KR100226393B1 - Shaped solid made with a rigid, interlocking mesh of neutralized carboxylic acid - Google Patents

Abstract

The present invention provides a molded solid three-dimensional framework structure comprising an interlocking mesh of relatively hard, neutralized crystalline carboxylic acid. In another aspect, the present invention provides an improved cleansing bar comprising said framework, ie a hard interlocking mesh of neutralized carboxylic acids, preferably sodium soap fibers. Such preferred cleaning bars can be formulated to be essentially bar smeared. Some cleansing bars contain surprisingly large amounts of water or other liquids and retain their rigidity and excellent smear properties even when immersed in water overnight.

Description

[Name of invention]

Molded solids of hard interlocking mesh of neutralized carboxylic acid

[Technical Field]

The present invention relates to neutralized carboxylic acid molded solid compositions, in particular, cleaning bars, cakes, solid soaps, similar soaps and the like.

[Background]

Products made in the form of molded solids, cakes and bars vary. Cleaning bars are well known in the art.

Cleaning bars with reduced smear have been reported in the art. For example, US Pat. No. 2,988,511 to Mills, issued June 13, 1961, incorporated herein by reference, describes a low smear bar.

It is a soft solid or dough formed on the surface of the bar when submerged in bar smears (or called bar slots) with water, which consumers consider to be messy, undesirable and uneconomical.

Products made in the form of molded solids, cakes and bars vary. For example, certain high humidity and low smear human cleansing bars are described in US Pat. No. 4,606,839 to Harding on August 19, 1986. Harding uses coconut and / or palm kernel oil soaps.

The human cleansing bar used in the bathroom should be examined to see if there is still a need for an improved bar with little or no smear.

A method for forming hard soap coagulation fibers of sodium laurate is described in the American Chemical Society, Vol. 63, pp. 1990-1993, (1940), reported by L. Marton et al. This article does not disclose the availability of soap products. Molded solids as defined herein are not disclosed by Marton et al.

Japanese Patent No. 57030798 filed July 30, 1980 describes a transparent solid framed or shaped soap bar wherein the fatty acids constituting the soap component are myristic acid, palmitic acid and stearic acid. Transparent soaps describe that at least 90% by weight of the fatty acids that make up the soap component are myristic acid, palmitic acid and stearic acid. The product is reported to be a clear solid soap with good foaming and solidification, good storage stability and low irritation to human skin. The method and transparent bar soap composition exemplified in Japanese Patent No. 57030798 appears to contain no synthetic surfactant.

It also contains relatively high content (15-40%) of water (particularly in the presence of most synthetic surfactants), hygroscopic surfactants and / or non-solid and soft solids such as higher water-soluble polyols and hydrocarbon greases. It is difficult to manufacture a solid non-stick bar.

Detailed description of the invention

[Overview of invention]

The present invention provides a molded solid three-dimensional framework structure comprising an interlocking mesh of relatively hard, neutralized crystalline carboxylic acid. In another aspect, the present invention provides an improved cleansing bar comprising said framework structure, ie a hard interlocking mesh of neutralized carboxylic acid, preferably sodium soap fibers. Surprisingly, some cleansing bars containing large amounts of water or other liquids retain their rigidity and excellent smearing properties even when soaked in water overnight.

Scanning electron microscopy (SEM) sample preparation involves breaking the shaped body with simple pressure to obtain a new inspection surface. The crushed sample is a rectangular (shaving blade) size of approximately 10 mm x 15 mm with a thickness of about 5 mm. This sample is placed on an aluminum SEM stub using silver paint adhesive. This sample is coated with about 300 kPa of gold / palladium in a Pelco sputter coating apparatus. Prior to coating, the sample is left under vacuum for a sufficient time to remove enough water from the bar to ensure an acceptable coating. After coating, the sample is transferred to an SEM chamber and examined under a standard SEM manipulation condition with a Hitachi model S570 scanning electron microscope to examine the frame (core).

Detailed Description of the Drawings

1 and 2 are photographs of a high magnification skeletal core structure comprising a rigid interlocking mesh of elongated neutralizing carboxylic acid crystalline fibers. More specifically, FIGS. 1 and 2 show enlarged C ₁₂ sodium soap fibers 5000 and 2500 times respectively. The structures of FIGS. 1 and 2 consist of 5% soap, 94% water and 1% sodium chloride (see Example 10 in Table 7 herein). The larger fibers in the interlocking mesh may be made of smaller fibers. There are also pores (see Figure 2).

3, 4 and 5 are photographs of the skeleton structure consisting of 25% sodium C ₁₂ soap, 74% water, 1% sodium chloride. Crystalline fibrous structures are shown at magnifications of 3000, 5000 and 1000 times, respectively.

6 is a photograph of a skeleton structure composed of 20% disodium salt of 1,12-dodecanedioic acid. The crystalline fibrous structure is shown at 2000 times magnification (see Example 26).

7 is a 1500x magnification photograph of a skeleton (core) structure comprising a crystalline lithium neutralized C ₁₄ carboxylic acid mesh (see Example 27).

8 is a photograph of a cleansing bar (hereinafter Example 1) comprising coated C ₁₄ -C ₁₆ sodium soap fibers. The fibers are coated and / or mixed with other bar components. The magnification is 1500 times.

Chapter 9 Commercially Available Sodium / Potassium Coconut / Tallow Soap IVORY (Available from The Procter and Gamble Company, Cincinnati, Ohio). 1000x magnification of a freezer bar sample. The air in the IVORY bar soap causes the soap to float.

10th Commercial Products NEUTROGENA (Available from Neutrogena Incorporation, Los Angeles, Calif.) A 1500 × magnification photograph of a transparent bar sample.

In Figures 1 and 2, the sample is first melted on a hot plate and then recooled on a glass plate. Other samples of FIGS. 3-10 are samples of conventional bar or original molded solid structures prepared as described herein.

The present invention provides a molded solid comprising two or more phases. One phase is a crystalline backbone structure comprising an open three-dimensional hard interlocking mesh of neutralized carboxylic acid stretch crystals. Kitty's essential phase is an aqueous phase that is soft or fluid at 25 ° C.

More specifically, the framework structure is an open three-dimensional, relatively hard interlocking mesh of neutralized mono- and / or di-carboxylic acid stretched crystals.

As used herein, the terms bone structure, core and skeletal frame are all used interchangeably.

The term molded solids herein includes forms such as bars, cakes, and the like. The term desired includes the forms of bars, cakes, and the like, unless stated otherwise herein.

The term mesh refers to an interlocking mesh of crystalline skeleton with pores or gaps when magnified and viewed under a scanning electron microscope.

In another aspect, the present invention provides an improved cleansing bar consisting of the skeletal structure. Some shaped solids are in the form of cleaning bars that contain very high amounts of the aqueous phase, including water, other liquids and soft materials. Despite the presence of a very high content of aqueous phase, the present invention retains its hard and excellent smear properties even when soaked in water overnight. Without wishing to be bound by theory, molded solids comprising these phases are similar to relatively hard wet sponges.

The crystalline phase comprises interlocking plates and / or crystals in the form of fibers, preferably fibers. Preferably the fiber consists of sodium soap. The interlocking mesh of the fibers and / or plates imparts strength to the three-dimensional structure even in the presence of relatively high amounts of water or other soft materials, even when immersed in water overnight.

