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United States Patent O?lice 3,057,144 Federated Dec. 4., 1962 2 1 of from about one to three parts of each component in the mixture, and preferably in a weight ratio of 1:1:1, respectively. The foregoing mixture may further be 3,067,144 DETERGENT COMPQSH‘IQN Edwin B. Michaels, Stamford, Comm, assignor to Stam ford Chemical Industries, The, Stamford, CGEIL, a cor poration of Delaware No Drawing. Filed Nov. 16, 1950, Ser. No. 352,980 9 Claims. (Cl. 252-13?) modi?ed by adding thereto of from about one to ten parts of any commercially available phosphate builder, as for instance, an alkali metal tripolyphosphate, a tetral kali metal pyrophosphate, an alkali metal hexametaphos phate and equivalents thereof as well as mixtures of the same; the alkali contemplated include: sodium, potassium, This invention relates to novel heavy-duty synthetic detergent compositions which can be successfully em 10 lithium as Well as ammonium radicals. It has been found that the de?ned compositions are effective when employed ployed over a wide range of washing temperatures. More in relatively dilute aqueous concentrations from 0.04% particularly, the invention is concerned with detergent to 2.0%, and preferably in concentrations from 0.1% to 0.3%. detergent, (2) a higher fatty alcohol of from 10 to 18 It has been further found that a large variety of non carbon atoms, and (3) a polyalkoxy dihydric alcohol 15 cationic synthetic detergents of the anionic and non-ionic which may be represented by the formula: compositions comprising: (1) an organic non-cationic types either alone or in admixture can be successfully used herein. These may be taken from the following /| 20 typical commercially available distinct classes: (1) Ethylene oxide-higher alkyl phenol condensates in which the alkyl substituent may contain from 8 to 12 \ A H carbon atoms. The condensates, polyoxyethylene ethers, are prepared by condensing 6 to 30 moles ethylene oxide with 1 mole of the alkyl-substituted phenol. They are or an isomer thereof wherein m stands for a whole 25 available commercially under such names as “Igepal number from about 7 to about 35 and n is an integer from about 3 to about 14. It is known that the class of either ionic or nonionic CA” and “Igepal CO,” (2) Water soluble salts of the higher fatty acid amides of lower molecular Weight amino alkyl sulfonic acids, including, for example,’ the sodium salt of oleic acid detergents has achieved a distinct status as a substitute for amide of N-methyl or N-cyclohexyl taurine, known as natural soap. However, such detergents suffer the dis “Igepon T” or “Igepon 'CN,” respectively, advantages of relative inferior detersiveness as compared (3) Water soluble salts of higher alkyl benzene sul to natural soap. Moreover, they are substantially in fonic acid, such as the dodecyl benzene sodium sulfonate, effective over a wide range of temperatures during use. sold under the trademark “Nacconol NRSF,” For many purposes, soap itself is unsatisfactory since (4) Water soluble salts of alkyl sulfonic acids as, for it tends to deposit a water insoluble residue, usually in 35 instance, the sodium salt of sulfonated mineral oil, the form of calcium oleate, upon the washed apparel. (5) Water soluble salts of the higher alcohol esters Such deposition inevitably imparts a distinct hard feel of sulfocarboxylic acids, thereto. Thus, if non-cationic detergents could be en (6) Water soluble salts of the higher alkyl sulfates of hanced whereby the detersiveness of soap is approached or exceeded without experiencing soap’s disadvantages, 40 10 to 14 carbon atoms, e.g., “Duponol C,” (7) Water soluble salts of higher fatty acids of mono such would be highly desirable. esters of monohydroxy alkyl or polyhydroxy alkyl sul A principal object of the invention is to provide a de fonic acid as, for example, the sodium salt of oleic acid tergent composition of enhanced properties applicable est-er of isethionic acid (e.g., “Igepon ACE-78”), over a wide range of temperatures. A further object is (8) Water soluble salts of the sulfuric acid esters of to provide a non-cationic detergent composition com 45 the fatty acid monoglycerides as