[1]3 1 , 0 @ 7 6 @ 7 6 6 Un'lted States Pateftt@ Office P'a'tented Feb. 5, 1963 3,676@766 DETERGENT BAR Ik'ayknoirkd Mi@ha'el Anstett, Hazlet ' N.J, assignor to Colgate-pwmolive Company, Nw Yo7@,l N.Y., a corporation Of Delaware No Drawing. , Filed Aug. 12@ @959, Ser. No. 833,152 4 Claims. (Cl. 252-117) This ln''yention rdlate@ io a ddtergent bak containing Wat@@ oliible soaij arid@ lesser amount@ of certain synthe@l,c, detergents. The inv,ented bar product has excel- 10 lent washiiig pr6@erties, @ields no undi@@p@rsed ctird in haid w@ater and posses@es the tactile properties, appear@ance, drying aclivity and processing ch@racttristies of ihe ordinar@ higher fatty acid soaps. Previoi@s woj7ker in the detirgent art have disclosed 15 that synthetic detergents may be m.Ln@ufactured iii bar form. In somd 6f the re6ommended formulations large amounis of non-deiergent builders and fill6rs had to be employed to im@rove the pro--essing qualities of the s@nthetic detei-geni. Sometimes these, addit-lve@ also inade 20 t . detergi, -nt pr6duct harder aiid reduced its solubility he in. water. Other resear@,li'ers haie suggested that mixtures of syntheti@, detergents may be made so that the end product could po@sess the advaniages of each component wasliipg agent. A number of patents have been 25 issued in which synt;hetic detergents and soaps were c I ombined, Often with otl'ier additivesj to iiiiprove their properties and several of these products have met with some nieasure of commercial success@ Although in cer30 tain types of formulations a degree of geiieralization is possible@ those of greatest skill and experience in this ar-t usually consider, with justification, th@t whe n the particular types of delergents are varied, new properties, o,ften undesirable, will be ob.served. Because the pur- 35 chdser of the gverage commercial toilet detergent bar or eak,o applies a high standard in evaluating detergent products of this type, and because the market conditions @re 8o corftpetitivo,, it is- nee.essary that each deteraent forfnulatibt intended for use in bar form must pass rigid 40 tests the WtiTnate of which is consiimer acceptaiice. The @hanges 6f ptoperti,es, observed in bars nlade from mixed detergents as variations are made in the n,ature of deterg&nt coiistitutnts, have resulted in a general concliision that each of theso complex formulas is a prob- 45 lerft 'within itself. The application of general principles, arrived at fr(im experience with seemingly analogou d&- tergents, can often be very misleading and might result iii a pr6duct which fails the test of a discrimitiating consumer public. 50 In aceordance with the presen,t invention it has been .disedvere'd that tL milled and plodded detergent bar formirig no undisi)ersed curd in us.e,. having excellent detergency, tactile qualities, latl@ering and foarrtin@ ability and gpod@ olu@ility, sloughing and drying properties, as well 55 as exceptionally good proces@ing characteristics, consists ps@eniiallv oi: 8 to @O 9' , alkali metal sa I It of @stib teilitially satur@Lted high6r fatty glyceryl stilfuric a:cid compound; 3 to 16@'o '@lk@li metal alkyl a@yl sulfonaic in :@which the aii@l g'@oup @s of 10 to 18 carbon atomsi and thO @ryl 60 @@di6,al is @ sele@ , ted ftom the gro@p consisting of bentene I ;tnd its s'ui@stitiltion compounds; 3 to 1001o alkaii metal salt 6f highot dc@l @mide oi @n amino 16wer aliphatic sulf6hic of i to ;4 o on@ I atoms; 45 to 65@'o s@oluble dlk@li 'metai soao with a major proportion thereof beng sodiiim soal), mGr6 than 65% of the soap fatty acid content being aturated fatty acids; and having a predominant an-ount, over 7501o, of the soap f@tty acid of I? to 19 6@ b atoms, of which fatty acids 25 to 60% is of r "n 12 to 14 carbon atoms and 7.5 to 40% is of 16 to 18 catbon atoms; 6 to 14% moisture; and less than 7% t6tai c@onte'nt .@Llkali metal sulfate and alkali metal chloride. In preferred formtil:ations there are ernployed 10 to 17% of sodium salt of substantially saturated higher iatty atid monoglyceride sulfate; 4 to 8% sodium alkyl aryl sulfonate in which the alkyl groiip is a propylene tetramer or pentamer and the aryl radical is benzene; 4 to 8 "lo sodium salt of higher acyl amide of N-methyl tauriiie; 50 to 60% soluble sodium sopp having more than 70% of its fatty acid coiitent of saturated fatty acids, over 85% <)f the soap fatty acid being of 12 to 18 @arbon atoms, bf wbich fatty acids 30 to 50% is of 12 to 14 carbon atoms and 70,to 50% is of 16 to 18 carbon atem's; 8 to 120/o moisture; and less than 5To total contentof @odium sulfate and sodium chloride. The alkali metal salt of substantially saturated higher fatty glyceryl sulfuric acid corhpound is made by any of various known fechniques in which 'a higher fatty radical i@ attached to a glyceryl stein converted to a correspondig sulfuric acid canipound. The detergent contailis ldnly one s@ulfuric acid type group and olily one higher @.atty