IE920906A1 - Mild personal cleansing bars with improved processability - Google Patents
Mild personal cleansing bars with improved processabilityInfo
- Publication number
- IE920906A1 IE920906A1 IE090692A IE920906A IE920906A1 IE 920906 A1 IE920906 A1 IE 920906A1 IE 090692 A IE090692 A IE 090692A IE 920906 A IE920906 A IE 920906A IE 920906 A1 IE920906 A1 IE 920906A1
- Authority
- IE
- Ireland
- Prior art keywords
- bar
- alkyl
- isethionate
- mild
- lathering
- Prior art date
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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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/006—Detergents in the form of bars or tablets containing mainly surfactants, but no builders, e.g. syndet bar
-
- 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
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
- C11D10/042—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active compounds and soap
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates thereof
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/126—Acylisethionates
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/16—Sulfonic acids or sulfuric acid esters; Salts thereof derived from divalent or polyvalent alcohols
Landscapes
- 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)
- Brushes (AREA)
Abstract
This invention is an improved mild personal cleansing syndet bar comprising: long chain alkyl sulfate having essentially saturated C15-C22, preferably C16-C18, alkyl chains, more preferably cetearyl sulfate, a high lathering, mild synthetic surfactants comprising C12-C14 alkyl isethionate, soap, fatty acids, and paraffin wax, preferably a high melting point paraffin wax. The bar has good processability, improved smears, and good in-use properties without meaningful lather negatives.
Description
TECHNICAL FIELD
This invention relates to personal cleansing bars based on synthetic surfactants and to processes of making them.
BACKGROUND OF THE INVENTION
Soap, since its appearance in history, has helped safeguard two of our greatest treasures: our health and our children. Health is directly related to cleanliness. Data proves that the higher the consumption of soap in a country, the lower will be the infant mortality rate.
in industrialized countries, soap is the most-taken-forgranted and readily available personal care product used on our body daily. Soap is also the most inexpensive product we use in relation to its per use cost. In many less fortunate countries both laundry and toilet soaps are still scarce, expensive essentials. . . .
Soap is most probably the oldest of toiletries, and, in spite of being readily available in most parts of the world, it is still scarce in many countries. The oldest literary reference to soap relates to the washing of wool and is found in clay Sumerian tablets dating about 2500 B.C.E. Sumerian was a language spoken in the area of the Tigris and Euphrates rivers, now Southern Iraq. The patriarch Abraham and his family came from Sumer. Another Sumerian tablet, dating 2200 B.C.E. gives the formula consisting of water, alkali and cassia oil.
Cleanliness is essential to our well being. A clean body, clean bath, clean home, and clean environment are the norm today.
(Soap Technology for the 1990's. L. Spitz et al., American Oil
- 2 Chemists' Society, Champaign, Illinois, pp. 1-2) This reference discusses syndet and combo bars, particularly on pp. 209-229.
Synthetic surfactant-based personal cleansing bars have attracted much interest recently because they can be selected to be milder to the skin than soap-based products. This mildness, however, comes with negatives to both the manufacturer and the consumer. The bar soap manufacturer experiences difficult processability due to the sticky nature of such products, as well as high raw material costs. The consumer experiences the negative performance properties of poor lather, messy smear, bar softness, and, consequently, high wear rates.
The use of paraffin wax in synthetic surfactant-based bars, per se, is known. However, the known bars suffer from a combination of harshness and/or lather deficiencies. E.g., U.S. Pat. No. 2,653,913, van Dijck et al., issued Sept. 29, 1953, discloses bars comprising 80% synthetic anionic surfactant (selected from sodium secondary or primary alkyl sulfates or sodium dodecylbenzene sulfonate), 18% paraffin, melting point (M.P.) 140-150’F, and 2% sodium alginate. The surfactants employed are non-mild surfactants.
U.S. Pat. No. 2,734,870, Lewis, issued Feb. 14, 1956, discloses bars comprising 40-60% paraffin (M.P. >125’F), 2-5% fatty acid, and 60-40% sodium alkyl aryl sulfonate. The high level of paraffin ih these bars results in unacceptably low lather.
U.S. Pat. No. 3,129,187, Meehan, issued Apr. 14, 1964, discloses bars comprising 50-75% sodium alkylbenzene sulfonate, 5-35% stearyl alcohol, 1-25% paraffin (M.P. 125-170’F), and 2-25% stearyl MEA. The harsh surfactants employed would result in harsh products.
U.S. Pat. No. 4,151,105, O'Roark, issued Apr. 24, 1979, discloses bars comprising 20-40% synthetic anionic surfactant (composed of sodium cocoyl isethionate and/or sodium lauryl sulfoacetate), 10-30% paraffin (M.P. 130-140‘F), 5-15% powdered starch, 10-30% dextrin and 5% fatty acid. The low melting point of the wax employed would cause a substantial soil load on the lather potential and result in poor lather volumes.
!E 920906
- 3 U.S. Pat. No. 4,335,025, Barker et al., issued June 15, 1982, discloses a process for making syndet bars containing a waxy extender.
OBJECTS OF THE INVENTION
One object of this invention is to provide a personal cleansing syndet bar composition which exhibits improved lather and reduced bar messiness, while not sacrificing the processability of the syndet bar.
SUMMARY OF THE INVENTION
This invention relates to an improved processable, mild personal cleansing syndet bar comprising: at least about 10% by weight long chain (45-C22 alkyl sulfate having essentially saturated, preferably C16-C18, alkyl chains, soap, free fatty acid, a lathering mild surfactant comprising C12-C14 alkyl isethionate, and a selected paraffin wax. The bar has improved bar messiness without a meaningful lather negative.
