JPH0144760B2 - - Google Patents

Description

[Detailed description of the invention]

BACKGROUND OF THE INVENTION Various bar soaps and methods for their production are known in the literature. Many soap manufacturing processes, such as those described in U.S. Pat. No. 2,686,761 and U.S. Pat. No. 2,970,116 (both incorporated herein by reference) utilize electrolytes such as sodium chloride and potassium chloride as processing aids. do. Therefore, soaps of this type often contain significant amounts of chloride ions. Additionally, it has been found advantageous to utilize potassium soaps in at least a portion of the soap composition. The presence of potassium soap improves clarity, so
Using potassium soap as described above
This is particularly advantageous if transparent soaps are desired to be produced. However, the presence of significant concentrations of both potassium soap and chloride ions in bar soap has been shown to cause crystal formation on or within the bar after use or storage, especially under hot and humid conditions. Ivy. Such crystals detract from the appearance and consumer desire of these soaps. It has now been discovered that the use of certain electrolytes in such bar soaps can overcome this resulting problem and provide the soaps with additional performance benefits. It is therefore an object of the present invention to provide a transparent bar soap containing significant concentrations of potassium soap and chloride ions, which does not form crystals during use or storage. It is a further object of the present invention to provide a bar soap that exhibits better foaming properties and reduced scum formation than similar bar soaps made using conventional electrolytes. It is also an object of the present invention to provide a transparent bar soap having better clarity than similar soaps made using conventional electrolytes. DETAILED DESCRIPTION The subject of the invention is a transparent bar soap which does not form undesirable crystals when used or stored, and which contains about 4 to 20% potassium soap, with the exception that the remainder of the soap components are sodium, ammonium or alkanolamine soap, and contains at least about 0.2% chloride ions, and further contains about 4% water.
~25% and potassium carbonate, sodium formate, potassium formate, potassium tartrate, sodium tartrate, potassium citrate, sodium citrate, potassium acetate, sodium acetate, ammonium potassium tartrate, ammonium acetate, ammonium carbonate, ammonium formate, ammonium citrate ,
From about 0.2% to an electrolyte selected from the group consisting of ammonium lactate, ammonium bisulfate and mixtures thereof.
A bar of soap containing about 5%, preferably about 0.5% to about 3%. A preferred composition includes potassium carbonate. Other preferred electrolytes include the sodium and/or potassium salts of formic, citric, acetic and tartaric acids. In this specification, "%", "ratio" and "parts" refer to "% by weight", "weight ratio" and "parts by weight", and are based on the composition of the finished soap, unless otherwise specified. The bar soap of the present invention mainly consists of soap ingredients. This ingredient generally accounts for about 60% to about 60% of the finished soap.
Present in an amount of 95%, preferably about 65% to about 85%. Soaps useful in this invention include alkali metal salts, ammonium salts, and alkanolamine salts of fatty acids having about 8 to 24 carbon atoms, preferably 10 to 20 carbon atoms. The compositions of this invention should contain about 4-20% potassium soap. In one embodiment, the bar soap of the present invention contains at least about 7% potassium soap, preferably from about 7% to about 20%.
In particular, it contains about 10% to about 17%. The potassium soap may be added directly to the composition or formed in situ during processing (eg, by adding sodium soap and potassium electrolyte into the bar soap). The presence of such components is an important factor that contributes to the crystal problem that the present invention aims to solve. The present invention provides a solution to this problem, as the use of potassium soaps is highly desirable, especially in the production of clear soaps, and this solution is preferred over eliminating these potassium soaps. Fatty acids suitable for use in the invention are naturally occurring, for example valuable or animal esters such as palm oil, coconut oil, babassu oil, soybean oil, castor oil, tallow, whale oil or fish oil, grease, lard and the like. mixture). The fatty acids may be synthetic (eg, by oxidation of petroleum or by hydrogenation of carbon monoxide by the Fischer-Tropsch process). Resin acids such as those present in tall oil can also be used. Naphthalic acid is also suitable. Sodium and potassium soaps can be produced by directly saponifying fats and oils or by neutralizing free fatty acids produced by other processes. Sodium and potassium soaps of mixtures of fatty acids derived from coconut oil and tallow, namely sodium tallow soap, sodium palm soap, potassium tallow soap and potassium palm soap, are particularly useful in the present invention. As used herein, the term "tallow" refers to 2.5%
A fatty acid mixture with an approximate carbon chain length distribution of C ₁₄ , 29% C ₁₆ , 23% C ₁₈ , 2% palmitoleic acid, 41.5% oleic acid and 3% linoleic acid (the first three fatty acids are saturated fatty acids) It is. Other mixtures with a similar distribution, such as fatty acids derived from various animal tallows and lard, are also encompassed by the term "tallow." As used herein, the term "coconut oil" means 8%
C ₈ , 7% C ₁₀ , 17% C ₁₄ , 8% C ₁₆ , 2%
It is a fatty acid mixture with an approximate carbon chain length distribution of C ₁₈ , 7% oleic acid and 2% linoleic acid (the first six fatty acids are saturated fatty acids). Other sources with similar carbon chain length distributions are also encompassed within the term "coconut oil", such as palm kernel oil and babassu kernel oil. Coconut oil fatty acids usually contain unsaturated fatty acids in a sufficiently low content to have satisfactory shelf life without further processing. Generally, however, fatty acids are hydrogenated to reduce the degree of unsaturation (especially polyunsaturation) in the fatty acid mixture. In preferred bar soaps, the soap ingredients are a mixture of about 20 to 14 carbon atoms.
80% and about 16-20 carbon atoms soap about 20-80%