radicil The siilfurid acid compound may be either a sulfzite 6rsulfoliate and the fatty portion may be of 10 to 18 carbon atoms, f preferably in straight line conguration, attached to the glyceryl stem thtough either -a carbonyl or ether linkage. As exan-iples of this specific type may be mentioned the sodium salt of coconut oil fatty acids monoglyceride si-ilfate@ wherein the cocbnut oil may be,hydrogenated if so desired, sodium laliryl ether glyceryl sulfonate, sodium and potassiun hydrogenate d tallow fatty @acids monoglyceride sulfates, sodium rr@yristyl mono,@lyceride sulfonate and sodium paimityl ether glyceryl sulfate, to name a few of these suitable detergents. These cotnpounds i-nay be used in naixtures if so desired. Some of tl-iis type of detergent, e.g., sodium and potassium lauryl ether glyceryl sulfonate, possess sufficiently good clrd dispetsion properties to allow repla@-,en-ient of some amide sulfonate constitutent too. The alkyl aryl sulfonate detergent is preferably the sodium salt of a polyalkyleite derivative of benzene sulfonic acid in which the alkyl group is of 10 to 18 carbon atoms, e.g., propylene tetramer or peiitamer. Other al@kyl grotipings obtained iii alkylation of berizene or its derivatives with kerosene fractions, as we, as co p .1 ni aratively straiglt chai-.1 alkyl radicals are also suitable; instead of the bdrizene nucleus, suitable benzene substitltion compound@ having relatively small or 16wer radicals substituted for the hydrogen tiiereon may be employed, such a@ toluene and xylene. The alkali metal salt of higher acyl amide of atm'no lower aliphatic sulfonic acid is one in which the acyl group is of 12 to 18 carbon atoms. The amino aliphatic sulfonic acid portion of the molecule may have a lower alkyl radiceil attached -to the amino nitrogen. The total 6f 6afbon atoms @in the lower aliphatic stem connecting the amino and sulfonic acid groups and in said lower alkyl raclical may be from 2 to 4. The lower alkyl of tile @'connecting'alkyl @sterh is of 2 to 3 carbon atoms and
[2]3 the lower alkyl which may be attached to the nitrogen may be of 1 to 2 carbon atoms. Among the compounds of this type which may be used in the disclosed detergent bars are sodium higher acyl amide of N-methyl taurine in which the acyl groupin.- is a rnixture of palmitoyl and stearoyl, sodium oleic acid amide of N-methyl taurine and sodium hydrogenated coconut oil fatty acids amide of amino propane sulfoilic acid. As is seen from the above examples it is preferred to use those compounds having 3 carbon atoms in the lower amino sulfonic acid portion of the molecule. The water soluble alkali metal soap of the invented compositions contains a major proportion of sodium soap, usually over 75%. The soap fatty acid content is 65% or more saturated. The soap also consists predominantly, of 12 to 18 carbon atom molecules, preferably 85% and niore being of this chain length. These soaps comprise specified amounts of fatty acid soaps of 12 to 14 carbon atoms and of others of 16 to 18 carbon atoms. Such materials may be made by combining in proper proportions certain natural oils of known fatty acid analyses. For example, it has been found that coconut oil or hydrogenated coconut oil may be mixed with tallow in the soap kettle in such proportions as to result in soaps of the type needed in the present detergent bar. Thus, it is possible to make such a isoap by mixing one part by weight of coconut oil with two parts by weight of commercial tallow, and similarly, a satisfactory soap can be produced from four parts coconut oil and one part tallow. Within the boundaries of such compositions are otlier satisfactory soap mixtures, the preferred embodiinent of which is one made from equal parts of these oils. Instead of coconut oil and tallow, other suitable sources of fatty acids or glycerides may be substituted to obtain a soap mixture of the type described. The combiiiation of three synthetic detergents and the soap in the proportions disclosed, together with the proper amou-@it of moisture and minimum content of sodium sul. fate and sodium chloride, less than 5%, results in a composition which can be made i-@ito bar form in substantially the manner employed to make soap cakes and which possesses excellent performance characteristics. If 5 to 7% total content of sodium chloride and sodium sulfate is present, more synthetic detergents should be employed thari is used for the preferred compositions, containing less than 5% of such salts. Although the constituents of the present composition do have properties which distinguish them, one from the other, it is found that when made i-iito a bar there is an interrelationship and interaction of the various components to produce a product which cannot be considered as merely the sum of the individual properties of its ingredients. Thus, it has been found that the detergent bar made according to the formulas given does not slough