CN1062759A - Shaped solids made from a rigid intertwined network of neutralized carboxylic acids - Google Patents

Abstract

The invention provides a three-dimensional skeleton structure of a shaped solid, which includes Contains: A fairly rigid intertwined network of crystalline carboxylic acids after neutralization. the other party On the other hand, the present invention provides a kind of neutralized carboxylic acid, preferably by sodium soap An improved cleansing bar of rigid interlaced network of fibers. this A preferred class of cleansing soap bars can be formulated to be substantially bar-free sex. Certain Cleansing Soap Bars Contain Surprisingly Large Amounts of Water and Other It is liquid, yet retains its rigidity even if it is soaked in water overnight and superior sticky properties.

Description

This application is a continuation-in-part of US Patent Application Serial No. 07/617827 filed November 26, 1990.

This invention relates to shaped solid compositions of neutralized carboxylic acids, particularly cleansing bars, bars, bars, synthetic cleansing bars, and the like.

Products in the form of shaped solids, blocks and bars are numerous. Cleansing bars of soap are well known in the art.

In the prior art, cleansing soap bars with reduced bar stickiness have been reported, such as U.S. Patent No. 2,988,511 to Mills (incorporated herein by reference) on June 13, 1961, which discloses a low Sticky bar of soap.

Soap bar goo, also known as inert, is the soft solid or paste that forms on the surface of a clean bar of soap when it is soaked in water, and is perceived by consumers as dirty, unattractive and unattractive Economy.

Products made in shaped solids, blocks and bars are numerous. For example, U.S. Patent No. 4,606,839 issued to Harding on August 19, 1986, discloses certain high moisture and low viscosity body cleansing bars. Harding uses coconut/and palm kernel oil.

One need only examine the body cleansing bars used in bathrooms to understand that there remains a need for improved cleansing bars with little or no stickiness.

In the 1940 Journal of American Chemical Society (Vol63, pp1990-1993), L. Marton et al reported the formation of rigid soap coagulum fibers of sodium laurate. This report does not refer to the use of soap coagulum. Shaped solids as defined herein are not disclosed by Marton et al.

Japanese Patent J5 7030-798 (1980, July, 30) discloses clear solid formed or molded soap bars in which the fatty acids constituting the soap components are myristic, palmitic and stearic acids. At least 90% by weight of said transparent soap, the fatty acids constituting the components of the soap are myristic acid, palmitic acid and stearic acid. The reported product is a transparent solid soap with good foaming and setting properties and low human skin irritation. The method and clear bar soap compositions exemplified in Japanese Patent J5 7030-798 are not shown to contain synthetic surfactants.

Higher levels (15-40%) of moisture (especially in the presence of many synthetic surfactants), hygroscopic surfactants and/or higher levels of non-solid and soft solids, such as those of water-soluble polyols and hydrocarbon oils Firm, non-sticky bars are also difficult to prepare.

The present invention provides a shaped solid three-dimensional framework comprising a relatively rigid interlocking network of crystalline carboxylic acids after neutralization and, in another aspect, the present invention provides a structure consisting of said framework, i.e., a carboxylic acid after neutralization. Improved cleansing bars of rigid interlocking network, preferably sodium soap fibers. Certain cleansing bars contain surprisingly large amounts of water and other liquids, yet retain their rigidity and excellent stickiness properties even when they are soaked in water overnight.

Figures 1-8 show enlarged views of soap bar samples of the present invention. Figures 9 and 10 show enlarged views of two different conventional soap bars.

Scanning Electron Microscopy (SEM) specimen preparation consists of simply applying pressure to break up the shaped solid to obtain a fresh surface for examination. The crushed specimen was reduced in size (with a razor blade) to a rectangle of about 10 mm x 15 mm with a thickness of about 5 mm. The sample was placed in an aluminum SEM stub with a silver paint adhesive. The mounted samples were plated with 300 Angstroms of gold/palladium in a Pelco sputter coater. The samples were subjected to vacuum prior to plating for a period sufficient to remove the bar moisture necessary to ensure plating quality. After plating, the samples were moved to the SEM chamber and examined with a Hitachi Model S570 scanning electron microscope under standard SEM conditions to observe the skeleton (core bone) structure.

Figures 1 and 2 are high magnification copies of photographs of a framework core structure comprising a rigid interlocking network of elongated neutralized carboxylic acid crystalline fibers. More specifically, elongated _C12 sodium soap fibers are shown at magnifications of 5000X and 2500X in Figures 1 and 2, respectively. The structures of Figures 1 and 2 were prepared with 5% soap, 94% water and 1% sodium chloride. See Example 10 in Table 7 herein. Note that larger fibers in an interlaced network can be composed of smaller fibers. Also watch out for "void" spaces. See Figure 2.

Figures 3, 4, and 5 are copies of photographs of framework structures made with 25% sodium _C12 soap, 74% water, and 1% sodium chloride, showing crystalline fibers at magnifications of 3000X, 5000X, and 1000X, respectively shape structure.

Figure 6 is a copy of a photograph of a backbone structure prepared with 20% disodium salt of 1,12-dodecanedioic acid. This crystalline fibrous structure is shown at 2000X magnification. See Example 26.

Figure 7 shows at 1500X magnification a copy of a photograph of the backbone (core bone) structure containing the crystalline lithium neutralized _C14 carboxylic acid network. See Example 27.

Figure 8 is a copy of a photograph of a cleansing soap bar (Example 1 hereinafter) comprising coated _C14-16 sodium soap fibers. These fibers are coated with and/or intermingled with other components. The magnification is 1500X.

冷冻器皂条的试样。IVORY皂条中的空气使其能漂浮。Figure 9 shows a commercially available IVORY made with sodium/potassium coconut/tallow soap at 1000X magnification

Samples of Freezer Soap Bars. The air in the IVORY bars allows them to float.

透明皂条的试样。Figure 10 shows a commercially available NEUTROGENA at 1500X magnification

Samples of transparent soap bars.

In Figures 1 and 2, the samples were first melted on a hot metal plate and then recooled on a glass slide. The other samples, Figures 3-10, were samples of pristine shaped solid structures or samples of conventional soap bars prepared as set forth herein.

The present invention provides a shaped solid having two or more phases. One phase is a crystalline framework structure comprising a rigid interlaced open three-dimensional network of elongated crystals of neutralized carboxylic acid. The additional base phase is an aqueous phase which is soft or flowable at 25°C.

More precisely, the framework structure is a rather rigid interlocking open three-dimensional network of elongated crystals of neutralized mono- and/or dicarboxylic acids.

The terms: skeleton structure, skeleton structure, core, and skeleton frame are often used interchangeably in this article.

As used herein, the term "shaped solid" includes forms such as bars, blocks, and the like. The term "strip" used herein, unless otherwise specified, includes the same meaning as above.

As used herein, the term "network" refers to a network of interlaced crystalline frameworks with voids or openings as seen under magnification with a scanning electron microscope.

In another aspect, the present invention provides an improved cleansing bar consisting of said backbone structure. Certain shaped solids are solids in the form of cleansing bars that contain unexpectedly high levels of the aqueous phase comprising water, other liquids and soft materials. Despite the large amount of aqueous phase, the preferred bars of the present invention retain their rigidity and excellent stick-related properties even when they are soaked in water overnight. Without being bound by any theory, the shaped solid comprising these phases resembles a stiffer wet sponge.

The crystalline phase includes interlaced lamellar crystals and/or fibrous crystals, preferably fibrous. Preferably, the fibers consist of sodium soap. The interlocking network of fibers and/or platelets imparts strength to this three-dimensional structure even when allowed to soak overnight in water, even in the presence of high levels of water or other soft substances. The strength of the skeleton structure can be measured indirectly by the hardness of the formed solid, that is, by determining the penetration resistance of the solid with a standard weighted pentrometer probe. See Bar Hardness Test below for details. A skeletal structure is a structure of sufficient stiffness to enable a penetration value of about 0 mm to about 12 mm, preferably about 1 mm to about 10 mm, more preferably about 3 mm, for cleansing bar samples 20 mm thick or thicker - about 8mm. Due to the size and other characteristics of the crystals, the bars of the present invention are distinguished from conventional clear soap bars. The size of crystals or crystal beams forming the interlaced network structure of the present invention should be suitable for light diffraction, so both diameter and length should be greater than 400 nm. In contrast, conventional clear soap bars are transparent due to crystal diameters or lengths smaller than the wavelength of white light (white light wavelengths greater than about 400nm). Therefore, light cannot be diffracted.

Once formed, the soap bar (shaped solid) containing the intertwined structure of the present invention, when it is subjected to such as in Small et al. U.S. Patent No. It immediately loses its rigidity when subjected to the breaking mechanical forces of those used in the conventional stamping soap bar manufacturing process disclosed in . This is because the crushing mechanical forces shear and break the rigid skeleton structure into smaller pieces. Thus, when the bars of the present invention are subjected to shear in a screw extruder, a much softer bar is formed.

Conversely, when a finished conventional soap bar is molded or remolded, the remolded conventional soap bar is still very hard. See Example 28 and Table 12 for details on this.

The framework structure has many "void" regions filled with a soft and/or liquid aqueous phase. What is surprising about the present invention is that the physical properties of the bar, such as bar hardness and little stickiness, depend essentially on the crystalline interlocking network structure, even when other phases make up the majority of the existing material. In a conventional soap bar, many components can affect the overall physical properties of the bar, because these components either change the phase and structure of the soap, or change the composition of synthetic surfactants, and the physical properties of the bar are mainly determined by them. The combination of two or more phases (such as soap and aqueous solution) drastically changes the colloidal structure, thereby changing the physical properties of conventional soap bars.

Thus, conventional soap bars are more limited in the type, amount and composition of soft phase materials that can be incorporated into the bar than the present invention. These phases consist mostly of either flowable liquid material, or material softer than the minimum hardness of an acceptable soap bar. These phases include aqueous solutions, liquid crystalline phases composed of water and surfactants, polymers; especially crystalline phases containing surfactants; especially crystalline phases containing hygroscopic surfactants, which react with water or other liquid phases. (including water-soluble organic compounds such as propylene glycol and glycerin), hydrophobic materials (such as mineral oil, liquid triglycerides), or soft hydrophobic materials (such as petrolatum, low-melting point paraffins, and low-melting point triglycerides) Tends to soften or thicken when mixed.

Physically, all of these phases can be characterized as flowable liquids, or so soft that a standard gravimetric pin penetration hardness tester probe as described above can penetrate it everywhere through a 12 mm thick sample. These phases are optionally included in the structure of the present invention without compromising the interlaced network structure and certain desirable properties.

The present invention is a shaped solid comprising a skeletal structure which is a relatively rigid interlocking, open three-dimensional network of elongated crystals of mono- and/or dicarboxylic acids after neutralization.