for instance, the sodium parable to soap’s detersiveness, absent insolubles which salt of coconut oil fatty acid ester of 1,2-dihydroxy may precipitate upon the washed apparel. Other ob propane-3-sulfuric acid, available as-“Syntex T,” jects and advantages will become apparent from a con (9) condensates of ethylene oxide-higher fatty acid sideration of the following detailed description. Surprisingly, the foregoing objects can be attained in a 50 (or higher fatty alcohols) prepared by reacting 1 mole of s‘tearic or oleic acid (lauryl or tallow alcohol) with 6 to straight forward manner by providing a detergent com— 30 moles ethylene oxide and are available under trade positionv mixture comprising (a) an organic non-cationic marks such as “Renex” of “Sterox AS” (or Sterox CD,” detergent, (b) a. higher fatty alcohol and (c) a poly “Siponic- E”), respectively, and alkoxy alcohol, hereinafter de?ned. None of the com ponents, other than the detergent, exhibits any noticeable detersiveness. Notwithstanding, the presence. of both a higher fatty alcohol and a polyalkoxy alcohol, a markedly (10) Polyoxypropylene glycol-ethylene oxide conden sates preparedby reacting polypropylene oxide and poly ethylene glycol, available as “Pluronic L—44.” improved detergent composition has been unexpectedly found, whereby the major disadvantages of the prior art pounds exhibits various degrees of detersive activity, its are obviated. The compositions of’ my invention may be character ized as being substantially- wate-r insoluble. They com prise the' above-mentioned components, all admixed in Although each of the aforementioned classes of com 60 detergency is markedly enhanced many fold by the incorporation therein of both a higher fatty alcohol characterized by the formula: R—OH hol and'polyalkox-y alcohol are present on a weight basis 65 where R is analkyl radical of from 10 to 18 carbon de?nite proportions. The detergent,. higher fatty alco enemas. 4. 3 atoms and a polyalkoxy dihydric alcohol. lowing. The latter alcohol may be represented by the general formula: As employed herein, “AATCC” means the American Association Textile Chemists and Colorists. In typical runs a standard soiled swatch and stain less steel balls, together with the speci?ed testing bath containing 0.2% detergent composition are charged to a launderometer jar. After a twenty minute wash cycle at 140° F., the washed swatch is removed from the jar, rinsed in ordinary tap water of 60 p.p.m. hardness, based on the presence of calcium and magnesium salts and isomers thereof, where m is an integer from about 10 and calculated as CaCO3 and Mg2CO3 in a weight ratio of approximately 2:1. This is performed to illustrate the 7 to about 35 (i.e., average molecular weight of about enhanced detergency of the compositions of the present 2000) and n is an integer from about 3 to about 14 (i.e., invention. Comparisons with known synthetic detergent average molecular weight of about 250 to 1000). compositions are made. In the following examples, vari The polyalkoxy dihydric alcohols may be prepared by ous detergent compositions with and without the higher known methods for instance, compound (I) is prepared alcohol and polymer in admixture are set forth; all parts by reacting 1 mole of 1,2-propylene glycol with at least are based on weight, unless otherwise speci?ed. The com about 6 moles of 1,2-propylene oxide. Resultant poly positions are then used in the concentrations indicated. propylene glycol polymer should not exceed a molecular Re?ectance readings of the soiled and unsoiled, washed weight (M.W.) of about 2000. Compound (11) can for example be prepared by reacting 1 mole of 1,2-butylene 20 and unwashed soil swatches are recorded. However, prior to washing, the reflectance reading of the soiled portion glycol with at least about 2 moles of 1,2-butylene oxide. of the standard swatch is recorded at 29, while the un Powever, the molecular weight (M.W.) of the resultant soiled portion of the same swatch is recorded at 100. polybutylene glycol polymer should not exceed about The percent detergency is determined by the formula: 1000. Although the structures as set forth are the pre ferred representations of the polyalhoxy alcohols, it