The strength of the skeletal structure can be measured indirectly by the hardness of the molded solid, as measured by the solids penetration resistance using a Standard Weighted Penetrometer Probe (more details will be discussed later. Hardness test). The skeletal structure has a hardness that is sufficient for a cleansing bar sample of 20 mm thickness or more to have a permeability of about 0 mm to about 12 mm, preferably about 1 mm to about 10 mm, more preferably about 3 mm to about 8 mm. Have

The bar of the present invention is distinguished in terms of conventional transparent bar and crystal size as well as other properties. The crystal or crystalline bundle composed of the interlocking mesh structure of the present invention is preferably of a size diffracting light, and therefore has a diameter or length of 400 nm or more. On the other hand, a typical transparent bar has transparency by obtaining a crystal diameter or length smaller than the wavelength of white light (greater than about 400 nm), and does not diffract light.

Bars (molding solids) comprising the hard skeletal structure of the present invention, once formed, are placed under mechanical destructive force, for example, US Pat. No. 4,812,253 to Small et al. Or US Patent No. to Medcalf et al. It loses its rigidity when placed under the force used in the conventional floated bar manufacturing process described in 4,820,447. This is because the mechanical breaking force breaks down the hard skeletal structure into smaller pieces. Therefore, when the bar of the present invention is subjected to shearing force in the floating device, a bar that is much softer is produced.

On the other hand, in case of floating or refloating the finished conventional bar, the refloated conventional bar is still very hard. This is described in detail in Example 28 and Table 12.

The framework structure contains a significant amount of pore regions filled with a soft and / or liquid aqueous phase. One surprising feature of the present invention is that the physical properties of the bars of the present invention, such as bar hardness, and little smear properties, even depend on the crystalline interlocking mesh structure, even if they occupy most of the other materials. In conventional bars, the components can affect the overall physical properties of the bar because most of the ingredients adjust the phase and structure of the soap or the synthetic surfactant component essentially determines the physical properties of the bar. The combination of two or more phases (eg soap and aqueous solution) greatly changes the colloidal structure and thus the physical properties of conventional bars.

These conventional bars are much more limited than the present invention in terms of the type, amount and composition of the soft phase material that can be incorporated into the bar. Such phases include flowable liquids, or most materials that are softer than the minimum hardness of an acceptable bar. These phases include an aqueous solution, a liquid crystalline phase consisting of water and a surfactant, a polymer; Especially surfactant-containing crystalline phases, and more particularly water-soluble organic compounds (e.g. propylene glycol and glycerin), hydrophobic materials (e.g. mineral oils, liquid triglycerides) or soft hydrophobic materials (e.g. mineral oils, low melting point paraffins and low melting points Hygroscopic surfactant-containing crystalline phases which tend to become soft or tacky when mixed with water or other liquid phases, including triglycerides).

In physical terms, all of these phases can be characterized as being so soft or flowable that the standard gravimetric permeate probe defined herein penetrates all 12 mm thick samples. These phases can optionally be included in the structure of the present invention without loss of interlocking mesh structure and certain desirable physical properties.

[Description of Preferred Embodiments]

The present invention is a molding solid comprising an open three-dimensional relatively hard interlocking mesh skeleton structure of neutralized mono- and / or di-carboxylic acid stretched crystals.

Preferred embodiments include at least two phases; (1) an aqueous phase having a penetration value of about 12 mm for a 12 mm thick sample that is soft or fluid; (2) neutralized mono- and / or di-carboxylic acid stretching. A cleansing bar comprising a hard crystalline phase comprising a hard crystalline phase skeleton structure comprising an open three-dimensional interlocking mesh of crystals, wherein the cleansing comprises the hard crystalline phase framework structure and the aqueous phase The bar has a penetration value of 0 to about 12 mm for a sample with a thickness of 25 mm and the penetration value is 200 g of conical needle (top 19/32 inch (1.51 cm) on top of a 47-g weight 9 inch (22.9 cm) shaft. And a total weight of 247 g standard weight penetrometer probe combined with a vertex value of 1/32 inch (0.08 cm).

The cleaning bar is selected from the group in which the neutralized carboxylic acid consists of lithium and / or sodium neutralized monocarboxylic acid (soap) and / or dicarboxylic acid and mixtures thereof; Wherein said monocarboxylic acid has an aliphatic alkyl (ene) chain having from about 12 to about 24 carbon atoms; The dicarboxylic acid has an aliphatic alkyl (ene) chain having about 12 to about 18 carbon atoms; At least about 80% of the carboxylic acids have a saturated alkyl (ene) chain; The hard crystalline phase skeleton structure comprises about 3 to about 75 volume percent of the cleansing bar; The neutralized carboxylic acid comprises about 5 to about 75 weight percent of the cleansing bar; It is preferred if the cleaning bar contains about 15 to about 94 weight percent water.

The cleaning bar is preferred when at least 80%, preferably 90% of the carboxylic acids have the following general formula;

Wherein a + b is 8 to 20, a and b are each 0 to 20, and x is H, OR, O- -R, R, or a combination thereof, R is C _1-3 alkyl, H or a combination thereof, and M is Na, Li or a combination thereof.

The cleaning bar is more preferable when the a + b is 10 to 16, each of a and b are 0 to 16, the X is H or OR, R is H, M is Na.

The cleansing bar, wherein the elongated crystals consist of fiber-like sodium fatty acid soap having at least about 25% of the saturated aliphatic alkyl chain having a single chain length; The bar comprises about 15 to about 75% of the sodium soap; Very preferred when the ratio of said non-neutralized (free) carboxylic acid to soap is from about 1: 2 to about zero. In other words, the free fatty acid is less than 50% by weight of the soap in the formulation.

The cleansing bar comprises the sodium soap and water; And alkylsulfate, paraffin sulfonate, alkyl glycerylether sulfonate, acyl sacosinate methylacyl taurate, linear alkyl benzene sulfonate, N-acyl glutamate, alkyl glucoside, alpha sulfo fatty acid ester, acyl isethionate, alkyl sulfonate Posuccinate, alkyl ethercarboxylates, alkyl phosphate esters, ethoxylated alkyl phosphate esters, methyl glucose esters, protein condensates, alkyl amine oxides, alkyl betaines, alkyl stannes, alkyl ether sulfates with 1 to 12 ethoxy groups And about 2 to about 60% of a synthetic surfactant selected from the group consisting of mixtures thereof; It is preferred if the surfactant contains a C _8-22 alkyl chain.

The cleaning bar is hygroscopic to the synthetic surfactant; The hygroscopic surfactant is defined as a surfactant that absorbs at least 20% of its dry weight of water for three days at 26 ° C. and 80% relative humidity; It is preferred if the bar is relatively non-swellable.

The cleansing bar is preferred if the hygroscopic surfactant is selected from the group consisting of alpha sulfofatty acid esters, alkyl sulfates, alkyl ethercarboxylates, alkyl betaines, alkyl steines, alkyl amine oxides, alkyl ether sulfates and mixtures thereof. .

The cleaning bar has a ratio of water to the soap of from about 1: 1 to about 5: 1; The water is present in an amount from about 25% to about 60%; The aliphatic alkyl chain is C ₁₄ to C ₂₂ ; The amount of soap in the bar is about 15% to about 35%; At least about 85% of said alkyl chain is saturated; The weight ratio of the non-neutralized (free) carboxylic acid to the soap is about 1: 4 to 0; The amount of synthetic surfactant is about 4 to about 25 weight percent of the bar; The surfactants are sodium acyl isethionate, sodium acyl sacosinate sodium alpha sulfo fatty acid esters, sodium paraffin sulfonate, sodium alkyl ether sulfate, sodium alkyl sulfate sodium linear alkyl benzene sulfonate, alkyl betaine, alkyl steine and It is preferred if it is selected from the group consisting of trialkylamine oxides.

