CA1104905A - Elastic detergent bar containing anionic and amphoteric synthetic: organic detergents - Google Patents
Elastic detergent bar containing anionic and amphoteric synthetic: organic detergentsInfo
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- CA1104905A CA1104905A CA292,179A CA292179A CA1104905A CA 1104905 A CA1104905 A CA 1104905A CA 292179 A CA292179 A CA 292179A CA 1104905 A CA1104905 A CA 1104905A
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Abstract
ABSTRACT OF THE DISCLOSURE:
An elastic detergent bar which may also be used by children as a toy or plaything while taking a bath, includes a mixture of anionic and amphoteric synthetic organic detergents, gelatin and water. The bars are substantially form-retaining and although they wear away during use, substantially retain their initial forms and elasticities for major pro-portions of their useful lives. They are easily manufactured and during the manufacturing process are moldable to finely figured and detailed shapes. Because of their elasticity they are resistant to breakge during shipping and use and because of their contents of both synthetic anionic and amphoteric organic detergents they exhibit less surface tackiness than other elastic detergent bars in which similar proportions of gelatin and water are present. In an improved process for the manufacture of such bars having a lesser tendency to shrink upon prolonged exposure to the atmos-phere, during the blending of the various bar components heating is employed and is continued for a long enough time to evaporate a substantial proportion of water from the mixture, after which the composition may be poured into molds and solidified.
An elastic detergent bar which may also be used by children as a toy or plaything while taking a bath, includes a mixture of anionic and amphoteric synthetic organic detergents, gelatin and water. The bars are substantially form-retaining and although they wear away during use, substantially retain their initial forms and elasticities for major pro-portions of their useful lives. They are easily manufactured and during the manufacturing process are moldable to finely figured and detailed shapes. Because of their elasticity they are resistant to breakge during shipping and use and because of their contents of both synthetic anionic and amphoteric organic detergents they exhibit less surface tackiness than other elastic detergent bars in which similar proportions of gelatin and water are present. In an improved process for the manufacture of such bars having a lesser tendency to shrink upon prolonged exposure to the atmos-phere, during the blending of the various bar components heating is employed and is continued for a long enough time to evaporate a substantial proportion of water from the mixture, after which the composition may be poured into molds and solidified.
Description
This invention relates to elastic detergent bars. More particular-lyg it relates to detergent bars intended for conventional toilet soap uses, either as hand "soaps" or bath or shower "soaps", which are elastic in nature and which include both synthetic organic anionic and amphoteric detergents. Such elastic detergent bars are less tachy than various other gelatin-based bars containing only either anionic or amphoteric detergent and such improved surface characteristic, together with their "squeeza-bility", which makes them like a plaything for children, help make bathing more pleasant both for the child and his parent. Additionally, they foam better than other detergent bars.
Soap, synthetic organic detergent and soap-synthetic detergent bars and cakes have been made from literally thousands of different materials. It has long 'been known to incorporate perfumes, co1Orcmts, abrasives, bleaches, fillers, emollients and bodying agents in soap bars and gelatin is one of the bodying or binding agents that has been employed.
Soap 'bars have usually contained glycerol and uater, both of which are produced and utilized in various soapmaking processes when soaps are produced by the saponification of triglycerides. United States patent
Soap, synthetic organic detergent and soap-synthetic detergent bars and cakes have been made from literally thousands of different materials. It has long 'been known to incorporate perfumes, co1Orcmts, abrasives, bleaches, fillers, emollients and bodying agents in soap bars and gelatin is one of the bodying or binding agents that has been employed.
Soap 'bars have usually contained glycerol and uater, both of which are produced and utilized in various soapmaking processes when soaps are produced by the saponification of triglycerides. United States patent
2~360~920 discloses the production of soap buds from an aerated aqueous solution of soap containing glycerine and a demulcent, such as may 'be made from a mi~ture of Irish moss and gelatin. United States patent 3~698,437 teaches the manufacture of malleable and non-hardenable detergent products from certain percentages of a fatty acid isethionate, water, gelatin, hydrocarbon and filler. The resulting bars, which may also contain glycerol or propylene glycol and other adjuvants, are said to be molda'ble and extrudable but not elastic. British patent 731,396 describes a shaped soaplass organic detergent composition in which the soapless detergent, such as triethanolamine alkylbenzene sulfonate~ is dispersed in a gelatin gel. Aeration of the gel to produce a frothy product is suggest~ed, as are the additions of various builders, fillers, nonionic detergents~ etc. In copending Canadian patent application Serial No. 292,190 filed December 1, 1977 and entitled Elastic Detergent Bar invented by Frank Schebece, improved synthetic organic detergent bars based on synthetic anionic detergent and cross-linked or denatured gelatin are described, as are detergent bars based on amphoteric detergents, with or without such cross-linking and/or denaturing agent~s). However, that application does not describe mixtures of synthetic organic anionic and amphoteric detergents in aqueous gelatin-based products and the unexpectedly beneficial advantages thereof.
Although the prior art has recognized that gelatin may be included in detergent compositions which may be desirably molded or shaped to bar or cake form and although the Schebece application mentioned teaches the employ-ment of amphoteric detergents as the synthetic organic detergent component o such a bar the art did not describe nor suggest the bars of this invention wherein both anionic and amphoteric synthetic organic detergents are utilized.
Furthermore, it did not suggest the advantages obtained due to such composition nor by the invented process wherein the moisture content of a composition of this invention is intentionally diminished to improve the ultimate properties of the molded bar.
In accordance with the present invention there is provided a hand squeezable, elastic, solid molded detergent product comprising about 35 to 70%
oE a mixture of anionic and amphoteric synthetic organic detergents in a proportion about 1:5 to 5:1, said anionic detergent being selected from the group consisting of water soluble alkali metal, trie~hanolamine and ammonium higher linear alkylbenzene sulfonates, paraffin sulEonates, olefin sulfonates, fatty alcohol sulfates, monoglyceride sulfates and fatty alcohol polyethylene glycol sulfates and mixtures thereof and said amphoteric detergent being selected from the group consisting of water soluble betaaminopropionates, betaiminodi~ropionates and imidazolinium salts and mixtures thereof, about 5 to 30% of gelatin and about 5 to 60% of water, which product is suEficiently s~ueezable and elastic so that a 2 cm. thickness thereof can be pressed between a thumb and forefinger to a 1 cm. thickness and upon release o~ such pressure - 2 ~
' .
will return within five seconds to within one ~n. of the 2 cm. thickness.
In preferred formulations the anionic detergent is a rnonoglyceride sulfa~e or a ~riethanolammonium higher fat~y alcohol sulfate and the amphoteri.c detergent is an imidazolinium betaine or a betaiminodipropionate, although betaaminopropionates may also be employed. In the process embodiment of the invention such a bar is made with a moisture content of about 5 to ~0%
by heating a mix containing more water so as to evaporate off from it about - 2a -~ ' ' 15 to 50% of the weight of the mixture~ as water, after which the composition may be deaerated (an optional step~ but preferred), poured into a mold, solidified and removed from the mold, ready for use.
The anionic synthetic organic detergents of this invention include sulfated, sulfonated and phosphonated hydrophobic moieties, especially those which include higher hydrocarbyl groups (preferably fatty)~ such as alkyl groups of 8 to 20 carbon atoms, preferably of 10 to 18 carbon atoms.
These compounds are usually employed as their water soluble salts, such as salts of alkali metals, e.g., sodium, potassium and triethanolamine and ammonia. For the present compositions these salts will usually be either sodium, potassium or triethanolamine salts and oE these the triethanol- -amine (or triethanolammonium) salts will often be preferred. ~long the various types of s~nthetic anionic organic dete~gents which may be useful are the linear higher alkylbenzene s~fonates~ especially those of 12 to 15 carbon atoms, e.g., sodium linear tridecylbenzene sul-fonate; paraffin sulfonates; olefin sulfonates; higher fatty alcohol suleates; monoglyceride -~
sulfates, especially the sulfated monoglycerides of coconut oil, tallow, - -hydrogenated coconut oil, hydrogenated tallow and synthetic higher fatty acids of ~ to 20 carbon atoms, e.g., sodium coconut oil monoglyceride sulfate~ ammonium cocomonoglyceride sulfate; corresponding sulfates and phosphonates and other equivalent organic sulfonates, in most of which the lipophilic group includes a chain of 10 to 18 carbon atoms. In the above description and else~here in the specification and in the claims when a material is characterized as a "monoglyceride sulfate" such terminology is intended to describe higher fatty acid monoglyceride sulfates wherein the higher fatty acid is of 8 to 20 carbon atoms~ preferably of 10 or 12 to 18 carbon atoms, such as lauric acid, myristic acidg palmitic acid, stearic acid and oleic acid. Additionally useful are the sulfates and sulfonates of nonionic detergents and of nonionic surface active agents~ in which _3_ , . . .
9~5i products the nonionic base will normally be a polyethylene oxide conde~-sation product of a higher fatty alcohol, such as a condensation product based on a higher fatty alcohol of 10 to 18 carbon atoms, wherein the ethylene oxide content is from 3 to 30, preferably 5 to 10 or 12 mols of ethylene oxide per mol of higher fatty alcohol. A specifically preferred anionic detergent is ammonium monoglyceride sulfate of 8 to 18 or 20 carbon atoms in the fatty acid group, e.g., ammonium cocomonoglyceride sulfate (coco indicates derivation of the fatty acids from coconut oils)g although alkali metal monoglyceride sulfates, such as sodium monoglyceride sulfate, are also useful. While sodium lauryl sulfate is an anionic sy~thetic organic detergent which may be employed, preferably in minor proportion with okher anionic synthetic org~ic detergents in the present compositions, its use is usually not preferab:Le and the corresponding triethanolammonium salt is normally used 1nstead because it can produce a clear bar of good washing and foaming ability which is also stable on storage and maintains its elasticity during use.
