CA1082560A - Process for making a toilet bar - Google Patents
Process for making a toilet barInfo
- Publication number
- CA1082560A CA1082560A CA279,844A CA279844A CA1082560A CA 1082560 A CA1082560 A CA 1082560A CA 279844 A CA279844 A CA 279844A CA 1082560 A CA1082560 A CA 1082560A
- Authority
- CA
- Canada
- Prior art keywords
- soap
- poly
- ethylene oxide
- chips
- bar
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D9/00—Compositions of detergents based essentially on soap
- C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
- C11D9/22—Organic compounds, e.g. vitamins
- C11D9/40—Proteins
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D9/00—Compositions of detergents based essentially on soap
- C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
- C11D9/22—Organic compounds, e.g. vitamins
- C11D9/225—Polymers
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Cosmetics (AREA)
Abstract
ABSTRACT
Process for preparing toilet soap bars containing high molecular weight polymers of ethylene oxide, said bars characterized by having a smooth surface like that of con-ventional soap bars.
Process for preparing toilet soap bars containing high molecular weight polymers of ethylene oxide, said bars characterized by having a smooth surface like that of con-ventional soap bars.
Description
10~2560 .:
PROCESS FOR MAKING A TOILET SOAP BAR
This invention relates to the incorporation of very high molecular weight poly (ethylene oxide) into a toilet soap bar.
The inclusion of such poly (ethylene oxide) makes it possible to provide a hard tough bar which has a degree of slipperiness when wetted which is especially pleasant to the user, gives a lather which is creamy, pleasant silky and effective, has good resistance to sloughing in use despite a high moisture pickup, has a long life and is flexible and tough even after much of the bar has been used up and provides a beneficial effect on the hands (e.g. reduces chapping and flaking, moisturizing the skin, particularly for dry skins).
When it is attempted to incorporate the high molecular weight poly (ethylene oxide), which is supplied as a dry powder, into a toilet bar using the methods by which powdered ingredien*s are conventionally added (e.g. by addition to the soap amalgamator along with the other ingredients) it is found that the resulting toilet bars have spaced visible and palpable specks. These specks are sometimes observed on the surface of the final pressed bar or 2Q they become evident when the bar is washed in cold water. For instance there may be some 50 to 500, or more, visible specks per bath size bar. Examination of these specks reveals that they are agglomerates or gels containing poly (ethylene oxide); typically, the volume of a speck is about 0.005 cubic millimeters (mm3) to 0.3 mm3. It is found that the formation of such specks can be substantially avoided by mixing soap chips with the poly ~ethylene oxide) powder ~le the surfaces of said soap chips aro in powder-ad~erent condition with respect to said polyethylene oxide powder, to produce soap chips having poly (ethylene oxide) bonded thereto, . ' .
r 1 --' .
.
then adding other ingredients of said toilet soap bar and mixing ~aid other ingredients wlth said bonded chips, then forming the resulting mixture into a soap bar. Two preferred processes are (a) add the powdered high molecular weight poly (ethylene oxide) to soap chips having a moisture content such that the powder adheres thereto (e.g. at least about 11% H20) and mixing before adding the other solid ingredients, or (b) add the powdered high molecular weight polyethylene oxide to soap chips havlng a lower moisture content, mix, and then carefully add some water ln a flnely dispersed state (e.g., to bring the water content, based on soap, to a level sufficient to provide powder adhesion) before adding the other solld ingredients. The reason for this læ not understood, but it appears that the particle~ of high molecular weight poly (ethylene - oxide) (who3e moisture sorption is below 3~ at a relative humldity f 60% at 250C accordlng to the manufacturer's bulletlns) take up sufficient moisture from the higher moisture content soap chips and become bonded, indlvidually, to the surfaces of the chip~ so that these particles are thus prevented from agglomeratlng; if there is not sufficient mo1sture for this to occur before the subsequent addition of other solid ingredients (particularly powders of low moisture contents, e.g., below about 8% water), the latter may compete for the limited amount of moisture available, and loose ~ particles of high molecular welght polyethylene oxlde may agglomerate ` in later stageæ.
The powder-adherent property of the soap chlps may be tested ln the manner illustrated in Example I below. Best and most cohæistent results are obtained when the molsture content of the suface is such that the powder "disappears" on remaining in contact with the surface for a short time (e.g. 1 to 2 minutes) as for the 15~ moisture chip in Example I.
PROCESS FOR MAKING A TOILET SOAP BAR
This invention relates to the incorporation of very high molecular weight poly (ethylene oxide) into a toilet soap bar.
The inclusion of such poly (ethylene oxide) makes it possible to provide a hard tough bar which has a degree of slipperiness when wetted which is especially pleasant to the user, gives a lather which is creamy, pleasant silky and effective, has good resistance to sloughing in use despite a high moisture pickup, has a long life and is flexible and tough even after much of the bar has been used up and provides a beneficial effect on the hands (e.g. reduces chapping and flaking, moisturizing the skin, particularly for dry skins).
When it is attempted to incorporate the high molecular weight poly (ethylene oxide), which is supplied as a dry powder, into a toilet bar using the methods by which powdered ingredien*s are conventionally added (e.g. by addition to the soap amalgamator along with the other ingredients) it is found that the resulting toilet bars have spaced visible and palpable specks. These specks are sometimes observed on the surface of the final pressed bar or 2Q they become evident when the bar is washed in cold water. For instance there may be some 50 to 500, or more, visible specks per bath size bar. Examination of these specks reveals that they are agglomerates or gels containing poly (ethylene oxide); typically, the volume of a speck is about 0.005 cubic millimeters (mm3) to 0.3 mm3. It is found that the formation of such specks can be substantially avoided by mixing soap chips with the poly ~ethylene oxide) powder ~le the surfaces of said soap chips aro in powder-ad~erent condition with respect to said polyethylene oxide powder, to produce soap chips having poly (ethylene oxide) bonded thereto, . ' .
r 1 --' .
.
then adding other ingredients of said toilet soap bar and mixing ~aid other ingredients wlth said bonded chips, then forming the resulting mixture into a soap bar. Two preferred processes are (a) add the powdered high molecular weight poly (ethylene oxide) to soap chips having a moisture content such that the powder adheres thereto (e.g. at least about 11% H20) and mixing before adding the other solid ingredients, or (b) add the powdered high molecular weight polyethylene oxide to soap chips havlng a lower moisture content, mix, and then carefully add some water ln a flnely dispersed state (e.g., to bring the water content, based on soap, to a level sufficient to provide powder adhesion) before adding the other solld ingredients. The reason for this læ not understood, but it appears that the particle~ of high molecular weight poly (ethylene - oxide) (who3e moisture sorption is below 3~ at a relative humldity f 60% at 250C accordlng to the manufacturer's bulletlns) take up sufficient moisture from the higher moisture content soap chips and become bonded, indlvidually, to the surfaces of the chip~ so that these particles are thus prevented from agglomeratlng; if there is not sufficient mo1sture for this to occur before the subsequent addition of other solid ingredients (particularly powders of low moisture contents, e.g., below about 8% water), the latter may compete for the limited amount of moisture available, and loose ~ particles of high molecular welght polyethylene oxlde may agglomerate ` in later stageæ.