The cleaning bar has a ratio of water to soap of about 1.5: 1 to about 2: 1; The ratio of the non-neutralized (free) carboxylic acid to the soap is about 1: 6 to 0; The amount of water is from about 30% to about 45%; The aliphatic alkyl chain is from about C ₁₄ to about C ₁₈ ; At least about 95% of said alkyl chains are saturated; The amount of soap is about 15% to about 30%; It is preferred if the amount of the synthetic surfactant is about 8% to about 16%.

The cleaning bars are microcrystalline waxes, mineral oils, carnauba waxes, palm waxes, candelilla waxes, sugar cane waxes, plant derived triglycerides beeswax, spemaceti, lanolin, wood waxes, shellac waxes, animals Containing from about 0.1% to about 40% hydrophobic material selected from the group consisting of triglycerides, montars, ozokerite, ceresin and Fischer-Tropsch waxes derived from desirable.

The cleansing bar comprises about 2% to about 35% hydrophobic material selected from the group consisting of mineral oil and wax, wherein the mineral oil and wax and mixtures thereof melt at about 49 ° C. (120 ° F.) to about 85 ° C. (185 ° F.). If it is preferable.

The cleaning bar is preferred when it comprises about 5 to about 25% by weight paraffin wax.

The cleansing bar contains about 1% to about 50% of a nonvolatile water-soluble nonionic organic material having a solubility of at least 5 parts by 10 parts of water, wherein the water-soluble nonionic organic material is represented by

Wherein R ₁ is H or C _1-4 alkyl, R ₂ is H or CH ₃ , n is from 1 to 200, a polyol, C _2-10 alkanediols, sorbitol, glycerin, sugars, sugar derivatives, Urea and the following structural formula

(HOCH ₂ CH ₂ ) _X NH _y

It is preferred if it is selected from the group consisting of ethanol amines, and mixtures thereof, wherein x is 1 to 3, y is 0 to 2, and x + y is 3.

The cleaning bar preferably contains about 2% to about 40% of the nonvolatile water-soluble nonionic organic material.

The cleansing bar comprises about 5 to about 20 weight percent of the nonvolatile water soluble nonionic organic material, wherein the organic material is preferably selected from the group consisting of propylene glycol, glycerin, sucrose and urea, and mixtures thereof. .

The cleansing bar comprises the sodium soap, the water and the synthetic surfactant, and about 1% to about 10% of the potassium soap; About 1% to about 35% of said magnesium soap; About 1% to about 35% of the calcium soap; About 1% to about 15% triethanolammonium soap; Micro water insoluble material selected from about 1% to about 60% calcium carbonate and talc; From about 0.1% to about 20% of cationic polysaccharides, preferably cationic guar gums having a molecular weight of 1,000 to 3,000,000; Cationic polyalkylene imines, epoxypolyalkylene imines and poly [N- [3- (dimethylammonio) propyl] -N '-[3-ethyleneoxyethylene dimethylammonio) propyl] urea dichloride]; Silicone gum; And silicone fluids; JR polymer; Celquat A polymeric skin feel aid selected from the crowd consisting of (available from National Starch and Chemical Company, Bridgewater, NJ); From about 0.5% to about 25% alumino silicate clay selected from the group consisting of zeolite, kaolin, kaolinite, montmorillonite attapulgite, elite, bentonite, halosite and sintered clay; And about 50% of cations and chlorides, bromide, sulfates, metasilicates selected from the group consisting of sodium, potassium, magnesium, calcium, aluminum, lithium, ammonium, monoethanol ammonium, diethanol ammonium and triethanol ammonium And salt hydrates with anions selected from the group consisting of orthophosphates, pyrophosphate polyphosphates, metaborates, tetraborates, carbonates, bicarbonates, hydrogen phosphates, methyl sulfates and mono- and polycarboxylates with up to 6 carbon atoms It preferably contains about 0.1 to 70% of the other components selected from the group consisting of:

The cleansing bar preferably includes the stretched crystals comprising a plate, and the soap consists of lithium neutralized monocarboxylic acid.

The cleansing bar is preferably wherein the elongated crystals are fibrous, the neutralized dicarboxylic acid is a disodium salt of 1,12-dodecanedioic acid and accounts for about 20 to about 70 weight percent of the bar.

[Production method of the preferred bar]

The method for producing the preferred cleaning bar of the present invention

I. preparing a molten aqueous liquid comprising from about 15 to about 94% of water and from about 6 to about 75% of said neutralized carboxylic acid;

II. Pouring the molten liquid into a bar forming mold; and

III. Crystallizing by cooling the shaped molten liquid to provide the cleaning bar.

The process is preferably prepared by neutralizing the molten aqueous liquid with sodium hydroxide or lithium hydroxide at a temperature of about 50 ° C. (120 ° F.) to about 95 ° C. (205 ° F.) with stirring.

The method preferably comprises from about 2 to about 15% by weight of the bar being a crystallinity enhancing salt selected from the group consisting of sodium or lithium salts of sulfate, chloride, acetate and citrate and mixtures thereof.

The process is carried out to increase the amount of the neutralized carboxylic acid dissolved in the molten aqueous phase in which the molten aqueous phase is a continuous phase in step I.

(a) the following structural formula

Wherein R ₁ is H or C _1-4 alkyl, R ₂ is H or CH ₃ , n is from 1 to 200, a polyol, C _2-10 alkanediols, sorbitol, glycerin, sugars, sugar derivatives, Urea and the following structural formula

(HOCH ₂ CH ₂ ) _x NH _y

A nonvolatile water soluble nonionic organic material selected from the group consisting of ethanol amines wherein x is 1 to 3, y is 0 to 2, and x + y is 3; (b) alcohols having 1 to 5 carbon atoms; (c) alkyl sulfates, paraffin sulfonates alkyl glyceryl ether sulfonates, anionic acyl sacosinates, methylacyl taurates, linear alkyl benzene sulfonates, N-acyl glutamate, alkyl glucosides, alpha sulfo fatty acid esters, acyl isethios Nate, alkyl sulfosuccinate, alkyl ether carboxylate, alkyl phosphate ester, ethoxylated alkyl phosphate ester, methyl glucose ester, protein condensate, alkyl amine oxide, alkyl betaine, alkyl sultine, 1 to 12 ethoxy groups Preference is given to containing from about 2 to about 40% solubilization aid selected from the group consisting of synthetic surfactants containing C _8-22 alkylene chains selected from the group consisting of alkyl alkyl sulfates and mixtures thereof.

The method is preferred when the aqueous phase contains about 20 to about 100 weight percent water.

The method is preferred when the hard crystalline phase contains from about 75 to about 100 weight percent of the neutralized carboxylic acid.

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

The method is preferred when the bar has a complex bicarboxylic acid phase comprising a crystal selected from wax, mineral oil and clay.