The amphoteric detergents which may be utilized to manufacture the elastic detergent bars of this in~ention include such compounds as Deripha ~ 151, which is sodium N-coco-betaaminopropionate (manuPactured by General Mills~ Inc.)~ Deriphat 160, a partial sodium salt of N-lauryl-betaiminodipropionate, and other betaaminopropionates and betaiminodi-propionates, ~iranol~ C2~ (anhydrous acid form, 1-carboxymethyl-1-carboxy-ethox~ethyl-2-coco-imidazolinium betaine), the water soluble salts thereof, especially the triethanolammonium salt, and other imidazolinium betaines, and other of the various known amphoterics, described in McCutcheon~s Deterc~ents and Emulsifiers, l973 ~nnual and in Surface ActiYe A~ents, ~ol.
II, by Schwartz, Perry and Berch (Interscience Publishers, 1958). For example, ~eriphats 151C~ 154~ 160, 160-C and 170-C, and Miranols C2Mg S2M
and SHD Conc. may be employed. Additionally even li~uid amphoteric ' ~
detergents may be used, at least in part, e.g., up to 25 or 50% of ~he amphoteric detergent content. The recited incorporated references also contain extensive descriptions of various suitable anionic detergents and of nonionic and cationic detergents which may be employed in small pro-portion(s) in the present compositions. The various long chain substituents ` in the mentioned amphoterics are of 8 to 20 carbon atoms, preferably of 10 to 18 carbon atoms and most prePerably are lauryl and coco.
/~ The nonionic detergents, while not required components of the invented products, may be present`in relatively small proportions therein in replacement of some of the anionic or amphoteric detergents. The non-ionics are preferab:Ly solid or semi-solicl at room temperature~ more preferably solid~ and include but are not limited to ethoxylated aliphatic alcohols having straight or branched chains (preferably straight chain) ; of from about 8 to 20 carbon atoms, with about 3 to about 30 ethylene oxide units per molecule. Particularly~ suitable nonionic detergents of such type are manufactured by Shell Chemical Company and marketed under the trademark Neodolo~. Of the various Neodols available~ Neodol ~5-7 (12-15 carbon atoms chain hlgher fatty alcohol condensed with an average of 7 etllylene oxide units per mol) and Neodol 45-11 (14-15 carbon atoms chain higher fatty alcohol condensed with an average of 1~ ethylene oxide units per mol) are particularly preferred. Another suitable class of ethoxylated aliphatic alcohol detergents is made by Continental Oil Company and is sold under the trademark Alfoni ~. Of the Alfonics the most pre-ferred is Alfonic 1618-65, which is a mixture of 16 to 18 carbon atoms primary alcohols ethoxylated so as to contain 65 mol percent of ethylene oxide. Additional ex~nples of nonionic synthetic organic detergents include those marketed by ~ASF Wyandotte under the trademark Pluronic~. Such compounds are made by condensation of ethylene oxide with a hydrophobic base formed ~y condensing propylene oxide ~ith propylene glycol. Thc hydrophobic portion of the molecule has a molecular weight of from about1,500 to 1,800 and the addi~ion of polyoxyethylene (or ethylene oxide) to such portion increases the water solubility of the molecule as a whole~
with the detergent being a solid at room temperature when the polyoxy-ethylene content is abo~e 50% of the total weight of the condensation product. Such a nonionic detergent is Pluronic ~-128 but F-68 may also be employed. Also useful nonionic detergents are the polyethylene oxide con-densates of alkyl phenols, such as the condensation products of such com-pounds wherein the alkyl group contains about 6 to 12 carbon atoms, in either a straight chain or branched chain configuration, with 5 to 25 mols of ethylene oxide per mol of alkyl phenol. The alkyl substituents in such compounds may be derived from polymeri~ed propylene or may be diisobutylene~
octene or nonene, for example.
Representative cationic detergents, which usually also possess antibacterial (and fabric softening) properties, include di-higher alkyl di-lower alkyl ammonium halides such as distearyl dimethyl am~onium chloride~ and 2-heptadecyl-l-methyl-1-~ (2-stearoylamido)ethyl~-imidazoli-nium methyl sulfate. The higher alkyls thereof are of 8 to 20 carbon atoms, preferably 12 to 18 and the lower alkyls are of 1 to ~ carbon atoms, preferably l and 2. Such materials are normally omitted from anionic detergent based products but may be employed in small proportions in mixed anionic-amphoteric detergent bars, especially when they contain more amphoteric detergent than anionic detergent and when the proportion of anionic de~ergent is relati~ely small.
Gelatin~ a complex mixture of collagen degradation products of molecular weight in the range of about 30,000 to 80,000 and higher, depen-ding on the hydrolytic conditions to ~hich it has been subjected~ is a vi;tal constituent of the present compositions. Apparently because of its cutst nding ability to form reversible gels, its high viscosity nd the excellent strengths of films thereof, it helps to make a detergent bar which is of satisfactory strength and cleaning power, due to gradual dis-solution of the ordinarily extremely soluble synthetic organic detergent component, and yet, which does not produce objectionable and unacceptable soft gels at bar surfaces which have been moistened. Additionally, and a major advantage of the present invention, the combination of gelatin and synthetic organic detergents, in the presence of water and -preferably also in the presence of a lower dihydric or polyhydric alcohol or other suitable plasticizer, and ofte~ too, a cross-linking agen~ or denaturant, yields elastic products. The elastic detergent bars made are sufficiently elastic so that a bar 2 cm. thick can be pressed between thumb and forefinger to a 1 cm. thickness and will immediately (within five seconds) return to the 2 cm. thickness or at least to with.in lmm. thereof, upon release of pressure.
The gelatin employed is essentially colorless and free from odor. It is amphoteric (about 45 milliequivalents of amino f~ctions and about 70 milliequivalents of carboxyl functions per hundred grams thereof).
It is normally used in formulating as a dry granular product which is crystalline in appearance although it is really amorphous. It is hlsoluble in cold water but swells rapidly in the presence of water ~mtil it has imbibed about 6 to 8 times its weight thereof and it melts to a viscous solution in water when warmed to above 40 to 45C. Gelatins are classified as either type A or type B, the former being from acid-cured stock, with an isoelectric point of about 8.3 - 8.5 and the latter being of alkali-cured stock, with an isoelectric point of about 4.8 - 5Ø Type A gelatins are preferred for the present applications but type B gelatins may ilso be used~ as may be mixtures of the two. The gelling powers of gelatins are normally measured by the Bloom test. Often too, viscos:ity will also be employe~ to characterize a gelatin and a gel strength~: viSCQSity ratio .
may be specified, e.g., 3:1 to 5:1. Gel strengths will range from 100 to 300 g. Bloom but will usually be in the range of 150 or 200 to 300, with gelatins of Bloom values of 22S g. and 300 g. being employed in the examples herein. The type A gelatins will generally be utilized with the usual detergent bar constituents, normally intended for employment in neutral or slightly basic aqueous media, and the type B gelatins will be preferred when acidic conditions are expected to be encountered.
Cross-linking agents for gelatin and for other proteins are metal salts ~hich cross-link ~arious geiatin molecules, apparently by reacting with free carboxyl functions thereof. This class of compounds is well known and the salts employed ~re usually those of aluminum, calcium~
magnesium and/or 7inc that are soluble in aqueous media~ In such salts the preferred anions are chloride, bromide~ iodide, sulfate, bisulfate and acetate but other suitable anions may also be included. Examples of such salts include potassium aluminum sulfate hydrate ~alum, KAl(S04)2.12 H2~J, - -aluminum chloride, vther alums, calcium chloride, magnesium sulfate and zinc acetate. Also useful for cross-linking is formaldehyde, usually as formalin. 0.1 to 1% of formaldehyde is normaIly adequate. ~lthough the presence of a cross-linking agent is often highly desirable in the formu-lations o-f the invented bar compositions, especially those based on anionic detergents primarily, it has been found that such are not as important or useful in those compositions based primarily on amphoteric ~ detergents.
; Instead of or in addition to a cross-linking agent there may be employed with the gelatin of the present compositions a denaturant. Such a compound also helps to reduce solubility of gelatin at and near its isoelectric point and inhibits crystalli.zatio~ ~lthough denaturation may be effected by various materials, including various detergents, ethanol, acetone, strong acids and strong aIkalis, chemical denaturation, usually by urea, dextrose or guanidine hydrochloride is preferred and of these -~
compounds urea is by far the preferred. Both cross-linking a~nd denaturation and the combination thereof are helpful in producing a lastingly elastic detergent bar of desired properties, suitable for repeated and satisfactory cleaning applications, but neither cross-linking agents nor denaturants for gelatin are required to make a satisfactory elastic detergent bar of the present invention.
The lower dihydric and/or polyhydric alcohol component(s) of the present bars functions as a mutua~l solvent and plasticizer for the bar components, especially the gelatin. It facilitates solubilizat:ion of the detergent at a desired rate and maintains the surface of the bar soEt. IE
the bar bec~me object:ionably hard at portions thereof this coulcL be cause for rejection of it by consumers. Such alcohol also helps to distribute the various components evenly throughout the bar or cake. Although a variety of lower dihydric or polyhydric alcohols may be employed, including various sugars and sugar alcohols~ having up to 6 carbon atoms and up to 6 hydroxyls per molecule, the most preferred are those of 2 to 3 carbon atoms and 2 to 3 hydroxyl groups per molecule. Such compounds include propylene glycol (1,2-dihydroxypropane or 1~2-propylene glycol), tri-methylene glycol (1,3-propylene glycol) and glycerol, of which 1,2-propylene glycol, glycerol and mixtures thereof are pre~erred. Other useful solvents are the Cellosolves~, the mono- and di-lower alkyl ethers of ethylene glycol. ~dditionally, sometimes monohydric alcohols, such as ethanol, are useful, primarily as supplementary solvents.
