JPS6131753B2 - - Google Patents

Description

[Detailed description of the invention]

Overfat solid cosmetics (such as those commercially available as facial cleansing or beauty products) are well known in the art and are described, for example, in the Megson et al.
3576749. As pointed out in the Megson patent, such bar soaps are manufactured from synthetic detergents (which, according to the patent, can remove very soft, slimy, and nasty stains that are unacceptable for bar soaps). This is different from (occurring). According to the Megson patent mentioned above, the presence of free fatty acids in the soap increases the volume and quality of the foam, resulting in a more stable foam with smaller bubbles, giving it a richer, smoother character for consumption. Foam is obtained. Fatty acids also tend to smooth the skin. The patent also teaches that such fatty acid soaps require relatively large amounts of sodium chloride and relatively high milling temperatures to achieve the hardness and stain resistance of solid soaps. According to the invention, a rich, smooth foam is formed, giving a very pleasant feel both during and after use. An overfat solid cosmetic set containing substantially, preferably no synthetic detergent is provided. Compared to commercially available superfat solid cosmetic soaps believed to be made in accordance with the teachings of Megson, the novel soaps of the present invention are believed to be significantly preferred by consumers with respect to foam properties and other properties. The soaps of the present invention are hard and highly resistant to softening or staining without the need to incorporate additional sodium chloride or use high kneading temperatures. According to one aspect of the invention, the overfat bar contains free higher fatty acids in an amount ranging from about 6 to 12%, such as about 8 to 10%, at least about 0.5%, usually about 1 to 4%; Preferably with an amount of high molecular weight poly(ethylene oxide) of about 1.5-2.5% or 3%. In addition, a poly(ethylene oxide)-containing superfat soap that has particularly good resistance to softening or staining is composed of approximately equal amounts of coconut oil fatty acid and beef tallow fatty acid, as can be seen from the data in the table of Example 1 below, for example. It was also discovered that sodium soap was superfatted with approximately equal amounts of coconut oil fatty acid and stearic acid. Setsuken, Encyclopedia Chemical Technology (2nd edition), Volume 18, P415-452
It is conveniently prepared from the saponification of fatty acids or esters (eg fats and oils) either by the "kama" method or by the continuous saponification method, as described in . According to the above literature, in both the kama method and the continuous saponification method, the final product is a neat soap containing approximately 30% water, and the 30% content of this material is It is stated that the concentration must be reduced to 10-15% before forming into a rod shape. Industrial manufacture of solid soaps has been carried out by adding powdered poly(ethylene oxide) to the soap chips in a soap amalgamator. This addition requires special care to avoid creating small scratches in the finished settsuken. There is also mention of the use of high molecular weight poly(ethylene oxide (Polyox resin)) in synthetic bars that may contain some detergent; It has been suggested that other materials are mixed into this melt (Davidson and Sittig, "Water Soluble Resins", 1962, p. 197-198).
Setsuken base material with approximately 30% moisture content (scam type setsuken) containing approximately 2% powdered poly(ethylene oxide)
A lumpy, poorly dispersible, and non-pumpable mixture was obtained. According to another aspect of the present invention, by mixing poly(ethylene oxide), preferably in powder form, into the melt of all or a part of the higher fatty acids used for superfatting the soup stock, an excellent addition of soup stock can be achieved. It was found that a blend of If this blend also contains a small amount of water,
Very good results are obtained. As can be seen from Example 3 below, the presence of water has a significant effect on the properties of the blend of fatty acid and high molecular weight poly(ethylene oxide), significantly reducing its viscosity. The presence of water also tends to make the blend opaque, which would imply the formation of a W/O type dispersion. Water-containing blends are easily pumped and their viscosities are at the upper viscosity range of materials that can be easily processed by ordinary reciprocating pumps (approximately 7000 or
8000cp). Therefore, it can be easily pumped for mixing with hook-type setsukuken. The poly(ethylene oxide)-containing solid soap produced by the method of the present invention foams well,
It has outstanding properties such as a particularly pleasant feel during and after use and good resistance to softening and wet cracking. Utilization of the present invention allows for the production of solid cosmetic soaps that produce a rich, smooth, but less unstable lather, and are hard and highly resistant to sloughing or cracking during use. The present invention will be further explained below with reference to Examples. In this specification, all amounts, ratios, and proportions are by weight unless otherwise specified. Example 1 (a) In a vessel equipped with a stirrer, 4.5 parts of stearic acid and 4.5 parts of coconut oil (coco) fatty acid were consistently melted at a temperature of 80°C. This was followed by high molecular weight poly(ethylene oxide) (“Polyox WRS N-750” commercially available from Union Carbide Company); molecular weight approximately 300,000; viscosity of a 5% aqueous solution at 25°C; approximately 550.