The powder-adherent property of the soap chlps may be tested ln the manner illustrated in Example I below. Best and most cohæistent results are obtained when the molsture content of the suface is such that the powder "disappears" on remaining in contact with the surface for a short time (e.g. 1 to 2 minutes) as for the 15~ moisture chip in Example I.
2--~08ZS60 Detailed Description of the Invention The soap constitutes at lea~t 60~, and preferably more than 70~, of the moisture-free welght of the bars of the present invention. The soap may be of a conventional type p~edo,~ I n ~n~ly A con6isting ~ ominatoly of 12 to 18 carbon atom molecules and may be produced by the saponification of fatty materials suitable for use in soap making, suitable fatty materials comprising, for example, the fats, oil6 and waxes of animal, vegetable, and marine origin, and the fatty acids derived therefrom or of synthetic origin More speclfically, the fatty acids may be of mlxed character such as are derived from natural or hydrogenated tallow, cottonseed oil, coconut oil, palm oil, palm kernel oll, baba6su nut oil, grea~e, fish oils, and fatty acids derlved therefrom by hydrolysis or saponification or may be pure materials such as lauric, myristic, palmitic, stearlc and oleic acids. It is generally preferred to ~15 use in the present invention the sodium salts of the mlxed fatty ; acids derived from tallow and coconut oil and mixtures thereof. A
; desirable blend has a weight ratio of sodium coco 80ap to sodium tallow soap in the range of about 50:50 to about 10:90, with a ~ ratio below about 30:70, e.g. a range of about 25:75 to about ; -~0 17:83 being especially preferred. As is known in the art, the higher coco contents give faster more coplous lather but more f irritation, in conventional soaps. It is within the broader scope ~ to use blends of the sodium soaps and the corresponding potassium -1 soaps (e.g. in mole ratios of sodium:potassium of 90:10 or 75:25).
~5 The high molecular weight poly (ethylene oxlde) ha~ an average molecular weight of at least about 100,000. Examples of such compound~ are those sold by Union Carbide Company under the trademark "Polyox". These polymers are nonionic and extremely t ~~ .
., ~
:, i '';'' ;
.' '' ' , ., - 1~)82S60 soluble in water and their molecular weights range from about 100,00() to about 5~000,000 or more. It i~ preferred to employ polymers having average molecular weights below 1,000,000, more preferably not aboVe 600,000 such as about 300,000 to 400,000.
me proportlon o~ high molecular welght polymer of ethylene oxide in the tollet bar iB generally below about 10% and is preferably more than about 0.5~ e.g. at least about 1%, and less than about 5%, more preferably below 4%. For the material having an average molecular weight o~ about 300,000 a proportion ln the neighborhood of 2~ has given excellent reBults. mis 300,000 ~e~ht molecular woighr material (sold as Polyox WSR N-750) has a viscosity at 25C. for a 2~ aqueous solution of about 40 centipoise~
r A (Brookfield Spindle No. 1 at 10 rpm) ~Y~ a 5% solution this viscosity is about 600-1000 centipois~. Uee of say 2% of extremely high molecular weight poly (ethylene oxide), e.g. of 4,000,000 average molecular weight, causes the lather to be pituitous, whlch is less desirable. According to the manufacturer the Polyox materials typically have a pH of about 10 (e.g. in 5% solutlon~.
Soap typically has a pH in 1~ aqueous ~olution of about 10 (e.g.
10.2).
The poly (ethylene oxide) is generally supplied as a powder and typically has the following particle size distribution s ;e~Je~
when a ~ample thereof is screened through a series of ooivc~, expressed a~ weight percent retained on the indicated Sle~e No.
~creen (U.S. Sleve Serle8): No. 20-5.2~: No. 40-31.2%: No. 60-20.7~;
No. 100-16.7% and through No. 100-balance~. It is often preferable to use a finer particle size poly (ethylene oxide) having the following dlstributlon as measured above: No. 20-0.3%; No. 40-13%; No. 60-13%;
` No. 100-13.9~ and through No. 100-balance.
The invention has found lts greatest utility so far in the production of bars containing hydrolyzed protein. A parti-cularly preferred hydrolyzed protein i8 Protein A sold by Croda Inc., New York, N Y. and is a partially enzymatically hydrolyzed protein derlved from beef collagen and characterized by having a zero Bloom gram gel strength, a 10% weight/weight water solution having a viscosity ra~ge of about 16-25 millipoises (mps)~ a pH
of 5.5-6.5, and in weight percent, a hydroxyproline content (mainly chemically combined hydroxyproline) of about 10-12~, a nitrogen content of about 15-18%, and a total nitrogen as amino nitrogen of about 5-12%, and a molecular weight of about 1,000 to about 3,000, such as about 2,000. Its ash content is generally low (e.g. below 10%). Other hydrolyzed prote1ns which may be used I include hydrolysis products comprising proteoses, peptones, and/or i~ 15 polypeptide8, typically having a molecular weight of at least about 600 and below about 12,000, preferably below about 5,000, and including moieties of a plurality of amino acids. mese hydrolysis products may be formed by partial enzymatic hydrolysis, such as by ~, the action of trypsin, erepsin or pancreatic enzymes on protein material (e.g. at about 35-50C. for about 12-48 hours). The partially degraded protein may also be a product obtained by partial hydrolysis of protein by heat and/or alkali. Proteins partlally ~l ~ degraded by heat may be prepared, for instance, by heatlng protein-,1 aceous material such as bones, feet, or skin of pork or beef which .~..
~`j 25 haæ been reduced to small pieces and immersed in water, by auto-''' 1 claving at about 2.8-3.5 kg/cm.2 of saturated steam (i.e. about 141.5-147.6C.) for about two hours; three phases includlng ~at, ~' the desired aqueous phase, and a residue may thus be obtalned; the ':''' !
~ -5-. . .
.
~,/,~ ., , ,.
,, .
aqueous phase which may contain about 8-10~ sollds may be con-centrat;ed in vacuo to about 50-60% solids at 60-71C. to obtain a "solubilized collagen," a heat degraded protein, which may be employed in this invention. Typical proteins which may be partially hydrolyzed for use in accordance with this invention include casein, gelatin, collagen, albumin, zein, gliadin, keratin, fibroin, globulin, glutenin, etc. Typical commercial partially enzymatically hydrolyzed protein~ include Bacto-Proteose (sold by Difco Laboratories, Detroit, Mich.), proteous-peptone, casein-peptone, gelatin-peptone, 10 Bacto-Peptone~sold by Difco Laboratories), vegetable peptones~ -~A such as ~ peptone, Proto-Peptone~ sold by Wilson Co., the peptone enzymatically derived from solubilized collagen using ground frozen pancreatic enzymes having a pH of 8. digestion being at about 49 C. for about 12-48 hours, the solubilized collagen being derived by heating bones, feet or skin of pork or beef). The preferred protein8 are solubilized beef collagen and solubilized pork collagen which may be prepared as described and are;generally characterized by a gel strength of about zero Bloom grams.