DETAILED DESCRIPTION OF THE INVENTION A mild synthetic surfactant-based (syndet) bar with improved processability, good lather and/or reduced messiness (smear) is indeed an advance in this art. The present invention provides such an improved syndet bar comprising: (1) from about 10% to about 40%, preferably from about 15% to about 35%, of C15-C22» preferably Οιθ-Οιβ, essentially saturated long chain alkyl sulfates; (2) from about 15% to about 40%, preferably from about 18% to about 35%, of mild, high lathering, synthetic surfactants with at least about 10% by weight of the bar being (42-(44 alkyl isethionate; (3) from about 8% to about 25%, preferably from about 10% to about 20%, of C1Q-C22» preferably C12-C18, essentially saturated fatty acids; (4) from about 2% to about 15%, preferably from about 3% to about 12%, C10-C22, preferably C12-C18, alkali metal soaps, preferably sodium or potassium soaps; (5) from about 10% to about 40%, preferably from about 13% to about 35%, paraffin wax with an average melting point of from about 130’F to about 180’F, preferably from about 140*F to about 165‘F, more preferably from about 142‘F to about 160‘F; (6) from 0% to about 10% auxiliary plastic binders such as polyethylene glycols and/or monoglyceride; and (7) from about 1.5% to about 10%, preferably
- 4 from about 2% to about 8%, more preferably from about 2% to about
%, water.
While not being bound to any theory, it is advantageous to think of a synbar as comprising two separate components: the matrix and the actives. The matrix provides the physical characteristics (processability and bar messiness) while the actives provide lathering and mild properties. The matrix, if not chosen correctly, can impede lather generation, cause poor bar feel, increase or decrease wear rate beyond an acceptable level, and/or reduce product mildness. Likewise, the actives must be chosen so as to provide acceptable levels of lathering without negatively impacting mildness, a trade-off in formulations.
Bars with improved processability comprising long chain alkyl sulfate and selected binders are described in commonly assigned, copending U.S. Patent Applications: Ser. No. 07/605,614, J.R. Schwartz, W.E. Eccard, T.A. Bakken, and L.A. Gilbert, filed Oct. 30, 1990; and Ser. No. 07/647,030, J.R. Schwartz, W.E. Eccard, T.A. Bakken, and L.A. Gilbert, filed Jan. 28, 1991, incorporated herein by reference. The present compositions yield bars having even better product performance in the areas of lather and/or bar messiness than those specifically exemplified in those patent applications.
It will be appreciated that the development of an appropriate bar matrix is a delicate balancing act between plasticity and brittleness while not compromising lather performance. Typical bar matrix plasticizer materials such as triglycerides, fatty alcohols, etc., which tend to form a sufficiently plastic matrix, but also tend to depress lather potential. Other commonly used additive matrix materials such as salts, polysaccharides, etc., tend to make an overly brittle and water-soluble matrix that induces poor bar messiness performance.
The terms synthetic bar, also syndet bar, as used herein mean that the bar has more synthetic surfactant than soap unless otherwise specified. The term AS syndet bar means a syndet bar containing alkyl sulfate surfactant or its equivalent, unless otherwise specified. The term long chain means C15 and C22, preferably C16-C20» and mixtures thereof. The terms C12-C14
- 5 alkyl and cocoyl as used herein are synonymous.
The percentages, ratios, and parts herein are on a total composition weight basis, unless otherwise specified. All levels and ranges herein are approximations unless otherwise specified.
An essential element of the present invention is the surfactant system. The long chain alkyl sulfate (hereinafter including its long chain equivalent synthetic surfactants) is key and is defined herein, as comprising C16-C18 alkyl chains at a level of at least about 90%, preferably about 93%, and more preferably about 97%. The long chain alkyl sulfate (and its equivalents) is derived from corresponding saturated straight chain alcohols. The preferred alkyl sulfate has a ratio of C16-C19 alkyl chains in the range of from about 100% Cjg to about 100% Cjs by weight. A commercially available Ci6-Cl8 alkyl sulfate is SIPON® EC-111 (formerly SIPEX® EC-111), sodium cetearyl sulfate, which is approximately 60% C}6 and 36% Cjs· SIPON® EC-111 is sold by Alcolac Company, Baltimore, MD 21226. Another source is Henkel Corp., Ambler, PA 19002. Henkel's sodium cetearyl sulfate, LANETTE E, is an estimated 50-50% Cig-Cjs alkyl sulfate sold as an emulsifier.
Other long chain surfactants which are equivalents to the long chain alkyl sulfate (mostly insoluble) could serve as either full or partial replacements for the long chain alkyl sulfate. Examples include long chain isethionates, sarcosinates, glyceryl ether sulfonates, etc. The acyl esters of isethionic acid salts, with esters of C15.-C18 acyl isethionates and no more than 25% or lower C14 acyl groups are also useful. Preferred is stearoyl isethioniate with (44 3%; Cje 50%; and Cjs 47%.
It is noted that surfactant mildness can be measured by a skin barrier destruction test which is used to assess the irritancy potential of surfactants. In this test the milder the surfactant, the lesser the skin barrier is destroyed. Skin barrier destruction is measured by the relative amount of radiolabeled water (3H-H2O) which passes from the test solution through the skin epidermis into the physiological buffer contained in the diffusate chamber. This test is described by T.J. Franz in the
J, Invest. Dermatol., 1975, 64, pp. 190-195; and in U.S. Pat. No.
- 6 4,673,525, Small et al., issued June 16, 1987, incorporated herein by reference, and which disclose a mild alkyl glyceryl ether sulfonate (AGS) surfactant based synbar comprising a standard alkyl glyceryl ether sulfonate mixture. Barrier destruction testing surprisingly shows that the long chain alkyl sulfates are milder than standard AGS. The long chain alkyl sulfate preferably comprises 15-40% by weight of the bars of this invention.
The present invention contains a mild lathering surfactant at a level of from about 15% to about 40%, preferably from about 18% to about 35%. Examples of a high lathering or lather enhancing surfactant, especially milder ones, are: C12-C14 alkyl isethionate; sodium lauroyl sarcosinate, C12-C14 alkyl glyceryl ether sulfonate. A high lathering surfactant as defined herein, is one which lathers better than the long chain C16-C18 alkyl sulfate. A mild surfactant as defined herein is one that is milder than sodium dodecyl sulfate.