The water employed is preferably deionized wa~er which will nor-mally contain less than 10 parts and preferably less than 1 part per million of hardness, as calcium carhonate, but normal city waters may also be utilized, such as those having hardnesses in the range of 10, 20 or 50 to 150 or 300 p.p.m., as CaC03.
_9_ .
With the basic elastic detergent bar composition there may be present various adjuvant materials in minor proportions to contrib~te their particular properties to the final product. Among such adjuvant materials are functional and aesthetic adjuvants, such as: perfumes; pigments; dyes;
optical brighteners; skingprotecting and conditioning agents~ e.g., lanolin, solubilized lanolins; bactericides; chemical stabilizers, e.g.~ sodium bisulfite; foam stabilizers, e.g., lauric myristic diethanolamide; buffering agents and pH adjusters, e.g. 3 triethanolamine, hydrochloric acid, phos- -phates; bodying agents, e.g., clàys; superfatting agents, e.g., stearic acid, anti-redeposition agents and soil dispersants, e.g., polyvinyl alcohol~ sodium carbo~ymethyl cellulose; gums, e.g., sodium alginate, which also functions as a slip improving agent; and abrasive or scouring compo-nents, e.g., silex. Usually the present bars do not and shoulcL not contain any fillers or builder salts other than those which may accompany, usually -unavoidably, other components of the product. However, in certain circum-stances, as when bars for heavy duty laundry use are made, it may be desirable to add fillers, such as sodium sulfate and sodium chloride and builder salts, such as pentasodium tripolyphosphate, sodium carbonate and sodium silicate.
The proportions of the various components of the present elastic detergent bars should be kept within ranges to be given to obtain the best ;
results and to produce a bar which will be desirably elastic, useful in place of conventional soap, soapdetergent and detergent bars and which will possess improved properties, such as a lesser tendency to slough when in contact with water, compared to such more conventional bars. The synthetic organlc detergent component, the mixture of anionlc and amphoteric detergents, will be about 10 to 80% of the product, preferably 35 to 65 or 70~ and more preferably 35 to 55~0 thereof. The content of cross-linking agent and/or denaturing agent for the gelatin~ when present, is usually -10- ~, , ' . .
s 0.1 to 5%, preferably 1 to 3% and more preferably 1 to 2% total. Normally the percentage of cross-linking agent ~Yill be 0.1 to 5%, preferably 1 to 2% and that of the denaturant will be 0.5 to ~%. The gelatin, preferably type A gelatin of 225 to 300 g. Bloom, will be about 5 to 30%, preferably 7 to 25~ and more preferably about 10 to 20% of the finished bar or cake and the moisture content will be about 5 to 60%, preferably 10 to ~0% and more preferably 10 to 30%~ e.g.~ 25%.
The lower dihydric or polyhydric alcohol~ which may be omitted if syneresis problems are encountered (usually due to a high percentage of normally liquid components of the product), will normally be present in the range of 3 to 20%, preferably 10 to l8%, e.g., l5%.
The total proportion of various adjuvants present, inc:l.uding any builders and fillers, will normally not exceed 10%, preferably will be less than 5~ and more preferably will be less tha~ 2%, with the pro-portion of any particular adjuvant usually being held to less than 5~, pre~erably less than 2% and more preferably less than 1%.
The manufacture of the present elastic detergent bars is com- ' paratively simple, requiring only the mixing together of the components under such conditions that the gelatin will form a gel with water and/or with any other components present. For example, all the components of a particular detergent composition may 'be mixed together and heated, with ' stirring, to dissolve the gelatin. Alternatively the gelatin may be first ~ `
dissolved in water and the other components may then be admixed or other ' operative mixing sequences may 'be adopted. If the components are soluble the product may be transparent or at least transluscent 'but if insoluble ingredients are employed, which may be done intentionally, an opaque gel results~ To clarify transparent gels and to increase the strengths and densities thereof these may be deaerated or degassed under vacuum or by allowing the hot or warm liquid to stand until it becomes clarified. The .
'' is solution or dispersion may then be poured into suitable molds, chilled and thereby solidified. Although gelatin dissolves at temperatures above 40 or 45C. it is normally undesirable to heat it to a temperature above 100C.
and preferably dissolving will take place at a temperature in the range of about 50 to 90 or 95C., more preferably about 60 to 80C.~ over 3 to 30 minutes. Molds will be at a temperature of 5 to 20C., preferably 5 to 15C.
After *he gelatin has completely set, which may take from about one minute to an hour, usually taking from three to ten minutes, the elastic detergent bar or cake may be removed from the mold and packed or it may be a~Llowed to be warmed to room temperature before packing, at which temperature it still remains firm, yet elastic.
In a preferred process embodi.ment o~` the invent:ion a firmer bar is made which has lesser tendency to shrink on storage and develop syneresis.
Such a bar may contain: 10 to 80% of the mixture of anionic and amphoteric synthetic organic detergents in a proportion between about 1:5 and 5:1, preferably 35 to 65% of such mixture in a proportion within the range of 1:4 to 2:1, and more preferably the anionic detergent is triethanolammonium lauryl sulfate ~nd the amphoteric detergent is triethanolammonium :l-carboxymethyl-l-carboxyethoxyethyl-2-coco-imidazolinium betaine; 5 to 30%
of gelatin, preferably 7 to 25% thereof and more preferably the gelatin is a type A gelatin of lS0 to 300 g. Bloom; and 5 bo ~0~, preferably 10 to 40% and more preferably about 10 to 25 or 30% water. In the improved process the components mentioned and ~ny other solventsg plasticizers, cross-linking agents, denaturants and adJuvants may be mixed together and the gelatin is dissolved in the mixture or in the water thereofg with heating. Preferably the total proportion of water plus solvent plus plasti-cizer present will be in the ranges previously mentioned for water alone in the fincal bar but during dissolving of the gelatin, during which the temperature may be raised, as previously described, enough additional water ,' . . ' '-' .
will be employed initially to facilitate solution of the gela-tin and it will be heated for a period sufficient to drive off water (or water plus solvent, etc.) to the extent of 15 to 50~ of the weight of the mixture, preerably 20 to 40% thereof. In addition to heat, vacuum may be used to facilitate removal o~ the moisture and any volatile solvent -present, such as ethanol. ~ormally the additional heating to remove moisture~ depending on whether or not vacuum is also employed, may take from one minute to thirty minutes and preferably will take from one minute to fifteen minutes.
After removal of the moisture the` mix may be molded in the manner previous-ly described~ but yields the superior product mentioned.
The elastic detergent bars of this invention possess an obvious novelty advantage over ordinary soap or detergent bars. They are especially attractive to children when molded into various special shapes, such as the shapes of storybook or cartoon characters, animals, etc., ancl promote the enjoyment of bathing by infants and young children. The elastic nature of the product allows a controlled dispensing of detergent and other foaming materials onto the skin~or into the bath water in response to repeated squeezings and relaxings of the bar. Thus, the utilitarian detergent is also a delightful toy. However, the product has various other advantages apart from :its play value. Thus, the presence of the gelatin adds a skin care ingredient to the composition and because of the bar's elasticity breakage during shipment and on storage are minimi7ed. Furthermore, large quantities of synthetic organic detergent may be present in the composition without the need for extensive use of waxes, plasticizers, bodying agents, etc.~ to control the dissolving thereof and give them desi~able tactile properties and good appearances. The bars do not slough excessively, as often do detergent and soap bars and additionally~ they maintain sub-stantially their original shapes during use, continually dispensing detergent in response to compression and expansion and rubbing against -13~
gL9~
areas to be cleansed. They have a different "feel" than soap when con-tacting the skin and this better contact assists in cleaning. The deter-gents in the bars or other shaped articles are readily released at -temperatures of 2~ to 40C. and higher and for cold water washing, at temperatures of 10C~ and less, more soluble and lower Bloom ~alue gelatins can be employed, wi~h appropriate solvents and adjuvants, to help release the detergentO When made by the preferred process, wherein the percentage of moisture in the final product is limited to 40~, and preferably is about 25%, any tendency of the bàr to shrink on storage is diminished and a firmer product results. Additionally, surface tackiness is noticeably decreased and the ~ar foams better than corresponding anionic ancl amphoter:ic bars~ respective:Ly.
It is to be understood that within the proportions of components given variations may be made to best promote desired properties of the bars manufactured and similarly, processing modifications may also be effected. Thus, proportions o~ gelatin, detergen*, water, cross-linking agent, denaturant, plasticizer and adjuvants may be adjusted, as may be the types of such materic~ls. For example~ if the bar is too soft ~n increase in the solids content and especially in the gelatin content may be desirable and the gelatin type may be changed to that of a higher Bloom Yalue to increase the firmness of the product. ~lso, in such a case it may be desirable to utilize more cross-linking agent and/or denaturant. If the bar is too firm, re~erse adjustments may be made. Those of skill in the art, with this specification before them, will be able to modify the properties of the described compositions to make them conform to desirable product standards and sumilarly will be able to modify the processes described.
The following examples illustrate but do not limit the invention.
Unless otherwise indicated all temperatures are in C. and all parta are :.