~900 cp; melting point around 65°C) was added with stirring while maintaining the blend at about 80°C. This blend was added in proportions such that the resulting mixture contained about 75 parts of sodium soap (as anhydrous soap), 4.5 parts of added stearic acid, 4.5 parts of added coco fatty acid, and 1.8 parts of poly(ethylene oxide). Mixed with kama-style sodium settsuken (70°C). This kama-style test tube saponifies a 50/50 mixture of coconut oil and beef tallow with an aqueous solution of sodium hydroxide, extracts and removes by-product glycerin, salts out with an electrolyte solution, and removes the actual electrolyte layer. All of these products have a moisture content of about 27 to 32% (for example, 30
%), glycerin approximately 1% or less (e.g. 0.5%),
It contained 0.3% or less of NaOH (eg, 0.1%) and 1% or less of NaCl (eg, 0.7%). After stirring the above mixture for a few minutes, the water content will be approximately
Form into 10% dry cake chips. This is done by first pumping a hot soap mixture onto a cooling roll, forming a thin film of soap on the roll, scraping off this thin film into chips or ribbons, and then drying the chips or ribbons. It will be done. The resulting chips are mixed with colorants and flavors (e.g. 0.7% TiO ₂ and 1.5
% fragrance) and then kneaded (e.g. approx. 15~
(at 35°C) and then extruded into rods in a conventional Ken extruder (e.g., at about 20-50°C, e.g. 40°C) and cut into pieces. After the surface of the set has been roughened, it is stamped into the desired shape (eg, with a pin-die press). (b) Repeat (a) above, but instead of using 4.5 parts stearic acid and 4.5 parts coco fatty acid, use parts stearic acid. (c) Repeat (a) above, but instead of using 4.5 parts stearic acid and 4.5 parts coco fatty acid, use 9 parts coco fatty acid. Testing of these solid soaps (after aging for at least 3 days) gave the following results.

[Table] The sponge foaming test measures the speed of foaming.The flat surface of a solid soap is alternately rubbed with a sponge and soaked in a shallow dish of water (hardness 123ppm, temperature 35℃). The number of vertical strokes required until continuous annular bubbles are formed in the water in a shallow dish is measured by vertical movement of this foaming tester. The smaller the Stroth number, the faster the foaming. In the softening test, a solid piece of soap is placed flat with one side submerged in a Petri dish for 17 hours, after which the soft and melted piece is removed with a finger. The % weight loss is reported as the softening percentage. In the melting loss (erosion) test, the weight reduction rate of the settsuken is measured by immersing it in water for 260 strokes (approximately 10 minutes) in a foaming test. In the hydration test, the settsuken is completely immersed in tap water for 2 hours and the weight gain is measured. The crack index is determined by scraping off one side of a solid settsuken to half its original thickness, placing it in a water condenser (hardness approximately 100 ppm) for 1 hour, taking it out, and polishing it until there are no traces of free water on the surface (usually 1 hour).
(Evening) Evaluation is based on the severity of the number of turtles in a test where the product is hung in the air to dry. The above-mentioned solid soap (a) has unexpectedly good foaming speed, unexpectedly low loss of collapse and loss due to dissolution, and extremely good crackability. Example 2 A solid soap was produced in the same manner as in Example 1(a), except that in this example it further contained 0.5% lanolin or 0.5% sodium caseinate. These components were incorporated into the hot fatty acid-poly(ethylene oxide) blend prior to mixing with the kama-style settsuken. Example 3 Example 1(a) was repeated, except that the following method was used to prepare the blend to be mixed with the kama-style settsuken. Approximately 5 parts of commercially available stearic acid (mp54℃) and 5 parts of coco fatty acid (mp25℃, iodine value 6)
It melts easily at a temperature of 102°C. Powdered high molecular weight poly(ethylene oxide) (“Polyox WSR
1 part of N-750”, mp about 65°C) is added to this under stirring. The viscosity of the mixture is about 750 cp at 102°C;
At 88°C it is about 400 cp and at 54°C it is about 5000 cp (measured with a Bruckfield viscometer). Then add another part of the same Polyox while stirring. The viscosity of this mixture is about 18000 cp at 94℃,
Approximately 19,000cp at 88℃, approximately 33,500cp at 66℃, approx. at 54℃
It is 42500 cp. Then 0.5 part of lanolin is added with stirring.