Highly preferred embodiments of the present invention comprise about 15 to about 50% sodium fatty acid soap consisting of at least about 50% of saturated aliphatic alkylene chains of C _12-24 having at least about 25% of a single chain; About 15 to about 60% of water; And about 2 to about 60% of a hygroscopic synthetic surfactant selected from surfactants that absorb at least about 20% of its dry weight of water for 3 days at 26 ° C. and 80% relative humidity. A human cleansing bar composition comprising a hard hard interlocking mesh.

The highly preferred human cleansing bar comprises a moisturizing composition wherein the hygroscopic synthetic surfactant is composed of alpha sulfo fatty acid esters, alkyl sulfates, alkyl ether carboxylates, alkyl betaines, alkyl sulfines, alkyl amine oxides, alkyl ether sulfates and mixtures thereof. More preferred if it is selected from.

Such highly preferred human cleansing bars are selected from the group consisting of sodium chloride, sodium sulfate, disodium hydrogen phosphate, sodium pyrophosphate, sodium tetraborate, sodium acetate, sodium citrate and other compatible salts of inorganic and short-chain organic acids, and / Or more preferably from about 0.5 to about 40% of a salt hydrate.

Such highly preferred human cleansing bars include various formulations of the core structure of sodium soap oil, water, mild synthetic surfactants, bar appearance satin, emollients, and other cleansing bar supplements. Such a preferred bar is formulated to be essentially bar smeared.

Some preferred embodiments of the present invention include a hard interlocking mesh of a neutralized carboxylic acid fibrous core consisting essentially of sodium fatty acid soaps consisting of at least 50% saturated _C12-24 saturated aliphatic alkyl chains. Preferably, at least about 25% of the saturated alkyl chains have a single chain length.

Some compositions of the present invention include water-containing hard meshes as defined above and hard meshes that do not contain water. These compositions should be formed with water or other suitable solvent system. These compositions can be prepared with large amounts of water and the water content in the final composition can be reduced by about 1% or 2%.

However, a particular advantage of some of the structures described herein is that they can be dehydrated without losing the integrity of the mesh. Some preferred molding solids can be dehydrated without slight changes in their external dimensions. The other bars contract while maintaining the three-dimensional shape. Some of the bars herein have a unique feature that is not destroyed by dehydration.

More complex bars of the present invention include framework structures comprising other fatty acid salts selected from potassium, magnesium, triethanol ammonium and / or calcium soaps used with selected amounts of sodium and / or lithium soaps. More complex cleaning bars may contain surprisingly large amounts of water, mild synthetic surfactants, bar appearance stabilizers, emollients and other cleaning bar aids and are still soft and have very good low smearing properties.

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

The percentages, proportions and parts herein are based on the total weight of the composition unless otherwise stated. All amounts and ranges herein are approximate unless otherwise stated.

The ranges shown in Table 1 are not essential. For example, some selected sodium soaps may be used in an amount of about 75%. Thus, the range is about 5 to about 75%. Preferred amounts and ratios can vary from monocarboxylic to polycarboxylic acids, depending on the cation and the like.

The bars shown in Table 1 are prepared using the indicated amount of water, but the water content of the final bar can be reduced to provide bars with reduced water content, much less water, or no water at all. . Preferred water contents are from about 20 to about 80 weight percent of the weight of the bar.

Table 2 below shows some preferred ranges of soap of single FA chain length. Table 3 shows some preferred ranges of unsaturation in FA used in the compositions of the present invention. Some preferred compositions contain little or no short chain FAs of C or less. The terms soap fatty acid (FA) salt and monocarboxylic acid salt are sometimes used herein in the same sense together. Soap is used because it is easier and preferred embodiment to relate.

Table 4 lists the ranges of some important preferred optional ingredients for the composite soap bar compositions of the present invention. None of these components is essential to the basic desirable bar core structure. 0 is the lowest level for each optional component. Some preferred ones may contain from about 0.1 to about 70% of such ingredients in total. Ideally in the present invention, the core bar may contain a large amount of other components in addition to soap and water. The ranges shown in Table 4 specifically describe what contains 5% to about 75% of the selected sodium soap and other ingredients.

Soap shaped solids may also be made of lithium soaps or neutralized polycarboxylic acids, but are expected to be somewhat different from the amounts and ratios given for sodium soaps.

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

Sodium soap is preferably at least about 50% of the soap present in the bar.

The amount of potassium soap and / or triethanolammonium soap should not exceed half of the sodium soap, preferably less than 1/3, more preferably less than 1/4, and the amount of magnesium soap is about 1/3 of the amount of sodium soap. It should not exceed, preferably less than about 1/4.

The sum of the other soaps, except lithium soaps, should preferably not exceed 1/2, more preferably 1/3 of the sodium soap.

The synthetic detergent component of the bar composition of the present invention may be defined as a detergent selected from the group consisting of anionic, nonionic, amphoteric and zwitterionic synthetic detergents. All surfactants of high and low foaming properties and high and low water solubility can be used in the bar compositions of the present invention.

Examples of synthetic detergents suitable for use in the present invention are described in column 6 line 70 to column 7 line 74 of Zimmerer, US Patent No. 3,351,558, issued November 7, 1967, which is incorporated herein by reference. Quote it as:

Examples are water soluble salts of organic sulfonic acids and water soluble salts of aliphatic sulfuric esters, ie, water soluble salts of organic sulfuric acid reaction products having alkyl radicals of C and radicals selected from the group consisting of sulfonic acid and sulfuric ester ester radicals.

Particularly important synthetic sulfate detergents are the alkali metal salts of the sulfate esters of the normal primary aliphatic alcohols of C, which are normal solids. Accordingly, alkyl sodium sulfate and potassium salts obtained from mixed higher alcohols derived by reduction of tallow or reduction of coconut oil, palm oil, stearin, palm kernel oil, babassu kernel oil or other coconut oil are included in the present invention. Can be used.

Other aliphatic sulfuric acid esters which may suitably be used include water soluble salts of polyhydric alcohol sulfuric acid esters which are incompletely esterified with high molecular weight soap-forming carboxylic acids. Such synthetic detergents include sodium and potassium salts of coconut oil fatty acid mono esters of 1,2-hydroxypropane-3-sulfuric acid ester, sodium and potassium salts of monomyristoyl ethylene glycol sulfate, and monolauroyl diglycerol sulfate Water soluble alkali metal salts of higher molecular weight fatty acid monoglyceride sulfate esters such as sodium and potassium salts.

Synthetic surfactants and other optional materials useful in conventional cleaning products are also useful in the present invention. Indeed, some components, such as certain hygroscopic synthetic surfactants that are usually useful in liquids and very difficult to incorporate into conventional cleaning bars, are very compatible with the bars of the present invention. Thus, all known synthetic surfactants useful in cleaning products are useful in the compositions of the present invention. The cleaning product patent literature often discloses synthetic surfactants. Some preferred surfactants as well as other cleansing product components are described in the literature below.

United States Patent Number Patent Date Inventor

No. 4,061,602 December 1977 Oberstar

No. 4,234,464 November 1980 Morshauser

No. 4,472,297 September 1984 Bolich et al.

No. 4,491,939 January 1985 Hoskins et al.

No. 4,540,507 September 1985 Grollier

No. 4,565,647 January 1986 Llenado

No. 4,673,525 June 1987 Small

No. 4,704,224 November 1987 Shaud

No. 4,788,006 November 1988 Bolwich, Junior, etc.

No. 4,812,253 March 1989 Small, etc.

No. 4,820,447 April 1989 Medcolf et al.

No. 4,906,459 March 1990 Cobb et al.

No. 4,923,635 May 1990, etc.