Consists of. A soap with such favorable chain length distribution properties is made from a mixture of tallow and coconut fatty acids.
It can be obtained by using a tallow:coconut weight ratio of 90:10 to 50:50, preferably about 80:20 to 60:40. The compositions of the present invention are particularly effective in inhibiting crystal growth when the mixture of tallow and coconut fatty acids contains at least about 15%, preferably at least about 20%, coconut fatty acid component. Preferred bar soaps containing the above soap mixtures and methods of making the same are described in U.S. Pat. No. 3,576,749;
U.S. Patent No. 3835058 and U.S. Patent No.
Since it is described in detail in the specification of No. 3988255,
All of these are references. Another factor contributing to the crystallization problem addressed by the present invention is the presence of significant amounts of chloride ions in soap compositions. That is, the bar soap of the present invention contains at least about 0.2% chlorine ions;
In particular, it contains about 0.2% to about 0.7%. Chloride ions are generally incorporated into soap compositions in the form of sodium chloride or potassium chloride electrolytes, which are used to improve the processability (ie, separation of the soap from alkaline materials) or clarity of the soap composition. Most importantly in the present invention, the soap composition contains about 0.2% to about 5%, preferably about 0.5% to about 3%, most preferably about 1% of the specified electrolyte.
% to about 3%. By selecting and formulating specific electrolytes, the aforementioned crystalline problems can be eliminated from bar soap compositions.
Generally, the electrolyte is selected to have a relatively bulky anion and a solubility significantly greater than the solubility of sodium chloride in water (ie, at least about 100 g/100 ml in water at 25°C).
Electrolytes useful in the present invention include potassium carbonate,
Potassium formate, sodium formate, sodium tartrate, potassium tartrate, sodium citrate, potassium citrate, sodium acetate, potassium acetate,
These include ammonium potassium tartrate, ammonium acetate, ammonium carbonate, ammonium formate, ammonium citrate, ammonium lactate, ammonium bisulfate and mixtures of these ingredients. A preferred composition is one that utilizes potassium carbonate. Additionally, the electrolytes utilized, particularly carbonate electrolytes, provide the bar soaps of the present invention with superior foaming properties and lower scum (i.e. calcium and magnesium soap) formation compared to bar soaps utilizing conventional electrolytes. do. A preferred group of compositions further comprises sodium and/or potassium (especially potassium) formates,
Containing citrate, acetate and tartrate (particularly potassium citrate). These compositions offer advantages over compositions containing potassium carbonate in that: (a) they eliminate the formation of crystals within the bar of soap (especially important in clear bar soaps); (b) Foaming properties in hard water are improved. (c) Improved translucency. (d) less mechanical work is required to achieve translucency; and (e) these preferred electrolytes complex with heavy metal ions and reduce oxidation of the ingredients, making them less oxidized (particularly fragrances and colourants). stability is improved. The present invention is particularly effective when used in milled transparent bar soaps, such as those described in US Pat. No. 2,686,761 (incorporated). Such bar soaps contain beta phase materials (beta phase materials) as described below.
-phase material) in high concentrations, for example at least about 70%. Here we will briefly explain beta phase materials. It is known that commercially available bar soaps exist in at least three mutually interchangeable crystalline phases called beta, delta, and omga. These phases appear either in the final product or at some stage during the manufacturing process and are sometimes present alone and sometimes in mixtures with other phases. Generally speaking, the beta phase is favored by the mechanical action of relatively low moisture soaps of conventional formulations at moderate temperatures, and the omega phase is favored by the mechanical action of relatively low moisture soaps of conventional formulations at moderate temperatures, and the omega phase favors such soaps by removing them from the molten state without agitation. The delta phase can also be said to be promoted by high moisture and low temperatures, such as when soap niggle solidifies, and by high molecular weight. Differences in crystal structure are reflected in differences in physical properties of the phases. Furguson et al. (Ind.Eng.Chcm.35, 1005
(1943) give data to illustrate this for three samples of the same soap, each processed differently in turn to give a different crystalline phase. Their data shows that soaps in the Beta phase as a result of Mirinda and Prodeing are much harder and more easily soluble, foam more easily than any of the phases mentioned above, and tend to expand more when soaked in water. It shows that they can be distinguished by certain things. This milling and prodding produces a beta phase under conditions that tend to orient and press the crystals together. If the conditions that give rise to the data phase are such that the crystals are not packed (e.g. by cooling and mechanically processing semi-molten soap when it is in a pasty state of softness), but are cohesively bonded, or If oriented in a parallel manner, the ease of lathering is retained but the characteristic waxy millability is lost and the bar tends to disintegrate in water and become generally flexible. The crystalline phases of various soaps are distinguished from each other and identified by certain characteristic X-ray diffraction rings. This ring remains virtually unchanged in a given phase even with variations in fat general formula, water content, and electrolyte content. However, the above fluctuation may determine the phase to be generated. A simple system of identification is based on the characteristic short spacings shown in the table below taken from the above-mentioned article by Ferguson. Ring diameter (cm) Lattice spacing (dm) Beta 6.35 2.75 Delta 6.05 and 4.65 2.85 and 3.55 Omega 5.85 2.95 (fixed ring of alpha phase is omitted) The presence or absence as well as the relative proportion of soap present in two or several coexisting phases can be estimated for unknown samples from the relative intensities of the identification rings. For example, if the omega phase gradually transforms into the beta phase, the relative strength of the 5.85 cm ring decreases and the relative strength of the 6.35 cm ring increases as the transformation progresses.