Numerous examples of surfactants in general are disclosed in the patents incorporated herein by reference. They include limited amounts of anionic acyl sarcosinates, methyl acyl taur20 ates, N-acyl glutamates, acyl isethionates, alkyl sulfosuccinates, alkyl phosphate esters, ethoxylated alkyl phosphate esters, trideceth sulfates, protein condensates, mixtures of ethoxylated alkyl sulfates and alkyl amine oxides, betaines, sultaines, and mixtures thereof. Included in the surfactants are the alkyl ether sulfates with 1 to 12 ethoxy groups, especially ammonium and sodium lauryl ether sulfates. Alkyl chains for these other surfactants are C8'C22» preferably Ci0“c18- Alkyl glycosides and methyl glucose esters are preferred mild nonionics which may be mixed with other mild anionic or amphoteric surfactants in the compositions of this invention.
The bars of this invention can have up to about 10% of high lathering, non-mild or shorter chain or traditional (coconut) alkyl sulfates and still maintain the mildness requirement of the bar.
A preferred syndet bar contains a mixture of C12-C14 alkyl isethionate (SCI) and sodium lauroyl sarcosinate in a ratio of from about 1:1 to about 3:1, preferably from about 1.5:1 to about
- 7 2.5:1.
The primary plastic binders of the present invention are: (1) free fatty acid and (2) paraffin wax.
The fatty acid material which is desirably incorporated into 5 the present invention includes material ranging in hydrocarbon chain length of from abut 10 to about 22, essentially saturated. These fatty acids may be highly purified individual chain lengths and/or crude mixtures such as those derived from fats and oils. The preferred composition is lauric and stearic acids in a ratio of from about 1:3 to about 3:1, more preferably from about 1:2 to about 2.5:1.
The composition may include soaps derived from hydrocarbon chain lengths of from about 10 to about 22, essentially saturated. It is preferred that the soap be the sodium salt, but other soluble soap can be used. Potassium, ammonium, triethanol ammonium, and mixtures thereof, are deemed acceptable. The soaps are preferably prepared by the in situ saponification of the corresponding fatty acids, but they may also be introduced as preformed soaps.
Insoluble soaps, e.g., magnesium and zinc soaps, are not included in the 2-15% level of soap in the composition definition. However, insoluble soaps can be used as non-lathering, non-soil-load diluents.
An important component of this invention is a wax having a melting point (M.P.) of from about 130’F to about 180’F (54’82’C), preferably From about 140’F to about 165’F (6O’-74‘C), and most preferably from about 142*F to about 160’F (61’-71’C). A preferred paraffin wax is a fully refined petroleum wax which is odorless and tasteless and meets FDA requirements for use as coatings for food and food packages. Such paraffins are readily available commercially. A very suitable paraffin can be obtained, for example, from The National Wax Co. under the trade name 6975.
The paraffin preferably is present in the bar in an amount ranging from about 10% to about 40% by weight. The paraffin ingredient is used in the product to impart skin mildness, plasticity, firmness, and processability. It also provides a glossy look and smooth feel to the bar.
• 8 The paraffin ingredient is optionally supplemented by a microcrystalline wax. A suitable microcrystalline wax has a melting point ranging, for example, from about 140’F (60°C) to about 185eF (85*C), preferably from about 145’F (62’C) to about
175F (79’C). The wax preferably should meet the FDA requirements for food grade microcrystalline waxes. A very suitable microcrystalline wax is obtained from Witco Chemical Company under the trade name Multiwax X-145A. The microcrystalline wax preferably is present in the bar in an amount ranging from about 0.5% to about 5% by weight. The microcrystalline wax ingredient imparts pliability to the bar at room temperatures.
Auxiliary plastic binders may be incorporated into the bar at levels of from 0% to about 10%. These binders may be selected from monoglycerides, polyethylene glycols, fatty alcohols, sugars, tallow alcohol ethoxylates, and mixtures thereof. Other plastic binders are identified in the published literature, such as J. Amer. Oil Chem. Soc. 1982, 59, 442. The binder system can contain several plasticizers.
The syndet bar of this invention may comprise 0% to about 5% of a suitably fast hydrating cationic polymer. The polymers have molecular weights of from about 1000 to about 3,000,000.
The cationic polymer (skin conditioning agent) is selected from the group consisting of:
(I) cationic polysaccharides; 25 (Π) cationic copolymers of saccharides and synthetic 30 (HI) cationic monomers, and synthetic polymers selected from the group consisting of: (A) cationic polyakylene imines (B) cationic ethoxy polyalkylene imines, and (C) cationic poly[N-[-3-(dimethylammonio)propyl]-N'-[3
(ethyleneoxyethylene dimethylammonio)propyl]urea dichloride].
Specific examples of members of the cationic polysaccharide class include the cationic hydroxyethy] cellulose JR 400 made by
Union Carbide Corporation; the cationic starches Stalok® 100, 200,
300 and 400 made by Staley, Inc.; the cationic galactomannans
- 9 920906 based on guar gum of the Galactasol 800 series by Henkel, Inc., and the Jaguar series by Celanese Corporation.
Examples of members of the class of copolymers of saccharides and synthetic cationic monomers include those composed of cel5 lulose derivatives (e.g., hydroxyethyl cellulose) and N,N-diallyl,Ν-Ν-dialkyl ammonium chloride available from National Starch Corporation under the trade name Celquat.
The cationic synthetic polymers useful in the present invention are cationic polyalkylene imines, ethoxypolyalkylene imines, and poly[N-[-3-(dimethylammonio)propyl]-N'-[3-(ethyleneoxyethylene dimethylammonio)propyl]urea dichloride] the latter of which is available from Miranol Chemical Company, Inc., under the trademark of Miranol A-15, CAS Reg. No. 68555-36-2.
Preferred cationic polymeric skin conditioning agents of the present invention are those cationic polysaccharides of the cationic guar gum class with molecular weights of 1,000 to 3,000,000. More preferred molecular weights are from 2,500 to 350,000. These polymers have a polysaccharide backbone comprised of galactomannan units and a degree of cationic substitution ranging from about 0.04 per anhydroglucose unit to about 0.80 per anhydroglucose unit with the substituent cationic group being the adduct of 2,3-epoxypropyltrimethyl ammonium chloride to the natural polysaccharide backbone. Examples are JAGUAR C-I4-S, C-15 and C-17 sold by Celanese Corporation. In order to achieve the benefits described in this invention, the polymer must have characteristics, either structural or physical which allow it to be suitably and fully hydrated and subsequently well incorporated into the soap matrix.