A preferred embodiment is a cleansing bar comprising at least 2 phases: (1) an aqueous phase having a penetration value of approximately 12 mm for a sample depth of 12 mm; said aqueous phase being soft or flowable; (2) comprising a rigid A rigid crystalline phase with a skeletal structure comprising an interlaced, open three-dimensional network of elongated crystals of mono- and/or dicarboxylic acids after neutralization; comprising said rigid crystalline phase skeletal structure as well as said aqueous phase The cleansing soap bar has a penetration value of 0 to about 12 mm on a 25 mm deep sample, where said penetration value is measured at 25°C with a 247 gram standard weighing needle hardness tester probe having A tapered needle attached to a 9" (22.9 cm) rod, weighing 47 grams, with 200 grams added to the top of said rod for a total weight of 247 grams as stated, said tapered needle tip being 19/32 inch (1.51cm), the tip is 1/32 inch (0.08cm).

The above cleansing bar is preferred when said neutralized carboxylic acid is selected from the group consisting of lithium and/or sodium neutralized monocarboxylic (soap) and/or dicarboxylic acids acids; and mixtures thereof; wherein said monocarboxylic acids contain aliphatic alkyl (alkylene) chains of from about 12 to about 24 carbon atoms; wherein said dicarboxylic acids contain from about 12 to about 18 carbon atoms fatty alkyl (alkylene) chains; wherein at least about 80% of said carboxylic acids contain saturated alkyl (alkylene) chains; wherein said rigid crystalline phase skeletal structure constitutes about 3% by volume of said cleansing bar or more to about 75%; wherein said neutralized carboxylic acid comprises more than about 5% to about 75%; wherein the cleansing bar contains from about 15% to about less than 94% water by weight of said cleansing bar.

The above cleansing bar is preferred when at least 80%, preferably 90%, of the carboxylic acid has the general formula:

in:

a+b=8-20

a, b = 0-20 each

、R，或这些基团同时存在X=H, OR,

, R, or these groups exist simultaneously

R=C ₁ -C ₃ alkyl, H, or these groups exist simultaneously

M=Na, Li or a combination thereof.

The cleansing soap bar above is more preferably when said a+b=10-16; said a, b each=0-16; said X=H, OR; R=H; and M=Na.

The cleansing soap bar above, consisting of at least about 25% of said saturated fatty acid alkyl chain in a single-segmented fibrous sodium fatty acid soap in said elongated crystalline system; wherein said soap bar contains: about 15% to about 75% of said sodium soap; wherein the ratio of said unneutralized (free) carboxylic acid to soap is about 1:2 to about 0, i.e. free fatty acid is not more than 50% by weight of soap in the formulation Especially preferred.

Such cleansing bars are preferred when said bars contain said sodium soap and water; from about 2% to about 60% of a synthetic surfactant selected from the group consisting of: alkyl sulfates, Paraffin Sulfonate, Alkyl Glycerol Ether Sulfonate, Acyl Sarcosinate, Methyl Acyl Taurate, Linear Alkyl Benzene Sulfonate, N-Acyl Glutamate, Alkyl Glucose Glycosides, alpha sulfo fatty acid esters, acyl isethionates, alkyl sulfosuccinates, alkyl ether carboxylates, alkyl phosphates, ethoxylated alkyl phosphates, methylglucose Sugar esters, protein condensates, alkyl amine oxides, alkyl betaines, alkyl Sultaines, alkyl ether sulfates containing 1-12 ethoxy groups, and mixtures thereof, wherein the surfactant contains C ₈ -C ₂₂ Alkyl chain.

The cleansing bars described above are preferred when the synthetic surfactant is hygroscopic; a hygroscopic surfactant is defined as absorbing at least its peak value in water for at least three days at 26°C and 80% relative humidity. 20% water by dry weight of surfactant wherein the bar is non-swellable.

The hygroscopic surfactant is selected from alpha sulfo fatty acid ester, alkyl sulfate, alkyl ether carboxylate, alkyl betaine, alkyl Sultaines, alkyl amine oxide, alkyl ether sulfate and their The cleansing bar described above is preferred when in the group consisting of a mixture of

The ratio of said water to said soap is about 1:1 to about 5:1; said water is present in an amount of about 25% to about 60%, wherein said fatty alkyl chain is C ₁₄ -C ₂₂ and in Said soap is present in said soap bar at a level of from about 15% to about 35%; wherein at least about 85% of said alkyl chains are saturated; wherein said unneutralized (free) carboxylic acid is associated with said soap The weight ratio of about 1:4-0; wherein the content of said synthetic surfactant is from about 4% to about 25% by weight of the soap bar, and said surfactant is selected from the group consisting of the following compounds The cleansing bars listed above are preferred: sodium acyl isethionate, sodium acyl sarcosinate, sodium alpha sulfo fatty acid ester, sodium paraffin sulfonate, sodium alkyl ether sulfate, sodium alkyl sulfate, direct Sodium Alkylbenzene Sulfonates, Alkyl Betaines, Alkyl Sultaines, Trialkylamine Oxide.

When the ratio of said water to soap is about 1.5:1 to about 2:1; the ratio of said non-neutralized carboxylic acid (free) to said soap is about 1:6-0; the content of said water is about 30% to about 45%; the fatty alkyl chain is about C ₁₄ -C ₁₈ ; wherein at least about 95% of the alkyl chain is saturated; the soap content is about 15% to about 30%; the The cleansing bars described above are preferred when the synthetic surfactant is present at from about 8% to about 16%.

Such cleansing bars are preferred when the bar contains from about 0.1% to about 40% of a hydrophobic material selected from the group consisting of microcrystalline wax, petrolatum, carnauba wax, carnauba wax, carnauba wax, Candelilla wax, sugarcane wax, vegetable-derived triglycerides, beeswax, spermaceti, lanolin, wood wax, shellac wax, animal-derived triglycerides, montar, ozokerite, ceresin, and Fischer-Tropsch ( Fischer-Tropsh) synthetic wax, the above cleansing bar is preferred.

The cleansing bar above, preferably when said bar contains from about 2% to about 35% of said hydrophobic material selected from the group consisting of petrolatum and wax, wherein said petrolatum and wax, and mixtures thereof melt at about 49°C (120°F) to about 85°C (185°F).

Such cleansing bars are preferred when the bars contain from about 5% to about 25% paraffin by weight of the bar.

When the bar contains from about 1% to about 50% of a non-volatile, water-soluble, non-ionic organic material having a solubility of at least 5 parts in 10 parts of water, and wherein the water-soluble non-ionic organic material is selected from the group consisting of Structure of polyols:

Wherein R ₁ =H, C ₁ -C ₄ ; R ₂ =H, CH ₃ ; and n = 1-200;

C ₂ -C ₁₀ alkane diols; sorbitol; glycerol, sugars, sugar derivatives; urea; and ethanolamines with the general structure (HOCH ₂ CH ₂ ) _x NH _y (where x = 1-3; y =0-2; x+y=3) and mixtures thereof, the above cleansing soaps are preferred.

The cleansing bars described above are preferably when said bars contain from about 2% to about 40% of said non-volatile, water-soluble, nonionic organics.

The above cleansing bar wherein said non-volatile, water-soluble, nonionic organic matter is from about 5% to about 20% by weight of the bar; and wherein said organic matter is selected from the group consisting of propylene glycol, glycerin, sucrose, urea, and It is preferred to use a combination of mixtures thereof.

Preferably said cleansing bars above contain said sodium soap, said water and said synthetic surfactant and from about 0.1% to about 70% of the following other ingredients selected from the group consisting of: Group:

about 1% to about 10% of said potassium soap;

about 1% to about 35% of said magnesium soap;

about 1% to about 35% of said calcium soap;

about 1% - about 15% triethanolammonium soap;

From about 1% to about 60% finely divided water-insoluble matter selected from the group consisting of calcium carbonate and talc;

所组成的物组。From about 0.1% to about 20% of polymeric skin sensory aids, wherein said polymeric skin sensory aids are selected from cationic polysaccharides, preferably cationic guar gums with a molecular weight of 1,000-3,000,000; cationic polyalkyleneimines, Ethoxylated polyalkyleneimine and poly[N-[-3-(dimethylammonium)propyl]-N′-[3-vinyloxyethylenedimethylammonium)propyl]urea Chloride], Silicone Amines, and Silicone Fluids, JR Polymers, Celquat

composed of groups of objects.

From about 0.5% to about 25% of aluminosilicate clays and/or other clays, wherein the aluminosilicates and clays are selected from the group consisting of zeolite, kaolin, kaolinite, montmorillonite, attapulgite, illite, In the group consisting of bentonite, halloysite, and cooked clay;

From about 1% to about 50% of salts and salt hydrates, and mixtures thereof, wherein said salts and salt hydrates contain sodium, potassium, magnesium, calcium, aluminum, lithium, ammonium, monoethanolammonium, diethanolammonium, and A cation of a substance in the group consisting of triethanolammonium, and wherein said salts and salt hydrates are selected from the group consisting of chlorides, bromides, sulfates, metasilicates, orthophosphates, pyrophosphates, polyphosphates , metaborates, tetraborates, carbonates, bicarbonates, hydrogen phosphates, methyl sulfate, and mono- and polycarboxylates with 6 or less carbon atoms anion of the substance.

Preferably, the cleansing bars described above comprise platelets within the elongated crystals, and wherein the soap system consists of lithium neutralized monocarboxylic acids.

The above cleansing bar wherein the elongated crystals are fibrous, and wherein the neutralized dicarboxylic acid is the disodium salt of 1,12-dodecanedioic acid, wherein the neutralized dicarboxylate accounts for Preferably from 20% to about 70% by weight of the bar.

BEST METHOD OF PREPARING THE SOAP BAR

The method of making the above-mentioned cleansing bar of the present invention comprises the following steps:

1. forming an aqueous molten liquid comprising from about 15% to about 94% by weight of water and from about 6% to about 75% of said neutralized carboxylic acid;

Ⅱ. Injecting the molten liquid into the soap bar forming mold;

III. Crystallization of said molded molten liquid upon cooling results in said cleansing bar.

The above process is preferably prepared by neutralizing an aqueous mixture of the carboxylic acid with sodium hydroxide or lithium hydroxide under agitation at a temperature of about 50°C (120°F) to 95°C (205°F). This aqueous molten liquid is obtained.

Preferably from about 2% to about 15% (by weight) of the bar is a "crystal enhancing salt" selected from the group consisting of sodium or lithium salts of sulfuric acid, chloride, acetic acid and citric acid and In the group composed of its mixture.