The partially hydrolyzed protein may have a relatively broad spectrum of molecular weights and may contain some (usually small amounts) of almost completely degraded polypeptides, such as dipeptides and tripeptides and even some amino acids as a result of the degradation process. If desired, these may be removed by dialysis, e.g., by placing the partially degraded protein in a cellophane bag which i~ then closed at both ends and is lowered into a tank into which deionized water continuously enters and from ~ Q~
1082s60 which it contlnuously exlts, products such as the tripeptides, dipeptides, and amino acids pass out of the cellophane by dialysis to mix wlth the deionized water and leave the partially degraded protein. When employed, the dialysis procedure has the additional advantage of removing the odors of the more completely hydrolyzed material The proportion of protein ingredient in the tollet bar ls generally about 0.1~ and below about 10%. Amounts in the range of about 1~ to about 5~ are preferred with a level of about 3~
belng especlally preferred. For the preferred protein mate~ial the 1-5% range provides a hydroxyproline content oP about 0.1 to 0.5%, preferably about 0.3%.
; In addition to, or in place of the protein, super-fatting agents may be included. It is found that in the bars of this lnventlon acetylated lanolin (such as, Modu~a ~sold by American chalesterol; ~ee U.S. Patent No. 2,725,334) gives especially good results. Other superfatting agents are hydroxy~ated lanolin, (e.g.~, OH Lan sold by American Cholesterol), higher (C~O c~8~ fatty , .
acids such as stearic acid, coconut oil fatty acid, hlgher (C10-C20) fatty alcohols, petrolatumand the like. Amounts of superfatting : agents less than 10~ total are generally employed, preferably about 1%-5% e.g., 2~-3%
The bars may also contain a synthetic surfactant of high foaming characteristics in hard water, such as alkali metal - 25 salts of organic sulfuric reaction products having in thelr molecular st~ucture an alkyl radical of from about 8 to about 22 carbon atoms, e g., alkyl benzene sulfonates, coconut oil fatty acid monoglyceride t-~R~ ~ 7 , ~O~Z560 CC/o - C/~,) sulforlates and sulfates, alkali metal fatty acid (C10 C ~
isethionates, among others, present in small amounts in the bar.
A part;icularly preferred ester is sodium coco isethionate sold as Igepon AC-78 by the General Aniline and Film Corporatlon. The proportlon of synthetic surfactant is generally within the range of about 0.5~ to about 5~ and preferably about 1~ to about 3% e.g., about 2%. Preferably the weight ratio of synthetic urfactant to high molecular weight poly (ethylene ox~de) is in the range of about 2:1 to 1:2, such as about 1:1.
In addition to the components listed above, it will be understood that the clean6ing bar of the invention may contain other conventional additives in minor amounts including those usually found in such cleansing bars, such as fillers, perfumes, dyes, fungicides, humectants~ (e.g. 0 2 to 1% of glycerine) and bacterlcldes.
Toilet soap bars range in size from the relatlvely 6mall hotel slze (waighing about 20-30 grams) to the regular size (about 100 grams) to the bath size (about 150g) to the extra large size (about 200g). The bars of thls invention may be of such sizes, particularly in the range of about 100 to 200 grams. The soap may also be aerated, ln a manner well known in the art to give lower density (floating) soaps, ~uch as those having a speciflc gravity o~ about o.8.
Ihe lnvention i6 particularly suitable for the making of mllled and plodded toilet soap bars. Bars of thls type are, of course, well known in the art; see for instance the ; description thereof in U. S. Patent No. 3,179,596. Also see "Encyclopedia of Chemical Technology," ~olume 12, edlted by Kirk Trademark 1~)82560 and Othmer, pages 573-598 and "Industrial Oil and Fat Products,"
Alton E. Bailey, Second Edition, 1951, pages 365-386 and 840-865 Thu~ one may take a kettle soap, form it into dried chips (as described in the foregoing reference~) and blend it with the various ingredients before milling and plodding.
The moisture contents of the toilet bars of this invention are such as to provide a solid non-tacky toilet bar Preferably they are well below 30%. For a milled, plodded bar they are generally less than 20~, prererably in the range o~ about lO to 17%, æuch as about 13~.
Miiled plodded ~oap~ typically are made up of ~ine crystals of hydrated fatty acid salt. me high molecular weight poly (ethylene oxide) appears to have an afflnity for the moisture in the soap as shown by the experiment in Example I, but the phy81cal state of thi8 material in relation to the soap crystal6 18 not presently known.
Variou~ embodlments of the present lnvention will now be illustrated by re~erence to the following specific examples.
It is to be understood, however, that such examples are presented for purpose o~ lllustration only, and the present invention i8 in no way to be deemed as limited thereby.
EXAMPLE I
In this Example there are employed soap chips of various moisture contont~ (3~, 9~, 11%, 13~ and 15~). lOO grams of soap chip~ are placed in a 400 cc. beaker and 2% of poly (ethylene oxide powder) is added thereto and mixed (tumbled) therewith by hand with a l inch wlde spatula, for one minute. The poly (ethylene oxide) employed has a flne particle size as lndlcated by the preferable , _9_ .
particle ~ize as lndicated hereinabove. The contents of the beaker are then spread on black paper. The paper i8 inspected with t;he naked eye to see the amount of powder le~t thereon and the chips are inspected under a 30-power microscope. When the chips contaln 3 and 9~ moisture substantially none of the powder adhere thereto and the black paper has a distinct layer of white powder. When the chips containing 11% moisture are stirred (with the spatula) the chips on the paper cause a noticeable release of powder (e.g. about 40% of the total powder) onto the paper; under the microscope the powder particles are ~een to be distinct and resting on the surface of the soap chips and loosely adhering thereto. When the chips contain 13% moisture the powder is found to be more tightly held (e.g. about 20~ to 30% is released when the chip~ are stirred on the paper); under the microscope one can see di~tinct powder particles on the chips surfaces. When the chips contain 15~ moisture substantially none of the powder is released onto the paper; microscopic examination, almost immediately, shows substantlally no powder particles resting on the chip surfaces; the surfaces look substantially the same a~ if no powder had been added.
EXAMPLE II
A soap bar of the following compo~ition i8 prepared ;~ by adding the ingredients in the order listed, to a conventional soap amalgamator (while the blades thereof are moving) operating at room temperature.
- ~082S60 Component Weight Soap ch~ps (17 coco Na soap/83 tallow Na soap)l 88.50 50~ aqueous solution of stannic 5 chloride (a preservative) 0 15 Poly (ethylene oxide)2 2.00 Water 1.00 Titanium dioxide-powder (substantially moisture-free), 10 ~a pigment) o.60 Protein A-powder (containing up to about 6% moisture~ 3.oo Sodium coco isethlonate-powder (containing about 1-2% moisture)2.00 ~ 15 Glycerine o.50 ; Acetylated lanolin3 1.00 Perfume 1.25 '. 100.00 ~ 1 Moistùre iB about 11.5~; bar moi~ture 10.5~, measured i~ 20 by weight 108B at 105C.