Other ingredients of the present invention are selected for the various applications. E.g., perfumes can be used in formulating the skin cleansing products, generally at a level of from about 0.1% to about 1.5% of the composition. Alcohols, hydrotropes, colorants, and fillers such as talc, clay, calcium carbonate and dextrin can also be used. Cetearyl alcohol is a mixture of cetyl and stearyl alcohols. Preservatives, e.g., sodium ethylenediaminetetraacetate (EDTA), generally at a level of less than 1% of the composition, can be incorporated in the
cleansing products to prevent color and odor degradation. Antibacterials can also be incorporated, usually at levels up to 1.5%. The following patents disclose or refer to such ingredients and formulations which can be used in the soap/synbars of this inven- 5 tion, and are incorporated herein by reference: Pat. No. Issue Date Inventor(s) 4,234,464 11/1980 Morshauser 4,061,602 12/1977 Oberstar et al. 4,472,297 9/1984 Bolich et al. 10 4,491,539 1/1985 Hoskins et al. 4,540,507 9/1985 Grollier 4,673,525 6/1987 Small et al. 4,704,224 11/1987 Saud 4,812,253 3/1989 Small et al. 15 4,820,447 4/1989 Medcalf et al. 4,954,282 9/1990 Rys et al. The syndet bars of this invention have a pH of from 4 to 9 in a 1% aqueous solution. The preferred pH is from 5 to 8, more 20 preferably about 6.5 to 7.5. Matrix Ratio Table
A matrix of ratios and key ingredients of the present invention is provided in following table. The Matrix Ratio Table shows the broad, preferred and more preferred levels and ratios of the several key ingredients. E.g., the bars of the present invention can have long chain alkyl sulfate at a level of 10-40% by weight of the bar and lathering mild synthetic surfactant at a level of 15-40% by weight of the bar. Their broad and preferred ratio ranges are, respectively, 2.5:1-0.3:1 and 2:1-0.4:1. Their more preferred and exemplified ratios are found in Examples 6 and 7 and are, respectively, 0.6:1/0.5:1. Another example of a reading of the Matrix Ratio Table is the lathering mild synthetic surfactant and paraffin which, respectively, have broad and preferred ratios of 4:1-0.4:1 and 2.5:1-0.5:1. In Examples 6 and 7, their ratios are, respectively, 1.7:1 and 0.9:1.
The percentages, ratios, and parts herein are on a total
- 11 composition weight basis, unless otherwise specified. All levels and ranges herein are approximations unless otherwise specified.
MATRIX RATIO TABLE 5 Lathering
Mild Synthetic
Surfactant Fattv Acids SoaDS Paraffin 10 Lonq Chain K16-181 Alkvl Sulfate Broad: 10-40% 2.5:1-0.3:1 5:1-0.4:1 20:1-0.7:1 4:1-0.3:1 Preferred: 15-35% 2:1-0.4:1 3.5:1-0.8:1 12:1-1:1 2.5:1-0.4:1 Form. 6/Form. 7 0.6:1/0.5:1 1.5:1/1.5:1 4:1/3.8:1 1:1/0.9:1 15 Latherinq Mild Synthetic Surfactant Broad: 15-40% N/A 5:1-0.6:1 20:1-1:1 4:1-0.4:1 20 Preferred: 18-35% N/A 3.5:1-0.9:1 12:1-1.5:1 2.5:1-0.5:1 Form. 6/Form. 7 N/A 2.8:1/2.8:1 7.2:1/7.4:1 1.7:1/1.8:1 Free Fattv Acids Broad: 8-25% * N/A 12.5:1-0.5:1 2.5:1-0.2:1 25 Preferred: 10-20% * N/A 7.1-0.8:1 1.5:1-0.3:1 Form. 6/Form. 7 * N/A 2.6:1/2.6:1 0.6:1/0.6:1 SoaDS Broad: 2-15% * * N/A 1.5:1-0.05:1 30 Preferred: 3-12% * * N/A 1:1-0.08:1 Form. 6/Form. 7 * * N/A 0.2:1/0.2:1 Paraffin Wax Broad: 10-40% * * * N/A 35 Preferred: 13-35% * * * N/A Form. 6/Form. 7 * * * N/A
♦Shown elsewhere in the Table.
- 12 10
Laboratory Assessment of Bar
The following test procedures are used to evaluate the critical bar performance attributes of mildness and bar processability.
Smear Test Procedure
Equipment:
1. #2-202C Fisher Brand Hexagonal Polystyrene weighing dishes (4 x 3).
2. #14-366A Fisher Brand Spatula.
3. Balance capable of weighing to two decimal points.
4. 120’F Temperature Room.
. Timer.
Test Method
1. Label and weigh the number of weighing dishes needed (two weighing dishes per sample, one labeled M for mush dish, one labeled S for soak dish).
2. Weigh the original bar and record the weight. Place bar in preweighed dish labeled S.
3. Add 30 mis room temperature city water to the dish containing the bar prototype (pour water down side of weighing dish).
Add 30 mis room temperature city water to the dish containing the control bar. When placing the bars in the dish make sure the bars are not touching the sides of the dishes.
4. Allow bars to soak in weighing dishes at room temperature for 2 hours undisturbed.
. After 2 hours of soaking, pick bar up carefully and allow to drain into the same dish for 15 seconds.
6. After 15 seconds, invert bar and place in preweighed dish labeled M.
7. Weigh soaked bar and record.
8. Scrape the wet surface or mush from the bar, with a spatula, into the same preweighed dish labeled M, weigh and record, this is the wet smear grade. Best results for scraping are seen when the spatula is held loose in hand being careful not to gouge the bar or to scrape too deeply. When the surface of the bar no longer appears to look wet or shiny, scraping is completed. To eliminate variability of scraping from |E 9209°6
- 13 person to person, results from each test will be reported relative to the control placed in that test.
9. Weigh and record the scraped bar.
. Place the soak dish, the mush dish, and the scraped bar in the 120’F Temperature Room for water evaporation for 48 hours.