is plated. For example, the polypropoxy linkage of the Rf (Washed soiled area) -—Rr(standard soiled area)'><100 Rf (standard unsoiled area)~Rf (standard soiled area) above compounds, may be written as: where R: is de?ned as the re?ectance reading value. to be understood that their isomers are also contem CH3 (Ia) Several compositions of the following examples illus CH3 30 trate various embodiments of my invention. They are employed to wash swatches that are standardized, im ----(!JB—CH2——O— : —OHz-— H—O— ——CH——CHz—O-—~ : ——CHz-—CH—O~— (Ila) (llzHs printed, oily-type, carbon soiled cotton. The swatches are (B2115 put in a launderometer maintained at 140° P. which approximates good laundry practice. The compositions Thus, (Ia) polypropoxy glycols of average molecular weight ranging from about 425 to 2000, preferably from 35 are all employed as an aqueous detergent bath which is adjusted to about 0.03%, based on the weight of the about 950 to 1200, and (Ila) polybutoxy glycols of active organic detergent component. However, based average molecular weight ranging from about 250 to 1000, and preferably from about 450 to 500, are con on the detergent component concentrations as low as include: decanol, undecanol, dodecanol, lauryl alcohol, tridecanol, myristyl alcohol, cetyl alcohol and stearyl by the appended claims. 0.01% and as high as 0.10% may also be employed templated in the practice of this invention. The higher fatty alcohols which are useful in the prac 4.0 advantageously. These examples are merely illustrative of the preferred modus operandi, and are not intended tice of the invention possess 10—18 carbon atoms and to be taken as limitative, except as to the extent de?ned alcohol, as well as their isomers and mixtures thereof. EXAMPLE 1 As stated previously, alkali metal phosphate builders ' are advantageously added to the above-de?ned multi Parts Nonyl phenol (1 mole) condensed with 10-11 moles components compositions. However, other adjuvants may also be added concomitantly in the present practice. ethylene oxide ____________________________ __ 14 Lauryl alcohol Such adjuvants are for instance starch, sodium carboxy 6 Polypropylene glycol polymer (l025—average mo methyl cellulose, glue, clay, sodium cellulose acetate and 50 lecular weight) ___________________________ __ equivalents, thereof all being added in conventional The detergent compositions are further characterized as being substantially water insoluble. They are, how ever, dispersible in water. The indications are that a 55 12 Tetrapotassium polyphosphate _________________ __ 25 amounts. EXAMPLEZ A composition of Example 1 is prepared except that the quantity of the polypropylene glycol polymer is increased 'to 16 parts of said polymer. cloudy solution appears at elevated temperatures of 120° F. or higher above. if desired, a wetting agent other than the detergent itself may be advantageously added EXAMPLE 3 to the composition in an amount approximating the Parts quantity of synthetic detergent, so as to solubilize the 60 Polyoxyethylene ether of oleyl alcohol (prepared by latter, particularly in a high phosphate salt environment. reacting 12 moles of ethylene oxide per mole of Such wetting agents include, for instance, the soluble oleyl alcohol) ____________________________ __ 10 salts either of xylene sulfonates, or of alkylsulfo-suc cinates, or of long chain fatty acid sulfates, or of un polyrnerized alkyl naphthalenesulfonic acids. More spe ci?cally, wetting agents such as sodium xylene sulfonate, lauryl sodium sulfate, dioctyl sodium sulfosuccinate and potassium isopropyl naphthalene sulfonate are contem plated herein. In general, any of the commercially available wetting agents may be used. Decanol Polypropylene glycol polymer (average molecular weight=1025) ___ __ 5 Tetrasodium pyrophosphate ___________________ __ 25 EXAMPLE 4 7 Parts Condensate of 1 mole of tallow alcohol and 11 moles The enhanced detergent properties of the composi of ethylene oxide _________________________ __ 10 tions according to the practice of the present invention Tridecanol are determined in a conventional manner. Polypropylene glycol polymer (average molecular The latter requires the use of a launderometer