluene sulfonate; 114 >303“ (d) ‘from about 3.5% to about 6% of silicate solids of 15 16 carbon atoms. phosphate; and the balance substantially (f) water, said composition being substantially free 6. The liquid detergent composition of claim 3 wherein the detergent anion is a mixture of R< the composition SiO2:Na2O, their weight ratio being from about 1.6:1 to about 2.6:]; (e) from about 10% to about 30% of potassium pyro R being an alkyl radical containing from about 9 to about 20 >~s Os-and R s or from amide suds-builders. References Cited in the ?le of this patent UNITED STATES PATENTS R being an alkyl radical containing from about 9 to about 16 carbon atoms. 7. The liquid detergent composition of claim 3 wherein the hydrotrope anion is toluene sulfonate. 25 8. A substantially clear high-sudsing liquid detergent composition consisting essentially of: (a) from about 3% to about 10% of an aliphatic ter 30 2,060,568 2,169,976 2,581,677 2,877,186 Graenacher et al _______ __ Nov. 10, Guenther et al _________ __ Aug. 15, Machlis et al ____________ __ Jan. 8, Krumrei _____________ __ Mar. 10, 1936 1939 1952 1959 FOREIGN PATENTS tiary amine oxide having the general formula R1R2R3N—>O where R1 is an alkyl radical containing 437,566 from about 10 to about 16 carbon atoms and R2 and “The Chemistry of Fatty Amines,” 1948, pub. by Ar R3 are each ‘methyl radicals, at least about 50% of Great Britain __________ .. Oct. 31, 1935 OTHER REFERENCES mour and Co., page 13.