No. 4,954,282 September 1990 Rys et al.

All of these patents are incorporated herein by reference. Some preferred synthetic surfactants are shown in the Examples herein. Preferred synthetic surfactant systems are optionally designed according to bar appearance stability, foamability, washability, and mildness.

Surfactant mildness can be measured by the skin wall breaking test used to measure the irritation of the surfactant. In this test, the milder the surfactant, the less the skin wall is destroyed. Skin wall breakage is measured by the relative amount of radiolabeled water (H-HO) that passes from the test solution through the skin epidermal tissue and into the physiological buffer contained in the diffusion chamber. This test is based on the paper [J. Invest. Dermatol., 1975, 64, pp. 190-195, to U.S. Patent No. 4,673,625, issued by TJ Franz, and Small et al., June 16, 1987, which are incorporated herein by reference. ), Which describe a mild alkyl glyceryl ether sulfonate (AGS) surfactant based synthesis bar comprising a standard alkyl glyceryl ether sulfonate mixture. Wall break tests are used to select mild surfactants. Some preferred mild synthetic surfactants are described in the Small et al. Patent and Rice et al. Some specific examples of preferred surfactants are used in the examples herein.

Some examples of good foam improving detergent surfactants (warmed ones) are sodium lauroyl sacosinate, alkyl glyceryl ether sulfonates, sulfonated aliphatic esters, paraffin sulfonates and sulfonated fatty acids.

Many examples of other surfactants are described in the patents incorporated herein by reference. These include other alkyl sulfates, anionic acyl sacosinates, methyl acyl taurates, N-acyl glutamate, acyl isethionates, alkyl sulfosuccinates, alkyl phosphate esters, ethoxylated alkyl phosphate esters, trideset sulfates , Protein condensates, mixtures of ethoxylated alkyl sulfates and alkyl amine oxides, betaines, sulfines and mixtures thereof. These surfactants include alkyl ether sulfates having 1 to 12 ethoxy groups, especially ammonium and sodium lauryl ether sulfate.

The alkyl chain of these other surfactants is C-C, preferably C-C. Alkyl glycosides and methyl glucose esters are preferred mild nonionic materials that can be mixed with other mild anionic or amphoteric surfactants in the compositions of the present invention. Alkyl polyglycoside detergents are useful foaming agents. In order to balance the hydrophilicity and hydrophobicity of the molecule, there may be about 8 to about 22 alkyl groups and about 1.1 to about 5 glycoside units per molecule. Alkyl polyglycosides of C-C, preferably C, with an average glycoside degree of about 1.1 to about 2.7, preferably about 1.2 to about 2.5, are preferred.

Preference is given to sulfonated esters of aliphatic esters in which the chain length of the carboxylic acid is C-C, preferably C-C, and the chain length of the ester alcohol is C-C. These include sodium alpha sulfomethyl laurate, sodium alpha sulfomethyl cocoate and sodium alpha sulfomethyl tallowate.

Amine oxide detergents are good foaming enhancers. Some preferred amine oxides are C-C preferably C-C alkyl dimethyl amine oxides and C-C, preferably C-C aliphatic acyl amidopropyl dimethyl amine oxides, and mixtures thereof.

Fatty acid alkanolamides are excellent foaming enhancers. Some preferred alkanolamides are C-C, preferably C-C monoethanolamide, diethanolamide and monoisopropanolamide, and mixtures thereof.

Other detergent surfactants are general formula

RO (CHCHO) CHCOOM

Alkyl ethoxy carboxylate wherein R is an alkyl group of C-C, K is an integer from 0 to 10 and M is a cation; And general formula

Wherein R ¹ is H, a C _1-4 alkyl group, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, R ² is C _5-31 hydrocarbyl, Z is a linear hydrocarbyl chain and Polyhydroxy hydrocarbyl having at least three hydroxy groups bonded directly) or alkoxylated derivatives thereof.

Betaine is an excellent foam enhancer. C ₈ -C _18, preferably C ₁₂ -C ₁₆ alkyl betaine, eg coco betaine or C ₈ -C ₁₈ preferably C ₁₂ -C ₁₆ acyl amido betaine, eg cocoamidopropyl Preferred are betaines such as betaine, and mixtures thereof.

Some preferred surfactants are hygroscopic synthetic surfactants that absorb at least about 20% of their dry weight for three days at 26 ° C. and 80% relative humidity. Hygroscopic surfactants improve the foaming of the bar. Some preferred hygroscopic synthetic surfactants are listed below (but not all are hygroscopic).

[Absorbency of some surfactants]

Hygroscopic surfactants are defined herein as having a moisture difference of at least 20% after 3 days at 26 ° C. and 80% relative humidity.

Class: Nonionic

Sulfonate Total Water Absorption * (%)

Sodium C ₈ Glyceryl Ether Sulfonate 39.8

Sodium C _12-14 Glyceryl Ether Sulfonate 22.9

Sodium C ₁₆ Glyceryl Ether Sulfonate 71.4

Sodium Comonoglyceride Sulfonate 3.5

(Sodium Salt of C _8-16 Alkyl Glaseryl Ether Sulfonate)

Alpha sulfo ester and acid total moisture uptake * (%)

Sodium Alpha Sulfo Methyl Laurate / Myristate 39.3

Sodium alpha sulfo methyl myristate 44.5

Sodium Alpha Sulfohexyl Laurate 23.2

Sodium alpha sulfo methyl / hexyl laurate and myristate 26.3

Sodium Alpha Sulfo Methyl Palmitate 3.7

Sodium Alpha Sulfo Methyl Stearate 4.2

Sodium 2-sulfolauric acid 0.2

Sodium 2-Sulfo Palmitic Acid 3.8

Sodium 2-sulfo stearic acid 0.0

_{^{(Na + R 1 -C (SO}} 3 -) -CO 2 R 2, R 1 = C 8-14 alkyl, R2 = C _1-8 alkyl)

Sodium Alkyl Isetionate Total Water Absorption * (%)

Sodium Lauryl Isethionate 31.7

Sodium cocoyl isethionate 11.0

Sarcosinate Total Water Absorption * (%)

Sodium Lauryl Sacosinate 8.8

Sodium Stearyl Sacosinate 13.3

Sodium Cocoyl Sacosinate 18.7

Alkyl Sulfate Total Water Absorption * (%)

Sodium Lauryl Sulfate 28.2

Sodium Lauret-1 Sulfate 37.6

Sodium Ole Sulfate 20.3

Sodium Cetearyl Sulfate 4.7

Sodium cetyl sulfate 2.25

(Na ⁺ R ₁ (OCH ₂ CH ₂ ) _n OSO _3- , R ₁ = C _8-14 alkyl, C _16-20 alkyl (lene) with at least one double bond, n = 0-18)

Acyl Glutamate Total Water Absorption * (%)

Sodium Cocoyl Glutamate 26.7

Sodium Lauryl Glutamate 17.8

Sodium Myristyl Glutamate 18.1

Sodium Stearyl Glutamate 12.0

Alkyl ether carboxylate total moisture uptake * (%)

Sodium Lauret-5 Carboxylate 32.2

Sodium Palmityl-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 Total Water Absorption * (%)

Disodium laureth sulfosuccinate 33.6

Phosphate Total Water Absorption * (%)

Sodium Monoalkyl (70% C ₁₂ /30% C ₁₄ ) Phosphate 21.1

Category: Amphoteric

Betaine Total Water Absorption * (%)