Preferably in the above method, the aqueous phase of the aqueous molten liquid contains about 2% to about 40% of a solubilizing aid selected from the group consisting of:

(a) Nonvolatile, water-soluble, nonionic organic solvents selected from the group consisting of:

The structural formula is

Polyols, wherein R ₁ = H, C ₁ -C ₄ ; R ₂ = H, CH ₃ ; and n = 1-200; C ₂ -C ₁₀ alkanediol; sorbitol; glycerol; sugars; Sugar derivatives; urea; and ethanolamines of the general formula (HOCH ₂ CH ₂ ) _x NH _y where x=1-3; y=0-2; x+y=3;

(b) Alcohols with 1-5 carbon atoms;

(c) Synthetic surfactants selected from the group consisting of: alkyl sulfates, paraffin sulfonates, alkyl glycerol ether sulfonates, anionic acyl sarcosinates, methylacyl taurine acid salt, linear alkylbenzene sulfonate, N-acyl glutamate, alkyl glucoside, alpha sulfo fatty acid ester, acyl isethionate, alkyl sulfosuccinate, alkyl ether Carboxylate, Alkyl Phosphate, Ethoxylated Alkyl Phosphate, Methyl Glucose, Protein Condensate, Alkyl Amine Oxide, Alkyl Betaine, Alkyl Sultaines, Containing 1-12 B Alkyl ether sulfates of oxy groups and mixtures thereof; wherein the surfactant contains C ₈ -C ₂₂ alkylene chains;

and mixtures thereof;

Wherein said solubilizing agent is added for increasing the amount of said neutralized carboxylic acid dissolved in said continuous molten aqueous phase in step I.

The above method is preferred when said aqueous phase contains from about 20% to about 100% water by weight of said aqueous phase.

This method is preferred when said rigid crystalline phase contains from about 75% to about 100% by weight of said crystalline phase of said neutralized carboxylic acid.

The above method is preferred when the bar has a penetration value for the 25 mm bar sample of about 3 mm to about 9 mm.

The above method is preferred when the soap bar contains a mixed non-carboxylic acid phase of droplets or crystals selected from wax, petrolatum, clay and the like.

A highly preferred embodiment of the present invention is: a body cleansing bar composition comprising a rigid crystalline interlocking network of elongated sodium soap crystals; said bar comprising: from about 15% to about 50%, consisting of at least about Sodium fatty acid soap of 50% saturated fatty alkylene chains having 12 to 24 carbon atoms (at least about 25% of said saturated fatty alkylene chains being single segments); about 15% to about 60 % of water; and from about 2% to about 60% (by weight) of a hygroscopic synthetic surfactant, wherein the hygroscopic synthetic surfactant is selected from three days of adsorption in water at a relative humidity of 80% at 26°C Surfactant with about 20% water by its dry weight.

The highly preferred body cleansing bars described above are even more preferred when the hygroscopic surfactant is selected from the group consisting of alpha sulfo fatty acid esters, alkyl sulfates, alkyl ether carboxylates , Alkyl Betaines, Alkyl Sultaines, Alkyl Amine Oxides, Alkyl Ether Sulfates, and mixtures thereof.

When said bar contains about 0.5% to about 40% salt and/or salt hydrate, and they are selected from the group consisting of the following materials, this highly preferred body cleansing bar is more Good: Sodium chloride, sodium sulfate, disodium phosphate, sodium pyrophosphate, sodium tetraborate, sodium acetate, sodium citrate, and other miscible salts of inorganic and short-chain organic acids.

A highly preferred bar contains various combinations of a core structure of sodium soap fibers, water, mild synthetic surfactants, bar appearance stabilizers, skin softening aids, and other cleansing bar adjuncts. Such preferred bars can be formulated so as to be substantially free of bar stickies.

Certain preferred soap bars of the present invention comprise: an interlocking network of rigid, neutralized carboxylic acid fibrous cores consisting essentially of fatty acid sodium soaps composed of at least 50% saturated Composition of aliphatic alkyl chains with 12-24 carbon atoms. Preferably, at least about 25% of said saturated alkyl chains are single segment chains.

Certain compositions of the present invention comprise an aqueous or non-aqueous rigid network as described above. These compositions must be formed with water or with another suitable solvent system. The article can be made with large amounts of water, and the water content in the final article can be reduced to about 1% or 2%.

However, a particular advantage of certain structures described herein is that they can be dehydrated without loss of network integrity. Certain preferred shaped solids can be dehydrated without significant change in their external dimensions. Other soap bars shrank while maintaining their three-dimensional shape. Certain soap bars herein have the excellent property of not breaking down due to dehydration.

The more complex soap bars of the present invention comprise a backbone structure containing other fatty acid salts selected from potassium, magnesium, triethanolammonium and/or calcium soaps for combination with selected levels of sodium and/or lithium soaps. More complex cleansing bars can contain surprisingly large amounts of water, mild synthetic surfactants, bar appearance stabilizers, skin softening aids and other cleansing bar adjuncts, yet they are mild and Has excellent low viscosity properties.

Tables 1-3 show some of the preferred soap bars made with the sodium salt of aliphatic carboxylic acid (FA) soaps.

Unless otherwise specified, percentages, ratios and parts herein are based on the total weight of the composition. Unless otherwise specified, all contents and ranges herein are approximate.

Table 1

Optimum bar, chain length and content

better better best

Water content 15-94% 25-60% 30-45%

Water: soap ratio 0.7:1 1:1-5:1 1.5:1-2:1

FA chain length C _12-24 C _14-22 C _14-18

The amount of FA soap in the total formula 6-50% 15-35% 15-30%

It is not necessary to show all high and low values in Table 1. For example, certain selected sodium soaps may be used at levels up to about 75%. Thus, the range is from about 5% to about 75%. This preferable content and ratio differ between cations and cations, etc., and between monocarboxylic acids and polycarboxylic acids.

The bars shown in Table 1 were made with the water levels indicated, but the water level in the final bars could be reduced to obtain bars with reduced or even little or no water. The preferred level of water is from about 20% to about 80% by weight of the bar.

Table 2 below shows some preferred levels of single FA segmented soaps. Table 3 shows some preferred levels of unsaturated FA in the FA used in the compositions of the invention. Certain preferred compositions contain few or no short chain FAs of 10 or fewer carbon atoms. As used herein, the terms "soap", "fatty acid (FA) salt" and "monocarboxylate" are sometimes used interchangeably. "Soap" is used because it is easier to explain and is a preferred embodiment.

Table 2

(total fibrous soap content) single-segment soap%

better better best

C _12-24 25-100% 50-100% 25-100%

table 3

Total % of unsaturated or low (C ₁₀ or less) chain length soaps

Average Better Better

C ₁₂ 0-15% 0-5% 0-1%

C _14-24 0-50% 0-10% 0-1%

Table 4 lists high and low values for certain key preferred optional ingredients of the complex soap bar compositions of the present invention. These ingredients are substantially absent from the core structure of the basic preferred soap bar. The minimum value for each optional component is 0. Certain preferred soap bars may contain these ingredients in a total amount of about 0.1% up to about 70%. This means that most soap bars can contain significant amounts of other ingredients besides sodium soap and water. The values listed in Table 4 are specific to illustrate soap bars containing greater than about 5% to about 75% of selected sodium soaps and other ingredients.

It should be understood that lithium soap alone or only the neutralized polycarboxylic acid may be used in solid form, but levels and ranges other than those established for sodium soaps are contemplated.

Table 4

High and low % by weight of other ingredients in more complex sodium soap bars

better better best

Neutralized dicarboxylic acid 1-40% 2-30% 5-25%

Lithium "soap" 1-40% 2-30% 5-25%

Potassium soap 1-10% 2-10% 5-8%

Magnesium or calcium soap 1-35% 1-12% 3-8%

Triethanolammonium soap 1-15% 2-15% 5-10%

Synthetic surfactant 1-60% 4-25% 8-16%

Other salts and salt hydrates 0.5-50% 1-25% 2-15%

Non-volatile water-soluble non-ionic organic matter 1.0-50% 2-40% 5-20%

Polymerization mild enhancer 0.1-20% 0.25-10% 1-5%

Wax 0.1-40% 2-35% 3-10%

Other fine water-insoluble substances 1-60% 4-25% 8-16%

Aluminosilicate/clay 0.5-25% 1-10% 3-8%

Soaps useful in the present invention may be of the same alkyl chain length, ie, those selected from those listed in Table 2 of 12 to 24 carbon atoms. The same chain length applies to other non-sodium soaps used in the soap bars of the present invention.

The sodium soap content is preferably at least about 50% of the soap in the bar.

The content of potassium soap and/or triethanolammonium soap should not exceed one-half, preferably one-third, preferably less than one-quarter of that of sodium soap, while the content of magnesium soap should not exceed that of sodium soap About one-third of the sodium soap content, preferably less than about one-quarter of the sodium soap content.

The total amount of other soaps, except lithium soap, should preferably not exceed 1/2 of that of sodium soap, more preferably not more than 1/3.

The syndet ingredients of the soap bar compositions of the present invention can be designated as syndets from anionic, nonionic, amphoteric and zwitterionic groups. Low and high sudsing and high and low water solubility surfactants can be used in the soap bar compositions of the present invention.

Examples of synthetic detergents suitable for use herein are those disclosed in U.S. Patent No. 3,351,558, issued November 7, 1967 to Zimmerer, column 6, line 70 to column 7, line 74, incorporated herein by reference.

Examples include water-soluble salts of organic acids, sulfonic acids and aliphatic sulfates, that is, water-soluble salts of organic sulfuric acid reaction products having an alkyl group with a molecular structure of 10-22 carbon atoms and A group composed of ester groups.

Synthetic sulfate detergents of particular interest are generally solid alkali metal salts of n-primary aliphatic alcohol sulfates having 10 to 22 carbon atoms. Sodium and potassium salts of alkylsulfates derived from mixed higher alcohols derived from reduced tallow or reduced coconut oil, palm oil, stearin oil, palm kernel oil, babassu kernel oil or Other coconut oil derived that can be used herein.

Other suitable aliphatic sulfates include the water-soluble salts of polyol sulfates which are incompletely esterified with high molecular weight soap-forming carboxylic acids. These synthetic detergents include water-soluble alkali metal salts of high molecular weight fatty acid monoglyceride sulfates, such as the sodium and potassium salts of 1,2-hydroxypropane-3-sulfate coco fatty acid monoester, monomyristyl ethylene Sodium and potassium glycol sulfates and sodium and potassium monolauroyl diglyceryl sulfates.