2 Polyox WSR N-750 in the form of powder, of size such that less than about 5% by weight (e.g. 0.3~) is retained on a 20 mesh screen (U. S. Standard).
; desirable blend has a weight ratio of sodium coco 80ap to sodium tallow soap in the range of about 50:50 to about 10:90, with a ~ ratio below about 30:70, e.g. a range of about 25:75 to about ; -~0 17:83 being especially preferred. As is known in the art, the higher coco contents give faster more coplous lather but more f irritation, in conventional soaps. It is within the broader scope ~ to use blends of the sodium soaps and the corresponding potassium -1 soaps (e.g. in mole ratios of sodium:potassium of 90:10 or 75:25).
~5 The high molecular weight poly (ethylene oxlde) ha~ an average molecular weight of at least about 100,000. Examples of such compound~ are those sold by Union Carbide Company under the trademark "Polyox". These polymers are nonionic and extremely t ~~ .
., ~
:, i '';'' ;
.' '' ' , ., - 1~)82S60 soluble in water and their molecular weights range from about 100,00() to about 5~000,000 or more. It i~ preferred to employ polymers having average molecular weights below 1,000,000, more preferably not aboVe 600,000 such as about 300,000 to 400,000.
me proportlon o~ high molecular welght polymer of ethylene oxide in the tollet bar iB generally below about 10% and is preferably more than about 0.5~ e.g. at least about 1%, and less than about 5%, more preferably below 4%. For the material having an average molecular weight o~ about 300,000 a proportion ln the neighborhood of 2~ has given excellent reBults. mis 300,000 ~e~ht molecular woighr material (sold as Polyox WSR N-750) has a viscosity at 25C. for a 2~ aqueous solution of about 40 centipoise~
r A (Brookfield Spindle No. 1 at 10 rpm) ~Y~ a 5% solution this viscosity is about 600-1000 centipois~. Uee of say 2% of extremely high molecular weight poly (ethylene oxide), e.g. of 4,000,000 average molecular weight, causes the lather to be pituitous, whlch is less desirable. According to the manufacturer the Polyox materials typically have a pH of about 10 (e.g. in 5% solutlon~.
Soap typically has a pH in 1~ aqueous ~olution of about 10 (e.g.
10.2).
The poly (ethylene oxide) is generally supplied as a powder and typically has the following particle size distribution s ;e~Je~
when a ~ample thereof is screened through a series of ooivc~, expressed a~ weight percent retained on the indicated Sle~e No.
~creen (U.S. Sleve Serle8): No. 20-5.2~: No. 40-31.2%: No. 60-20.7~;
No. 100-16.7% and through No. 100-balance~. It is often preferable to use a finer particle size poly (ethylene oxide) having the following dlstributlon as measured above: No. 20-0.3%; No. 40-13%; No. 60-13%;
` No. 100-13.9~ and through No. 100-balance.
The invention has found lts greatest utility so far in the production of bars containing hydrolyzed protein. A parti-cularly preferred hydrolyzed protein i8 Protein A sold by Croda Inc., New York, N Y. and is a partially enzymatically hydrolyzed protein derlved from beef collagen and characterized by having a zero Bloom gram gel strength, a 10% weight/weight water solution having a viscosity ra~ge of about 16-25 millipoises (mps)~ a pH
of 5.5-6.5, and in weight percent, a hydroxyproline content (mainly chemically combined hydroxyproline) of about 10-12~, a nitrogen content of about 15-18%, and a total nitrogen as amino nitrogen of about 5-12%, and a molecular weight of about 1,000 to about 3,000, such as about 2,000. Its ash content is generally low (e.g. below 10%). Other hydrolyzed prote1ns which may be used I include hydrolysis products comprising proteoses, peptones, and/or i~ 15 polypeptide8, typically having a molecular weight of at least about 600 and below about 12,000, preferably below about 5,000, and including moieties of a plurality of amino acids. mese hydrolysis products may be formed by partial enzymatic hydrolysis, such as by ~, the action of trypsin, erepsin or pancreatic enzymes on protein material (e.g. at about 35-50C. for about 12-48 hours). The partially degraded protein may also be a product obtained by partial hydrolysis of protein by heat and/or alkali. Proteins partlally ~l ~ degraded by heat may be prepared, for instance, by heatlng protein-,1 aceous material such as bones, feet, or skin of pork or beef which .~..
~`j 25 haæ been reduced to small pieces and immersed in water, by auto-''' 1 claving at about 2.8-3.5 kg/cm.2 of saturated steam (i.e. about 141.5-147.6C.) for about two hours; three phases includlng ~at, ~' the desired aqueous phase, and a residue may thus be obtalned; the ':''' !
~ -5-. . .
.
~,/,~ ., , ,.
,, .
aqueous phase which may contain about 8-10~ sollds may be con-centrat;ed in vacuo to about 50-60% solids at 60-71C. to obtain a "solubilized collagen," a heat degraded protein, which may be employed in this invention. Typical proteins which may be partially hydrolyzed for use in accordance with this invention include casein, gelatin, collagen, albumin, zein, gliadin, keratin, fibroin, globulin, glutenin, etc. Typical commercial partially enzymatically hydrolyzed protein~ include Bacto-Proteose (sold by Difco Laboratories, Detroit, Mich.), proteous-peptone, casein-peptone, gelatin-peptone, 10 Bacto-Peptone~sold by Difco Laboratories), vegetable peptones~ -~A such as ~ peptone, Proto-Peptone~ sold by Wilson Co., the peptone enzymatically derived from solubilized collagen using ground frozen pancreatic enzymes having a pH of 8. digestion being at about 49 C. for about 12-48 hours, the solubilized collagen being derived by heating bones, feet or skin of pork or beef). The preferred protein8 are solubilized beef collagen and solubilized pork collagen which may be prepared as described and are;generally characterized by a gel strength of about zero Bloom grams.
The partially hydrolyzed protein may have a relatively broad spectrum of molecular weights and may contain some (usually small amounts) of almost completely degraded polypeptides, such as dipeptides and tripeptides and even some amino acids as a result of the degradation process. If desired, these may be removed by dialysis, e.g., by placing the partially degraded protein in a cellophane bag which i~ then closed at both ends and is lowered into a tank into which deionized water continuously enters and from ~ Q~
1082s60 which it contlnuously exlts, products such as the tripeptides, dipeptides, and amino acids pass out of the cellophane by dialysis to mix wlth the deionized water and leave the partially degraded protein. When employed, the dialysis procedure has the additional advantage of removing the odors of the more completely hydrolyzed material The proportion of protein ingredient in the tollet bar ls generally about 0.1~ and below about 10%. Amounts in the range of about 1~ to about 5~ are preferred with a level of about 3~
belng especlally preferred. For the preferred protein mate~ial the 1-5% range provides a hydroxyproline content oP about 0.1 to 0.5%, preferably about 0.3%.