The viscosity of the resulting mixture is now approximately
It had a similar viscosity at 15,000 cp and 70°C. Then add 1 part of water. As a result, the previously clear mixture becomes cloudy and opaque. Viscosity is about 5000cp at 77℃, about 4000cp at 71℃, 50-63℃
It is about 3250 cp. Another portion of water is then added while stirring.
The viscosity of the resulting mixture is approximately 2250 cp at 84°C.
1500cp at 81℃, 930cp at 71℃, 470cp at 67℃, 60
It is 234cp at ℃ and 114cp at 52℃. Next, 2.5 parts of sodium caseinate solution (containing 20% casein) are added. The resulting mixture is white. Viscosity is approximately 2900cp at 81℃, 2520cp at 71℃,
It is 1700cp at 66℃ and 1800cp at 60℃. It can be seen that the addition of water results in a mixture in which the viscosity at, for example, 70° C. is significantly reduced (for example to a value significantly lower than half of the value before the addition of water). Also, the viscosity of water-containing mixtures decreases significantly with decreasing temperature (e.g., when the temperature is 70 or 80
When the temperature decreases by 10°C, the viscosity decreases by significantly more than 10%). The blend obtained above is heated to a temperature of about 60 to 85 degrees Celsius,
(70℃), about 75 parts of sodium soap (as anhydrous soap), 4.5 parts of added stearic acid, and 4.5 parts of added coco fatty acid.
and 1.8 parts of poly(ethylene oxide). Example 4 Example 1(a) is repeated, except that in preparing the blend, 10 parts of stearic acid are first melted, 2 parts of poly(ethylene oxide) from Example 1 are added thereto, and then water is added. Add 1.5 parts while bringing the mixture to approx.
The method is to maintain the temperature at 70 to 90°C and stir. Example 5 Example 4 is repeated, except that coco fatty acid is used instead of stearic acid. The water-containing blend of poly(ethylene oxide) and higher fatty acids comprises about 2 to 20 parts (especially about 4 to 8 parts) of fatty acid and about 0.5 to 5 parts (especially about 1 to 2 parts) for every part of poly(ethylene oxide). It is preferable that the water contains 50% of water. The amount of water in each component added to the kama-style setsuken is determined so that the water:setsuken ratio is no more than about 33:67 (e.g., 27:73 to 32:3) to minimize the formation of the less-desirable gel-setsuken phase.
68). Particularly in compositions containing relatively high amounts of coco fatty acids (e.g. 1 a above), the water content may be reduced to about 18 % or less, preferably about 5 to 12%. For the same purpose, the extrusion temperature should be relatively low, the outer surface of the bar-shaped settsuken should be pre-cooled and pre-dried before compression in the die, and the die should be lubricated (e.g. 16% NaCl and 25% in an aqueous solution containing glycerin; the lubricant is then preferably blown off with air from the surface of the stamped set. High molecular weight poly(ethylene oxide) has an average molecular weight of at least about 100,000. Examples of such compounds are is commercially available from Union Carbide Company under the trademark "Polyox." This polymer is a water-soluble, nonionic material with molecular weights ranging from about 100,000 to about 5,000,000 or more. 1,000,000 or less, more preferably about 600,000 or less, for example about 300,000 to 400,000. For materials with an average molecular weight of about 300,000, proportions of around 2% have given good results. The material (commercially available as Polyox WSR N-750) is 25
The viscosity at °C is about 40 cp for a 2% aqueous solution (Bruckfried shaft number 1, 10 rpm) and about 600 to 1000 cp for a 5% aqueous solution. For example, if the average molecular weight
For example, 2% of extremely high molecular weight poly(ethylene oxide) of 4,000,000 would result in a slimy foam, which is less desirable. According to the manufacturer, Polyox materials typically have a PH of about 10 (eg, in a 5% aqueous solution). Setsuken is generally 1%
The pH of the aqueous solution is about 10 (e.g. 10.2), but the superfat soup stock of the present invention generally has a slightly lower pH (e.g.