The present invention also employs synthetic surfactants and other optional materials used in conventional detergent products. In fact, certain ingredients, such as certain hygroscopic synthetic surfactants that are typically used in liquid form and are difficult to incorporate into conventional cleansing bar soaps, are quite compatible in the bars of the present invention. Thus, essentially all known synthetic surfactants used in detergent products are useful in the compositions of the present invention. The patent literature for detergent products fully discloses synthetic surfactants. Certain preferred surfactants, as well as other detergent product ingredients, are disclosed in the following documents:

Patent No. Grant Date Inventor

4061602 12/1977 Oberstar et al

4234464 11/1980 Morshauser

4472297 9/1984 Bolich et al

4491539 1/1985 Hoskins et al

4540507 9/1985 Grollier

4565647 1/1986 Llenado

4673525 6/1987 Small et al

4704224 11/1987 Saud

4788006 11/1988 Bolich, Jr., et al.

4812253 3/1989 Small et al

4820447 4/1989 Medcalf et al

4906459 3/1990 Cobb et al

4923635 5/1990 Simion et al

4954282 9/1990 Rys et al

All of these above-mentioned patents are combined with this article for reference. Certain preferred synthetic surfactants are shown in the Examples herein. Bar appearance stability, lather, detergency and mildness are selectively indicated for preferred synthetic surfactant systems.

It should be noted that surfactant mildness can be determined by the Skin Barrier Breakdown Test, which is used to test the irritation of surfactants. In this test, the milder the surfactant, the less disrupted the skin barrier. Breakdown of the skin barrier was measured by the relative amount of radiolabeled water ( ^3HH2O ) passed from the test solution through the skin surface into the physiological buffer contained in _the exudate chamber. This test is disclosed in J. Invest. Dermatol. (TJ Franz, 1975, 64, PP 190-195) and U.S. Patent No. 4,673,525 (Small et al., issued June 16, 1987), incorporated herein by reference, which disclose Mild Alkyl Glyceryl Ether Sulfonate (AGS) Surfactant Based Synthetic Soap Bar Containing "Standard" Alkyl Glyceryl Ether Sulfonate Blend. The skin barrier breakdown test is used to select mild surfactants. Some mild synthetic surfactants are disclosed in the aforementioned Small et al. and Rvs et al. patents. In the present examples, some specific examples of preferred surfactants are used.

Examples of good lather enhancing detergent surfactants, mild surfactants, are eg sodium lauroyl sarcosinate, alkyl glyceryl ether sulfonates, sulfonated fatty esters, paraffin sulfonates and sulfonated fatty acids.

Examples of many other surfactants are disclosed in the patents incorporated herein by reference. They include other alkyl sulfates, anionic acyl sarcosinates, methyl acyl taurates, N-acyl glutamates, acyl isethionates, alkyl sulfosuccinates, alkyl phosphates Esters, ethoxylated alkyl phosphate esters, trideceth sulfates, protein condensates, ethoxylated alkyl sulfates and alkylamine oxides, betaines, mixtures of Sultaines and mixtures of the above. The surfactants also include alkyl ether sulfates containing 1-12 ethoxy groups, especially ammonium and sodium lauryl ether sulfates.

The alkyl chains of these other surfactants are C ₈ -C ₂₂ , preferably C ₁₀ -C ₁₈ . Alkyl glycosides and methyl glucosides are preferred mild nonionic surfactants which may be admixed with other mild anionic or amphoteric surfactants in the compositions of the present invention. Alkyl polyglycoside detergents are useful suds boosters. The alkyl groups can vary from 8 to about 22, and the glycosidic units per molecule can vary from about 1.1 to about 5, to provide the proper balance between the hydrophilic and hydrophobic portions of the molecule. Preferably, the combined C ₈ -C ₁₈ , preferably C ₁₂ -C ₁₆ alkyl polyglycosides have an average degree of glycosylation of about 1.1-2.7, preferably about 1.2-2.5.

Preferred are sulfonated esters of aliphatic esters, wherein the carboxylic acid chain length is C ₈ -C ₂₂ , preferably C ₁₂ -C ₁₈ ; the ester alcohol chain length is C ₁ -C ₆ . These include sodium alpha-sulfomethyl laurate, sodium alpha-sulfomethyl cocoate and sodium alpha-sulfomethyl tallowate.

Amine oxide detergents are good suds boosters. Some of the preferred amine oxides are C ₈ -C ₁₈ , more preferably C ₁₀ -C ₁₆ alkyl dimethyl amine oxides and C ₈ -C ₁₈ , more preferably C ₁₂ -C ₁₆ fatty amidopropyl dimethylamine oxides. amine oxides and mixtures thereof.

Fatty acid alkanolamides are good suds boosters. Some of the preferred alkanolamides are C ₈ -C ₁₆ , more preferably C ₁₂ -C ₁₆ monoethanolamides, diethanolamides, monoisopropanolamides and mixtures thereof.

Other detergent surfactants are alkyl ethoxy carboxylates having the general formula:

Wherein R is a C _8-22 alkyl group, K is an integer of 0-10, and M is a cation; there are also polyhydroxy fatty acid amides with the following general formula:

Wherein R ¹ is H, C _1-4 alkyl, 2-hydroxyethyl, 2-hydroxypropyl or these groups exist at the same time, R ² is C _5-31 hydrocarbon group, and Z has at least one band directly connected to the chain The straight-chain hydrocarbon group polyhydroxyl hydrocarbon group with 3 hydroxyl groups on it, or its alkoxylated derivatives.

Betaine is a good foam booster. Betaines such as C ₈ -C ₁₆ , more preferably C ₁₂ -C ₁₆ alkyl betaines such as coconut betaines or C ₈ -C ₁₆ , more preferably C ₁₂ -C ₁₆ amido betaines such as cocoamide Propyl betaine, and mixtures thereof, are preferred.

Some preferred surfactants are hygroscopic synthetic surfactants which absorb at least about 20% of their dry weight over three days at 26°C and 80% relative humidity. Hygroscopic surfactants help improve the lather of the bar. Some preferred hygroscopic synthetic surfactants are listed below. Note that this is not all hygroscopic synthetic surfactants.

Hygroscopicity of some surfactants

The hygroscopic surfactants specified in this invention have a minimum total humidity increase of 20% after three days at 26°C and 80% relative humidity.

non-ionic type

Sulfonate Absorbed Total Moisture % ^*

Sodium _C8 glyceryl ether sulfonate 39.8

Sodium C _12-14 Glyceryl Ether Sulfonyl 22.9

Sodium C ₁₆ glyceryl ether sulfonate 71.4

Sodium Coconut Monoglyceride Sulfonate 3.5

C ₈ -C ₁₆ Alkyl Glyceryl Ether Sulfonate Sodium Salt

Alpha-Sulfoester and Acid Absorption Total Moisture % ^*

Sodium α-sulfomethyl laurate/sodium myristate 39.3

Sodium α-sulfomethyl myristate 44.5

Sodium α-sulfohexyl laurate 23.2

Sodium alpha-sulfomethyl/hexyl laurate and sodium myristate 26.3

Sodium α-sulfomethyl palmitate 3.7

Sodium α-sulfomethyl stearate 4.2

Sodium 2-Sulpholaurate 0.2

Sodium 2-sulfopalmitate 3.8

Sodium 2-sulfostearate 0.0

Na ⁺ R ₁ -C(SO- ₃ )-CO ₂ R ₂ R ₁ =C ₈ -C ₁₄ alkyl R ₂ =C ₁ -C ₆ alkyl

Sodium Alkyl Isethionate Absorbed Total Moisture % ^*

Sodium lauryl isethionate 31.7

Sodium Cocoyl Isethionate 11.0

Sarcosinate Absorbed Total Moisture % ^*

Sodium lauryl sarcosinate 8.8

Sodium stearyl sarcosinate 13.3

Sodium Coconut Sarcosinate 18.7

Alkyl Sulfate Absorbed Total Moisture % ^*

Sodium lauryl sulfate 28.2

Sodium lauryl polyoxyethylene-1 (Laureth-1) sulfate 37.6

Sodium oleyl sulfate 20.3

Mixed Cetearyl-Stearyl (Cetearyl) Sodium Sulfate 4.7

Sodium cetyl sulfate 2.25

Na ⁺ R ₁ (OCH ₂ CH ₂ ) _n OSO ^- ₃ R ₁ = C ₈ -C ₁₄ alkyl, with at least one double bond

C _16-20 (alkylene) alkyl, n=0-18

Acyl Glutamate Absorption Total Moisture % ^*

Sodium Cocoyl Glutamate 26.7

Sodium Lauroyl Glutamate 17.8

Sodium myristoyl glutamate 18.1

Sodium Stearoyl Glutamate 12.0

Alkylether Carboxylate Absorbed Total Moisture % ^*

Sodium Laureth-5 Carboxylate 32.2

Sodium Palm-20 Carboxylate 50.2

Na ⁺ R ₁ -(O-CH ₂ CH ₂ ) _n CO ^- ₂ R ₁ = C _8-18 alkyl, n = 1-30

Sulfosuccinate Absorbed Total Moisture % ^*

Laureth 33.6

Disodium sulfosuccinate

Phosphate Absorbed Total Moisture % ^*

Sodium monoalkyl (70%C ₁₂ /30%C ₁₄ ) phosphate 21.1

Betaine Absorbed Total Moisture % ^*

Coconut Betaine 70.0

Cocamidopropyl Betaine 48.2

Palmimidopropyl Betaine 46.5

Isostearamidopropyl Betaine 44.3

Sultaines Absorbed Total Moisture % ^*

Cocamide Propyl Hydroxy Sultaine 59.5

Amine Oxide Absorbed Total Moisture % ^*

Palmyl Dimethylamine Oxide 34.0

Myristyl dimethylamine oxide 46.0

Cocamidopropylamine Oxide 43.3

Protein Derived Absorbed Total Moisture % ^*

Na/TEAC ₁₂ Hydrolyzed Keratin 34.7

＊3 days, 26℃/80% relative humidity

Polymeric skin softening aids are disclosed in the Small et al. and Medcalf et al. patents. Cationic polysaccharides and cationic synthetic polymers are disclosed. Cationic synthetic polymers useful in the present invention are cationic polyalkyleneimines, ethoxylated polyalkyleneimines, and poly[N-[-3-(dimethylammonium)-propyl]-N'-[ 3-(Ethyleneoxyethylenedimethylammonium)propyl]urea dichloride, the latter can be purchased by Miranol Chemical Company, Inc., under the trademark Miranol A-15, CAS Reg.No.68555-36 -2.

Preferred cationic polymeric skin conditioning agents of the present invention are cationic polysaccharides of the cationic guar type having a molecular weight of 1,000-3,000,000. More preferred molecular weight is 2500-350000. These polymers all have a polysaccharide backbone composed of galactomannan units and have a cationic degree of substitution of about 0.04 per anhydroglucose unit to about 0.80 per anhydroglucose unit, the cationic substituents of which are 2,3- Adducts of glycidyltrimethylammonium chloride on natural glycan backbones. Examples are the JAGUAR C-14-S, C-15 and C-17, sold by Celanese Corporation. In order to achieve the advantages described in the present invention, the polymer must be characterized by suitable structure and physical properties and be well hydrated and subsequently well incorporated into the soap matrix.