as fully described in the “AATCC” year book for 1955, page 55 and fol 75 _________________________________ __ weight=l025) ____________________________ c- 5 6 Tetrasodium pyrophosphate __________________ __ 25 3,067,144 6 The re?ectance data was collected and recorded in the EXAMPLE 5 table as follows. For the condensate of tallow alcohol and ethylene oxide of Example 4 is substituted sodium lauryl sulfate and the Table 1 composition therein otherwise identical, is prepared. Br Ex. EXAMPLE 6 The components of the composition in Example 4 are admixed as indicated, except that sodium dodecyl benzene sulfonate is substituted for the condensate of tallow al cohol and ethylene oxide. Rn? v(soiled portion Percent deter- soiled portion Percent deter- Percent increase Temp, of swatch after gencyl altercleaning ge'neyl in detergency ° F. 82 75 50 30 Y 150 140 84 86 78 80 50 53 30 354 160 1120 140 120 71 84 59 78 60 5,8 43 41 36 90 140 140 cleaning) 84 EXAMPLE7 Parts Tridecyl alcohol ‘(1 mole) condensed with ethylene 78 45 23 76 66 56 38 82 77 80 75 68 49 49 54 28 28 35 72 250 160 74 r 160 165 140 100 7140 160 140 oxide (10 moles) ___________________________ __ 5 Tetradecanol ________________________________ __ 5 1 As de?ned above. Polypropylene glycol polymer (average molecular I 2 Ru and percent detergeney are determined in usual manner utilizing detergent compositions of the respective examples in which the alcohol weight +425) ___________ __ ________________ __ 5 20 and the polymer have been omitted. Percent increase in detergeney is determined by comparing the compositions of the invention to that of Tetrasodium pyrophosphate ____________________ __ 5 the prior art. In the above table, the water hardness (Ca-Mg) in parts per million utilized in each of the examples except Parts 25 ing Example 4 is 60. However, the water hardness used Tridecyl alcohol (1 mole) condensed with ethylene in Example 4 is 200. oxide (8 moles) __________________________ __ 5 EXAMPLE 11 Tridecyl alcohol ___________________________ __ 5 A mixture is prepared which comprises 105 parts of Polypropylene glycol polymer (average molecular EXAMPLE 8 weight=2000) decanol, 10.5 parts of polypropylene glycol polymer of ___________________________ __ 30 average molecular weight equal to about 1025, 15 parts iTetrasodium pyrophosphate __________________ __ 100 Carboxymethylcellulose _____________________ __ 1 Sodium metasilicate ________________________ __ 25 sodium salt of oleic acid amide of N-methyl taurine and 15 parts of tetrapotassium pyrophosphate. T0 this mix ture is added 30 parts sodium xylene sulfonate. Suf?cient water is added to increase the total number of parts of The enhanced detergency property of the above-de?ned 35 the composition to 185. The wetting agent, sodium xylene compositions has been noted at the usual laundry tem sulfonate, is advantageously added principally to e?ect erature of 140° F. However, temperatures as low as solubilization of the detergent to form a substantially room temperature and as high as 200° F. may be used clear solution.v When the stated composition is employed herein. In general, temperatures in the range of 120° C.-160° 40 in dilute aqueous concentration of 0.3%, 0.4% and 0.5%, respectively, re?ectance readings subsequent to washing C. are preferred when using the C12 alcohols, 140°-180° at 140° F. are 75, 76v and 84, respectively. F. when employing the C14 alcohols and 160° to 210° F. EXAMPLE 12 A mixture was prepared containing/V the ingredients: when using the C1648 alcohols. EXAMPLE 9 Parts 45 (1') Condensate of 12 moles ethylen oxide andil mole ' Parts ‘of oleyl Polyoxyethylene ether of stearyl alcohol prepared by reacting one mole of stearyl alcohol with 12 moles of ethylene oxide __________________________ __ Commercial lauryl alcohol (70% C12, 20% C14, 10% Cid-l8) taurine 5 50 _______ __,_ ____ n, _______ __ 6 _____________ ___ ____ ___ ___________ __ (4) 5 Tridecanol __________ __, _______ ____ _______ __ 55 Suf?cient water was then added‘ to dilute the mixture 150 parts. Parts Polyoxyethylene ether of stearyl alcohol (prepared by reacting one mole of stearyl alcohol with 12 moles of ethylene oxide ____________________ __ 5 Myristyl alcohol _____________________________ __ 3 8 10 (5) Sodium-xylene sulfonate __________________ __ 40 (6) Tetrasodium pyrophosphate _______________ __ 11 Tetrasodium pyrophosphate __________________ __ 25 EXAMPLE 10 10 (3) Polybutylene glycol’ polymer (av. mol. wt. of 1000)v ___________________ __,_______v___.