; In addition to, or in place of the protein, super-fatting agents may be included. It is found that in the bars of this lnventlon acetylated lanolin (such as, Modu~a ~sold by American chalesterol; ~ee U.S. Patent No. 2,725,334) gives especially good results. Other superfatting agents are hydroxy~ated lanolin, (e.g.~, OH Lan sold by American Cholesterol), higher (C~O c~8~ fatty , .
acids such as stearic acid, coconut oil fatty acid, hlgher (C10-C20) fatty alcohols, petrolatumand the like. Amounts of superfatting : agents less than 10~ total are generally employed, preferably about 1%-5% e.g., 2~-3%
The bars may also contain a synthetic surfactant of high foaming characteristics in hard water, such as alkali metal - 25 salts of organic sulfuric reaction products having in thelr molecular st~ucture an alkyl radical of from about 8 to about 22 carbon atoms, e g., alkyl benzene sulfonates, coconut oil fatty acid monoglyceride t-~R~ ~ 7 , ~O~Z560 CC/o - C/~,) sulforlates and sulfates, alkali metal fatty acid (C10 C ~
isethionates, among others, present in small amounts in the bar.
A part;icularly preferred ester is sodium coco isethionate sold as Igepon AC-78 by the General Aniline and Film Corporatlon. The proportlon of synthetic surfactant is generally within the range of about 0.5~ to about 5~ and preferably about 1~ to about 3% e.g., about 2%. Preferably the weight ratio of synthetic urfactant to high molecular weight poly (ethylene ox~de) is in the range of about 2:1 to 1:2, such as about 1:1.
In addition to the components listed above, it will be understood that the clean6ing bar of the invention may contain other conventional additives in minor amounts including those usually found in such cleansing bars, such as fillers, perfumes, dyes, fungicides, humectants~ (e.g. 0 2 to 1% of glycerine) and bacterlcldes.
Toilet soap bars range in size from the relatlvely 6mall hotel slze (waighing about 20-30 grams) to the regular size (about 100 grams) to the bath size (about 150g) to the extra large size (about 200g). The bars of thls invention may be of such sizes, particularly in the range of about 100 to 200 grams. The soap may also be aerated, ln a manner well known in the art to give lower density (floating) soaps, ~uch as those having a speciflc gravity o~ about o.8.
Ihe lnvention i6 particularly suitable for the making of mllled and plodded toilet soap bars. Bars of thls type are, of course, well known in the art; see for instance the ; description thereof in U. S. Patent No. 3,179,596. Also see "Encyclopedia of Chemical Technology," ~olume 12, edlted by Kirk Trademark 1~)82560 and Othmer, pages 573-598 and "Industrial Oil and Fat Products,"
Alton E. Bailey, Second Edition, 1951, pages 365-386 and 840-865 Thu~ one may take a kettle soap, form it into dried chips (as described in the foregoing reference~) and blend it with the various ingredients before milling and plodding.
The moisture contents of the toilet bars of this invention are such as to provide a solid non-tacky toilet bar Preferably they are well below 30%. For a milled, plodded bar they are generally less than 20~, prererably in the range o~ about lO to 17%, æuch as about 13~.
Miiled plodded ~oap~ typically are made up of ~ine crystals of hydrated fatty acid salt. me high molecular weight poly (ethylene oxide) appears to have an afflnity for the moisture in the soap as shown by the experiment in Example I, but the phy81cal state of thi8 material in relation to the soap crystal6 18 not presently known.
Variou~ embodlments of the present lnvention will now be illustrated by re~erence to the following specific examples.
It is to be understood, however, that such examples are presented for purpose o~ lllustration only, and the present invention i8 in no way to be deemed as limited thereby.
EXAMPLE I
In this Example there are employed soap chips of various moisture contont~ (3~, 9~, 11%, 13~ and 15~). lOO grams of soap chip~ are placed in a 400 cc. beaker and 2% of poly (ethylene oxide powder) is added thereto and mixed (tumbled) therewith by hand with a l inch wlde spatula, for one minute. The poly (ethylene oxide) employed has a flne particle size as lndlcated by the preferable , _9_ .
particle ~ize as lndicated hereinabove. The contents of the beaker are then spread on black paper. The paper i8 inspected with t;he naked eye to see the amount of powder le~t thereon and the chips are inspected under a 30-power microscope. When the chips contaln 3 and 9~ moisture substantially none of the powder adhere thereto and the black paper has a distinct layer of white powder. When the chips containing 11% moisture are stirred (with the spatula) the chips on the paper cause a noticeable release of powder (e.g. about 40% of the total powder) onto the paper; under the microscope the powder particles are ~een to be distinct and resting on the surface of the soap chips and loosely adhering thereto. When the chips contain 13% moisture the powder is found to be more tightly held (e.g. about 20~ to 30% is released when the chip~ are stirred on the paper); under the microscope one can see di~tinct powder particles on the chips surfaces. When the chips contain 15~ moisture substantially none of the powder is released onto the paper; microscopic examination, almost immediately, shows substantlally no powder particles resting on the chip surfaces; the surfaces look substantially the same a~ if no powder had been added.
EXAMPLE II
A soap bar of the following compo~ition i8 prepared ;~ by adding the ingredients in the order listed, to a conventional soap amalgamator (while the blades thereof are moving) operating at room temperature.
- ~082S60 Component Weight Soap ch~ps (17 coco Na soap/83 tallow Na soap)l 88.50 50~ aqueous solution of stannic 5 chloride (a preservative) 0 15 Poly (ethylene oxide)2 2.00 Water 1.00 Titanium dioxide-powder (substantially moisture-free), 10 ~a pigment) o.60 Protein A-powder (containing up to about 6% moisture~ 3.oo Sodium coco isethlonate-powder (containing about 1-2% moisture)2.00 ~ 15 Glycerine o.50 ; Acetylated lanolin3 1.00 Perfume 1.25 '. 100.00 ~ 1 Moistùre iB about 11.5~; bar moi~ture 10.5~, measured i~ 20 by weight 108B at 105C.
2 Polyox WSR N-750 in the form of powder, of size such that less than about 5% by weight (e.g. 0.3~) is retained on a 20 mesh screen (U. S. Standard).
3 Modulan-added in molten state (temperature of about 120 F).
When added to the soap chip~ in the amalgamator, the individual particles of the homopolymer of ethylene oxide stick to the chips, especially when the water is then sprinkled onto the moving chips. The other ingredients are then added in the order indicated, while mixing is continued for a total of about 2 minutes.
At this time the mixture ls not clumped together, but is still flowable, in ~hip form.