Mild cleansing bars of the present invention may contain from about 0.5% to 20% of a mixture of silicone colloids and silicone fluids, wherein the colloid:fluid ratio is from about 10:1 to about 1:10, more preferably about 4:1 to about 1:4, preferably about 3:2 to about 2:3.

Silicone colloids and fluid mixtures as shampoos and/or conditioners are disclosed in U.S. Patent No. 4,906,459 (Cobb et al., issued March 16, 1990), 4,788,006 (Bolich, Jr. 29), 4741855 (Grote et al., awarded May 3, 1988), 4728457 (Fieler et al., awarded March 1, 1988), 4704272 (Oh et al., awarded November 3, 1987) and 2,826,551 (Geen, issued March 11, 1958), all of which are hereby incorporated by reference.

The silicone component may be present in the bar in an amount effective to impart a skin softening benefit, such as from about 0.5% to 20%, more preferably from about 1.5% to 16%, and most preferably from about 3% of the composition -12%. As used herein, silicone fluids are those having silicone viscosities of from about 5 to 600,000 centistokes, preferably from about 350 to 100,000 centistokes at 25°C. The silicone colloids used in the present invention refer to silicones with a molecular weight of about 200,000-1,000,000 and a viscosity greater than about 600,000 centistokes. The molecular weight and viscosity of a particular chosen silicone will determine whether it is a gel or a fluid. The silicone colloids and fluids are mixed together for incorporation into the compositions of the present invention.

Other components of the present invention are selected for each application. For example, fragrances are used in formulated skin cleansing products, typically at levels of about 0.1% to 2.0% of the composition. Alcohols, hydrotropes, colorants and fillers such as talc, clay, finely divided calcium carbonate and dextrin which are insoluble in water may also be used. Cetearyl alcohol is a mixture of cetyl and stearyl alcohols. Preservatives, such as sodium ethylenediaminetetraacetate (EDTA), generally present at less than 1% of the composition, can be added to skin cleansing products to prevent color and odor degradation. Antibacterial agents can also be added, and the general content does not exceed 1.5%. The above patents disclosing or relating to such ingredients and formulations which may be used in the soap bars of the present invention are incorporated herein by reference.

Some soap bars of the present invention contain from about greater than 5% to about 75% of the above sodium fatty acid soap fibers; from about 10% to about less than 94% water; and at least about 1% of another soap bar ingredient selected from the group consisting of: other soaps, Wetting agents, colourants, solvents, fillers, syndet surfactants, polymeric skin sensate and softening aids, fragrances, preservatives and mixtures thereof.

Certain soap bars of the present invention contain: greater than 5%-50% fibrous sodium fatty acid soap containing at least about 50% saturated aliphatic alkyl chains having 12-24 carbon atoms, at least About 25% are single segments.

Certain soap bars of the present invention contain the above-mentioned fibers in an amount of from about 3% to 75%, more preferably from about 15% to 40%, by volume of the bar structure.

Certain soap bars contain greater than 5% to 75% sodium fatty acid soaps of a rigid, low sticky structure containing at least about 50% saturated aliphatic alkyl chains having 12 to 24 carbon atoms, the aforementioned saturated aliphatic alkyl chains at least about 25% of the chains are single-segment; the above bar also contains about 10% to 94% water; listed groups.

Certain body cleansing soap bar compositions contain a rigid interlocking network of sodium soap fibers; wherein the sodium fatty acid soap contains at least about 50% saturated aliphatic alkyl chains having 12-24 carbon atoms, said saturated aliphatic alkyl chains being at least about 25% is single segment; said soap bar also contains about 2%-40% (weight) hygroscopic synthetic surfactant, wherein said hygroscopic synthetic surfactant is selected from the group that absorbs at least 3 days at 26°C and 80% relative humidity. About 20% of its dry weight is surfactant.

Soap Bar Appearance Aids

Preferred bar appearance (moisture retention and/or shrink prevention) aids are selected from the group consisting of those listed in Table 4 above:

Compatible salts and salt hydrates;

Water-soluble organics such as polyols, urea;

Aluminosilicates and clays; and mixtures thereof.

Water soluble organics also serve to stabilize the appearance of the bars of the present invention. Some preferred water soluble organics are propylene glycol, glycerol, ethylene glycol, sucrose and urea, and other compatible polyols.

A particularly suitable water-soluble organic is propylene glycol. Other compatible organics include polyols such as ethylene glycol or 1,7-heptanediol, polyethylene glycol and polypropylene glycol of mono and molecular weights not greater than about 8000, respectively, any mono C _1-4 alkyl thereof Ether, sorbitol, glycerol, monosaccharide (glycose), diglycerin, sucrose, lactose, dextrose, 2-pentanol, 1-butanol, mono-, di- and triethanolammonium, 2-amino - 1-butanol and the like, especially polyols.

The term "polyol" as used herein includes non-reducing sugars such as sucrose. Sucrose does not reduce Fehling's solution and is thus classified as a "non-reducing" disaccharide. As used herein, unless otherwise specified, the term "sucrose" includes sucrose, its derivatives, and similar non-reducing sugars and similar polyols that are substantially stable at soap processing temperatures not exceeding about 210°F (98°C), such as tris Trialose, raffinose, and stachyose; and sorbitol, lactitol, and maltitol.

Use compatible salts and salt hydrates to stabilize bar appearance by retaining moisture. Some preferred salts are sodium chloride, sodium sulfate, disodium hydrogen phosphate, sodium pyrophosphate and sodium tetraborate.

Generally, compatible salts and salt hydrates include sodium, potassium, magnesium, calcium, aluminum, lithium, and ammonium salts of inorganic acids and small chain (6 carbon atoms or less) carboxylic acids or other organic acids, the corresponding hydrated substances and mixtures thereof, these are applicable. Inorganic salts include chlorides, bromides, sulfates, silicates, orthophosphates, pyrophosphates, polyphosphates, metaborates, tetraborates and carbonates. Organic salts include acetates, formates, methylsulfates and citrates.

Water soluble ammonium salts can also be used. Preferred are monoethanolamine, diethanolamine and triethanolammonium (TEA) chloride salts.

Aluminosilicates and other clays are also useful in the present invention. Some preferred clays are disclosed in US Patent Nos. 4,605,509 and 4,274,975, incorporated herein by reference.

Other types of clays include zeolites, kaolinites, montmorillonites, attapulgites, illites, bentonites, and halloysites. Another preferred clay is kaolin.

Waxes include paraffin-based waxes (paraffin, microcrystalline, and petrolatum), plant-based waxes (carnauba, carnauba, candelilla, sugarcane, and plant-derived triglycerides), animal-based waxes ( Beeswax, spermaceti, wool wax, lac wax and triglycerides obtained from animals), mineral waxes (montar, ozokerite and ozokerite) and synthetic waxes (Fischer-Tropsch wax).

Preferred waxes are used in the examples of the present invention. The practical wax melting point (M.P.) is about 120°F-185°F (49-85°C), more preferably about 125°F-175°F (52-79°C). The preferred wax is a fully refined wax having a melting point of about 130°F-140°F (49-60°C). This wax is odorless and tasteless and meets FDA requirements for use as a coating on food and food packaging. These paraffins are readily available commercially. A very suitable paraffin is available, for example, from The Standard Oil Company of Ohio under the tradename Factowax R-133.

Other suitable waxes are sold by the National Wax Co. under the trade names 9182 and 6971, respectively, having melting points of 131°F and 130°F (-55°C).

The level of paraffin in the bar is preferably from about 5% to about 20% by weight. Use paraffin wax ingredients in products to give them soft skin, plasticity, firmness and shaping properties. Also provides shine and smoothness to the bar.

The paraffin component is optionally supplemented with microcrystalline wax. Suitable microcrystalline waxes have melting points, for example, from about 140°F (60°C) to 185°F (85°C), preferably from about 145°F (62°C) to 175°F (79°C). The wax should preferably meet FDA requirements for food grade microcrystalline waxes. A very suitable microcrystalline wax is commercially available from the Witco Chemical Company under the tradename Multiwax X-145A. Microcrystalline wax is preferably present in the soap bar at a level of from about 0.5% to about 5% by weight. The microcrystalline wax component imparts flexibility to the bar at room temperature.

Example

The examples described below do not limit the scope of the present invention. The unneutralized or "free" fatty acids used in the examples are of the same chain length as those used to make the bars unless otherwise stated. Unless otherwise indicated, all levels and ranges, temperatures, results, etc., used herein are approximations.

Frame process method for making soap bar of the present invention

Unless otherwise stated, the cleansing bars in the examples were made by the following process:

1. Mix the fatty acid precursor, propylene glycol, sodium chloride and water (not considering the water brought in by other raw materials) and heat to 71°C.

2. Add caustic alkali solution (50% sodium hydroxide) and stir the mixture until a water-containing molten liquid containing 15%-94% water and 5.5%-75% soap (neutralized carboxylic acid) is formed stably. The temperature rose to ~95°C as the melt was neutralized.

3. It is best to add other ingredients in the following order and keep the temperature at ~88°C: coconut betaine, sodium lauroyl sarcosinate or sodium α-sulfomethyl cocoate, kaolin clay or hydrated zeolite (synthetic silica-alumina sodium nitrate) and paraffin; finally add the fragrance.

4. Inject the molten liquid mixture into the molding die.

5. The molten liquid crystallizes (solidifies) upon cooling to room temperature and the resulting bar is removed from the mold.

Unless otherwise stated, the bars of these examples were made using the general procedures described above.