Coco betaine 70.0

Cocoamidopropyl betaine 48.2

Palmitylamidopropyl Betaine 46.5

Isostearylamidopropyl betaine 44.3

Sultine Total Water Absorption * (%)

Cocoamidopropylhydroxy Sultine 59.5

Amine Oxide Total Water Absorption * (%)

Palmityl Dimethyl Amine Oxide 34.0

Myristyl Dimethyl Amine Oxide 46.0

Cocoamidopropyl amine oxide 43.3

Protein Derivative Total Water Absorption * (%)

Na / TEA C ₁₂ hydrolyzed keratin 34.7

* 3 days, 26 ℃ / 80% relative humidity

Polymeric emollients are described in Small et al. And Medcholp et al. Both cationic polysaccharides and cationic synthetic polymers are described. Cationic synthetic polymers useful in the present invention include cationic polyalkyleneimines, ethoxypolyalkylene imines and poly [N- [3- (dimethylammonio) propyl] -N '-[3-ethylene oxyethylene dimethyl ammonio ) Propyl] urea dichloride], the latter being sold by Miraolol Chemical Company, Inc. as Miranol A-15 (CAS reg. No. 68555-36-2).

Preferred cationic polymeric skin protectants of the present invention are cationic polysaccharides of the cationic guar gum class with a molecular weight of 1,000 to 3,000,000. More preferred molecular weight range is 2,500 to 350,000. These polymers have a polysaccharide backbone comprising galacmananane units and a cationic degree of substitution ranging from about 0.04 to about 0.8 per anhydroglucose unit, wherein the substituted cationic groups are 2,3-epoxypropyltrimethyl to the native polysaccharide backbone Adduct of ammonium chloride. Examples are JAGUAR C-14-15, C-15 and C-17 sold by Celanese Corporation. In order to achieve the advantages described in the present invention, the polymer must have structural or physical properties that allow it to be adequately completely dehydrated and later incorporated into the soap matrix.

The mild skin cleansing bar of the present invention comprises about 10: 1 to about 1:10, preferably about 4: 1 to about 1: 4, most preferably about 3: 2 to about 2: 3, of silicone gum and silicone fluid. The proportion of the mixture may contain from about 0.5 to about 20%.

Blends of silicone gum and fluids are described in US Pat. No. 4,906,459 to Cove et al., Issued March 6, 1990; No. 4,788,006 to Bolich, Jr., et al., Issued Nov. 29, 1988; 4,741,855 to Grote et al., Issued May 3, 1988; No. 4,704,272 to Oh et al., Issued November 3, 1987; And 2,826,551 to Geen, issued March 11, 1958, for use in shampoos and / or conditioners, all of which are incorporated herein by reference.

The silicone component is applied to the bar in an amount effective to impart skin softening properties, such as from about 0.5 to about 20% of the composition, preferably from about 1.5 to about 16% and most preferably from about 3 to about 12%. May exist. Silicone fluid as used herein refers to silicone having a viscosity at 25 ° C. in the range of about 5 to about 600,000 centistokes, most preferably about 350 to about 100,000 centistokes. As used herein, silicone gums represent silicones having a molecular weight of about 200,000 to about 1,000,000 and a viscosity of at least about 600,000 centistokes. The molecular weight and viscosity of the selected siloxane will depend on whether it is a gum or a fluid. The silicone gum and the fluid are mixed together and incorporated into the composition of the present invention.

Other components of the present invention are selected according to various uses. For example, perfumes may generally be used at the level of about 0.1 to about 2.0% of the composition in formulating skin cleansing products. Alichols, hydrotrope, colorants and fillers such as talc, clays, water insoluble particulate calcium carbonate and dextrins can also be used. Cetearyl alcohol is a mixture of cetyl alcohol and stearyl alcohol. Preservatives such as ethylene diamine sodium tetraacetate (EDTA) may be incorporated into cleansing products in an amount of generally less than 1% of the composition to prevent color and odor degradation. Antimicrobial materials may also be incorporated in amounts of usually up to 1.5%. These patents describe or relate to such ingredients and combinations that may be used in the bar of the present invention, which are incorporated herein by reference.

Some bars of the present invention include from about 5% to about 75% of said fatty acid sodium soap fibers; About 10% to about 94% of water; And another bar component selected from at least about 1% other soaps, humectants, colorants, solvents, fillers, synthetic detergent surfactants, polymeric skin feel and softening aids, flavors, preservatives, and mixtures thereof.

Some of the bars of the present invention comprise 5-50% fibrous fatty acid sodium soap, wherein at least about 25% consists of at least about 50% of saturated aliphatic alkyl chains of C _12-24 having a single chain length.

Some of the bars of the present invention comprise such fibers that comprise about 3 to about 75 volume percent, preferably about 15 to about 40 volume percent, of the bar structure.

Some bars include 5 to 75% of a fibrous fatty acid sodium soap consisting of at least about 50% of saturated aliphatic alkyl chains of C _12-24 having at least about 25% of C _12-24 ; About 10 to about 94% of water; And from about 0% to about 70% of the hard low smear characteristic structure in total from other soap bar components selected from the crowds listed in Table 4 above.

Some human cleansing soap bar compositions include a hard interlocking mesh of sodium soap fibers consisting of at least about 50% of saturated aliphatic alkyl chains of C _12-24 with at least about 25% having a single chain length; And from about 2% to about 40% by weight of a hygroscopic synthetic surfactant selected from surfactants that absorb at least about 20% water by weight of their dry weight for 3 days at 20 ° C. and 80% relative humidity.

[Bar appearance supplements]

Bar appearance (water-retaining and / or anti-shrinkage) adjuvants preferably include compatible salts and salt hydrates as described in Table 4 above; Water soluble organic compounds such as polyols, urea; Aluminosilicates and clays; And a crowd consisting of mixtures thereof.

Water soluble organic compounds are also used to stabilize the appearance of the bar soaps of the present invention. Some preferred water soluble organic compounds are propylene glycol, glycerin, ethylene glycol, sucrose and urea, and other compatible polyols.

Particularly suitable water soluble organic compounds are propylene glycol. Other compatible organic compounds include polyols such as ethylene glycol or other 1,7-heptanediol, mono- and polyethylene and propylene glycols having a molecular weight of about 8,000 or less each, all mono-C _1-4 alkyl ethers, sorbitol Polyhydric alcohols such as glycerol, glycos, diglycerol, sucrose, lactose, dextrose, 2-pentanol, 1-butanol, mono-, di- and tri-ethanol ammonium, 2-amino-1-butanol do.

The term polyol as used herein includes non-reducing sugars such as sucrose. Sucrose does not reduce the Fehling solution and is therefore classified as a non-reducing disaccharide. Unless stated otherwise, the term sucrose as used herein refers to sucrose, derivatives thereof, and similar non-reducing sugars and similar polyols that are substantially stable at soap processing temperatures of up to about 210 ° F. (98 ° C.) such as tree Allose, raffinose, and steziose, and sorbitol, lactitol and maltitol.

Compatible salts and salt hydrates are used to stabilize the bar soap appearance through retention of water. Some preferred salts are sodium chloride, sodium sulfate, disodium hydrogen phosphate, sodium pyrophosphate, sodium tetraborate.