11. After 48 hours, weigh and record the dry weight of the soak dish, the mush dish and the scraped bar.
12. Calculate the surface area of the scraped portion of the bar by measuring (in inches) length times width.
13. Add the number of dry grams of mush (smear) to the number of dry grams of soak. This is the dry smear grade in grams.
All series of testing should include control, and all samples 15 should be run in duplicates. A maximum of 7 products (6 plus a control) can be tested at one time, and an interval of 10 minutes between every 4 samples should be allotted for the addition of water as to not allow any products a lag time for soaking longer than 2 hours.
Bar Soap Handwash Lather Volume Test
The handwash lather test is used to provide in-use lather volume measurements for the lather performance of skin cleansing bars. The test measures both the ultimate lather volume generated and the volume which is generated after a very short lathering period (to reflect lathering ease). The lather volumes are generated under soil-loaded conditions.
Synthetic soil is used for the soil-loaded lather volume test reported herein. Its formula and procedure for making it are set out below.
920901°
- 14 TABLE 1
Synthetic Soil
Inqredients Wt. % Hyfac 430a 1.87 Lauric Acid15 1.42 Neo-fat 14c 5.68 Neo-fat 16^ 11.16 Neo-fat 18e 5.40 Neo-fat 90-04^ 9.81 Industrene 2269 1.26 Paraffin Wax 7.30 Squalaneh 3.70 Lanolin Anhydrous 19.40 Coconut Oil 3.30 Tallow 29.70 100.00% Emery Industries, Inc., Cincinnati, Ohio Emery Industries, Inc., Cincinnati, Ohio
c Armour Industrial Chemical Co., Chicago, Illinois d Armour Industrial Chemical Co., Chicago, Illinois e Armour Industrial Chemical Co., Chicago, Illinois f Armour Industrial Chemical Co., Chicago, Illinois
Humko Products, Memphis, Tennessee h Robeco Chemicals, Inc., New York, New York
Procedure
1. Heat above materials together stirring continuously between 160-175’F.
2. Mix 25 parts of above formula with 25 parts of a 5% to 80% tallow/20% coconut soap solution and 50 parts of distilled water at 150*F.
3. Cool mixture to room temperature while stirring constantly.
4. Store in covered glass container.
Equipment
The following equipment is used:
1. Water source and sink with temperature control. The water source should be medium hardness (6-9 grain/galIon) for
- 15 most testing, although water of lower and higher hardness can be used for special purposes.
2. Synthetic soil (see Table 1).
3. Paper towels.
4. Test bars.
. Control bars.
Procedure
The following procedure is used:
1. Set temperature at 95-100*F.
2. Rub 0.22 cc of soil on hands.
3. Wet hands.
4. Rotate bar 3 times in both hands.
. Add a little water, rub both hands 5 times.
6. Rotate hands 3 times (without soap), grade for flash volume.
7. Rotate 7 more times, grade for ultimate volume.
8. Collect lather and deposit on sink top.
9. Compare volume with standard bar target volume and assign grade.
Grading Scale
Soil Loaded
- Exceptional
- Very much higher than target 5 - Higher than target 4 - Target volume
3 - Slightly lower than target
- Lower than target
In Vitro Skin Barrier Penetration Test (Mildness)
This test was performed according to the procedure described in U.S. Pat. No. 4,812,253, Small et al., issued Mar. 14, 1989, said patent incorporated herein by reference.
Frequently, materials which tend to improve processability also tend to have other negatives, particularly in terms of product mildness. Referring to Table 2, using the barrier destruction method to assess product mildness, individual raw materials sodium cetearyl sulfate is shown to be surprisingly more mild than the ultra mild sodium cocoglyceryl ether sulfonate, as
20906 well as a shorter chained AS, sodium dodecyl sulfate. The lower the number in Table 2 the milder the product.
TABLE 2
Mq 3H?0 Transported
Water 0.137 Sodium Cetearyl Sulfate 0.302 Sodium Cocoglyceryl ether Sulfonate 0.458 Sodium Dodecyl Sulfate 1.289 Sodium Laurate 1.805
A Method of Making Syndet Bars
Crutchinq
1. Add melted sodium cetearyl sulfate to the crutcher.
2. Add predetermined quantity of Hamposyl L-30 solution to the crutcher mix.
3. Add the predetermined quantity of AGS paste to the water in the crutcher. The AGS paste can be at ambient temperature or preheated to 150’F (65’C).
4. Turn on the agitator and recirculation pump and maintain temperature in crutcher at 130-150’F (54-65’C) by adjusting steam and water valves.
. Allow contents in crutcher mix to return to 130-150’F (54-65*C) prior to adding predetermined quantity of stearic acid.
6. Add to heated crutcher mix predetermined quantity of soap or NaOH to form in-situ soap.
7. Allow the contents in the crutcher to mix and/or react for about 15 minutes while maintaining the temperature at 130-150’F (54-65’C).
8. Add sodium chloride plasticizer and titanium dioxide to the heated crutcher mix.
9. Add lauric and/or coconut fatty acids to crutcher mix and allow contents of crutcher to mix for about 15 minutes while maintaining temperature at 130-150’F (54-65’C).
. Add paraffin wax in a molten form and allow crutcher to mix approximately 1/2 hour until uniform.
- 17 Drying
The crutcher mix is dried and cooled using a combination flash chamber and chill roll or chill belt. The crutcher mix is first heated to approximately 300’F (149’C) by a heat exchanger and then flash dried in a chamber above the chill roll or chill belt. From the flash chamber the hot, dried mix is extruded onto the chill roll or chill belt. The chill belt or chill roll provides a uniform, thin, cool (85-95‘F, 29-35’C) product in flake or chip form. Typical moisture for the flake is 1-10%, preferably about 2-4.5%. The ways to regulate the moisture, in the order of preference, are (1) increasing or decreasing steam pressure on the heat exchanger; (2) increasing or decreasing crutcher mix rate to the heat exchanger; and (3) increasing or decreasing crutcher mix temperature to the heat exchanger.
Amalgamating
The flakes are weighed and mixed in a batch amalgamator to obtain uniform flake size. Preweighed perfume is added to the flakes and mixed in the amalgamator to obtain the desired finished product perfume level. The perfumed flakes are transferred to the mix hopper or directly to the plodder.