In order to make such estimates more precise, a mixture of known phases, each in the purest form possible, is first taken as a standard and the relative intensities of its characteristic rings are recorded.
The relative intensities of the rings in the diffraction pattern of the unknown sample are then compared to these standards. For example 6.35cm
The mixture of Beta and Omega of approximately equal strength in the ring and the 5.85cm ring is actually about 75% Beta and 25%
% of the omega phase. Soaps that are mostly beta but contain less than about 5% omega will clearly show the beta ring, but the omega ring will be hardly visible. On the other hand, to obtain a detectable beta ring in a soap that is mostly omega, one would have to add as much as 15 or 20% beta soap to it. Now, the bar soap of the present invention necessarily contains some moisture (water). Moisture assists the processing of bar soap,
This is necessary to obtain optimal processing conditions. in general,
The finished bar soap of this invention contains about 4-25% water by weight, preferably about 10-23% water. The bar soap of the present invention can contain various arbitrary substances in addition to the above-mentioned components. These optional substances include, for example, skin conditioning ingredients, free fatty acids, processing aids, antimicrobial and disinfectant agents, dyes, fragrances, and colorants. The bar soap of the invention may optionally contain free fatty acids in addition to the neutralized fatty acids that form the actual soap ingredients. Free fatty acids improve the volume and especially the quality of lather from soap bars. Free fatty acids tend to make foams containing relatively small air bubbles more stable, which give the user a foam that is unique in that it is "rich" and "creamy." Furthermore, free fatty acids act as plasticizers in bar soaps containing large amounts of salt. Without free fatty acids, some bar soaps have a greater tendency to form wet cracks. The free fatty acids useful in this invention are the same types of fatty acids used to form soap ingredients.
Such fatty acids generally contain 8 to 20, especially 8 to 14
Contains carbon atoms. In preferred bar soaps, at least about 25% of the free fatty acid component is 12 carbon fatty acids. Free fatty acids, when present, generally amount to about 1-15% by weight of the soap bar.
It is. The use of free fatty acids in bar soaps is described in U.S. Pat. No. 3,576,749 and U.S. Pat.
Specification No. 3835058 (both specifications are referred to)
is described in detail. There may be substances present that facilitate the manufacture of the bar soap of the present invention. Thus, to facilitate processing of the bar soap, for example, common salt (sodium chloride) and preferably glycerin can be added to the crutcher or amalgamator. Such materials, when present, generally represent about 0.2 to 10% by weight of the finished bar soap. Additionally, emulsifiers, such as polyglycerol esters (e.g. polyglycerol monostearate), propylene glycol esters and other chemically stable non-ionic substances, can be added to the bar soap to enhance the effect of various ingredients on the skin, especially sorbitan esters. It may also assist in solubilizing the conditioning agent. Conventional antibacterial and disinfectant agents can be added to the bar soap of the present invention without compromising the crystallization control effect. Typical antibacterial disinfectants include 3.
4-di- and 3,4',5-tri-promsalicyl-anilide, 4,4'-dichloro-3-(trifluoromethyl)carbanilide, 3,4,4'-trichlorocarbanilide and these substances There is a mixture of The use of these materials in bar soaps is described in detail in US Pat. No. 3,256,200 (incorporated by reference). Antimicrobial and disinfectant agents, when present, generally represent about 0.5 to 4% by weight of the finished soap bar. Bar soaps of the present invention may optionally contain various emolliens and skin conditioning agents. Substances of this type are, for example, sorbitan esters, as described in US Pat. No. 3,988,255 (incorporated), lanolin, cold cream, mineral oil, isopropyl myristate, and similar substances. Such irritation relievers and skin conditioning agents generally represent about 0.5 to 5% by weight of the bar of soap. The soap bars may contain conventional fragrances, dyes and colorants commonly utilized in commercial soap bars to improve the properties of such products.
Such fragrances, dyes and colorants, when present, represent about 0.2 to 5% by weight of the soap bar. The bar soap of the present invention is manufactured by a conventional method. A water-containing soap base of the type described above having the required potassium soap and chloride ion content is mixed with the electrolyte components and other optional ingredients such as fragrances in a crutcher or amalgamator, and then mixed in a conventional manner under normal conditions. It is milled, punched and extruded into bars to make bar soap. Conventional methods can also be used to produce clear bar soaps. The method for producing bar soap of the present invention is described in US Patent No.
3,835,058, US Pat. No. 3,576,749, and US Pat. No. 3,523,909, all of which are incorporated by reference. The bar soap of the present invention, its advantages in terms of inhibiting crystal growth, and its usefulness in routine hand and body washing are illustrated by the following examples, but the invention is not limited thereto. Example 1 A A bar soap having the following composition is manufactured by the following method. Dried tallow/coconut (80/20) sodium soap was mixed in an amalgamator with one, several, or all of the ingredients listed in the table below; triethanolamine (TEA), glycerin, potassium palm soap, and chloride. potassium. The mixture was then milled to maximum clarity. Maximum clarity was usually obtained after four passes through a three roll mill. When potassium palm soap was added to bar soap, it was necessary to dry it on a hot mill before cold milling. The soap of the present invention is prepared by mixing the sodium and potassium soaps in a crutcher, drying the mixture in a vacuum flash dryer to the desired moisture content, and mixing the remaining ingredients in an amalgamator. You can also do that.