excessively although a combination of alkyl aryl sulfonate and sodium salt of higher fatty -lyceryl sulfuric acid compound tends to cause ordinary soap bars to slough when added thereto in amounts sufficient to give other acceptable performance characteristics. The present detergent bar is excellent insofar as curd dispersion or scum formation in hard water is concerned although similar formulations made from different soaps and detergents do cause objectionable curd production. T'he present composition dries relatively fast to an exceptionally attractive glossy appearance. This rapid drying in normal use occurs while otherwise substantially satisfactory bars containing monoglyceride sulfate, alkyl aryl stiffonate and ordinary soap dry slowly, leading to rejection by the consumer. As was said above, the present detergent bars are the products of interacting detergent components present in the proportions specified. Although each component affects the properties of the others, within the formulas disclosed it is possible to set forth a set of principles to assist one skilled in the detergent art in manufacturing the best detergent bars. The monoglyceride sulfate or other suitable sulfuric acid compound aids in the production of 3,076,766 4 a bar having excellent foaming properties. This type compound also exhibits curd dispersing activity, but in itself, in the quantities employed, is not sufficiently effeetive in this respect. The alkyl aryl sulfonate improves the r) hard water foaming ability of the formulation and also contributes a desirable slip or lubricity to the detergent bar. The amide of amino sulfonic acid is a most excellent curd disperser in these formulas and has foaming powers. The soap employed in the present compositions has been 10 found to result in producing much less soap curd in water containing calcium and mignesium ions than soaps of lesser saturation and greater content of 16 and 18 carbon atoms. Because of this behavior it is possible to make a bar of the relatively low synthetic detergent content range 15 given and still obtain a de.-ree of foaming and curddispersion formerly associated principally with products of higher synthetic detergent: soap ratios. The present soaps also produce more foam than does ordinary soap in bars containing the disclosed mixture of synthetic detergents, 20 yielding a quicker, richer and creamier lather. As the moisture content is increased, the bar becomes softer, more soluble and tends to slough more readily, while below a minimum amount the composition is very difficult or impossible to mill and plod. The presence of sodium 25 sulfate and sodium chloride in amounts in excess of the limit given tends to cause crystallization and sometimes produces in the detergent bar a graininess which is objectionable to the user. In formulating detergent bars according to the teaching 30 Of this specification, amounts of components may be adjusted within the ranges given but best results are obtained by selection of proportions in accordance with the following principles. If the amount of amide sulfonate compound is near the maximum, that of glyceryl sulfuric 35 salt may be decreased, allowing use of an amount thereof sufficient to yield a good foaming product in donjunction with the formula amotints of other detergents employed. On the other hand, if a maximum of glyceryl sulfuric salt is used, less amide is needed for satisfactory 40 curd dispersion. The amide compound is a more effective curd dispersant and the glyceryl sulfuric salt is a better foaming agent in these compositions. A decrease in total synthetic detergent concentration permits use of more lower molecular weight soap (made from fatty acids of 45 12 and 14 carbon atoms) and an increase of such detergents indicates that more of the higher soaps can be used and should be added to improve bar hardness and decrease any excessive solubility. The alkali metal of the detergents and soaps is preferably sodium but potassium 50 compounds are also useful. The amounts of sodium and potassium soaps and detergents should be chosen to obtain a bar of satisfactory hardness and solubility. Other considerations in formulations, similar to those recited above, will be apparent to one of skill in the art from 5,5 the disclosure. Although good foaming, curd dispersion, slip, appearance -and detergency lare desirable, even very important properties of detergent bars, those prioducts intended for personal use should also possess other attributes to make (;o them acceptable to the consumer. Among the more important of these properties are those of speedy drying and, associated therewith, aesthetically pleasing appearance and tactile properties <)f a wetted bar. The ordinary fatty acid soaps, being water soluble, dissolve to 65 some extent when in contact with water in the soap dish or on the wash stand. In addition to dissolving some of the soap at the surface of the bar, water contacting the bar is absorbed by the soap and forms with it a soft gellike surface layer which is easily removed and deposited 70 on the soap dish or hands of the user. Although the soap gel described is undesirable, soap dries and hardens fairly quickly and therefore a cale of soap is normally of acceptable hardness in ordinary usage, provided that it is not stored continuously in water and if it is given 75 sufficient time to drain and dry between washings.