Milling
The 3-roll soap mills are set up with the first roll at 120’F (49’C) and the other two mills at about 44*F (7’C). The material is passed through the mills several times to provide a homogeneous mixture of perfume and dried flakes.
Plodding and Stamping
The plodder is set up with the barrel temperature at about 115’F (46’C) and the nose temperature at 114-122’F (45-50’C). The ideal plodder is a dual stage plodder that allows use of a vacuum of about 15-25 inches of Hg. The plugs should be cut in 5 sections and stamped with a cold die block using die liguor such as alcohol, if appropriate.
EXAMPLES AND FORMULAS
The following formulas and examples are illustrative and are not intended to limit the scope of the invention(s). The methods of making milled bars are well known. All levels and ranges,
- 18 temperatures, results etc., used herein are approximations unless otherwise specified. The bars of this invention in the Formulas and Examples all have a pH of about 7 to about 7.5.
The level of the water in the above syndet bars stabilizes 5 upon storage from about 3.75% to about 2%-3%.
COMPARATIVE EXPERIMENTAL FORMULA A Comparative Experimental Formula A is the control bar for assessing lather and/or smear of the bar of this invention.
Comparative Formula A is typical of an alkyl sulfate-based product disclosed in commonly assigned, copending U.S. Pat. Application Ser. No. 07/605,614, supra. Formulas 1 through 7 described below have improved smears compared to Comparative Formula A, without sacrificing processability. In some cases of Formulas 1 through
7, the lather volume has been reduced, these are included to teach the scope of the patent. Acceptable soil lather grades are those that are of magnitude 3.0 or greater.
FORMULAS 1-3
Formula 1 demonstrates the large improvement in smear (lower numbers) upon incorporation of 21% paraffin wax relative to Comparative Formula A. See bottom of Table 3. Formulas 1-3 demonstrate the surprising benefit that paraffin waxes can impart to syndet bars containing long chain alkyl sulfates. Formula 2 further demonstrates that paraffin wax of a higher melting point (155*F/69’C) than that used in Formula 1 still provides an improved smear but without the large detriment to lather that the lower melting point (135’F/59*C) paraffin imparted to Formula 1. Formula 3 contains a mixture of the two paraffins which demon30 strate intermediate properties between Formulas 1 and 2.
Inaredient - 19 TABLE ComD. Form. A (Wt.%) 3 Form. 1 (Wt.%) Form. 2 (Wt.%) Form. 3 (Wt.%) 5 Sodium Cetearyl Sulfate 30.5 20.0 20.0 20.0 Sodium Lauroyl Sarcosinate 12.0 12.0 12.0 12.0 10 Sodium Cocoglyceryl- ether Sulfonate 16.0 20.0 20.0 20.0 Sodium Soap (in situ) 7.5 5.0 5.0 5.0 Stearic Acid 13.0 8.7 8.7 8.7 Laurie Acid 6.0 4.3 4.3 4.3 15 Paraffin (M.P. -I35eF/59eC) 21.0 6.0 Paraffin (M.P. ~155’F/69’C) . . 21.0 15.0 PEG-150 10.0 4.0 4.0 4.0 20 Perfume 1.0 1.0 1.0 1.0 Titanium Dioxide 0.25 0.25 0.25 0.25 Water 3.75 3.75 3.75 3.75 25 Performance Data: Avg. Soil Lather 4.4 0.5 3.0 2.8 Smear, Wet 4.3 1.8 3.8 2.5 Smear, Dry 2.2 1.1 1.7 1.5
Inqredient TAfiLO Form. 4 20 - - Continued Form. 5 Form. 6 Form. 7 (Wt.%) (Wt.%) (Wt.%) (Wt.%) Sodium Cetearyl Sul fate 20.0 20.0 20.0 19.0 Sodium Lauroyl Sarcosinate 12.0 12.0 12.0 13.0 Sodium Cocoglyceryl - ether Sulfonate 24.0 20.0 24.0 24.0 Sodium Soap (in situ) 5.0 5.0 5.0 5.0 Stearic Acid 8.7 4.3 4.3 4.3 Lauric Acid 4.3 8.7 8.7 8.7 Paraffin (M.P. -135*F/59’C) . Paraffin (M.P. -155*F/69’C) 21.0 21.0 21.0 21.0 PEG-150 - 4.0 - - Perfume 1.0 1.0 1.0 1.0 Titanium Dioxide 0.25 0.25 0.25 0.25 Water 3.75 3.75 3.75 3.75 Performance Data: Avg. Soil Lather 3.0 3.0 3.5 4.0 Smear, Wet 3.3 3.1 2.3 3.2 Smear, Dry 1.6 1.5 1.3 1.6 Formulas 4 through FORMULAS 4-6 6 demonstrate the effects of auxiliary
plasticizers such as polyethylene glycol (PEG) on the paraffincontaining long chain alkyl sulfate matrix. Formula 4 has lower (better) smear (3.3/1.6 vs. 3.8/1.7) than Formula 2, the difference being the presence of PEG in Formula 2. This smear improvement is achieved with no detriment to lather volume (3.0/3.0). Formulas 5 and 6 differ in a similar way: Formula 6 (no PEG) has better smear than Formula 5; surprisingly, Formula 6 actually has improved lather as well.
- 21 FORMULA 7
Formula 7 demonstrates that lather can further be improved by increasing the level of high lathering synthetic surfactants (Form. 6 with 12% vs. Form. 7 with 13%), such as sodium lauroyl sarcosinate, surprisingly without substantially harming smear (Form. 6 with 3.5 lather vs. Form. 7 with 4.0 lather, and Form. 6 with smears of 2.3 and 1.3 vs. Form. 7 with smears of 3.2 and 1.6).
Both Formulas 6 and 7 are highly preferred syndet bars which have very good lathers and improved smears while still being highly processable.
EXAMPLE I
Example I is a highly preferred personal cleansing bar of the present invention. It is the same as Formula 6, except that sodium cocoyl isethionate (SCI) is used in place of sodium cocoglycerylether sulfonate (AGS).