Table: These bar soaps were then tested for clarity, foaming, and crystal growth using the methods described below. The transparency of these bar soaps is guaranteed by U.S. Patent No.
It was determined by measuring the transmittance of light through each bar of soap, as described in US Pat. No. 2,970,116 (incorporated by reference). In this method, a bar of soap is placed in a completely dark room at the apex of a cone surrounding a light source of variable voltage. The cone has a diameter of approximately 1/2 inch (1.27 cm) at the top and approximately 6.35 cm (6.35 cm) at the bottom surrounding the surface where the light source resides.
(2 1/2 inches) in diameter. The apex of the cone is approximately 24.13 cm (9 1/2 cm) from the surface where the lamp is located.
2 inches) and the lamp is 220V, 15
This is a microscope lamp with Watt's clear glass bulb. The voltage applied to the bulb is adjusted so that the light from the top of the cone shines through the 1-inch-thick bar of soap, forming a barely perceptible circular image. The voltage applied to the bulb is used as a measure of transparency independent of color. That is,
The lower the voltage, the clearer the soap bar. The foaming properties of bar soap are based on Belgian patent no.
The test was carried out using the method described in 823776 (incorporated as a reference). In the test used, the tester did not wear gloves when lathering the bar of soap, and the lather produced was relatively graded in arbitrary units. At least four testers are required to repeat the test, and the results are averaged over the number of testers involved. The higher the foaming degree, the better the foaming property. Crystal growth was tested by visual examination of the surface and interior of the soap bars, exposing the bars to various storage and use conditions. Specifically, bar soaps were observed: (a) after storage under ambient conditions, (b) after storage under conditions of accelerated aging (50°C, 50% relative humidity), and (c) after repeated use ( 4 times a day for 1 week), then after storage under ambient conditions. The performance of the bar soap in each test is summarized in the table below.