9.5). Poly(ethylene oxide) is generally supplied in powder form and usually has the following particle size distribution (the sample is sieved through a set of sieves and the percentage remaining on the screen with the indicated sieve number is expressed in weight percent). ): No.20−5.2%, No.40−31.2,%, No.60−
20.7%, No. 100 − 16.7% and No. 100 passed − the remainder. It may be preferable to use a finer-grained poly(ethylene oxide) with the following particle size distribution (same indication as above): No. 20 − 0.5%,
No.40−13%, No.60−13%, No.100−13.9%,
Passed No.100 - remaining. Very good results have so far been obtained using a setken made by saponifying a blend of approximately equal amounts of beef tallow and coconut oil. It is generally preferred to use a tallow:coconut oil ratio within the range of about 2:1 to 1:2, such as 3:2 or 2:3. It is preferable to stabilize the kama-style settsuken before mixing it with the various additive components. Stabilization is carried out, for example, by adding and mixing approximately 0.06% SnCl ₄ and 0.024% ethylenediaminetetraacetic acid tetrasodium salt as aqueous solutions, respectively. With regard to fatty acids for superfatting, best results have so far been obtained when using approximately equal mixtures of stearic acid and coconut (coco) fatty acids. It is generally preferred to use both fatty acids in a ratio of about 2:1 to 1:2, such as 3:2 or 2:3. The total amount of superfatting fatty acids in a set is generally about 15% or less. It is understood that because cation exchange of Na and H can occur during the processing of the Setsuken-fatty acid mixture, it is convenient to display the chain length distribution of the mixture as saponified and unsaponified fatty acids together. It will be. A representative distribution of the preparations of the present invention thus expressed is shown in the table below.

[Table] For moisture content below about 12% during the manufacturing process, the moisture content may increase during post-manufacturing use or storage (see, for example, hydration data in Example 1), but preliminary experimental results indicate that It has been found that the soup stock of the present invention has a significantly lower tendency to hydrate than commercially available superfat soup stock. The conventional kama-type settsuken has up to about 1% (for example, 0.7
%) of sodium chloride. Although the products of the invention have good stain resistance without the need for the addition of sodium chloride, the addition of sodium chloride (as in the Megson patent, supra) is not excluded from the scope of the invention. When the preparation of the present invention is kneaded at a conventional relatively low temperature, 90〓(32
°C) has a good hardness comparable to or higher than ordinary cosmetics (i.e. 90 °C)
〓Dietert hardness is about 85 or more, for example, 90 ~
92). It will also be appreciated that although it is not necessary to use high milling temperatures such as those described in the Megson patent, the use of such elevated milling temperatures is within the scope of the present invention. Megson U.S. Patent No. 3,576,749 for the type and relative quantitative relationship of fatty acids in fatty acids
Something like the one described in is fine. That is,
These fatty acids have about 8 to 20 carbon atoms. The superfatting fatty acid may contain a fatty acid having an odd number of carbon atoms. For example, it is also possible to use a fatty acid mixture (Monsanto, CR-1157) containing equal amounts (1/3 each) of C ₁₁ , C ₁₂ and C ₁₃ saturated fatty acids. The bar soap of the present invention may contain conventional additive ingredients such as opacifiers (e.g. 0.4% titanium dioxide added to amalgamators), lanolin (e.g. 0.5% added to neat soaps, preferably mixed with superfatting agents). ), glycerin (e.g. 1% added to the amalgamator or soap base), soap fragrance (1-3%, e.g. 1.5-2% added to the amalgamator), antioxidants (e.g. 0.02% di-t-butyl- p-cresol or BHT added to neat soaps), proteins (e.g. 0.5% sodium caseinate added to neat soaps, or added to amalgamators in aqueous solution).
Megson Patent and Kaniecki U.S. Patent No.
Antibacterial substances or disinfectants such as those described in 3598746 can also be incorporated. The solid soap can be aerated by methods well known in the art to produce lower density (floating) soap, e.g.