EXAMPLES II and III
Example II is similar to Example I, but 5% less cocoyl isethionate is used and 5% sodium isethionate is used. Example III is also similar to Example I, but a mixture of lauric and coconut fatty acids is used, and less lauric acid is used.
Advantages
Examples Ι-ΣΙΙ retain all of the advantages of Formula 6, but replacing the AGS with SCI results in a bar with substantially improved processability. Specifically, the product is a little softer during extrusion, flakes are more friable, and the product (bar) is slightly less sticky. The next of these differences is improved processability and an improved personal cleansing bar.
- 22 TABLE 4
Inqredient Sodium Cetearyl Sulfate E)C_1 (Wt.%) 20.0 Ex. II (Wt.%) 20.0 Ex. II (Wt.%) 20.0 5 Sodium Lauroyl Sarcosinate 12.0 12.0 12.0 Sodium Cocoyl Isethionate 24.0 19.0 24.0 Sodium Isethionate - 5.0 - Sodium Soap (in situ) 5.0 5.0 5.0 10 Stearic Acid 4.3 4.3 4.3 Lauric Acid 8.7 8.7 8.7 Coconut Fatty Acid - - 3.0 Paraffin (M.P. -155*F/69*C) 21.0 21.0 21.0 15 Perfume 1.0 1.0 1.0 Titanium Dioxide 0.25 0.25 0.25 Water 3.75 3.75 3.75 20 Performance Data: Avg. Soil Lather 3.3 N/A N/A Smear, Wet 3.2 N/A N/A Smear, Dry 1.9 N/A N/A
Claims (11)
1. A personal cleansing bar comprising: from about 1U% 10 About 40% of essentially saturated long chain C15-C22 alkyl sulfate; from about 10% to about 40% of paraffin wax having a melting point of from about 130*F/54*C to about 18O’F/82'C; from about 15% to about 40% lathering mild synthetic surfactant; and wherein said lathering mild synthetic surfactant is selected from C12-C14 Isethionate, C)2~Ci4 alkyl glyceryl ether sulfonate, sodium lauroyl sarcosinate, and mixtures thereof; from about 8% to about 25% free fatty acid; from about 2% to about 15% soap; and from about 1.5% to about 10% water; end wherein et least about 10% of said bar 1s said mild lathering Ci2*Ci4 alkyl Isethionate.
2. A personal cleansing bar comprising: from about 15% to about 35% of saturated long chain (C15-C18) alkyl sulfate; from about 3% to about 12% of soap; from about 18% to about 35% of lathering mild surfactant; from about 13% to about 35% of paraffin wax having a melting point of from about 140*F/60*C to about 165*F/74*C; end from about 2% to about 8% water; lauric (C12) an ^ stearic (C15-C18) free fatty acids having a ratio of from about 2.5:1 to about 1:2, said free fatty acids being present at a level of from about 10% to about 20%; and wherein said bar has a pH of from about 4.0 to about 9.
3. A personal cleansing bar comprising: from about 10% to about 40% of essentially saturated long chain (C15-C22 alkyl) synthetic surfactant selected from the group consisting of: alkyl sulfate, acyl Isethionate, alkyl sarcosinate, alkyl glyceryl ether sulfonate, and mixtures thereof; from about 10% to about 40% of paraffin wax having a melting point of from about 130*F/54*C to about 180*F/82*C; from about 15% to about 40% lathering mild synthetic surfactant; and wherein said lathering mild synthetic surfactant 1s selected from C12-C14 isethionate, C12-C14 alkyl glyceryl ether sulfonate, sodium lauroyl sarcosinate, end mixtures thereof; and wherein at least about 10% of said bar 1s said mild lathering C12-C14 alkyl Isethionate; from about 8% to about 25% free fatty acid; from about 2% to about 15% soap; and from about 1.5% to about 10% water.
4. The bar of Claim 1, 2 or 3 wherein said wax has a melting point of from about 140*F/60*C to about 165*F/74’C; and preferably wherein said wax has a melting point of from about 142‘F/61*C to about 160*F/71*C.
5. The bar of Claim 1, 3 or 4 wherein said bar contains from about 10% to about 20% of said free fatty acid; and preferably wherein said fatty acids are mixtures of lauric (C12) acid and stearic (Cig-Cie) acid having a ratio of from about 3:1 to a about 1:3.
6. The bar of Claim 5 wherein the ratio of said lauric acid to said stearic acid 1s from about 2.5:1 to about 1:2.
7. The bar of Claim 1, 2, 3, 4 or 5 wherein said lathering mild synthetic surfactant is selected from C12-C14 alkyl glyceryl ether sulfonate and sodium lauroyl sarcosinate and mixtures thereof.
8. The bar of Claim 7 wherein said C12-C14 alkyl isethionate and said sodium lauroyl sarcosinate have a ratio of from about 1:1 to about 3:1; preferably wherein said C12-C14 alkyl isethionate and said sodium lauroyl sarcosinate ratio is about 1.5:1 to about 2.5:1.
9. The bar of Claim 1, 2, 3, 5, 6, 7 or 8 wherein said wax melting point is from about 142’F/61*C to about 16O‘F/71’C, said water level is from about 2% to about 4%, and said pH is from about 6.5 to about 7.5; and wherein said long chain synthetic surfactant is a mixture of Cje-Cis alkyl sulfate and Cjg-Cis acyl isethionate.
10. The bar of Claim 9 wherein said bar contains from about 10% to about 20% of said free fatty acid and said long chain synthetic surfactant is predominately Cig-Cjs acyl isethionate.
11. A personal cleansing bar according to any one of C-laims 1-3, substantially as hereinbefore described and exemplified .