[Table] This table shows that the inclusion of potassium soap in bar soaps has the advantage of high transparency and remarkable foaming properties, but the presence of such potassium soaps may cause undesirable crystal formation in bar soaps. This shows that this occurs. It is also found that the inclusion of triethanolamine can avoid the crystal growth problem while retaining the advantage of foaming properties, but the inclusion of TEA sharply reduces the transparency of the soap. . B Using the production method described above, tallow/coconut (65/35) fatty acids are combined with sodium hydroxide and potassium hydroxide using sodium chloride or potassium chloride as the electrolyte as shown in the table below.
Bar soap was made by direct saponification with a 50/50 mixture. Bar soap is about 15% to 18%
contained water. The resulting soap bars were tested for clarity and crystal growth as described above.

Table: These tests show that transparency is clearly increased by incorporating electrolytes into soap compositions. However, the presence of the conventional electrolytes tested causes undesirable crystal formation in the bar soap. C Utilizing the manufacturing method described above, the final composition of tallow/coconut (80/20) sodium soap 62.4%, potassium palm soap 10.4%, glycerin 6.0%, and additional ingredients shown in the table below, percentages indicated, was prepared. He made a bar of soap with The bar soap contained about 15% to about 18% water. These bar soaps were then tested for clarity and crystal growth using the methods described above.