[3]The iatge majority of synthe:tic dete rgents is @onsidetabl,y more soluble than soap@ and usually such products dissolve too rapidly to be useful toilet bar detergefits by themselves. When mixed with soap in amounts - sufficient io yi6ld a curd-free washing solution of satisfactory foam5 ing power and detergency they' aggravate the tendency of th6 bar to dissolve' @nd increase the amount of surface s@ftening and gelation. Sometimes this leads to uiiacceptable degree .of slougliing and unisightly dep6sits of gel in the soap, dish. . In some formuta@ the synthetic 10 @detergent deci-eases the drying rate of t,,h6 soap, giving a product that appears wet ajid, jellified -at the surface for comparativ6ly lo-iig peri6ds after usage. The pr-,sent detergent bdr is exceptional in that, it is of sufficient solub.ility a@d excellent, p,6rformance characteiistics but does 15 not exhibit either ex@essive slo'ughing and gel form@tion nor does it dr@ slowly,.as might have been expected@ In comparative tests against a large number of other detergent @bar formulations, after an extended period of immersion in water the invented product dried more 20 qpickly than any other formul@a tested, being @as go6d in this respect as commercial toilet soap cakes. Possibly @s imp.orta,it as the improved drying rate of t-his product is the -fact that the bar not only dries to an attractive s-arfade but also appears to the consumer to be dry. 25 in the composition of this inventio-@i there may be incorporated in minor amounts various adjuvant materials designed to contribute sl)ecifir, properties to the b@r@ included among this group of materials are: bactericides, e.@ hexachlorophene, trichlorcarbanilide, balosaiicyi 30 haloanilides, merctirials; perfumes; pigments and opacifying agents, e.g., titanium dioxide; -dyes and - colorants, brigateners, e.g., aminostilbenes; sequestrants, e.g., tetrasodium ethylene diamiiie tetraacetate; @antioxidants and stabilizers, e.g.,,sequestrants for metal impurity c@talysts, 35 stannic chloride, stannous chloride, di-tertiary-butyl para cresol; emollients, e.g., lanolin. The aniount of adjuvant sho-aldbe sufficient to impart the desired activity but not to substantially adversely affect the bar properties. Also present in these bars there @will sometimes be foli I nd small 40 quantities of so-called ether solubles, which are usually unreacted oils or fats or by-product oils, fatty acids or other compounds from t-he mantifacture of the detergents and soaps. As with someof the adjuvants it is pref.erred 45 to hold t,,his ingredient to a practical minimuni - consistent with detergent manufacturiiig considerations but small amounts, e.g., 1-4%, rdo not interfere with production of ,a atisfactory bar. n. e bars of this invention may be iiiade according to 5( the usual methods employed in the manufacture of cOrrespon@ding soap products with only minor adju@tments known to those:skilled in the -art of making combination soap-detergent bars. The constituents: of the formula may be mixed in the crutcher and dried to proper moi '- 55 ture content, or altematively, rnay be blended in the amalgatnator. If -desired, neutralizati6n @or other reactions may be effected in the crutcher. For example, the acylated amino sulfonic acid, together with unreacted or excess fatty acid, may b'e crutcher neutralized. Drying of ro tile crutched,detergent nlixttire may be by known ttinnel-, flash-, spray- Or film-drying techiiiques. In the amalgamation step the desired moisture content of the final product may be adjusted by any of various known methods. Water may be added to the formula constituents, 65 if needed, -or one lor more of t-he coinponents may be added in water soltition or siurry. Usually the minor ladjuvaiits of the bar compositiori are blended with the detergents in t@,he amalgamator. T@he formula is then milled to forrn a homogeneous chip which is compacted 70 aiid extruded, usually by a soap plodder. After plodding the extruded -bar is cut to leiigths and pressed in a conveptional soap press, such as a standard high speed, duplex press in which opposed dies form the soap cake in a rotatable die box. "5 The following exam'@pleg are given to illustrate the inventibn biit are not +,o be regarded, as limiting. AU and pereenia.