~0~32560 The blend is then milled on a conventional five-roll soap mill to a thickness of about 0.05 to O.l~n the resulting milled ChipB having a temperature o~ about 34-370C. The chips are fed directly lnto a ~acketed soap plodder and extruded to form a continuous bar ("plodder bar"). The plodding is controlled in one run to produce a plodder bar whose core temperature measured directly a~ter extrusion i8 about 34-380c; in a second run the temperature is controlled to give a plodder bar core temperature of 40-43C. The plodder used is a Doelger-Kirsten eight inch double barrel Vacuum Plodder, Schwantes Design. The plodder bars are cut in conventional fashion to give units whose volumes are suitable for a toilet bar (e.g. about 140g for a bath size bar and about lOOg for a regular size bar) pressed in conventional metal soap-pressing dies to the flnal roundèd shape of the tollet bar.
The unlt8 mado ~rom the higher temperature plodder bars are more difflcult to press, without sticking to the die, but when the same plodder bar is cooled to about 380C., the pressing ls much better ~xamination and use of the bars ~how a smooth ~urface, similar to that of normal ~oap bars. They are hard, tough, and shiny, have a degree of slipperiness when wetted whlch ls especially pleasant to the user, give a lather whlch is creamy, pleasant, sllky and e~ective, have good resis~ance to sloughing in use despite a high moi~ture pickup, have long use lives and are flexible and tough even after much of the bar has been used up, provide a beneficial effect on the hands (e.g. reduce chapping and ~laking~ moi~turizing the skin, particularly for dry skins).
~.
;, `" 10~256 EXAMPLE III
Example II is repeated except that the sodium coco i~ethlonate i6 omltted from the formulation and the soap content i8 correspondi~g ly increased.
; 5 EXAMPLE IV
Example II is repeated except that the acetylated lanolin is omitted from the formulation and the soap content i8 correspondingly increased.
EXAMPLE V
Example II is repeated, except that the coco ~nd tallow i soap ratio i8 25/75, the soap chip~ have a higher molsture content ; (about 14~ moisture), there is no separate addition of water (and -- the bar moisture content is thus about 13%), and higher plodder - temperatures are used so as to produce a bar having a core temperature Of about 50 C. The bar Burface is then cooled (with cool air), and ' a film of presslne lubrlcant (e.g. an aqueous solution containing : 16~ NaCl and 25~ glycerol) is directly applied to the pressing dies i before each pressing operation.
I EXAMPLE VI
(a) Example II i8 repeated with the followlng formulation:
Component Weight Soap chlps (25 coco/75 tallow) 89.25 50~ aqueous solution of stannlc ~hloride0.15 50~ aqueous solutlon of cltric acid (to 25 react wlth any excess alkall) 0.25 Poly (ethylene oxide)l 2.00 ; Titanium dioxide o.60 - Protein A 3.00 !
~.
.,~ ' ',~ ;
Sodium coco isethionate 2.00 Hydroxylated lanolin 1.00 Glycerine o.50 Perfume 1.25 1~0.00 (1) Added as Polyox WSR N-750 (b) Example VI (a) is repeated except that the proportion of poly (ethylene oxide) is reduced to 1% and the oap A content is raised by 1~, Users prefer the product of ~*~e V
(c) Example VI (a) is repeated but a second poly (ethylene oxide), 0.5~ Polyox WSR-N-3000 (molecular weight 400,000), is also included and the soap content is correspondingly lowered to 88.75%.
EXAMPLE VII
~xample VI is repeated except that the sodium coco i~ethionate 16 omitted (the soap chips being increased to 91.25%) and the polyethylene oxide has an average molecular weight of ; about 400,000 (Polyox WSR-N-3000).
EXAMPLE VIII
A ~eries o~ soap bars are prepared as in Example II
having the following comp~sition:
Component Weight Soap (25 coco Na soap/75 Tallow Na soap) 88.9 25 Stearic acid 4.7 Poly (ethylene oxide) (Polyox WSR N-750) 1.8 ; Water 2.4 Titanium dioxide o.7 30 Perf~e 1.5 .....
' -14-. .
: 1()8Z560 The stearic acid is added to a hot kettle soap, in a crutcher, and the resulting blend is then drled and formed into soap chips having a moisture content of 10.6% (measured by weight 108s at 105C.). The other ingredients are added in the amalgamator in the order listed The moisture content o~ the bars is about 13%.
When these bars were evaluated by a handwashing panel against a commercial beauty soap, these bars were pre~erred in terms of over-all preference, lather, amount of lather, .: 10 creaminess and richn~ss of lather, and skin-feel. In contrast, when the same formulation, except for omission of poly (ethylene oxide) was similarly tested, the commercial beauty soap was pre~erred.
; . EXAMPLE IX
~ 1 Example VIII is boing repeated using (a) coconut oil fatty acids or (b) palm ~atty acids in place of the stearic :~ acid.
EXAMPLE X
; ~ Example II is repeated except that 0 25% of a 50%
aqueous solution of cltric acid is added, the sodium coco isethionate is omitted (the soap chips;belng increased to 91.25~) and the polyethylene oxide has a molecualr weight of about 400,000 (Polyox WSR-N-3000).
It will be apparent that many changes and modifications of the several ~eatures described herein may be made without departing from the spirit and scope o~ the invention. It is, therefore, apparent that the foregoing description is by way of illustration of the invention rather than limitation of the invention . .
When added to the soap chip~ in the amalgamator, the individual particles of the homopolymer of ethylene oxide stick to the chips, especially when the water is then sprinkled onto the moving chips. The other ingredients are then added in the order indicated, while mixing is continued for a total of about 2 minutes.
At this time the mixture ls not clumped together, but is still flowable, in ~hip form.
~0~32560 The blend is then milled on a conventional five-roll soap mill to a thickness of about 0.05 to O.l~n the resulting milled ChipB having a temperature o~ about 34-370C. The chips are fed directly lnto a ~acketed soap plodder and extruded to form a continuous bar ("plodder bar"). The plodding is controlled in one run to produce a plodder bar whose core temperature measured directly a~ter extrusion i8 about 34-380c; in a second run the temperature is controlled to give a plodder bar core temperature of 40-43C. The plodder used is a Doelger-Kirsten eight inch double barrel Vacuum Plodder, Schwantes Design. The plodder bars are cut in conventional fashion to give units whose volumes are suitable for a toilet bar (e.g. about 140g for a bath size bar and about lOOg for a regular size bar) pressed in conventional metal soap-pressing dies to the flnal roundèd shape of the tollet bar.
The unlt8 mado ~rom the higher temperature plodder bars are more difflcult to press, without sticking to the die, but when the same plodder bar is cooled to about 380C., the pressing ls much better ~xamination and use of the bars ~how a smooth ~urface, similar to that of normal ~oap bars. They are hard, tough, and shiny, have a degree of slipperiness when wetted whlch ls especially pleasant to the user, give a lather whlch is creamy, pleasant, sllky and e~ective, have good resis~ance to sloughing in use despite a high moi~ture pickup, have long use lives and are flexible and tough even after much of the bar has been used up, provide a beneficial effect on the hands (e.g. reduce chapping and ~laking~ moi~turizing the skin, particularly for dry skins).