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: . ~ . . . : .
, . ~ ' 49~
by weight~
Percent Triethanolammonium lauryl sulfate 8.0 Gelatin (300 g. Bloom type A) 10 0 Propylene glycol 10.0 Triethanolamine salt of Miranol C2M anhydrous acid 28.0 - (triethanolamine l-carboxymethyl-l-carboxy-ethoxyethyl-2-coco-imidazolinium betaine) Water 44.0 The components of the above formula are blended together ~nd are heated with stirring, to a temperature in the range of 60 to 80C.
to dissolve the gelatin ancl the various other materials. ~Et~r about 5 to 10 minutes a clear solution or gel is obtained, which is poured into shaped molds and chilled to 15C. Upon solidification, which takes about eight minutes~ the elastic detergent bar or cake is removed from the mold and is ready for use. The product is satisfactorily elastic and cleans well when it is employed as a bath or hand "soap". It foams very well on initial use and although the ~oam is diminished upon subsequent uses the bar is a useful washing product and maintains its elasticity throughout repeated washings and dryings. Such bar~ containing amphoteric and anionic synthetic organic detergents, with gelatin~ does not slough objectionably during use and is less tacky and better foaming than previous bars based on only anionic or amphoteric detergents, respectively.
In a modification of the manufacturing process the hot mixture of bar components is allowed to stand at an elevated temperature in the range of 45 to 55C. for a period of one hour so as to allow all air bubbles therein to be dissolved or to rise to the top of the mix and separate therefrom before setting of the gel. The products resulting are `
:
brighter and clearer in appearance following such deaeration, during which relatively little water and other solvents are evaporated. However, when the temperature of the mixture is raised, e.g., to 60 or 65 to 80 to 90C., as it is in other embodiments of this example, appreciable loss of water and other volatile materials results and the moisture content of the resulting bar is appreciably diminished. Thus, utilizing a 15 to 30 minute heating ~ -period at 80C.~ especially in the presence of vacuum, e.g., 250 mm. Hg absolute pressure, 20 to 40%, e.g., 25% of the mix weight is removed. After the evaporation off of 25% of the mix the elastic detergent bar produced includes 11% of triethanolammonium lauryl sulfate, 13% o gelatin, 13% of propylene glycol, 38% of Miranol C2M as the triethanolammonium salt and 25%
of water. The elastic detergent bars resulting (deaeration may be effected, too) are firmerJ tougher and less liable to shrink upon proLongecl exposure to the atmosphere during storage.
When the formula is modiied to replace the triethanolammonium lauryl sulfate with the same weight of other suitable anionic detergent, such as ammonium cocomonoglyceride sulfate or a mixture of equal parts of ammonium cocomonoglyceride sulfate and sodium cocomonoglyceride sulfate and when the propylene glycol is replaced by glycerol a procluct of com-parable properties results. Similarly, when the ~iranol C2M salt is replaced by Deriphat 151 or Deriphat 160 or other suitable amphoteric detergentJ especially one of the imidazolinium betaine, betaaminopropionate or betaiminodipropionate type and when the gelatin is replaced by 15% of 225 g. Bloom type A gelatin (type B may also be used but is not usually as good) essentially the same type of elastic detergen~ bar results.
Similarly, when 2% of potash alum ~cross-linking agent) or 1% of urea (denaturant) is present in replacement of a corresponding percentage of ~ater a irmer bar results. When adjuvants are employed, such as fluorescent brighteners; bactericides, emollients; solvents; foaming agentsJ e.g~
lauric myristic dlethanolamide; pH adjusting agents, e.g., ':"
- 16 _ :, :
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- .. ... , - .. - . , , . . .. .- .. . . -hydrochloric acid, triethanolamine; perfumes; colorants, including dyes and pigments, and preservatives, they contribute their speciic properties to the final bar.
In further modifications of the formula small proportions of dyes and pigments are incorporated to color and opacify the products and : -gels are molded inichilled molds into the shapes of specific storybook, nursery rhyme, cartoon and animil characters, with the proportions of dyes and pigments employed being about 0.02% for the dyes and about 0.2%
for the pigments. The dyed bars are transparent or translucent and the pigmented bars are opaque. The opacities of the pigmented bars are further increased by additions of 1~ 2 and 5% of powdered clay to the initial mixture~ which also converts the colors to pastels.
The formulas described :in this example are modified proportionate-ly ~10%, +20, and ~30~, within the ranges given and the products resulting are useful elastic detergent bars of this invention.
Percent Ammonium cocomonoglyceride sulfate 24.2 (47% active ingredient) Tr:iethanolamine salt of Miranol C2M 28.0 Gelatin ~300 g. Bloom, type A) 10.0 propylene glycol 10.0 Water 27.8 Elastic detergent bars of the above formula and of such a formula less 25% of water removed in a drying operation after dissolving o the gelatin~a~e made according *o the method of Example 1. The bars produced are useful elastLc detergent bars for bath use or handwashing and are less tacky and better foaming than similar bars not containing the mixture of anionic and amphoteric detergents. Also, the bars made by a : .:
process including removal of moisture, as described, are less liable to shrink on storage exposed to the air than are similar bars containing the greater percentages of moisture. The improved bars, made by reducing the moisture content, analyze about 30~0 of ammoniumcocomonoglyceride sulfate, 35~ of triethanolammonium 1-carboxymethyl-1-carbo~yethoxyethyl-2-coco-imidazolinium betaine, 13% of gelatin, 12%of propylene glycol and 10% of water. The removal of moisture in~he above-described process and other such processes of this invention takes place at a temperature of 30 to 90C., preferably 40 to 80C., with the lower temperatures being used most when vacuum is also employed.
EXA~PLE 3 Percent Miranol C2M, anhydrous acid 21 Triethanolamine 7.5 Propylene glycol 10.0 Gelatin (300 g. Bloom, Type A) 10.0 Triethanolamine lauryl sulfate 28.5 (40% active ingredient, a~ueous solution) ~mmonium cocomonoglyceride sulfate 23.0 (47~ active ingredient, a~ueous solution) Following the procedllre of Example 1~ products o:E the above formula ;~
are made, without moisture removcil. They are good elastic detergent bars for both bath use and handwashing and are less tacky and better foaming than similar bar~ containing either anionic detergent or amphoteric ~;-detergent alone. Also, because of their comparatively low moisture content :
the bars are less liable to shrinkage on storage and when exposed to air than are similar bars containing more moisture.
In normal handwashing use a 100 gram molded bar and molded items in the shapes of cartoon characters, automobiles and animals last for at least 200 handwashings at a water temperature of 40C., give a copious ~: :
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foam and wash well. They clean well and leave the hands feeling sOftg apparently due to the gelatin and amphoteric detergent contents of the products. When 150 gram bars or articles are utilized they last for as many as 20 normal baths~ with good foaming throughout such use. During wearing down of the ~bars~ they substantially retain their general original shapes, colors and foaming and washing abilities.
~XA~IPLE 4 The product of Example 3 is made from an initial mixture which includes 45% of water instead of the 30% in the final product and in the mix of Example 3. The excess moisture is removed during manufacturing by -~
heating for about 45 minutes at a temperature of about 75C., without vacuum. Comparison of the products of ~xamples 3 and 4 shows little difference between them except that the product of Example ~ may have the components thereof more ~miformly distributed thro~lghout it due to the initial dissolvings of more of them in the a~ueous medium before removal of excess moisture. Also, initial mixing and dissolving of the mix of this example is much easier. In a further modification of this example the density of the product is diminished ~0%, so that it will float in warm bath water, by distributing small bubbles of ~ir throughout it after removal of the excess moisture from the mixed solution and after cooling of such mix~ Eollowing the procedure in an application by John C. Carson, Jr. and James A. Bowers, entitled Elastic Detergent Bar of Improved ~levated Temperature Stability, filed simultaneously with this application.
The product resulting is an excellent "floating soap" for use inrthe bath tub but unlike soap, it and the other products of this invention leave no -bathtub ring and it is a superior floating toy for the child when he takes a bath.
The invention has been described with respect to various embodi-ments and illustrations thereof but is not to be limited to these because ~4~i5 it is evident that one of skill in the art with the present specification -before him will be able to utilize substitutes and equivalents wi~hout departing from the spirit of the invention.
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Although the prior art has recognized that gelatin may be included in detergent compositions which may be desirably molded or shaped to bar or cake form and although the Schebece application mentioned teaches the employ-ment of amphoteric detergents as the synthetic organic detergent component o such a bar the art did not describe nor suggest the bars of this invention wherein both anionic and amphoteric synthetic organic detergents are utilized.
Furthermore, it did not suggest the advantages obtained due to such composition nor by the invented process wherein the moisture content of a composition of this invention is intentionally diminished to improve the ultimate properties of the molded bar.
In accordance with the present invention there is provided a hand squeezable, elastic, solid molded detergent product comprising about 35 to 70%
oE a mixture of anionic and amphoteric synthetic organic detergents in a proportion about 1:5 to 5:1, said anionic detergent being selected from the group consisting of water soluble alkali metal, trie~hanolamine and ammonium higher linear alkylbenzene sulfonates, paraffin sulEonates, olefin sulfonates, fatty alcohol sulfates, monoglyceride sulfates and fatty alcohol polyethylene glycol sulfates and mixtures thereof and said amphoteric detergent being selected from the group consisting of water soluble betaaminopropionates, betaiminodi~ropionates and imidazolinium salts and mixtures thereof, about 5 to 30% of gelatin and about 5 to 60% of water, which product is suEficiently s~ueezable and elastic so that a 2 cm. thickness thereof can be pressed between a thumb and forefinger to a 1 cm. thickness and upon release o~ such pressure - 2 ~
' .
will return within five seconds to within one ~n. of the 2 cm. thickness.