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US67428291A | 1991-03-21 | 1991-03-21 | |
US70321291A | 1991-05-20 | 1991-05-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
IE920906A1 true IE920906A1 (en) | 1992-09-23 |
Family
ID=27101128
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
IE090692A IE920906A1 (en) | 1991-03-21 | 1992-03-20 | Mild personal cleansing bars with improved processability |
Country Status (17)
Country | Link |
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EP (1) | EP0646169A1 (en) |
JP (1) | JPH06506260A (en) |
CN (1) | CN1065483A (en) |
AR (1) | AR244797A1 (en) |
AU (1) | AU1877192A (en) |
BR (1) | BR9205789A (en) |
CA (1) | CA2105086A1 (en) |
CZ (1) | CZ196493A3 (en) |
FI (1) | FI934108A0 (en) |
HU (1) | HUT65146A (en) |
IE (1) | IE920906A1 (en) |
MA (1) | MA22472A1 (en) |
MX (1) | MX9201237A (en) |
NO (1) | NO933301L (en) |
PT (1) | PT100276A (en) |
SK (1) | SK101493A3 (en) |
WO (1) | WO1992016610A1 (en) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5294363A (en) * | 1991-09-23 | 1994-03-15 | The Procter & Gamble Company | Mild personal cleansing bar composition with balanced surfactants, fatty acids, and paraffin wax |
EP0631615B1 (en) * | 1993-01-19 | 1998-09-16 | Unilever Plc | Soap bar composition comprising silicone |
ATE224946T1 (en) * | 1993-11-08 | 2002-10-15 | Procter & Gamble | SKIN CLEANING SOAP BAR CONTAINING COCOYLISETHIONATE BASED ON PREMIUMLY LONG CHAIN ACYL RESIDENTS (C12-C18) |
US5496493A (en) * | 1994-05-10 | 1996-03-05 | The Procter & Gamble Company | Ultra mild personal cleansing bar containing smaller-sized particulate wax |
US6228822B1 (en) | 1995-05-09 | 2001-05-08 | Basf Corporation | Synthetic detergent base material and synthetic detergent bar produced therefrom |
US5866144A (en) * | 1996-11-22 | 1999-02-02 | Colgate-Palmolive Co. | Skin cleaning compostition |
US6326339B1 (en) * | 1997-03-04 | 2001-12-04 | Lever Brothers Company, Division Of Conopco, Inc. | Cleansing system comprising synthetic detergent bar and pouf |
GB9717723D0 (en) | 1997-08-21 | 1997-10-29 | Ici Plc | Synthetic detergent formulations |
KR100316601B1 (en) * | 1999-07-29 | 2001-12-12 | 성재갑 | Manufacturing process of combination bar soap containing monoglyceride sulfonate |
CN101608150B (en) * | 2009-07-14 | 2011-05-11 | 江南大学 | Formula of foaming agent in neutral soap |
US20130029899A1 (en) * | 2011-07-28 | 2013-01-31 | Conopco, Inc., D/B/A Unilever | Concentrated fatty acyl amido surfactant compositions |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2653913A (en) * | 1950-01-21 | 1953-09-29 | Shell Dev | Synthetic detergent cakes |
DD32812A1 (en) * | 1962-11-20 | 1965-07-05 | Process for improving the processability of mixtures of components of personal body cleansers | |
ZA677791B (en) * | 1966-12-29 | |||
GB1257679A (en) * | 1969-02-20 | 1971-12-22 | ||
GB1294754A (en) * | 1969-12-01 | 1972-11-01 | Unilever Ltd | Synthetic detergent toilet bars |
US4100097A (en) * | 1977-02-02 | 1978-07-11 | The Hewitt Soap Company, Inc. | Low pH detergent bar |
US4335025A (en) * | 1980-02-19 | 1982-06-15 | Witco Chemical Corporation | Process for the preparation of synthetic detergent bars, and products produced thereby |
EP0239165A3 (en) * | 1986-03-27 | 1988-03-23 | Cornelis Van Buuren | Synthetic soap and method for the preparation thereof |
DE3707035A1 (en) * | 1987-03-05 | 1988-09-15 | Henkel Kgaa | MOLDED DETERGENTS |
-
1992
- 1992-01-31 JP JP4510174A patent/JPH06506260A/en active Pending
- 1992-01-31 CZ CS931964A patent/CZ196493A3/en unknown
- 1992-01-31 BR BR9205789A patent/BR9205789A/en not_active Application Discontinuation
- 1992-01-31 WO PCT/US1992/000802 patent/WO1992016610A1/en not_active Application Discontinuation
- 1992-01-31 AU AU18771/92A patent/AU1877192A/en not_active Abandoned
- 1992-01-31 HU HU9302648A patent/HUT65146A/en unknown
- 1992-01-31 SK SK1014-93A patent/SK101493A3/en unknown
- 1992-01-31 EP EP92917282A patent/EP0646169A1/en not_active Withdrawn
- 1992-01-31 CA CA002105086A patent/CA2105086A1/en not_active Abandoned
- 1992-03-13 AR AR92321928A patent/AR244797A1/en active
- 1992-03-20 MX MX9201237A patent/MX9201237A/en unknown
- 1992-03-20 MA MA22761A patent/MA22472A1/en unknown
- 1992-03-20 PT PT100276A patent/PT100276A/en not_active Application Discontinuation
- 1992-03-20 IE IE090692A patent/IE920906A1/en unknown
- 1992-03-21 CN CN92101996.3A patent/CN1065483A/en active Pending
-
1993
- 1993-09-16 NO NO933301A patent/NO933301L/en unknown
- 1993-09-20 FI FI934108A patent/FI934108A0/en unknown
Also Published As
Publication number | Publication date |
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WO1992016610A1 (en) | 1992-10-01 |
CZ196493A3 (en) | 1994-12-15 |
BR9205789A (en) | 1994-06-28 |
NO933301L (en) | 1993-11-18 |
PT100276A (en) | 1993-07-30 |
FI934108A (en) | 1993-09-20 |
MX9201237A (en) | 1992-10-01 |
CA2105086A1 (en) | 1992-09-22 |
SK101493A3 (en) | 1994-07-06 |
EP0646169A1 (en) | 1995-04-05 |
MA22472A1 (en) | 1992-10-01 |
HUT65146A (en) | 1994-04-28 |
FI934108A0 (en) | 1993-09-20 |
NO933301D0 (en) | 1993-09-16 |
CN1065483A (en) | 1992-10-21 |
HU9302648D0 (en) | 1993-12-28 |
AU1877192A (en) | 1992-10-21 |
AR244797A1 (en) | 1993-11-30 |
JPH06506260A (en) | 1994-07-14 |
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