In general, compatible salts and salt hydrates include the sodium, potassium, magnesium, calcium, aluminum, lithium and ammonium salts of the inorganic and lower (up to 6 carbon) carboxylic acids or other organic acids, the corresponding hydrates and mixtures thereof. Inorganic salts include hydrochloride, bromate, sulfate, metasilicate, orthophosphate, pyrophosphate, polyphosphate, metaborate, tetraborate and carbonate. Organic salts include acetates, formates, methylsulfates and citrates.

Water soluble amine salts may also be used. Monoethanolamine, diethanolamine and triethanol ammonium (TEA) hydrochloride are preferred.

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

Other types of clays include zeolites, kaolinite, montmorillonite, attapulgite, illite, bentonite and halosite. Another preferred clay is kaolin.

Waxes include petroleum waxes (paraffins, microcrystalline and mineral oil waxes), vegetable waxes (carnauba, palm waxes, candelillas, sugarcane waxes and vegetable triglycerides), animal waxes (wax, spermaceti, wool waxes, shellac waxes). And animal triglycerides), mineral waxes (monttar, ozercurite and ceresin) and synthetic waxes (Fisher-Tropsch).

Preferred waxes are used in the examples herein. Useful waxes have a melting point (M. P.) of about 120 ° F. to about 185 ° F. (49 to 85 ° C.), preferably about 125 ° F. to about 175 ° F. (52 to 70 ° C.). Preferred paraffin waxes are fully refined petroleum waxes having melting points ranging from about 130 ° F. to about 140 ° F. (49 to 60 ° C.). This wax is odorless and meets FDA requirements for use as a coating for food and food packages. Such paraffins are readily commercially available. Highly suitable paraffins are commercially available under the trade name Factowax® R-133, for example from The Standard Oil Company, Ohio.

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

Paraffin is preferably present in the bar in an amount ranging from about 5% to about 20% by weight. Paraffin ingredients are used to impart skin softness, plasticity, firmness and processability to the product. This also gives the bar a glossy appearance and a soft touch.

The paraffin component is optionally supplemented with microcrystalline wax. Suitable microcrystalline waxes have, for example, melting points in the range of about 140 ° F. (60 ° C.) to about 185 ° F. (85 ° C.), preferably about 145 ° F. (62 ° C.) to about 175 ° F. (79 ° C.). The wax should preferably satisfy the FDA requirements for food grade microcrystalline wax. Very suitable microcrystalline waxes are commercially available from Witco Chemical Company under the trade name Multi Wax X-145A. The microcrystalline wax is preferably present in the bar in an amount ranging from about 0.5 to about 5% by weight. The microcrystalline wax component gives the bar flexibility at room temperature.

[Brief Description of Drawings]

1 to 8 show enlarged views of bar samples of the present invention, and FIGS. 9 and 10 show enlarged views of two other conventional soap bars.

EXAMPLE

The following examples are illustrative and do not limit the scope of the invention. Unneutralized or free fatty acids used in the examples are those having the same chain length as those used to prepare the soap unless otherwise stated. All amounts, ranges, temperatures, results, etc., as used herein, are approximate unless stated otherwise.

Basic process for the manufacture of bars of the present invention

In the examples the cleansing bars are prepared by the following process unless otherwise stated;

1. Mix fatty acid precursor, propylene glycol, sodium chloride, and water (excluding water mixed with other raw materials) and heat to 71 ° C.

2. Add caustic solution (50% sodium hydroxide) and stir the mixture until a molten aqueous liquid is formed comprising 15-94% water and 5.5-75% soap (neutralized carboxylic acid). The temperature during neutralization of the molten liquid is increased to approximately 95 ° C.

3. The other ingredients are preferably added in the following order and the temperature is maintained at approximately 88 ° C .: cocobetaine; Sodium lauroyl sacosignite; Or sodium alpha sulfo methyl cocoate, kaolin clay; Or hydrated zeolites (synthetic sodium aluminosilicate); And paraffin perfume is added last.

4. Pour the molten liquid mixture into the molding mold.

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

The bars of the examples are prepared by the above general process unless otherwise stated.

It should be noted that conventional floating or freezer treatment of the blends used in the embodiments of the present invention results in the formation of very soft bars or no bars. Example II is a very preferred general bar.

[Description of Test in Example]

[Bar Hardness Test]

1. The hardness of the bar is determined by measuring at 25 ° C the depth (mm) of penetration of the bar by a 247 g standard weight penetrometer probe with a 47 g 22.9 mm (9 inch) shaft and a 200 g conical needle coupled to its top. do. Hardness values of 5 mm or less indicate a very hard bar; 5-10 mm represents a moderately hard bar; 10 to 12 mm represents a rather soft bar with an upper limit of acceptance; More than 12 mm represents a very soft bar that is unacceptable for most applications. Unless stated otherwise, this defines the hardness used herein.

Bar smear test

2. Smear grades were: (1) placed on a test bar in a 1400 mm diameter round dish; (2) 200 ml of room temperature water was added to the dish so that the bottom 3 mm of the bar could be dipped in water; (3) the bar was immersed overnight (15 hours); (4) The bar is taken out and determined by evaluating the combined amount of smear, the characteristics of the smear, and the depth of the smear, wherein in the evaluation, 10 indicates no smear, 8.0 to 9.5 indicates less smear, and 5.0 to 7.5 Indicates a medium smear similar to that on the market, and 4.5 or less indicates very poor smear.

Soap bars sold by The Peocter Gamble Company, Cincinnati, Ohio, for example SAFEGUARD. , ZEST , IVORY And LAVA Have smears of about 5, 6, 6 and 6, respectively. See Table 12 for more data.

[Bar Shrink Test]

3. Shrinkage is measured by placing freshly prepared unpacked bars for one week in a room kept at 26 ° C. and 15% relative humidity. The amount of shrinkage in the original bar shape is determined by quality assessment, with 0 indicating no contraction, + representing slight contraction, ++ representing moderate contraction, and +++ representing large contraction.

In Tables 6 and 7, soap bars 1-10 are illustrated as showing bar hardness, smear and shrinkage for C ₁₀ , C ₁₂ , C ₁₄ , C ₁₆ and C ₁₈ alkyl chain soaps as shown. Preferred alkyl chain soaps of the invention are illustrated in Tables 1 and 2 above.

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

NOTE 1 Despite the hardness of 8.9, Example 1 has very poor smear characteristics because the soluble C soap dissolves in the smear measurement method.

** Solid unsaturated bar did not form solid bar.

Example 10 has a hard structure but is not preferred as a cleaning bar because the hardness is 14.

** No solid bar formed due to too much unsaturated C soap.

Examples 12-16 are turbid of the present invention.

* Composition by chain length, brackets indicate actual amount of material.

** Emersol 132 is available from Henkel Corporation of Amble, PA.

Examples 17-19 consist of a more complex soap mixture than the previous examples. These form an excellent bar of the present invention. They have little or no smear. A comparison of these with those made from conventional tallow and coconut soap is shown in Table II.

* Composition by chain length, brackets indicate actual amount of material.

These comparative examples 20, 21 and 22 do not form the hard structure of the present invention. These are made of typical commercial soaps. These are soft soaps with poor smear characteristics. Compared to Example 15 of the present invention made from 65% water and C and C saturated soaps to form a smear free hard bar.

Example 23 is a bar of the invention containing more synthetic surfactant than soap. It has a low smear and good foamability. Example 24 is a bar of the present invention containing a polymer and other bar soap components.