In preferred formulations the anionic detergent is a rnonoglyceride sulfa~e or a ~riethanolammonium higher fat~y alcohol sulfate and the amphoteri.c detergent is an imidazolinium betaine or a betaiminodipropionate, although betaaminopropionates may also be employed. In the process embodiment of the invention such a bar is made with a moisture content of about 5 to ~0%
by heating a mix containing more water so as to evaporate off from it about - 2a -~ ' ' 15 to 50% of the weight of the mixture~ as water, after which the composition may be deaerated (an optional step~ but preferred), poured into a mold, solidified and removed from the mold, ready for use.
The anionic synthetic organic detergents of this invention include sulfated, sulfonated and phosphonated hydrophobic moieties, especially those which include higher hydrocarbyl groups (preferably fatty)~ such as alkyl groups of 8 to 20 carbon atoms, preferably of 10 to 18 carbon atoms.
These compounds are usually employed as their water soluble salts, such as salts of alkali metals, e.g., sodium, potassium and triethanolamine and ammonia. For the present compositions these salts will usually be either sodium, potassium or triethanolamine salts and oE these the triethanol- -amine (or triethanolammonium) salts will often be preferred. ~long the various types of s~nthetic anionic organic dete~gents which may be useful are the linear higher alkylbenzene s~fonates~ especially those of 12 to 15 carbon atoms, e.g., sodium linear tridecylbenzene sul-fonate; paraffin sulfonates; olefin sulfonates; higher fatty alcohol suleates; monoglyceride -~
sulfates, especially the sulfated monoglycerides of coconut oil, tallow, - -hydrogenated coconut oil, hydrogenated tallow and synthetic higher fatty acids of ~ to 20 carbon atoms, e.g., sodium coconut oil monoglyceride sulfate~ ammonium cocomonoglyceride sulfate; corresponding sulfates and phosphonates and other equivalent organic sulfonates, in most of which the lipophilic group includes a chain of 10 to 18 carbon atoms. In the above description and else~here in the specification and in the claims when a material is characterized as a "monoglyceride sulfate" such terminology is intended to describe higher fatty acid monoglyceride sulfates wherein the higher fatty acid is of 8 to 20 carbon atoms~ preferably of 10 or 12 to 18 carbon atoms, such as lauric acid, myristic acidg palmitic acid, stearic acid and oleic acid. Additionally useful are the sulfates and sulfonates of nonionic detergents and of nonionic surface active agents~ in which _3_ , . . .
9~5i products the nonionic base will normally be a polyethylene oxide conde~-sation product of a higher fatty alcohol, such as a condensation product based on a higher fatty alcohol of 10 to 18 carbon atoms, wherein the ethylene oxide content is from 3 to 30, preferably 5 to 10 or 12 mols of ethylene oxide per mol of higher fatty alcohol. A specifically preferred anionic detergent is ammonium monoglyceride sulfate of 8 to 18 or 20 carbon atoms in the fatty acid group, e.g., ammonium cocomonoglyceride sulfate (coco indicates derivation of the fatty acids from coconut oils)g although alkali metal monoglyceride sulfates, such as sodium monoglyceride sulfate, are also useful. While sodium lauryl sulfate is an anionic sy~thetic organic detergent which may be employed, preferably in minor proportion with okher anionic synthetic org~ic detergents in the present compositions, its use is usually not preferab:Le and the corresponding triethanolammonium salt is normally used 1nstead because it can produce a clear bar of good washing and foaming ability which is also stable on storage and maintains its elasticity during use.
The amphoteric detergents which may be utilized to manufacture the elastic detergent bars of this in~ention include such compounds as Deripha ~ 151, which is sodium N-coco-betaaminopropionate (manuPactured by General Mills~ Inc.)~ Deriphat 160, a partial sodium salt of N-lauryl-betaiminodipropionate, and other betaaminopropionates and betaiminodi-propionates, ~iranol~ C2~ (anhydrous acid form, 1-carboxymethyl-1-carboxy-ethox~ethyl-2-coco-imidazolinium betaine), the water soluble salts thereof, especially the triethanolammonium salt, and other imidazolinium betaines, and other of the various known amphoterics, described in McCutcheon~s Deterc~ents and Emulsifiers, l973 ~nnual and in Surface ActiYe A~ents, ~ol.
II, by Schwartz, Perry and Berch (Interscience Publishers, 1958). For example, ~eriphats 151C~ 154~ 160, 160-C and 170-C, and Miranols C2Mg S2M
and SHD Conc. may be employed. Additionally even li~uid amphoteric ' ~
detergents may be used, at least in part, e.g., up to 25 or 50% of ~he amphoteric detergent content. The recited incorporated references also contain extensive descriptions of various suitable anionic detergents and of nonionic and cationic detergents which may be employed in small pro-portion(s) in the present compositions. The various long chain substituents ` in the mentioned amphoterics are of 8 to 20 carbon atoms, preferably of 10 to 18 carbon atoms and most prePerably are lauryl and coco.
/~ The nonionic detergents, while not required components of the invented products, may be present`in relatively small proportions therein in replacement of some of the anionic or amphoteric detergents. The non-ionics are preferab:Ly solid or semi-solicl at room temperature~ more preferably solid~ and include but are not limited to ethoxylated aliphatic alcohols having straight or branched chains (preferably straight chain) ; of from about 8 to 20 carbon atoms, with about 3 to about 30 ethylene oxide units per molecule. Particularly~ suitable nonionic detergents of such type are manufactured by Shell Chemical Company and marketed under the trademark Neodolo~. Of the various Neodols available~ Neodol ~5-7 (12-15 carbon atoms chain hlgher fatty alcohol condensed with an average of 7 etllylene oxide units per mol) and Neodol 45-11 (14-15 carbon atoms chain higher fatty alcohol condensed with an average of 1~ ethylene oxide units per mol) are particularly preferred. Another suitable class of ethoxylated aliphatic alcohol detergents is made by Continental Oil Company and is sold under the trademark Alfoni ~. Of the Alfonics the most pre-ferred is Alfonic 1618-65, which is a mixture of 16 to 18 carbon atoms primary alcohols ethoxylated so as to contain 65 mol percent of ethylene oxide. Additional ex~nples of nonionic synthetic organic detergents include those marketed by ~ASF Wyandotte under the trademark Pluronic~. Such compounds are made by condensation of ethylene oxide with a hydrophobic base formed ~y condensing propylene oxide ~ith propylene glycol. Thc hydrophobic portion of the molecule has a molecular weight of from about1,500 to 1,800 and the addi~ion of polyoxyethylene (or ethylene oxide) to such portion increases the water solubility of the molecule as a whole~
with the detergent being a solid at room temperature when the polyoxy-ethylene content is abo~e 50% of the total weight of the condensation product. Such a nonionic detergent is Pluronic ~-128 but F-68 may also be employed. Also useful nonionic detergents are the polyethylene oxide con-densates of alkyl phenols, such as the condensation products of such com-pounds wherein the alkyl group contains about 6 to 12 carbon atoms, in either a straight chain or branched chain configuration, with 5 to 25 mols of ethylene oxide per mol of alkyl phenol. The alkyl substituents in such compounds may be derived from polymeri~ed propylene or may be diisobutylene~
octene or nonene, for example.
Representative cationic detergents, which usually also possess antibacterial (and fabric softening) properties, include di-higher alkyl di-lower alkyl ammonium halides such as distearyl dimethyl am~onium chloride~ and 2-heptadecyl-l-methyl-1-~ (2-stearoylamido)ethyl~-imidazoli-nium methyl sulfate. The higher alkyls thereof are of 8 to 20 carbon atoms, preferably 12 to 18 and the lower alkyls are of 1 to ~ carbon atoms, preferably l and 2. Such materials are normally omitted from anionic detergent based products but may be employed in small proportions in mixed anionic-amphoteric detergent bars, especially when they contain more amphoteric detergent than anionic detergent and when the proportion of anionic de~ergent is relati~ely small.
Gelatin~ a complex mixture of collagen degradation products of molecular weight in the range of about 30,000 to 80,000 and higher, depen-ding on the hydrolytic conditions to ~hich it has been subjected~ is a vi;tal constituent of the present compositions. Apparently because of its cutst nding ability to form reversible gels, its high viscosity nd the excellent strengths of films thereof, it helps to make a detergent bar which is of satisfactory strength and cleaning power, due to gradual dis-solution of the ordinarily extremely soluble synthetic organic detergent component, and yet, which does not produce objectionable and unacceptable soft gels at bar surfaces which have been moistened. Additionally, and a major advantage of the present invention, the combination of gelatin and synthetic organic detergents, in the presence of water and -preferably also in the presence of a lower dihydric or polyhydric alcohol or other suitable plasticizer, and ofte~ too, a cross-linking agen~ or denaturant, yields elastic products. The elastic detergent bars made are sufficiently elastic so that a bar 2 cm. thick can be pressed between thumb and forefinger to a 1 cm. thickness and will immediately (within five seconds) return to the 2 cm. thickness or at least to with.in lmm. thereof, upon release of pressure.
The gelatin employed is essentially colorless and free from odor. It is amphoteric (about 45 milliequivalents of amino f~ctions and about 70 milliequivalents of carboxyl functions per hundred grams thereof).