[Table] Compositions of the present invention (compositions 15, 16, 17 and 19)
has good transparency and does not grow crystals, but
It has been found that soap compositions utilizing only conventional sodium chloride and potassium chloride electrolytes exhibit undesirable crystal growth. All or a portion of the potassium carbonate electrolyte in Compositions 15, 16, 17 or 19, sodium formate, potassium formate, sodium tartrate, potassium tartrate,
Substituting sodium citrate, potassium citrate, sodium acetate, potassium acetate, potassium ammonium tartrate, ammonium acetate, ammonium carbonate, ammonium formate, ammonium citrate, ammonium lactate, ammonium bisulfate and mixtures of these ingredients also provides approximately Similar results are obtained. Example 2 The foaming properties of bar soap compositions of the present invention were compared to those of bar soaps utilizing sodium chloride and potassium chloride electrolytes well known in the literature using the method described in Example 1 above. . Using the method described in Example 1, a bar soap was made containing 62.4% tallow/coconut (80/20) sodium soap, 10.4% potassium palm soap, 6.0% glycerin, and additional ingredients in the amounts indicated above. This bar soap was tested for foaming properties in tap water (hardness = 17 grains/gal) and distilled water. This bar soap contained approximately 15% to 18% water.

TABLE Example 3 The compositions listed in the table below are illustrative of various embodiments of the bar soap of the present invention. These bar soap compositions can be manufactured using any conventional method described herein, particularly using the method described in Example 1 above. Use other common electrolytes such as potassium chloride in place of sodium chloride below, or use other fatty acids in place of coconut fatty acid below, or all of the potassium carbon or potassium citrate electrolytes below. Or in place of a part of sodium formate, potassium formate, sodium tartrate, potassium tartrate, sodium citrate, sodium acetate, potassium acetate, ammonium potassium tartrate, ammonium acetate, ammonium carbonate, ammonium formate, ammonium citrate,
Similar compositions can be made using ammonium lactate, ammonium bisulfate, or mixtures of these compounds. In the table below, the components indicated as A, B, C, D, E, etc. represent the following: A- Sodium tallowate B- Sodium cocoate C- Potassium tallow fatty acid D - Potassium coconut fatty acid E - Sodium chloride F - Potassium carbonate G - Potassium citrate H - Coconut fatty acid I - Glycerin J - Polyacrylamide K - Water L - Minor components, such as fragrances, colorants, etc. Composition numbers 30-32 in the following table are for comparison.

【table】

Claims (1)

Claims: 1. Essentially about 4% to 20% potassium soap (with the remainder of the soap ingredients comprising sodium, ammonium or alkanolamine soap), at least about 0.2% chlorine anions, and about 4% to about 25% water. , and potassium carbonate, sodium formate, potassium formate, sodium tartrate, potassium tartrate, sodium citrate, potassium citrate, sodium acetate, potassium acetate, potassium ammonium tartrate, ammonium acetate, ammonium carbonate, ammonium formate, ammonium citrate, ammonium lactate. , ammonium bisulfate, and mixtures thereof. 2. The bar soap of claim 1, comprising about 0.5% to about 3% of said electrolyte. 3 The electrolyte is potassium formate, potassium citrate, potassium acetate, potassium tartrate, sodium formate, sodium citrate, sodium acetate,
3. A bar soap according to claim 2, which is selected from the group consisting of sodium tartrate and mixtures thereof. 4. The solid soap according to claim 3, wherein the electrolyte is potassium citrate. 5. The bar soap of claim 1 which is milled and contains at least about 70% beta phase material. 6. A bar soap according to claim 1, additionally comprising about 0.2% to about 10% glycerin.