______ -------------------------------- —-.-~ Polypropylene glycol polymer _________________ __ alcohol ('2) Sodium salt of oleic acid amide of; N-methyl A When a test soiled swatch in a launderometer at 140° F. as described previously is’ washed using 0.3% concentra tion of the foregoing detergentpcomposition, aid-re?ectance 60 reading of 78 is ‘observed. Polyproylene glycol polymer (av. mol. wt. 1200)____ 5 EXAMPLE 13 The above, Example 12 was repeated; in every, respect Tetrasodium pyrophosphate ____ ______________ ______ 25 except the polybutylene glycol polymer was. replaced by Although it is generally recognized in the laundry art molecular weightof about 500., When the soiled swatch vention. Further, even in the absence of soft water and where hard water is used (200+ p.p.m. Ca-Mg cal mixing the components together in the form of a. dry mix< ture, dispersion, suspension ,andthe like, either in the pres 6 parts of polybutylene glycol polymer of. an average is washed in the detergent compositioma re?ectance read that an increase in washing temperature above about 140° ing of 76 is observed, F. decreased the detergency value of the synthetic deter It is an important advantage of‘ the present invention gent swiftly, surprisingly, a contrary effect is noted with the enhanced detergent compositions of the: present in 70 that the detergent compositions can be prepared by ad ence or absence of additional alkali metal phosphates. culated as CaCO3 and Mg2CO3 in 2:1 weight ratio), the In this fashionLthe compositions can be packaged with re?ectance reading of the unsoiled area of the standard 75 ease. cotton swatch is noted in each case to be 999+. 3,067,144 7 8 EXAMPLE 14 n is an integer from about 3 to about 14, and isomers thereof, and A 25 pound load of soiled white shirts and containing (d) 1 to 10 parts by weight of ‘an alkali metal phos phate builder selected from the class consisting of a standard soiled swatch is charged to a conventional commercial washer containing hot water (160° F.). To the latter is next charged 8 ounces of detergent consisting of 14 parts of a condensate prepared by reacting 1 mole tridecanol and 12 moles of ethylene oxide, 6 parts of an alkali metal pyrophosphate and a mixture of an alkali metal pyrophosphate and an alkali metal ortho phosphate. 2. The detergent composition of claim 1 in which the Weight ratio is 1:1: 1:5 of the components, respectively. phosphates comprising tetrasodium pyrophosphate (50%), 10 3. The ‘detergent composition of claim 1 in which the non-cationic detergent is the condensate of 1 mole of trisodium phosphate (49%) and carboxymethylcellulose nonyl phenol and about 10 moles of ethylene oxide; the (1%). After a ten minute washing cycle, the wash Water fatty alcohol is lauryl alcohol, the polyalkoxy alcohol is is discarded and the wash is further treated ‘for an addi polypropylene glycol polymer of average molecular tional ten minutes with four ounces of the above deter~ gent composition previously defined. The wash water is 15 weight 1025; and the alkali metal phosphate is tetrasodium pyrophosphate. discarded again, the load is bleached, rinsed ?rst with 4. The detergent composition of claim 1 in which the hot water, then with cool water and, ?nally, dried. detergent is the condensate of 1 mole of octyl phenol and Re?ectance reading of the standard swatch included about 8 moles of ethylene oxide; the fatty alcohol is along with the shirts is observed as 95 (93% detergency), decanol; the polyalkoxy alcohol is polypropylene glycol and none of the washed shirts had to be withdrawn from polymer of average molecular weight equal to about 1025; the load to be rewashed for cuff or collar stains and soils. and the alkali metal phosphate is tetrapotassium pyro The percent whiteness retention was found to be 100%. phosphate. ' EXAMPLE l5 5. The detergent composition of claim 1 in which the Repeating the procedure of Example 