It is normally used in formulating as a dry granular product which is crystalline in appearance although it is really amorphous. It is hlsoluble in cold water but swells rapidly in the presence of water ~mtil it has imbibed about 6 to 8 times its weight thereof and it melts to a viscous solution in water when warmed to above 40 to 45C. Gelatins are classified as either type A or type B, the former being from acid-cured stock, with an isoelectric point of about 8.3 - 8.5 and the latter being of alkali-cured stock, with an isoelectric point of about 4.8 - 5Ø Type A gelatins are preferred for the present applications but type B gelatins may ilso be used~ as may be mixtures of the two. The gelling powers of gelatins are normally measured by the Bloom test. Often too, viscos:ity will also be employe~ to characterize a gelatin and a gel strength~: viSCQSity ratio .
may be specified, e.g., 3:1 to 5:1. Gel strengths will range from 100 to 300 g. Bloom but will usually be in the range of 150 or 200 to 300, with gelatins of Bloom values of 22S g. and 300 g. being employed in the examples herein. The type A gelatins will generally be utilized with the usual detergent bar constituents, normally intended for employment in neutral or slightly basic aqueous media, and the type B gelatins will be preferred when acidic conditions are expected to be encountered.
Cross-linking agents for gelatin and for other proteins are metal salts ~hich cross-link ~arious geiatin molecules, apparently by reacting with free carboxyl functions thereof. This class of compounds is well known and the salts employed ~re usually those of aluminum, calcium~
magnesium and/or 7inc that are soluble in aqueous media~ In such salts the preferred anions are chloride, bromide~ iodide, sulfate, bisulfate and acetate but other suitable anions may also be included. Examples of such salts include potassium aluminum sulfate hydrate ~alum, KAl(S04)2.12 H2~J, - -aluminum chloride, vther alums, calcium chloride, magnesium sulfate and zinc acetate. Also useful for cross-linking is formaldehyde, usually as formalin. 0.1 to 1% of formaldehyde is normaIly adequate. ~lthough the presence of a cross-linking agent is often highly desirable in the formu-lations o-f the invented bar compositions, especially those based on anionic detergents primarily, it has been found that such are not as important or useful in those compositions based primarily on amphoteric ~ detergents.
; Instead of or in addition to a cross-linking agent there may be employed with the gelatin of the present compositions a denaturant. Such a compound also helps to reduce solubility of gelatin at and near its isoelectric point and inhibits crystalli.zatio~ ~lthough denaturation may be effected by various materials, including various detergents, ethanol, acetone, strong acids and strong aIkalis, chemical denaturation, usually by urea, dextrose or guanidine hydrochloride is preferred and of these -~
compounds urea is by far the preferred. Both cross-linking a~nd denaturation and the combination thereof are helpful in producing a lastingly elastic detergent bar of desired properties, suitable for repeated and satisfactory cleaning applications, but neither cross-linking agents nor denaturants for gelatin are required to make a satisfactory elastic detergent bar of the present invention.
The lower dihydric and/or polyhydric alcohol component(s) of the present bars functions as a mutua~l solvent and plasticizer for the bar components, especially the gelatin. It facilitates solubilizat:ion of the detergent at a desired rate and maintains the surface of the bar soEt. IE
the bar bec~me object:ionably hard at portions thereof this coulcL be cause for rejection of it by consumers. Such alcohol also helps to distribute the various components evenly throughout the bar or cake. Although a variety of lower dihydric or polyhydric alcohols may be employed, including various sugars and sugar alcohols~ having up to 6 carbon atoms and up to 6 hydroxyls per molecule, the most preferred are those of 2 to 3 carbon atoms and 2 to 3 hydroxyl groups per molecule. Such compounds include propylene glycol (1,2-dihydroxypropane or 1~2-propylene glycol), tri-methylene glycol (1,3-propylene glycol) and glycerol, of which 1,2-propylene glycol, glycerol and mixtures thereof are pre~erred. Other useful solvents are the Cellosolves~, the mono- and di-lower alkyl ethers of ethylene glycol. ~dditionally, sometimes monohydric alcohols, such as ethanol, are useful, primarily as supplementary solvents.
The water employed is preferably deionized wa~er which will nor-mally contain less than 10 parts and preferably less than 1 part per million of hardness, as calcium carhonate, but normal city waters may also be utilized, such as those having hardnesses in the range of 10, 20 or 50 to 150 or 300 p.p.m., as CaC03.
_9_ .
With the basic elastic detergent bar composition there may be present various adjuvant materials in minor proportions to contrib~te their particular properties to the final product. Among such adjuvant materials are functional and aesthetic adjuvants, such as: perfumes; pigments; dyes;
optical brighteners; skingprotecting and conditioning agents~ e.g., lanolin, solubilized lanolins; bactericides; chemical stabilizers, e.g.~ sodium bisulfite; foam stabilizers, e.g., lauric myristic diethanolamide; buffering agents and pH adjusters, e.g. 3 triethanolamine, hydrochloric acid, phos- -phates; bodying agents, e.g., clàys; superfatting agents, e.g., stearic acid, anti-redeposition agents and soil dispersants, e.g., polyvinyl alcohol~ sodium carbo~ymethyl cellulose; gums, e.g., sodium alginate, which also functions as a slip improving agent; and abrasive or scouring compo-nents, e.g., silex. Usually the present bars do not and shoulcL not contain any fillers or builder salts other than those which may accompany, usually -unavoidably, other components of the product. However, in certain circum-stances, as when bars for heavy duty laundry use are made, it may be desirable to add fillers, such as sodium sulfate and sodium chloride and builder salts, such as pentasodium tripolyphosphate, sodium carbonate and sodium silicate.
The proportions of the various components of the present elastic detergent bars should be kept within ranges to be given to obtain the best ;
results and to produce a bar which will be desirably elastic, useful in place of conventional soap, soapdetergent and detergent bars and which will possess improved properties, such as a lesser tendency to slough when in contact with water, compared to such more conventional bars. The synthetic organlc detergent component, the mixture of anionlc and amphoteric detergents, will be about 10 to 80% of the product, preferably 35 to 65 or 70~ and more preferably 35 to 55~0 thereof. The content of cross-linking agent and/or denaturing agent for the gelatin~ when present, is usually -10- ~, , ' . .
s 0.1 to 5%, preferably 1 to 3% and more preferably 1 to 2% total. Normally the percentage of cross-linking agent ~Yill be 0.1 to 5%, preferably 1 to 2% and that of the denaturant will be 0.5 to ~%. The gelatin, preferably type A gelatin of 225 to 300 g. Bloom, will be about 5 to 30%, preferably 7 to 25~ and more preferably about 10 to 20% of the finished bar or cake and the moisture content will be about 5 to 60%, preferably 10 to ~0% and more preferably 10 to 30%~ e.g.~ 25%.
The lower dihydric or polyhydric alcohol~ which may be omitted if syneresis problems are encountered (usually due to a high percentage of normally liquid components of the product), will normally be present in the range of 3 to 20%, preferably 10 to l8%, e.g., l5%.
The total proportion of various adjuvants present, inc:l.uding any builders and fillers, will normally not exceed 10%, preferably will be less than 5~ and more preferably will be less tha~ 2%, with the pro-portion of any particular adjuvant usually being held to less than 5~, pre~erably less than 2% and more preferably less than 1%.
The manufacture of the present elastic detergent bars is com- ' paratively simple, requiring only the mixing together of the components under such conditions that the gelatin will form a gel with water and/or with any other components present. For example, all the components of a particular detergent composition may 'be mixed together and heated, with ' stirring, to dissolve the gelatin. Alternatively the gelatin may be first ~ `
dissolved in water and the other components may then be admixed or other ' operative mixing sequences may 'be adopted. If the components are soluble the product may be transparent or at least transluscent 'but if insoluble ingredients are employed, which may be done intentionally, an opaque gel results~ To clarify transparent gels and to increase the strengths and densities thereof these may be deaerated or degassed under vacuum or by allowing the hot or warm liquid to stand until it becomes clarified. The .
'' is solution or dispersion may then be poured into suitable molds, chilled and thereby solidified. Although gelatin dissolves at temperatures above 40 or 45C. it is normally undesirable to heat it to a temperature above 100C.
and preferably dissolving will take place at a temperature in the range of about 50 to 90 or 95C., more preferably about 60 to 80C.~ over 3 to 30 minutes. Molds will be at a temperature of 5 to 20C., preferably 5 to 15C.
After *he gelatin has completely set, which may take from about one minute to an hour, usually taking from three to ten minutes, the elastic detergent bar or cake may be removed from the mold and packed or it may be a~Llowed to be warmed to room temperature before packing, at which temperature it still remains firm, yet elastic.
In a preferred process embodi.ment o~` the invent:ion a firmer bar is made which has lesser tendency to shrink on storage and develop syneresis.
Such a bar may contain: 10 to 80% of the mixture of anionic and amphoteric synthetic organic detergents in a proportion between about 1:5 and 5:1, preferably 35 to 65% of such mixture in a proportion within the range of 1:4 to 2:1, and more preferably the anionic detergent is triethanolammonium lauryl sulfate ~nd the amphoteric detergent is triethanolammonium :l-carboxymethyl-l-carboxyethoxyethyl-2-coco-imidazolinium betaine; 5 to 30%
of gelatin, preferably 7 to 25% thereof and more preferably the gelatin is a type A gelatin of lS0 to 300 g. Bloom; and 5 bo ~0~, preferably 10 to 40% and more preferably about 10 to 25 or 30% water. In the improved process the components mentioned and ~ny other solventsg plasticizers, cross-linking agents, denaturants and adJuvants may be mixed together and the gelatin is dissolved in the mixture or in the water thereofg with heating. Preferably the total proportion of water plus solvent plus plasti-cizer present will be in the ranges previously mentioned for water alone in the fincal bar but during dissolving of the gelatin, during which the temperature may be raised, as previously described, enough additional water ,' . . ' '-' .
will be employed initially to facilitate solution of the gela-tin and it will be heated for a period sufficient to drive off water (or water plus solvent, etc.) to the extent of 15 to 50~ of the weight of the mixture, preerably 20 to 40% thereof. In addition to heat, vacuum may be used to facilitate removal o~ the moisture and any volatile solvent -present, such as ethanol. ~ormally the additional heating to remove moisture~ depending on whether or not vacuum is also employed, may take from one minute to thirty minutes and preferably will take from one minute to fifteen minutes.