-es in the specificatiort and clAin@8 will be by weight unless @otherwise indicated. txamp'le I Perce-nt sodium!4ydrogenated coconut 6il i@tt@ @@ias m' onoglyq@pride sulfate --------------------------- 15 Sodium dodec@l benzen6 sulfonate (@lk@l irou@ being principally propylene tetrarner) --------- 5 Sodium higher fatty (mixed C16, C18) @acid amide o f N-methyl taurine ------- -- ----- 5 ------- 7-- So dium soap (1: I cbronut oil: tallow ratio) ---- -- 55 So dium sulfate ---- -------------------------- 1.4 So dium chloride ---- ------------------------- 1.6 Mo isture ---- ------------------ 12 Other ingredients (bactericide, perfume, pigment opacifier, color solution, unreacted and by@product ether solubleoils, fatty acids, etc.) ---- -- 5 100.0 Thd synthetic de-tergents tind soap 6re ertitchdd together (with accompanying sodium salts and ether solum in ic e m sbles) and ard dried in a fil drier t6 -the @ d@ ai d @ oi ture content after which they are mixed in an amalgamator with desired adjuvants. The -amalgariidted coMPosition is then milled three times to homogeneity, plodded in a vacuum plodder, cut and pressed in essentially the @ame manner employed for making soap. Bats madc were tested for various properties indic@,tive of utility of the product in hard and soft water, a'm@ong which wero lather and foam, hand washing, curd dis. persion, drying c haract6ristics, slough @nd appearance. They produced e8se-@itially -no undispersed curd, gave a copious, creamy i,ather, dried even fasfor than ordinaiy soap alone, and were rated as excellent bar detergents. In the formula given, either all or part of the sod'@UM hydrogenate@[ cocolmonogi@cerid- sulfate mAy be replaced by 6thers of the higher fatty glyceryl sulfuric acid products @described elsewhere, in accordance vvith the t ca@hing's of @this specification. The resulting products will also be excellent bar detergents. Example 11 Perc ent Sodi um higher fatty acids monoglyceride sulfate@@ 11 Sodi um dodecyl benzene sulfonate ----- L -------- 6 S.odi um soap I ------------------------------ 59 Tota l alkali metal sulfate and sodium ch,loiide ---- 2.8 Mois ture ---------------------------------- 11 Othe r ingredients ---------------- ------ 5'.2 Sodi um higher fatty acid amide of N-methyl tauriii6 5 100.0 1 71% @aturated fatty acid soap of whicb, 940/, is of 12 to 18 c,%rboii atoms, 38% of whic',i i@ of 12 to 114 carbon tms and 62% of which is of 16 to 18 carbon atoms. Exampte III Percent Sodium higher fatty acid inonoglycerid6 sul.fate ---- 12 86dium higher alkyl bdil2@ene 'slilf6iiate ------------- 6 Sodium higher fatty acid amide of Nmethyl taurine (Igepon TE-42) ---------------------------- 5 Alkali metal (sodium) soap (3: 1 coconiit oil:tallow ratio) -------------------------------------- 59 Total sodium sulfate and sodium chloride --------- 3 Moisture ------------------------------------ 11 Other ingredients ----------------------------- 4 100
[4]7 Example IV Percent Sodium coconut oil fatty acids monoglyceride sulfate --------------------------------------- 12 Sodium dodecyl benzene sulfonate --------------- 6 Sodium higher fatty acid amide of N-methyl taurine 6 Sodium soap I -------------------------------- 60 Total alkali metal sulfate and chloride (sodium salts) -------------------------------------- 3 Moisture ------------------------------------ 10 Other ingredients ----------------------------- 3 100 181@l, saturated fatty acid soap of wbich 910/, is of 12 to 18 carbon atoms, 561/o of -,vhich is ot 12 to 14 carbon atoras and 44% of wbich is of 16 to 18 carbon atoms. The N-methyl tauride of this formula may be replaced either wholly or in part by other amides of amino lower aliphatic sulfonic acids previously mentioned. When such substitution is made and the teachings of this sp.-cification are followed the bar resulting will produce little or no undispersed curd and will have the other desired qualities of the above compositions. The formulas of Examples 11, III and IV were made into bars by amalgamation with adjuvants and amounts of water which would yield good products of satisfactory processing characteristics. The compositions were milled, plodded and pressed. The bars made were subjected to rigid tests similar to those described after Example I. They were found to give a wash water free of objectionable curd, even at very dilute concentrations of the composition in hard water. They foamed very well in hard and soft water and made a rich, creamy lather. The bars dried rapidly to an attractive glossy appearance and possessed comparatively little jellied material on their surfaces after immersion in water. They passed other evaluation tests with excellent ratings and were found to be exceptionally fine toilet detergent products. The above invention has been described in conjunction with illustrative examples thereof. It will be obvious to those skilled in the art who read this specification that other variations and modifications of the invention can be made and various equivalents substituted therein without departing from the principles disclosed or going outside the scope of the specification or purview of the claims. What is