It is important to note that when the formulations used in the examples of the present invention were conventionally pressed or freezer processed, very soft or no soap bars were formed. Example II is a very highly preferred generic soap bar.

table 5

preferred soap bar

Ingredients Example I Example II Example III Example IV

(weight %) (weight %) (weight %) (weight %)

C ₁₄ Na soap 20 20 - -

C ₁₆ Na soap - - 20 16

C ₁₆ K soap - - - 4

Free fatty acids 1 1 1 1

Sodium lauroyl sarcosinate 7 7 12 -

Sodium α-sulfomethyl cocoate - - - 7

Coconut Betaine 5 5 7 5

Sodium chloride 3.0 3.0 3.0 3.0

Propylene glycol 14.5 14.5 14.5 15.0

Hydrated Zeolite A (aluminosilicate) 4.0 - 4.0 -

Kaolin Clay - 4.0 - 4.0

Paraffin (M.P.＝55℃) 6.5 6.5 4.5 -

Spices 1 1 1 1

Water 37.25 37.25 31.95 36.25

Hardness (mm) 5.5 6.4 4.2 5.1

Goo 9.5 9.0 8.5 8.5

Example Test Description

Soap bar hardness test

1. Determine the hardness of the soap bar by measuring the penetration depth (in millimeters) of a 247-gram standard weight needle through the hardness tester probe into the soap bar at 25°C. The needle is a conical needle, which is installed at 22.9cm (9 inches) on the rod, which weighs 47 grams, add 200 grams to the top of the rod. A measured hardness of 5mm or less indicates that the bar is very hard; 5-10mm indicates that the bar is medium firm; 10-12mm indicates that the bar is slightly softer but acceptable; and greater than 12mm indicates that the bar is very soft and unacceptable for most uses . Unless otherwise stated, "hardness" as used herein is so defined.

Soap bar sticky test

2. The degree of stickiness is determined by (1) placing the soap bar on the shaft of a 1400mm diameter disc; (2) adding 200ml of room temperature water to the disc to immerse the bottom 3mm of the soap bar in the water; (3) making Soak the soap bar overnight (15 hours); (4) Turn over the soap bar to qualitatively grade the binding amount of the sticky matter and the characteristics of the sticky matter. On the scale, the depth of the sticky matter is equal to no sticky matter at 10, and equal to no sticky matter at 8.0-9.5 Low stickiness, 5.0-7.5 equals medium stickiness, which is similar to most commercial soap bars; and 4.5 or less equals very poor stickiness.

、ZEST 、IVORY

和LAVA 的粘性物值分别为约5、6.6、和6。更多的数据参见表12。Soap bars sold commercially, such as SAFEGUARD

、ZEST 、IVORY

and LAVA The sticky values for ® were about 5, 6.6, and 6, respectively. See Table 12 for more data.

Soap Bar Shrinkage Test

3. Shrinkage is measured by placing freshly prepared unpackaged soap bars in a room maintained at 26°C and with a relative humidity of 15% for one week. The amount of shrinkage of the original soap type is determined on a qualitative scale, with 0 indicating no shrinkage, + indicating slight shrinkage, ++ indicating moderate shrinkage, and +++ indicating great shrinkage.

Bars 1-10 are listed in Tables 6 and 7 to represent the soap hardness, stickiness and shrinkage of the indicated _C10 , _C12 , _C14 , _C16 and _C18 alkyl chain soaps. Preferred alkyl chain soaps of the present invention are listed in Tables 1 and 2 above.

The term "X" means that the example is a comparative example.

Table 6

Ingredients Example 1 Example 2 Example 3 Example 4 Example 5

(weight %) (weight %) (weight %) (weight %) (weight %)

sodium soap

C ₁₀ 33 - - - -

C ₁₂ - 33 - - -

C ₁₄ - - 33 - -

C ₁₆ - - - 33 -

C ₁₈ - - - - 33

Free Fatty Acid 1.0 1.0 1.0 1.0 2.0

excess sodium hydroxide

Sodium chloride 2.0 1.0 1.0 1.0 1.0

water 64 65 65 65 64

Hardness (mm) 8.9 2.3 2.2 5.4 4.2

Goo 3 10 10 9.5 10.0

shrink +++ +++ + 0

Note: Example 1 had very poor stickiness, despite a hardness of 8.9, because the sticky procedure dissolved the soluble _C10 soap.

Table 7

Composition X6 Example 7 Example 8 Example 9 Example 10

(weight %) (weight %) (weight %) (weight %) (weight %)

sodium soap

C ₁₂ - - - 15 5

C ₁₆ - 10 - - -

C ₁₈ - - 10 - -

C _18:1 33 - - - -

Free Fatty Acid 1.0 - 2.0 1.0 -

Excess sodium hydroxide - 0.07 - - -

Sodium chloride 1.0 1.0 1.0 1.0 1.0

Water 65 87 82.8 83 94

Hardness (mm) ＊＊ 11.8 11.9 14.0

Goo 10.0 10.0 9.0

shrink 0 +++ ++++ ++++

*Due to too much unsaturated soap, no solid bar is formed.

Example 10 has a rigid structure but is not the best as a cleansing bar since it has a hardness of 14.

Table 8

Double Segment Sodium Soap/Water Analysis

Composition X 11 Example 12 Example 13

Sodium soap (weight %) (weight %) (weight %)

C ₁₀ - - 16.5

C ₁₂ 16.5 - -

C ₁₄ - 16.5 16.5

C _16: 1 16.5 16.5 -

Free Fatty Acid 1.0 1.0 1.0

excess sodium hydroxide

Sodium chloride 1.0 1.0 1.0

water 65 65 65

Hardness (mm) ＊＊ 9.0 9.0

Goo 9.0 8.0

**Due to too much unsaturation combined with _C12 soap, no solid bar formed.

Table 9

Analysis of Double Saturated Chain Length Sodium Soap/Water

Ingredients Example 14 Example 15 Example 16

weight% weight% weight%

sodium soap

C ₁₂ 16.5 - -

C ₁₄ 16.5 - -

C ₁₆ - 16.5 10

C ₁₈ - 16.5 10

Free Fatty Acid 1.0 1.0 1.0

Sodium chloride 1.0 1.0 1.0

Water 65 65 78

Hardness (mm) 2.8 4.5 7.3

Sticky 9.5 10.0 10.0

shrink 0 ++

Examples 12-16 are excellent bars of this invention.

Table 10

Analysis of Complex Chain Length Sodium Soap/Water

Ingredients Example 17 Example 18 Example 19

weight% weight% weight%

Sodium soap*

Emersol132 - (33) (15)

C ₈ 0.56 - -

C ₁₀ 0.64 - -

C ₁₂ 10.14 0.12 8.1 (8.0)

C ₁₄ 4.54 0.79 10.4 (10.0)

C ₁₆ 8.51 15.6 7.10

C ₁₇ 0.76 0.76 0.35

C ₁₈ 19.85 15.3 7.0

C ₂₀ - 0.26 0.12

Free Fatty Acid - 1.0 -

Sodium chloride 1.1 1.0 1.0

Water 53.9 65 66

Hardness (mm) 7.6 4.7 5.8

Goo 9.5 10 9.5

shrink + ++

* Components by chain length, () indicates the actual content of the material.

Examples 17-19 were made with more complex soap mixtures than the previous examples. They form very good soap bars according to the invention. They have little or no stickiness. Its firmness and stickiness are shown in Table 11 in comparison to bars made with conventional tallow and coconut soaps.

Table 11

Analysis of Complex Chain Length Sodium Soap/Water

Composition Comparative Example 20 Comparative Example 21 Comparative Example 22

weight% weight% weight%

Sodium soap*

Tallow (33) - (26.4)

Coconut Soap - (33) (6.6)

C ₈ - 2.31 0.46

C ₁₀ - 2.0 0.40

C ₁₂ - 16.5 3.3

C ₁₄ 1.0 5.94 4.95

C ₁₆ 7.92 2.81 6.90

C ₁₈ 0.5 - 0.40

C ₂₀ 6.6 1.0 5.48

C _14: 1 0.33 - 0.26

C _16: 1 0.83 - 0.66

C _18:1 14.2 2.0 11.76

C _18:2 0.75 0.5 0.7

Free Fatty Acid 1.0 1.0 1.0

Sodium chloride 1.0 1.0 1.0

water 65 65 65

Hardness (mm) Soft 15.8 12.5

Sticky Poor 3.0 5.0

* Components by chain length, () indicates the actual content of the material.

Comparative Examples 20, 21 and 22 did not form the rigid structure of the present invention. Be aware that they are made with typical commercially available soaps. They were soft soaps with excessive stickies compared to Inventive Example 15 which was made from 65% water and _C16 and _C18 saturated soaps and formed hard bars with no stickies.

Example 23 is a soap bar of the present invention which contains more synthetic surfactant than soap. It has low stickiness and good lather. Example 24 is a soap bar of the present invention comprising polymers and other bar ingredients.

Example 23

Synthetic Detergent Soap Regulations

Composition Weight %

Sodium palmitate 20

Sodium lauroyl sarcosinate 9 ^*

Sodium laureth-3 (laureth-3) sulfate 7 ^*

Mixed Cetearyl Sodium Sulfate 5 ^*

Free fatty acids (palmitic) 1

Sodium chloride 3

Propylene glycol 14

Hydrated Zeolite A 3

Spice 1

water 37

＊The total amount of synthetic surfactant is 21%

Example 24

Containing polymer examples

Composition Weight %

Sodium palmitate 20

Sodium α-sulfomethyl cocoate 8.7

Coconut Betaine 4.65

Jaguar C376 1.5

Propylene Glycol 15

Kaolin clay 5

Paraffin (M.P.＝55℃) 4.5

Sodium chloride 3

Spice 1

Water 35.5

Examples 23 and 24 are similar to Example IV of Table 5.

Example 24 is a mild soap formulation containing a polymeric skin mildness aid.

Examples 25-27

Ingredients Example 25 Example 26 Example 27

weight% weight% weight%

Lithium myristate 33 - -

Lithium chloride 5 - -

Disodium salt of dodecanedioic acid - 20 20

Sodium Lauroyl Sarcosinate - - 5

Water 62 80 75

Penetration Value N/A N/A N/A

N/A = not available

For Example 25, the formulation was made by heating the fatty acid precursor to 71°C, adding the lithium hydroxide separately to the water, then adding the fatty acid and lithium hydroxide solutions together, maintaining the heat at at least 71°C, mixing them in Together for 30 minutes, add lithium chloride salt and stir for 5 minutes, then pour into molds, allow to cool and solidify. This results in a solid toilet soap with superior stick properties.

For Examples 26 and 27, the diacid was melted (150-180°C) and hot (90°C) caustic solution (2 equivalents of NaOH) was added. The mixture was stirred for ~5 minutes. For Example 27, sodium lauroyl sarcosinate was pre-dissolved in the caustic/water solution. Cooling makes the soap solid and further hardens as it degrades, eg, to about 35-40% water by weight of the soap.

Example 25 demonstrates the ability to form a high moisture, strong and sticky-free toilet bar without the need for sodium soap. Examples 26 and 27 demonstrate the ability to form a completely soap-free product and still obtain a fairly rigid interwoven network fibrous structure.