After removal of the moisture the` mix may be molded in the manner previous-ly described~ but yields the superior product mentioned.
The elastic detergent bars of this invention possess an obvious novelty advantage over ordinary soap or detergent bars. They are especially attractive to children when molded into various special shapes, such as the shapes of storybook or cartoon characters, animals, etc., ancl promote the enjoyment of bathing by infants and young children. The elastic nature of the product allows a controlled dispensing of detergent and other foaming materials onto the skin~or into the bath water in response to repeated squeezings and relaxings of the bar. Thus, the utilitarian detergent is also a delightful toy. However, the product has various other advantages apart from :its play value. Thus, the presence of the gelatin adds a skin care ingredient to the composition and because of the bar's elasticity breakage during shipment and on storage are minimi7ed. Furthermore, large quantities of synthetic organic detergent may be present in the composition without the need for extensive use of waxes, plasticizers, bodying agents, etc.~ to control the dissolving thereof and give them desi~able tactile properties and good appearances. The bars do not slough excessively, as often do detergent and soap bars and additionally~ they maintain sub-stantially their original shapes during use, continually dispensing detergent in response to compression and expansion and rubbing against -13~
gL9~
areas to be cleansed. They have a different "feel" than soap when con-tacting the skin and this better contact assists in cleaning. The deter-gents in the bars or other shaped articles are readily released at -temperatures of 2~ to 40C. and higher and for cold water washing, at temperatures of 10C~ and less, more soluble and lower Bloom ~alue gelatins can be employed, wi~h appropriate solvents and adjuvants, to help release the detergentO When made by the preferred process, wherein the percentage of moisture in the final product is limited to 40~, and preferably is about 25%, any tendency of the bàr to shrink on storage is diminished and a firmer product results. Additionally, surface tackiness is noticeably decreased and the ~ar foams better than corresponding anionic ancl amphoter:ic bars~ respective:Ly.
It is to be understood that within the proportions of components given variations may be made to best promote desired properties of the bars manufactured and similarly, processing modifications may also be effected. Thus, proportions o~ gelatin, detergen*, water, cross-linking agent, denaturant, plasticizer and adjuvants may be adjusted, as may be the types of such materic~ls. For example~ if the bar is too soft ~n increase in the solids content and especially in the gelatin content may be desirable and the gelatin type may be changed to that of a higher Bloom Yalue to increase the firmness of the product. ~lso, in such a case it may be desirable to utilize more cross-linking agent and/or denaturant. If the bar is too firm, re~erse adjustments may be made. Those of skill in the art, with this specification before them, will be able to modify the properties of the described compositions to make them conform to desirable product standards and sumilarly will be able to modify the processes described.
The following examples illustrate but do not limit the invention.
Unless otherwise indicated all temperatures are in C. and all parta are :.
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by weight~
Percent Triethanolammonium lauryl sulfate 8.0 Gelatin (300 g. Bloom type A) 10 0 Propylene glycol 10.0 Triethanolamine salt of Miranol C2M anhydrous acid 28.0 - (triethanolamine l-carboxymethyl-l-carboxy-ethoxyethyl-2-coco-imidazolinium betaine) Water 44.0 The components of the above formula are blended together ~nd are heated with stirring, to a temperature in the range of 60 to 80C.
to dissolve the gelatin ancl the various other materials. ~Et~r about 5 to 10 minutes a clear solution or gel is obtained, which is poured into shaped molds and chilled to 15C. Upon solidification, which takes about eight minutes~ the elastic detergent bar or cake is removed from the mold and is ready for use. The product is satisfactorily elastic and cleans well when it is employed as a bath or hand "soap". It foams very well on initial use and although the ~oam is diminished upon subsequent uses the bar is a useful washing product and maintains its elasticity throughout repeated washings and dryings. Such bar~ containing amphoteric and anionic synthetic organic detergents, with gelatin~ does not slough objectionably during use and is less tacky and better foaming than previous bars based on only anionic or amphoteric detergents, respectively.
In a modification of the manufacturing process the hot mixture of bar components is allowed to stand at an elevated temperature in the range of 45 to 55C. for a period of one hour so as to allow all air bubbles therein to be dissolved or to rise to the top of the mix and separate therefrom before setting of the gel. The products resulting are `
:
brighter and clearer in appearance following such deaeration, during which relatively little water and other solvents are evaporated. However, when the temperature of the mixture is raised, e.g., to 60 or 65 to 80 to 90C., as it is in other embodiments of this example, appreciable loss of water and other volatile materials results and the moisture content of the resulting bar is appreciably diminished. Thus, utilizing a 15 to 30 minute heating ~ -period at 80C.~ especially in the presence of vacuum, e.g., 250 mm. Hg absolute pressure, 20 to 40%, e.g., 25% of the mix weight is removed. After the evaporation off of 25% of the mix the elastic detergent bar produced includes 11% of triethanolammonium lauryl sulfate, 13% o gelatin, 13% of propylene glycol, 38% of Miranol C2M as the triethanolammonium salt and 25%
of water. The elastic detergent bars resulting (deaeration may be effected, too) are firmerJ tougher and less liable to shrink upon proLongecl exposure to the atmosphere during storage.
When the formula is modiied to replace the triethanolammonium lauryl sulfate with the same weight of other suitable anionic detergent, such as ammonium cocomonoglyceride sulfate or a mixture of equal parts of ammonium cocomonoglyceride sulfate and sodium cocomonoglyceride sulfate and when the propylene glycol is replaced by glycerol a procluct of com-parable properties results. Similarly, when the ~iranol C2M salt is replaced by Deriphat 151 or Deriphat 160 or other suitable amphoteric detergentJ especially one of the imidazolinium betaine, betaaminopropionate or betaiminodipropionate type and when the gelatin is replaced by 15% of 225 g. Bloom type A gelatin (type B may also be used but is not usually as good) essentially the same type of elastic detergen~ bar results.
Similarly, when 2% of potash alum ~cross-linking agent) or 1% of urea (denaturant) is present in replacement of a corresponding percentage of ~ater a irmer bar results. When adjuvants are employed, such as fluorescent brighteners; bactericides, emollients; solvents; foaming agentsJ e.g~
lauric myristic dlethanolamide; pH adjusting agents, e.g., ':"
- 16 _ :, :
' ~
- .. ... , - .. - . , , . . .. .- .. . . -hydrochloric acid, triethanolamine; perfumes; colorants, including dyes and pigments, and preservatives, they contribute their speciic properties to the final bar.
In further modifications of the formula small proportions of dyes and pigments are incorporated to color and opacify the products and : -gels are molded inichilled molds into the shapes of specific storybook, nursery rhyme, cartoon and animil characters, with the proportions of dyes and pigments employed being about 0.02% for the dyes and about 0.2%
for the pigments. The dyed bars are transparent or translucent and the pigmented bars are opaque. The opacities of the pigmented bars are further increased by additions of 1~ 2 and 5% of powdered clay to the initial mixture~ which also converts the colors to pastels.
The formulas described :in this example are modified proportionate-ly ~10%, +20, and ~30~, within the ranges given and the products resulting are useful elastic detergent bars of this invention.
Percent Ammonium cocomonoglyceride sulfate 24.2 (47% active ingredient) Tr:iethanolamine salt of Miranol C2M 28.0 Gelatin ~300 g. Bloom, type A) 10.0 propylene glycol 10.0 Water 27.8 Elastic detergent bars of the above formula and of such a formula less 25% of water removed in a drying operation after dissolving o the gelatin~a~e made according *o the method of Example 1. The bars produced are useful elastLc detergent bars for bath use or handwashing and are less tacky and better foaming than similar bars not containing the mixture of anionic and amphoteric detergents. Also, the bars made by a : .:
process including removal of moisture, as described, are less liable to shrink on storage exposed to the air than are similar bars containing the greater percentages of moisture. The improved bars, made by reducing the moisture content, analyze about 30~0 of ammoniumcocomonoglyceride sulfate, 35~ of triethanolammonium 1-carboxymethyl-1-carbo~yethoxyethyl-2-coco-imidazolinium betaine, 13% of gelatin, 12%of propylene glycol and 10% of water. The removal of moisture in~he above-described process and other such processes of this invention takes place at a temperature of 30 to 90C., preferably 40 to 80C., with the lower temperatures being used most when vacuum is also employed.
EXA~PLE 3 Percent Miranol C2M, anhydrous acid 21 Triethanolamine 7.5 Propylene glycol 10.0 Gelatin (300 g. Bloom, Type A) 10.0 Triethanolamine lauryl sulfate 28.5 (40% active ingredient, a~ueous solution) ~mmonium cocomonoglyceride sulfate 23.0 (47~ active ingredient, a~ueous solution) Following the procedllre of Example 1~ products o:E the above formula ;~
are made, without moisture removcil. They are good elastic detergent bars for both bath use and handwashing and are less tacky and better foaming than similar bar~ containing either anionic detergent or amphoteric ~;-detergent alone. Also, because of their comparatively low moisture content :
the bars are less liable to shrinkage on storage and when exposed to air than are similar bars containing more moisture.