It is also within the scope of the present invention to have a value of 0.8. The sizes of solid cosmetics range from a relatively small hotel size (approximately 20 to 30 g in weight), regular size (approximately 100 g), bath size (approximately 150 g), and extra-large size (approximately 200 g). The set of the present invention may be of such size, especially about
The amount may range from 100 to 200 g. As mentioned above, poly(ethylene oxide) is added in two stages: a portion (for example, approximately half to two-thirds of the total amount of the polymer) is mixed into the neat soap, and the remainder is added to the soap chips in an amalgamator. It may be mixed in by any method. To reduce the tendency for scratches to form when making the latter addition in an amalgamator, the polymer in this case is a very fine material (for example, a material with a particle size that passes 98% through a No. 100 screen of the American Sieving Standard). ), and it is desirable to disperse this powdered polymer on the surface of the amalgamator chips before adding other ingredients such as pigments. By incorporating a significant portion of the total polymer into the neat soap, the soap becomes less sticky while the rest of the polymer is incorporated in the amalgamator, making the amalgamation process easier and less powerful. Can be implemented. It will be understood that the above description is merely illustrative and that various modifications may be made within the scope of the invention.

Claims (1)

[Claims] 1. Approximately 8 carbon atoms as a substantially independent detergent component
~20 higher fatty acids, about 6 to 12% superfatted higher fatty acids having about 8 to 20 carbon atoms, about 1 to 4% poly(ethylene oxide) with a molecular weight in the range of about 100,000 to 5,000,000, and about water. Solid cosmetics consisting essentially of 5 to 18%. 2. The solid cosmetic set according to claim 1, wherein the molecular weight is about 300,000 to 600,000, and the proportion of poly(ethylene oxide) is about 1.5 to 3%. 3. The solid cosmetic soap according to claim 1 or 2, wherein the sodium soap is a mixture of beef tallow soup and coconut oil soup in a ratio of about 1:2 to 2:1. 4. The solid cosmetic soap according to claim 1 or 2, wherein the sodium soap is a mixture of approximately equal amounts of beef tallow soup and coconut oil soup. 5. The solid cosmetic set according to any one of claims 1 to 4, wherein the superfatted fatty acid is a mixture of stearic acid and coconut oil fatty acid in a ratio of about 2:1 to 1:2. 6. The solid cosmetic set according to any one of claims 1 to 4, wherein the superfatted fatty acid is a mixture of approximately equal amounts of stearic acid and coconut oil fatty acid. 7 Approximately 8 carbon atoms as a substantially independent detergent component
~20 higher fatty acids, about 6 to 12% superfatted higher fatty acids having about 8 to 20 carbon atoms, about 1 to 4% poly(ethylene oxide) with a molecular weight in the range of about 100,000 to 5,000,000, and about water. A method for producing a solid cosmetic soap comprising 5 to 18%, comprising: mixing the sodium soap and the soap containing about 30% water with the poly(ethylene oxide) blend in the superfatted higher fatty acid melt; The manufacturing method comprises drying the resulting mixture and then forming the mixture into a superfatted solid cosmetic set. 8. The manufacturing method according to claim 7, wherein the molecular weight is about 300,000 to 600,000 and the proportion of poly(ethylene oxide) is about 1.5 to 3%. 9. The manufacturing method according to claim 7 or 8, wherein the sodium soap is a mixture of beef tallow soup and coconut oil soup in a ratio of about 1:2 to 2:1. 10. The manufacturing method according to claim 7 or 8, wherein the sodium soap is a mixture of approximately equal amounts of beef tallow soup and coconut oil soup. 11. The method of claims 7 to 10, wherein the superfatted fatty acid comprises a mixture of stearic acid and coconut oil fatty acid in a ratio of about 2:1 to 1:2. 12. The production method according to claim 7 or 10, wherein the superfatted fatty acid is a mixture of approximately equal amounts of stearic acid and coconut oil fatty acid. 13 The blend is the poly(ethylene oxide)
13. The method of claims 7 to 12, containing about 2 to 20 parts per part of said superfatted fatty acid. 14. A process according to any of claims 7 to 13, wherein the blend contains a small amount of dispersed water which reduces its viscosity. 15 the blend is the poly(ethylene oxide)
14. A process according to any of claims 7 to 13, containing about 0.5 to 5 parts water per part. 16 the blend is the poly(ethylene oxide)
For each part, about 4 to 8 parts of the superfatted fatty acid and about 1 part
2 parts of water.