Frozen Soap Bar Example 28

Example 28 below was prepared according to the frozen soap bar process disclosed in commonly assigned U.S. Patent Application Serial No. 07/731,163, Taneri et al., filed July 15, 1991. The process provides a body cleansing frozen soap bar having a fairly rigid, interlaced, semi-continuous, open, three-dimensional skeleton structure of a crystalline network of neutralized carboxylic acid soaps, prepared as follows :

(1) Mixing a molten mixture comprising from about 15% to about 85% soap by weight of the bar and from about 15% to about 40% water:

(2) Cool the above mixture into a semi-solid in a scraped wall heat exchange cooler;

(3) extruding the semi-solid mixture into a soft cylinder; and

(4) The soft column is further cooled and crystallized until it is firm to obtain a body cleansing frozen soap bar.

Step 1 - Mix

Soaps as formulated are prepared on site by mixing the required fatty acids, especially those containing C ₁₂ -C ₂₄ chain lengths, with a suitable base or a mixture of bases, especially sodium hydroxide, lithium, magnesium, calcium and potassium, with triethanolamine , prepared by mixing. Soap is formed by mixing fatty acids, alkali and water at about 170°F to about 200°F (76-93°C). In Example 28, 180°F was used. Use enough water so that the mixture can be stirred. Maintaining the temperature at about 180°F to about 200°F (82-93°C), add the other ingredients. Example 28 uses 180°F. The optimum mixing temperature may vary according to a particular formulation.

Step 2 (optional) - aeration, minor additives and flash drying (optional)

The mixture is aerated with a positive displacement pump or other in-line mixer (optional) and flavors are added (only when dry) and other minor additives. Example 28 was not aerated or dry. The mixture of step (1) is optionally dried so that the amount of water is reduced to the desired level, preferably 20-40% water. Flash dry at a pressure of about 30 to 100 Psi (115-517 mmHg) at a temperature of about 225°F to about 315°F (135-157°C).

Step 3 - Freeze

If dry, cool the mixture in a scraped-wall heat exchanger (freezer) from a starting temperature of about 180°F to about 200°F (82-93°C) or about 200°F to about 200°F (93° -104°C) to a final temperature of about 135°F to about 180°F (57-82°C) to partially crystallize the components, more preferably about 145°F to about 180°F ( 63-82°C), preferably about 155°F to about 175°F (68-79°C). In this context, this final temperature (also referred to as the Freezer Outlet Temperature (FOT)) is generally the highest temperature at which a smooth column forms and retains its shape after extrusion onto the conveyor belt (step 4) . The FOT of Example 28 was 175°F.

Step 4 - Extrude

The cooled mixture from step 3 is extruded onto the conveyor belt in soft cylinders, then the cylinders are allowed to cool and fully crystallize, then printed and packaged. The columns are preferably formed by extrusion as described in the aforementioned US Patent No. 3,835,059. Some of the components crystallized in the freezer (step 3) and further crystallized after extrusion in order to obtain a semi-solid with sufficient viscosity to stand on the belt, resulting in a hard bar. The final crystallization of the sodium soap results in the formation of an interlaced, semi-continuous, open network in the frozen soap bars of the present invention.

Example 28

Composition Weight %

Sodium _C14 Soap 27.99

Magnesium _C14 Soap 5.00

Sodium Lauroyl Sarcosinate 3.00

Coconut Betaine 10.00

Propylene Glycol 3.50

Petrolatum 22.49

Sodium chloride 2.58

Free fatty acid (C ₁₄ ) 0.50

Spice 0.50

water 24.44

Hardness Test of Molded and Embossed Soap Bars

，一种研制皂条;ZEST

，一种研制的皂/合成物皂条;IVORY

，一种冷冻皂条和LAVA

一种框制皂条。将这些市售皂条和实施例28与Ⅱ中形成的皂条的试样按下述的工艺模压。Die-indent soap bar hardness tests are used in order to differentiate soap bars of the present invention from other soap bars. Choose from four commercially available soap bars representing various soapmaking methods: SAFEGUARD

, a developed soap bar; ZEST

, a developed soap/synthetic soap bar; IVORY

, a frozen bar of soap and LAVA

A framed soap bar. Samples of these commercial soap bars and bars formed in Examples 28 and II were molded according to the procedure described below.

In general, the commercial bars were molded to be much stiffer and had better stickiness than the molded samples of Example 28 or Example II. Detailed data are listed in Table 12. It is clear that this test is a superior method for distinguishing soap bars with a rigid frame structure from other soap bars. In short, the soap bars of the present invention are much softer after remolding than conventional soap bars.

The molding process is as follows:

1. Without vacuum, the formed soap bar (approximately 2.5 kg or more) is placed into a single stage molding machine (4 inch/10.16 cm cap single stage molding machine) and passed through the bar plate. The soap bar plate has 19 holes of 0.37 inch (0.93 cm) on a 3.1 inch (8 cm) face. The barrel temperature was 120°F (49°C) and the end temperature was 110°F (43.5°C).

2. Repeat step 1 with the soap bar.

3. Put the soap bar from step 2 into a vacuumed single-stage molding machine (4 inch/10.16 cm cap-shaped single-stage molding machine) and pass it through the small holes of the brick grid. A brick-lattice column measuring approximately 1.88 inches (4.6 cm) (height) by 1.16 inches (3 cm) (width) by 3 inches (7.6 cm) (length) was extruded. These columns have an internal temperature of 90°F (32°C) to 105°F (41°C).

4. The columns are pressed into the brickwork and allowed to cool to room temperature (at least 12 hours) before measurement.

Table 12

Soap Bar Molding Data

Soap bar hardness (mm) ^*

市售皂条 3.181SAFEGUARD

Commercial soap bar 3.18

（模压/压印） 3.132SAFEGUARD

(moulded/embossed) 3.13

δ (value of soap bar 1-soap bar 2) 0.05

市售皂条 2.251 ZEST

Commercial soap bar 2.25

（模压/压印） 2.332ZEST

(molded/embossed) 2.33

δ (0.08)

市售皂条 1.931IVORY

Commercial soap bar 1.93

（模压/压印） 3.032IVORY

(molded/embossed) 3.03

δ (1.10)

市售皂条 1.901LAVA

Commercial soap bar 1.90

（模压/压印） 2.472LAVA

(molded/embossed) 2.47

δ (0.57)

1 Example 28 (formed soap bar) 3.35

2 Example 28 (molded/embossed) 10.67

δ (7.32)

1 Example II (Soap Bar Formed) 6.43

2 Example II (moulded/not embossed) 18.07

δ (11.64)

*The "hardness" of the "molded/embossed" bar is reported as Bar 2 in Table 12 for each bar tested. This hardness test also appears elsewhere herein.

While not being bound by theory, molded bars with delta values of 4 or greater strongly indicate that there is a skeletal structure in the original bar that was crushed or destroyed during molding. The hard soap bars of the present invention form soft sticky bars when molded in conventional soapmaking processes.

The bars of Example 28 were first made by the freezing method described above, and the bars of Example II were first made by the frame soap method described above.

About 5-10kg of each soap is molded and stamped.

和LAVA

模压皂条（2）比原皂条稍软一点。Commercially available soap bars are made from tallow and coconut butter natural soaps. MOLDED SAFEGUARD and ZEST The firmness of the soap bar is about the same as the original bar firmness. IVORY

and LAVA

The molded bar (2) is slightly softer than the original bar.

On the other hand, the molded bar 2 of Example 28 was much softer than the raw bar 1 of Example 28. Even more surprising, the molded soap bar 2 of Example II disintegrated when molded and was too soft to imprint. After molding, its hardness is the hardness of the soft aqueous phase, which means that the rigidity of the skeleton structure has basically disappeared.

Claims (31)

CLAIMS 1. A shaped solid characterized in that it contains a relatively rigid, interlocking, open, three-dimensional network framework structure of elongated crystals of neutralized mono- and/or bis-carboxylic acids. 2. A cleansing bar characterized in that it contains at least two phases: Aqueous phase with a penetration value of 12mm for a 12mm deep sample, which is soft or flowable at 25°C; Rigid crystalline phase framework structure of interlaced, open, three-dimensional networks containing elongated crystals of neutralized mono- and/or bis-carboxylic acids; wherein said cleansing bar comprising said rigid crystalline phase skeletal structure and said aqueous phase has a breakthrough value of 0 to about 12 mm for a 25 mm deep sample of said cleansing bar; Wherein, the above penetration values are measured at 25°C with a standard weight of 247 grams of a needle penetration hardness tester probe, which has a tapered needle attached to a 9 inch (22.9 cm) rod and weighs 47 grams, plus the above 200 grams on top of rod, 247 grams total, 19/32" (1.51cm) at the top of the aforementioned tapered needle, and 1/32" (0.08cm) at the tip. 3. The cleansing bar of claim 2 wherein said neutralized carboxylic acid is selected from the group consisting of lithium and/or sodium neutralized monocarboxylic (soap) and/or dicarboxylic acids and mixtures thereof; wherein said monocarboxylic acid has an aliphatic (alkylene) chain of about 12 to about 24 carbon atoms; wherein said dicarboxylic acid has an aliphatic (alkylene) chain of about 12 to about 18 carbon atoms, and wherein at least about 80% of said carboxylic acids have saturated alkyl chains; Wherein said rigid crystalline phase framework comprises from about 3% to about 75% by volume of said cleansing bar. wherein said neutralized carboxylic acid comprises greater than 5% to about 75% by weight of said cleansing bar; and Wherein, said cleansing bar contains from about 15% to about 94% water. 4. The cleansing bar of claim 2 wherein at least 80% of said carboxylic acids have the general formula:

in: a+b=8-20 Each a, b=0-20 X=H, OR,

, R or these groups exist simultaneously, R=C ₁ -C ₃ alkyl, H or these groups exist simultaneously, M=Na, Li or a combination thereof. 5. The cleansing bar of claim 4 wherein said a+b=10-16, each a, b=0-16; said X=H, OR; R=H; and M=Na. 6. The cleansing bar of claim 3, wherein said elongated crystals are composed of fibrous sodium fatty acid soap having at least about 25% of said saturated aliphatic alkyl chains of single chain length; and wherein said bar contains about 15% % to about 75% of said sodium soap; wherein said soap bar contains no more than 50% by weight of said soap of unneutralized (free) carboxylic acid. 7. The cleansing bar of claim 6, wherein said bar comprises said sodium soap and water; and from about 2% to about 60% of a synthetic surfactant selected from the group consisting of alkyl sulfates, paraffin sulfonates Alkyl glycerol ether sulfonates, acyl sarcosinates, methyl acyl taurates (taurates), linear alkylbenzene sulfonates, N-acyl glutamates, alkyl glucosinolates Glycosides, alpha-sulfo fatty acid esters, acyl isethionates, alkyl sulfosuccinates, alkyl ether carboxylates, alkyl phosphates, ethoxylated alkyl phosphates, methyl Glucose esters, protein condensates, alkyl amine oxides, alkyl betaines, alkyl sultaines, alkyl ether sulfates with 1 to 12 ethoxy groups or mixtures thereof, wherein the above surfactants contain C ₆ -C ₂₂ alkyl chains. 8. The cleansing bar of claim 7, wherein said synthetic surfactant is hygroscopic; said hygroscopic surfactant being defined as a surface which absorbs at least 20% of its dry weight of water in three days at 20°C and 80% relative humidity Actives where the bar is relatively non-swelling. 9. The cleansing bar of claim 8, wherein said hygroscopic surfactant is selected from the group consisting of alpha-sulfo fatty acid esters, alkyl sulfates, alkyl ether carboxylates, alkyl betaines, alkyl Sultaines, alkyl Amine oxides, alkyl ether sulfates or mixtures thereof. 10. The cleansing bar of claim 7, wherein the ratio of said water to said soap is from about 1:1 to about 5:1; said water is present in an amount from about 25% to about 60%; wherein said soap has _C14 - _C22 aliphatic alkyl chains, said soap is present in said soap bar at a level of from about 15% to about 35%, wherein at least about 85% of said soap alkyl chains are saturated; wherein said soap The unneutralized (free) carboxylic acid is 0 to about 25% by weight of the soap, wherein the synthetic surfactant is present in an amount of about 4% to about 25% by weight of the bar, and the surfactant Sodium acyl isethionate, sodium acyl sarcosinate, sodium α-sulfo fatty acid ester, sodium paraffin sulfonate, sodium alkyl ether sulfate, sodium alkyl sulfate, sodium linear alkylbenzene sulfonate, Alkyl Betaines, Alkyl Sultaines or Trialkylamine Oxide. 11. The cleansing bar of claim 10 wherein the ratio of said water to said soap is from about 1.5:1 to about 2:1 and said unneutralized (free) carboxylic acid is 0% by weight of said soap. to about 17%, the water content is about 30% to about 45%; the aliphatic alkyl chain of the soap is about C ₁₄ to about C ₁₈ ; wherein at least 95% of the alkyl chain is saturated, The soap is present at about 15% to about 30%, and the synthetic surfactant is present at about 8% to about 16%. 12. The cleansing bar of claim 7, wherein said bar contains from about 0.1% to about 40% of a hygroscopic material selected from the group consisting of microcrystalline wax, petrolatum, carnauba wax, carnauba wax, candelilla wax , sugarcane wax, vegetable-derived triglycerides, beeswax, spermaceti, lanolin, wood wax, shellac wax, animal-derived triglycerides, montar, ozokerite, ceresin or Fischer-Tropsch wax. 13. The cleansing bar of claim 12, wherein said bar contains from about 2% to about 35% of a hygroscopic material selected from the group consisting of petrolatum and waxes and mixtures thereof having a melting point of about 49 °C (120°F) to about 85°C (185°F). 14. The cleansing bar of claim 13 wherein said bar contains from about 5% to about 25% paraffin by weight of the bar. 15. The cleansing bar of claim 7, wherein said bar contains from about 1% to about 50% of a nonvolatile, water-soluble, nonionic organic material having a solubility of at least 5 parts in 10 parts of water, Wherein the water-soluble non-ionic organic substance is selected from structural formula as:

(where R ₁ = H, C ₁ -C ₄ alkyl; R ₂ = H, CH ₃ ; n = 1-200) polyalcohol, C ₂ -C ₁₀ alkanediol, sorbitol, glycerin, Sugars, sugar derivatives, urea and ethanolamines of general formula (HOCH ₂ CH ₂ ) _x NH _y (where X=1-3; Y=0-2; X+Y=3) or mixtures thereof. 16. The cleansing bar of claim 15 wherein said bar contains from about 2% to about 40% of said nonvolatile, water soluble, nonionic organic material. 17. The cleansing bar of claim 16, wherein said non-volatile, water-soluble, nonionic organic material comprises from about 5% to about 20% by weight of the bar, wherein said organic material is selected from the group consisting of propylene glycol, glycerin, sucrose , urea or mixtures thereof. 18. The cleansing bar of claim 7, wherein said bar comprises said sodium soap, said water, and said synthetic surfactant and from about 1% to about 70% of other ingredients selected from the group consisting of: from about 1% to about 10% of said potassium soap, from about 1% to about 35% of said magnesium soap, from about 1% to about 35% of said calcium soap, about 1% to about 15% triethanolammonium soap, From about 1% to about 60% finely divided water-insoluble materials selected from calcium carbonate and talc, From about 1% to about 20% polymeric skin sensory aid, About 0.5% to about 25% aluminosilicate clay and/or other clay; clay, bentonite, halloysite or cooked clay. From about 1% to about 50% of salts and salt hydrates and mixtures thereof; wherein said salts and salt hydrates have Ammonium or triethanolammonium cations; wherein said salts and salt hydrates have a compound selected from the group consisting of chlorides, bromides, sulfates, silicates, orthophosphates, pyrophosphates, polyphosphates, metaborates, Anions of tetraborate, carbonate, bicarbonate, hydrogenphosphate, methylsulfate or mono- and polycarboxylates of 6 carbon atoms or less. 19. The cleansing bar of claim 2 wherein said elongated crystals comprise platelets and wherein said soap is composed of lithium neutralized monocarboxylic acids. 20. The cleansing bar of claim 2, wherein said elongated crystals are fibrous, wherein said neutralized dicarboxylic acid is the disodium salt 1,12-dodecanedioic acid, wherein the neutralized dicarboxylic acid From about 20% to about 70% by weight of the bar. 21. A method of making a cleansing soap bar characterized by comprising at least two phases: an aqueous phase having a penetration value of about 12 mm for a 12 mm deep aqueous phase sample; the aqueous phase is soft or flowable at 25°C; Rigid crystalline phase with a rather rigid, interlaced, open, three-dimensional network skeletal structure of elongated crystals of neutralized mono- and/or bis-carboxylic acids; Wherein the cleansing bar comprising a rigid crystalline phase framework structure and an aqueous phase has a breakthrough value of 0 to about 12 mm for a 25 mm deep sample. The above penetration values are measured at 25°C with a 247g standard needle penetration hardness tester probe, which has a tapered needle connected to a 9-inch (22.9cm) rod, weighing 47g, plus the above 200g on top of stem, for a total weight of 247g, the aforementioned tapered needle has a 19/32" (1.51cm) top and a 1/32" (0.08cm) tip; Above-mentioned method is characterized in that comprising the following steps: 1. forming an aqueous melt comprising from about 20% to about 94% water by weight of the soap bar and from about greater than 5% to about 75% of said neutralized carboxylic acid; Ⅱ. Pour the melt into a soap bar forming mold; and III. Cooling to crystallize the melt to obtain the cleansing soap bar. 22. The process of claim 21 wherein said aqueous melt is an aqueous mixture of said carboxylic acid neutralized with hydroxide and heated at a temperature of about 50°C (120°F) to about 95°C (205°F). Prepared under stirring, the above-mentioned hydroxide is selected from sodium hydroxide or lithium hydroxide and mixtures thereof. 23. The method of claim 21 wherein from about 2% to about 15% by weight of said bar is a "crystal enhancing salt" selected from the group consisting of sodium or lithium sulfates, chlorides, acetates and citrates or a mixture thereof. 24. The method of claim 21, wherein the aqueous phase comprising said aqueous melt contains from about 2% to about 40% of a solubilizing aid selected from the group consisting of: (a) non-volatile, water-soluble, non-ionic organic solvent, the solvent is selected from the structural formula: (where R ₁ = H, C ₁ -C ₄ alkyl; R ₂ = H, CH ₃ ; n = 1-200) polyalcohol, C ₂ -C ₁₀ alkanediol, sorbitol, glycerin, Sugars, sugar derivatives, urea and ethanolamines of the general formula (HOCH ₂ CH ₂ ) _x NH _y (where X=1-3; Y=0-2; and X+Y=3); (b) Alcohols with 1-5 carbon atoms; (c) Surfactants selected from the group consisting of alkyl sulfates, paraffin sulfonates, alkyl glycerol ether sulfonates, anionic acyl sarcosinates, methylacyl taurates (taurates), linear Alkylbenzene Sulfonates, N-Acyl Glutamates, Alkyl Glucosides, Alpha-Sulfo Fatty Acids, Acyl Isethionates, Alkyl Sulfosuccinates, Alkyl Ether Carboxylates, Alkyl Phosphate Esters, Ethoxylated Alkyl Phosphate Esters, Methyl Glucose Esters, Protein Condensates, Alkyl Amine Oxides, Alkyl Betaines, Alkyl Sultaines, Alkanes with 1-12 Ethoxy groups Base ether sulfates or mixtures thereof, wherein the above-mentioned surfactants contain C ₈ -C ₂₂ alkyl chains and mixtures thereof; and Wherein the above-mentioned solubilizing aid is added to increase the amount of the neutralized carboxylic acid dissolved in the continuous melting aqueous phase described in step 1. 25. The method of claim 21 wherein said aqueous phase comprises from about 20% to about 100% by weight of said aqueous phase water. 26. The method of claim 21 wherein said rigid crystalline phase contains from about 75% to about 100% by weight of said crystalline phase of neutralized carboxylic acid. 27. The method of claim 21 wherein said soap bar has a breakthrough value of about 3 mm to about 9 mm for a 25 mm bar sample. 28. The method of claim 21 wherein said soap bar comprises a mixed non-carboxylic acid phase comprising droplets or crystals selected from waxes, petrolatum and clays. 29. A body cleansing bar composition comprising a rigid crystalline interlocking network of elongated sodium soap crystals, the bar comprising from about 15% to about 50% of said sodium fatty acid soap, the sodium soap being composed of at least 50% of Saturated aliphatic alkyl chains, the chain has 12-24 carbon atoms, and at least about 25% of the saturated aliphatic alkyl chains are single chain lengths; the cleansing bar also contains about 15% to about 60% water ; containing from about 2% to about 60% by weight of a hygroscopic synthetic surfactant selected from the group consisting of water which absorbs at least about 20% of its dry weight in three days at 26°C and 80% relative humidity of surfactants. 30. The body cleansing bar of claim 29, wherein said hygroscopic synthetic surfactant is selected from the group consisting of alpha-sulfo fatty acid esters, alkyl sulfates, alkyl ether carboxylates, alkyl betaines, alkyl sultaines , alkyl amine oxides, alkyl ether sulfates or mixtures thereof. 31. The soap bar of claim 29, wherein said soap bar contains from about 0.5% to about 40% of a salt and/or salt hydrate selected from the group consisting of sodium chloride, sodium sulfate, disodium hydrogen phosphate, sodium pyrophosphate , sodium tetraborate, sodium acetate, sodium citrate or other compatible salts of inorganic acids and short-chain organic acids.

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