~.
;, `" 10~256 EXAMPLE III
Example II is repeated except that the sodium coco i~ethlonate i6 omltted from the formulation and the soap content i8 correspondi~g ly increased.
; 5 EXAMPLE IV
Example II is repeated except that the acetylated lanolin is omitted from the formulation and the soap content i8 correspondingly increased.
EXAMPLE V
Example II is repeated, except that the coco ~nd tallow i soap ratio i8 25/75, the soap chip~ have a higher molsture content ; (about 14~ moisture), there is no separate addition of water (and -- the bar moisture content is thus about 13%), and higher plodder - temperatures are used so as to produce a bar having a core temperature Of about 50 C. The bar Burface is then cooled (with cool air), and ' a film of presslne lubrlcant (e.g. an aqueous solution containing : 16~ NaCl and 25~ glycerol) is directly applied to the pressing dies i before each pressing operation.
I EXAMPLE VI
(a) Example II i8 repeated with the followlng formulation:
Component Weight Soap chlps (25 coco/75 tallow) 89.25 50~ aqueous solution of stannlc ~hloride0.15 50~ aqueous solutlon of cltric acid (to 25 react wlth any excess alkall) 0.25 Poly (ethylene oxide)l 2.00 ; Titanium dioxide o.60 - Protein A 3.00 !
~.
.,~ ' ',~ ;
Sodium coco isethionate 2.00 Hydroxylated lanolin 1.00 Glycerine o.50 Perfume 1.25 1~0.00 (1) Added as Polyox WSR N-750 (b) Example VI (a) is repeated except that the proportion of poly (ethylene oxide) is reduced to 1% and the oap A content is raised by 1~, Users prefer the product of ~*~e V
(c) Example VI (a) is repeated but a second poly (ethylene oxide), 0.5~ Polyox WSR-N-3000 (molecular weight 400,000), is also included and the soap content is correspondingly lowered to 88.75%.
EXAMPLE VII
~xample VI is repeated except that the sodium coco i~ethionate 16 omitted (the soap chips being increased to 91.25%) and the polyethylene oxide has an average molecular weight of ; about 400,000 (Polyox WSR-N-3000).
EXAMPLE VIII
A ~eries o~ soap bars are prepared as in Example II
having the following comp~sition:
Component Weight Soap (25 coco Na soap/75 Tallow Na soap) 88.9 25 Stearic acid 4.7 Poly (ethylene oxide) (Polyox WSR N-750) 1.8 ; Water 2.4 Titanium dioxide o.7 30 Perf~e 1.5 .....
' -14-. .
: 1()8Z560 The stearic acid is added to a hot kettle soap, in a crutcher, and the resulting blend is then drled and formed into soap chips having a moisture content of 10.6% (measured by weight 108s at 105C.). The other ingredients are added in the amalgamator in the order listed The moisture content o~ the bars is about 13%.
When these bars were evaluated by a handwashing panel against a commercial beauty soap, these bars were pre~erred in terms of over-all preference, lather, amount of lather, .: 10 creaminess and richn~ss of lather, and skin-feel. In contrast, when the same formulation, except for omission of poly (ethylene oxide) was similarly tested, the commercial beauty soap was pre~erred.
; . EXAMPLE IX
~ 1 Example VIII is boing repeated using (a) coconut oil fatty acids or (b) palm ~atty acids in place of the stearic :~ acid.
EXAMPLE X
; ~ Example II is repeated except that 0 25% of a 50%
aqueous solution of cltric acid is added, the sodium coco isethionate is omitted (the soap chips;belng increased to 91.25~) and the polyethylene oxide has a molecualr weight of about 400,000 (Polyox WSR-N-3000).
It will be apparent that many changes and modifications of the several ~eatures described herein may be made without departing from the spirit and scope o~ the invention. It is, therefore, apparent that the foregoing description is by way of illustration of the invention rather than limitation of the invention . .
Claims (7)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Process for preparing toilet soap bars containing, approximately by weight, at least 60% of soap and between 0.5 and 10% of poly(ethylene oxide) having an average molecular weight of at least about 100,000 which comprises forming a first mixture of said soap in the form of chips and said poly(ethylene oxide) in the form of powder, said first mixture containing at least about 11% of moisture by weight of said chips whereby the surfaces of said soap chips are in powder-adherent condition with respect to said poly (ethylene oxide) powder, to produce soap chips having poly(ethylene oxide) bonded thereto, then mixing other conventional soap bar ingredients with said bonded chips to form a second mixture, then forming said second mixture into a soap bar.
2. Process as in claim 1 wherein the moisture content of the soap chips is at least about 11% by weight.
3. Process as in claim 1 wherein the moisture content of the soap chips is less than about 11% by weight and sufficient water is added to said first mixture to provide said powder-adherent condition.
4. Process as in claim 1, 2 or 3 wherein said other ingredients con-tain only about 0.5 to 5% of synthetic surfactant by weight of the bar.
5. Process as in claim 1, 2 or 3 wherein the other ingredients are selected from the group consisting of hydrolyzed protein, superfatting agent and a synthetic surfactant of high foaming characteristics and mixtures there-of.
6. A toilet soap bar containing by weight about 0.5 to 10% of poly (ethylene oxide) having a molecular weight of at least 100,000 and at least 60% of soap, said bar being substantially free of visible specks caused by said poly(ethylene oxide).