14 in every mate 25 detergent is the condensate of 1 mole of oleyl alcohol rial detail except that natural soap is substituted for the and 12 moles of ethylene oxide; the fatty alcohol is tri synthetic detergent mixture, a re?ectance reading taken decanol; the polyalkoxy alcohol is polypropylene glycol polymer of average molecular weight equal to 1025; and on the included test soiled swatch is noted as 53.5 (35% the alkali metal phosphate is tetrasodium pyrophosphate. detergency) and the whiteness retention is recorded as 6. The detergent composition of claim 1 in which the 99.5%. However, more than one-fourth of the load used 30 detergent is the condensate of 1 mole of tallow alcohol in this example had to be rewashed for cuff and collar and 11 moles of ethylene oxide; the fatty alcohol is tri stains. decanol; the polyalkoxy alcohol is polypropylene glycol It will be readily noted that in comparing the values polymer of average molecular weight equal to 1025; and of Examples 14 and 15, the detergent mixture of this in vention represents a more than 150% increase of soil re 35 the alkaline metal phosphate is tetrasodium pyrophos lauryl alcohol and 8 parts polypropylene glycol polymer (average molecular weight 1025) and 120 parts of mixed phate. moval over soap. 7. The detergent composition of claim 1 in which the organic detergent is a mixture which consists essentially I claim: 1. An improved multi-component cleaning and laundry detergent composition substantially water insoluble which consists essentially of: v v of the condensate of 12 moles ethylene oxide and 1 mole 40 of oleyl alcohol and the sodium salt of oleic acid amide of N-methyl taurine; the polyalkoxy alcohol in poly butylene glycol polymer of average molecular weight equal to about 1000; the fatty alcohol is tridecanol; and the alkali metal phosphate is tetrasodium pyrophosphate. (a) l to _3 parts by weight of a non-cationic organic synthetic detergent selected from the class con sisting of ethylene oxide—higher alkyl phenol condensates, water soluble salts of high fattty acid amides of lower molecular weight amino alkyl sul 45 8. The detergent composition of claim 1 in which the fonic acid, water soluble salts of higher alkyl ben detergent is the condensate of 1 mole of stearyl alcohol zene sulfonic acid, water soluble salts of alkyl sul and 12 moles of ethylene oxide; the alcohol is lauryl fonic acids, water soluble salts of higher alcohol alcohol; the polyalkoxy alcohol is polypropylene glycol esters of sulfocarboxylic acids, water soluble salts of polymer of average molecular weight equal to about 1200; 50 the higher alkyl sulfates, water soluble salts of higher and the alkali metal phosphate is tetrapotassium pyro fatty acids of monoesters of monohydroxy alkyl sul phosphate. fonic acids, water soluble salts of higher fatty acids 9. The detergent composition of claim 1 in which the of monesters of polyhydroxy alkyl sulfonic acid, detergent is the condensate of 1 mole of stearyl alcohol water soluble salts of the sulfuric acid esters of fatty acid monoglycerides, condensates of ethylene oxide 55 and 12 moles of ethylene oxide; the fatty alcohol is and higher fatty acids, condensates of ethylene oxide . undecanol; the polyalkoxy alcohol is polypropylene glycol polymer of average molecular weight equal to 1025; and and higher fatty alcohols and polyoxypropylene gly the alkali phosphate is tetrasodium pyrophosphate. col-ethylene oxide condensates. (b) 1 to 3 parts by weight of a fatty alcohol character 60 ized by the general formula: References Cited in the ?le of this patent ROH UNITED STATES PATENTS where R is an alkyl group of from 10 to 18 carbon atoms. (0) 1 to 3 parts by weight of a polyalkoxy dihydric 65 alcohol characterized by and selected from the struc ture consisting of: _/ _ H L OH \ZH O rojm and / H Jacoby et al ___________ __ Nov. 13, 1951 2,806,001 Fong et a1 ____________ __ Sept. 10, 1957 2,855,367 Buck __________________ __ Oct. 7, 1958 FOREIGN PATENTS 70 Hz 2,575,276 729,531 Great Britain __________ __ May 4, 1955 OTHER REFERENCES “Synthetic Organic Chemicals,” pub. by Carbide and where m .is an integer from about 7 to about 35 and 75 Carbon Chem. (30., 13th ed., 1952, page 56.