In normal handwashing use a 100 gram molded bar and molded items in the shapes of cartoon characters, automobiles and animals last for at least 200 handwashings at a water temperature of 40C., give a copious ~: :
, . : ~ . . . .
4~S
foam and wash well. They clean well and leave the hands feeling sOftg apparently due to the gelatin and amphoteric detergent contents of the products. When 150 gram bars or articles are utilized they last for as many as 20 normal baths~ with good foaming throughout such use. During wearing down of the ~bars~ they substantially retain their general original shapes, colors and foaming and washing abilities.
~XA~IPLE 4 The product of Example 3 is made from an initial mixture which includes 45% of water instead of the 30% in the final product and in the mix of Example 3. The excess moisture is removed during manufacturing by -~
heating for about 45 minutes at a temperature of about 75C., without vacuum. Comparison of the products of ~xamples 3 and 4 shows little difference between them except that the product of Example ~ may have the components thereof more ~miformly distributed thro~lghout it due to the initial dissolvings of more of them in the a~ueous medium before removal of excess moisture. Also, initial mixing and dissolving of the mix of this example is much easier. In a further modification of this example the density of the product is diminished ~0%, so that it will float in warm bath water, by distributing small bubbles of ~ir throughout it after removal of the excess moisture from the mixed solution and after cooling of such mix~ Eollowing the procedure in an application by John C. Carson, Jr. and James A. Bowers, entitled Elastic Detergent Bar of Improved ~levated Temperature Stability, filed simultaneously with this application.
The product resulting is an excellent "floating soap" for use inrthe bath tub but unlike soap, it and the other products of this invention leave no -bathtub ring and it is a superior floating toy for the child when he takes a bath.
The invention has been described with respect to various embodi-ments and illustrations thereof but is not to be limited to these because ~4~i5 it is evident that one of skill in the art with the present specification -before him will be able to utilize substitutes and equivalents wi~hout departing from the spirit of the invention.
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Claims (13)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A hand squeezable, elastic, solid molded detergent product comprising about 35 to 70% of a mixture of anionic and amphoteric synthetic organic detergents in a proportion about 1:5 to 5:1, said anionic detergent being selected from the group consisting of water soluble alkali metal, triethanolamine and ammonium higher linear alkylbenzene sulfonates, paraffin sulfonates, olefin sulfonates, fatty alcohol sulfates, monoglyceride sulfates and fatty alcohol polyethylene glycol sulfates and mixtures thereof and said amphoteric detergent being selected from the group consisting of water soluble betaaminopropionates, betaiminodipropionates and imidazolinium salts and mixtures thereof, about 5 to 30% of gelatin and about 5 to 60% of water, which product is sufficiently squeezable and elastic so that a 2 cm. thickness thereof can be pressed between a thumb and forefinger to a 1 cm. thickness and upon release of such pressure will return within five seconds to within one mm. of the 2 cm. thickness.
2. An elastic detergent bar according to claim 1 wherein the anionic synthetic organic detergent is selected from the group consisting of alkali metal monoglyceride sulfate, ammonium monoglyceride sulfate, triethanol-ammonium higher fatty alcohol sulfate and mixtures thereof, the amphoteric synthetic organic detergent is selected from the group consisting of imidazolinium betaines and betaiminodipropionates and mixtures thereof, the proportion of anionic to amphoteric synthetic organic detergent is in the range of 1:4 to 2:1 and the gelatin is a type A gelatin of 100 to 300 g. Bloom.
3. An elastic detergent bar according to claim 2 wherein the mixture of anionic and amphoteric synthetic organic detergents is from 35 to 70% of the bar, the gelatin is of 200 to 300 g. Bloom and is 7 to 25% of the bar and the moisture content is from 10 to 40%.
4. An elastic detergent bar according to claim 3 which comprises about 3 to 20% of lower dihydric or polyhydric alcohol.
5. An elastic detergent bar according to claim 3 wherein the anionic synthetic organic detergent is triethanolammonium lauryl sulfate and the amphoteric synthetic organic detergent is triethanolammonium 1-carboxy-methyl-1-carboxyethoxyethyl-2-coco-imidazolinium betaine.
6. An elastic detergent bar according to claim 3 wherein the anionic synthetic organic detergent is ammonium cocomonoglyceride sulfate and the amphoteric synthetic organic detergent is triethanolammonium 1-carboxy-methyl-1-carboxyethoxyethyl-2-coco-imidazolinium betaine.
7. An elastic detergent bar according to claim 4 wherein the anionic synthetic organic detergent is triethanolammonium lauryl sulfate and the amphoteric synthetic organic detergent is triethanolammonium 1-carboxy-methyl-1-carboxyethoxyethyl-2-coco-imidazolinium betaine.
8. An elastic detergent bar according to claim 4 wherein the anionic synthetic organic detergent is ammonium cocomonoglyceride sulfate and the amphoteric synthetic organic detergent is triethanolammonium 1-carboxy-methyl-1-carboxyethoxyethyl-2-coco-imidazolinium betaine.
9. An elastic detergent bar according to claim 7 comprising about 11%
of triethanolammonium lauryl sulfate, about 38% of triethanolammonium 1-carboxymethyl-1-carboxyethoxyethyl-2-coco-imidazzolinium betaine, about 13% of 300 g. Bloom gelatin, about 13% of propylene glycol, and about 25%
of water.
of triethanolammonium lauryl sulfate, about 38% of triethanolammonium 1-carboxymethyl-1-carboxyethoxyethyl-2-coco-imidazzolinium betaine, about 13% of 300 g. Bloom gelatin, about 13% of propylene glycol, and about 25%
of water.
10. An elastic detergent bar according to claim 8 comprising about 30%
of ammonium cocomonoglyceride sulfate, about 35% of triethanolammonium 1-carboxymethyl-1-carboxyethoxyethyl-2-coco-imidazolinium betaine, about 13%
of 300 g. Bloom gelatin, about 12% of propylene glycol and about 10% of water.
of ammonium cocomonoglyceride sulfate, about 35% of triethanolammonium 1-carboxymethyl-1-carboxyethoxyethyl-2-coco-imidazolinium betaine, about 13%
of 300 g. Bloom gelatin, about 12% of propylene glycol and about 10% of water.
11. A method o making a squeezable, elastic, solid molded detergent product comprising about 35 to 70% of a mixture of anionic and amphoteric synthetic organic detergents in a proportion about 1:5 to 5:1, said anionic detergent being selected from the group consisting of water soluble alkali metal, triethanolamine and ammonium higher linear alkylbenzene sulfonates, paraffin sulfonates, olefin sulfonates, fatty alcohol sulfates, monoglyceride sulfates and fatty alcohol polyethylene glycol sulfates and mixtures thereof and said amphoteric detergent being selected from the group consisting of water soluble betaaminopropionates, betaiminodipropionates and imidazolinium salts and mixtures thereof, about 5 to 30% of gelatin and about 5 to 40% of water, which comprises heating together a mixture of such components, with additional water to promote solubilization of the gelatin, then evaporating off water in a proportion from 15 to 50% of the weight of the mixture and molding it to a product of the above-described composition which is sufficiently squeezable and elastic so that a 2 cm. thickness thereof can be pressed between a thumb and forefinger to a 1 cm. thickness upon release of such pressure and will return within five seconds to within 1 mm. of the 2 cm. thickness.
12. A method according to claim 11 wherein the elastic detergent bar comprises about 35 to 65% of a mixture of triethanolammonium lauryl sulfate and triethanolammonium 1-carboxymethyl-1-carboxyethoxyethyl-2-coco-imidazolinium betaine in a proportion within the range of 1:4 to 2:1, 7 to 25% of a type A gelatin of 100 to 300 g. Bloom and 10 to 40% of water which comprises heating a mixture of such components in an aqueous medium containing 25 to 60% of water until the gelatin is dissolved, continuing heating until 20 to 40% of the mix weight of water is removed, deaerating the composition and pouring it into a mold.
13. A method according to claim 11 wherein the elastic detergent bar comprises about 35 to 70% of a mixture of ammonium cocomonoglyceride sulfate and triethanolammonium-1-carboxymethyl-1-carboxyethoxyyethyl-2-coco-imida-zolinium betaine in a proportion within the range of 1:4 to 2:1, 7 to 25% of a type A gelatin of 100 to 300 g. Bloom and 10 to 40% of water which comprises heating a mixture of such components in an aqueous medium containing 25 to 60%
of water until the gelatin is dissolved, continuing heating until 20 to 40%
of the mix weight of water is removed, deaerating the composition, pouring it into a mold, chilling and solidifying it and removing it from the mold.
of water until the gelatin is dissolved, continuing heating until 20 to 40%
of the mix weight of water is removed, deaerating the composition, pouring it into a mold, chilling and solidifying it and removing it from the mold.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US74699576A | 1976-12-02 | 1976-12-02 | |
| US746,995 | 1976-12-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1104905A true CA1104905A (en) | 1981-07-14 |
Family
ID=25003229
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA292,179A Expired CA1104905A (en) | 1976-12-02 | 1977-12-01 | Elastic detergent bar containing anionic and amphoteric synthetic: organic detergents |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1104905A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113025437A (en) * | 2021-03-11 | 2021-06-25 | 河南瑞奇特新材料有限公司 | Washing whitening agent and preparation method thereof |
-
1977
- 1977-12-01 CA CA292,179A patent/CA1104905A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113025437A (en) * | 2021-03-11 | 2021-06-25 | 河南瑞奇特新材料有限公司 | Washing whitening agent and preparation method thereof |
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