7. A soap bar as in claim 6 wherein the poly(ethylene oxide) has a molecular weight of about 300,000 to about 400,000.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US69307676A | 1976-06-04 | 1976-06-04 | |
| US693,076 | 1976-06-04 |
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| CA1082560A true CA1082560A (en) | 1980-07-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA279,844A Expired CA1082560A (en) | 1976-06-04 | 1977-06-03 | Process for making a toilet bar |
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| US (1) | US4148743A (en) |
| JP (1) | JPS52148509A (en) |
| AT (1) | AT364059B (en) |
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| CA (1) | CA1082560A (en) |
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| ZA (1) | ZA773077B (en) |
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|---|---|---|---|---|
| SE439646B (en) * | 1977-07-15 | 1985-06-24 | Colgate Palmolive Co | COMPOSITION FOR THE PREPARATION OF TOILET SOAPS IN PIECE AND PROCEDURE FOR PREPARING THE COMPOSITION |
| IT1165608B (en) * | 1978-01-19 | 1987-04-22 | Unilever Nv | DETERGENT BAR, PARTICULARLY FOR PERSONAL WASHING |
| US4231904A (en) * | 1978-03-01 | 1980-11-04 | Lever Brothers Company | Detergent bars with improved properties |
| JPS55133496A (en) * | 1979-02-06 | 1980-10-17 | Procter & Gamble | Soap |
| US4285826A (en) * | 1980-04-14 | 1981-08-25 | Armour-Dial, Inc. | Toilet soap bars imparting improved moisturing and skin feel characteristics |
| US4310434A (en) * | 1980-05-28 | 1982-01-12 | The Procter & Gamble Company | Poly(ethylene oxide) compositions with controlled solubility characteristics |
| US4396522A (en) * | 1981-05-13 | 1983-08-02 | The Proctor & Gamble Company | Polyethylene oxide cake with reduced gelling for flush toilet wastewater sanitation |
| JPS58206699A (en) * | 1982-05-25 | 1983-12-01 | 株式会社資生堂 | Framed soap |
| US4582626A (en) * | 1982-06-04 | 1986-04-15 | Ferrara Peter J | Soap compositions and process with emollients, bath oils and polymeric ethylene oxide slip agents |
| GB2138438B (en) * | 1983-04-20 | 1986-11-05 | George Herman Michel | Shaving composition |
| US5028353A (en) * | 1988-10-07 | 1991-07-02 | Colgate-Palmolive Company | Process of preparing a combination detergent and soap bar with enhanced mildness |
| US5560859A (en) * | 1989-07-26 | 1996-10-01 | Pfizer Inc. | Post foaming gel shaving composition |
| US4992266A (en) * | 1989-08-14 | 1991-02-12 | S. C. Johnson & Son, Inc. | Reducing the ocular irritancy of anionic shampoos |
| GB9313859D0 (en) * | 1993-07-05 | 1993-08-18 | Unilever Plc | Improvements relating to soap bars |
| US6251843B1 (en) | 1994-03-15 | 2001-06-26 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Synthetic detergent bar and manufacture thereof |
| WO1995030737A2 (en) * | 1994-05-10 | 1995-11-16 | The Procter & Gamble Company | Personal cleansing soap-synthetic bar compositions with low levels of nonionic, polyethylene/polypropylene glycol polymers for improved mildness |
| DE69614706T2 (en) * | 1995-10-16 | 2003-05-15 | Procter & Gamble | HAIR CARE SHAMPOO CONTAINING POLYALKYLENE GLYCOL |
| KR100292708B1 (en) * | 1995-10-16 | 2001-10-26 | 데이비드 엠 모이어 | Conditioning Shampoo Composition |
| ATE214591T1 (en) * | 1995-10-16 | 2002-04-15 | Procter & Gamble | CONDITIONING SHAMPOO COMPOSITIONS WITH IMPROVED STABILITY |
| US6200554B1 (en) | 1996-10-16 | 2001-03-13 | The Procter & Gamble Company | Conditioning shampoo compositions having improved silicone deposition |
| IN189608B (en) * | 1997-03-21 | 2003-03-29 | Lever Hindustan Ltd | |
| EP1891935A1 (en) * | 2006-08-14 | 2008-02-27 | Cognis IP Management GmbH | Emulsion concentrate |
| JP5509958B2 (en) * | 2010-03-18 | 2014-06-04 | 日油株式会社 | Solid soap composition |
| MX2021003171A (en) * | 2018-09-24 | 2021-05-14 | Colgate Palmolive Co | Solid cleansing compostions and methods for the same. |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH281601A (en) * | 1950-03-13 | 1952-03-15 | Ignaz Dr Reichstein | Soap-free body cleanser. |
| NL220670A (en) * | 1956-09-11 | |||
| US2999068A (en) * | 1959-04-27 | 1961-09-05 | Procter & Gamble | Personal use detergent lotion |
| US3248333A (en) * | 1963-04-03 | 1966-04-26 | Hewitt Soap Co Inc | Low ph detergent bar |
| CA807629A (en) * | 1966-06-30 | 1969-03-04 | Eigen Edward | Lotion and detergent compositions |
| US3598746A (en) * | 1969-05-09 | 1971-08-10 | Armour Dial Inc | Cosmetic soap bar |
| US3676538A (en) * | 1970-02-04 | 1972-07-11 | Purex Corp Ltd | Method for soap bars having marble-like decoration |
| US3726815A (en) * | 1970-11-16 | 1973-04-10 | Colgate Palmolive Co | Compositions containing amino-polyureylene resin |
| AU464487B2 (en) * | 1971-06-16 | 1975-08-11 | Colgate-Palmolive Pty. Ltd. | Light duty detergent formulations |
| US3941722A (en) * | 1974-05-06 | 1976-03-02 | Chattem Drug & Chemical Company | Bath beads containing allantoin |
| DE2427986C2 (en) * | 1974-06-10 | 1982-10-28 | Henkel KGaA, 4000 Düsseldorf | Bar detergents with improved tear resistance |
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1977
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- 1977-05-23 AU AU25408/77A patent/AU512803B2/en not_active Expired
- 1977-05-23 NZ NZ184181A patent/NZ184181A/en unknown
- 1977-05-25 SE SE7706115A patent/SE430259B/en not_active IP Right Cessation
- 1977-05-27 GB GB22528/77A patent/GB1566810A/en not_active Expired
- 1977-05-31 DE DE19772724549 patent/DE2724549A1/en not_active Withdrawn
- 1977-06-02 AT AT0389777A patent/AT364059B/en not_active IP Right Cessation
- 1977-06-03 CA CA279,844A patent/CA1082560A/en not_active Expired
- 1977-06-03 CH CH688577A patent/CH626400A5/de not_active IP Right Cessation
- 1977-06-03 FR FR7717096A patent/FR2353636A1/en active Granted
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- 1977-06-03 NO NO77771953A patent/NO150685C/en unknown
- 1977-06-03 JP JP6567077A patent/JPS52148509A/en active Granted
- 1977-06-03 DK DK246177A patent/DK246177A/en not_active Application Discontinuation
- 1977-06-03 IE IE1156/77A patent/IE45629B1/en unknown
- 1977-12-06 US US05/858,044 patent/US4148743A/en not_active Expired - Lifetime
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1983
- 1983-12-30 MY MY78/83A patent/MY8300078A/en unknown
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| FR2353636B1 (en) | 1982-02-05 |
| ZA773077B (en) | 1979-01-31 |
| ATA389777A (en) | 1981-02-15 |
| NO150685B (en) | 1984-08-20 |
| NO771953L (en) | 1977-12-06 |
| GB1566810A (en) | 1980-05-08 |
| MY8300078A (en) | 1983-12-31 |
| BE855376A (en) | 1977-10-03 |
| IE45629L (en) | 1977-12-04 |
| AU512803B2 (en) | 1980-10-30 |
| US4148743A (en) | 1979-04-10 |
| AT364059B (en) | 1981-09-25 |
| IE45629B1 (en) | 1982-10-20 |
| FR2353636A1 (en) | 1977-12-30 |
| NO150685C (en) | 1984-12-05 |
| NZ184181A (en) | 1979-10-25 |
| AU2540877A (en) | 1978-11-30 |
| JPS6119680B2 (en) | 1986-05-19 |
| SE7706115L (en) | 1977-12-05 |
| JPS52148509A (en) | 1977-12-09 |
| SE430259B (en) | 1983-10-31 |
| CH626400A5 (en) | 1981-11-13 |
| DE2724549A1 (en) | 1977-12-15 |
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