Example 23

Synthetic detergent bar

Component weight%

Sodium Palmitate 20

Sodium Lauroyl Sacosinate 9

Sodium Laureth-3-Sulfate 7

Sodium cetearyl sulfate 5

Free fatty acids (palmitic acid) 1

Sodium chloride 3

Propylene Glycol 14

Hydrated Zeolite A 3

Spices 1

Water 37

* Total 21% synthetic surfactant

Example 24

Polymer-Containing Bars

Component weight%

Sodium Palmitate 20

Sodium Alpha-Sulfo Methyl Cocoate 8.7

Coco Betaine 4.65

Jaguar C376 1.5

Propylene Glycol 15

Kaolin clay 5

Paraffin (melting point = 55 degrees Celsius) 4.5

Sodium chloride 3

Spices 1

Water 35.5

* Jaguar C376 is available from Celanese Corporation, New York, NY, USA

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

Example 24 is a soft bar formulation with a polymeric emollient.

[Examples 25 to 27]

Example 25 Example 26 Example 27

Ingredient (% by weight)

Lithium Myristate 33--

Lithium Chloride 5--

Dodekanidosan-20 20

Disodium salt

Sodium Lauroyl--5

Sacosinate

Water 62 80 75

Penetration value N / A N / A N / A

N / A = not available

For Example 25, the fatty acid precursor was heated to 71 ° C. and lithium hydroxide was added separately to water, then the fatty acid and lithium hydroxide solution were added together and the temperature maintained at least 71 ° C. with stirring for 30 minutes, followed by lithium chloride Formulations are made by adding salt, stirring for 5 more minutes, then pouring into molds to cool and solidify.

For Examples 26 and 27, the diacid is melted (150-180 ° C.) and hot (90 ° C.) caustic solution (NaOH 2 equivalents) is added. The mixture is stirred for about 5 minutes. For Example 27, sodium lauroyl sacosinate is predissolved in caustic / water solution. Upon cooling the bar becomes solid and further cures, for example up to a water content of about 35 to 40% by weight of the bar.

Example 25 shows the ability to form high humidity firm, non-smear bars without sodium soap. Examples 26 and 27 show the ability to form completely soap free products and still obtain a relatively rigid interlocking fiber structure.

[Freezer Bar Example 28]

Example 28 relates to the freezer bar preparation described in US patent application Ser. No. 07 / 731,163, filed on July 15, 1991, to Taneri et al. This way

(1) mixing a melt mixture comprising about 15 to 85 weight percent of neutralized carboxylic acid soap and about 15 to 40 weight percent water, based on the weight of the freezer bar;

(2) cooling the mixture to a semi solid in a scraped wall heat exchanger freezer;

(3) extruding the semi-solid as a soft plug; And

(4) a relatively hard, semicontinuous, open three-dimensional crystalline interlocking mesh of neutralized carboxylic acid soap, prepared by the step of further cooling and crystallizing until the soft plug is firm to provide a human cleansing freezer bar. Provided is a cleansing freezer bar for a human body comprising a frame structure having a frame.

Step 1-Blend

The soaps specified in the formulations are prepared in situ by mixing the desired fatty acid consisting essentially of the C chain length with the appropriate base or mixture of bases consisting essentially of sodium hydroxide, lithium, magnesium, calcium and potassium and triethanolamine. . Fatty acid, base and water are mixed at about 170 ° F. to about 200 ° F. (76 to 93 ° C.) to form a soap. In Example 28 180 ° F. is used. Sufficient water is used to stir the mixture. The other ingredients are added while maintaining the temperature between about 180 ° F. and about 200 ° F. (82-93 ° C.). In Example 28 180 ° F. is used. The optimum mixing temperature may vary depending on the particular formulation.

Step 2 (Optional)-Aeration, Add Traces, and Instant Dry (Optional)

The mixture is vented (optional), fragrance (only when dried) and other trace ingredients are added using a positive discharge pump or other in-line mixer. In Example 28, it is not vented or dried. The mixture of step 1 is optionally dried to reduce the water content to the desired level, preferably 20 to 40%. The instant drying temperature is about 225 ° F. to about 315 ° F. (135 to 157 ° C.) under a pressure of about 30 to about 100 psi (115 to 517 mm Hg).

Step 3-freezer

If dried using a scraped wall heat exchanger (freezer), at an initial temperature of about 180 ° F. to about 200 ° F. (82 to 93 ° C.) or about 200 ° F. to about 220 ° F. (93 to 104 ° C.), preferably final Temperatures from about 135 ° F. to about 180 ° F. (57 to 82 ° C.), more preferably from about 145 ° F. to about 180 ° F. (63 to 82 ° C.) and most preferably from about 155 ° F. to about 175 ° F. (68 to 79 ° C.) The mixture is cooled to partially cure the components. This final temperature (also referred to herein as the freezer outlet temperature (FOT)) is typically the maximum temperature that forms a soft plug that retains its shape upon extrusion with a moving belt (step 4). The FOT of Example 28 is 175 ° F.

Step 4-Extrusion

The cooled mixture of step 3 is extruded onto a soft plug on a moving belt which is then cooled and fully crystallized, stamped and packaged. The plug is preferably formed by the extrusion operation shown in the above-cited US Pat. No. 3,385,059. The composition is slightly crystallized in the freezer (step 3) to provide a semi solid with sufficient viscosity to stand on the belt, while further crystallization occurs after extrusion to cure the bar. The final crystallization of the sodium soap forms a semicontinuous open interlocking mesh structure in the freezer bar of the present invention.

Example 28

% By weight

Sodium C Soap 27.99

Magnesium C Soap 5.00

Sodium Lauroyl Sacosinate 3.00

Coco Betaine 10.00

Propylene Glycol 3.50

Mineral oil 22.49

Sodium Chloride 2.58

Free fatty acids, C 0.50

Spices 0.50

Water 24.44

Floating scamped bar hardness test

Floating stamped bar hardness tests can be used to distinguish between bars of the present invention and other bars. Choose a commercially available bar that represents the various soap formulations; SAFEGUARD (Available from The Procter & Gamble Company, Cincinnati, Ohio); soap ground bars; ZEST Soap / synthetic milled bars; IVORY , Freezer bar; And LAVA , Frame bar. These commercial bar samples and the molded bars of Examples 28 and II were floated according to the following process.

Overall, the commercial bars after flotation are much harder and have better smearing as compared to Example 28 or Example II. It is obvious that this test is an excellent way to distinguish between bars with hard frames and other bars. In short, the bars of the present invention will become much softer after refloating than conventional bars. The process is as follows.

1. Place the forming bars (2.5 kg or more) in a one-step plotter (4 inch / 10.16 cm bonnet one-step plotter) without vacuum and pass through the noodle plate. The noodle plate has 19 holes of 0.37 inch (0.93 cm) in a 3.1 inch (8 cm) plate. Set the barrel temperature to 120 ° F. (49 ° C.) and the nose temperature to 110 ° F. (43.5 ° C.).

2. Repeat step 1 using the noodle.

3. Place the noodle of step 2 into a vacuumed one-stage feeder (4 inch / 10.16 cm bonnet one-stage floater) and pass the brick hole. Brick plugs with approximate dimensions of 1.88 in. (4.6 cm) in height x 1.16 in. (3 cm) in width x 3 in. (7.6 cm) in length are extruded. These plugs should have an internal temperature of 90 ° F. (32 ° C.) to 105 ° F. (41 ° C.).

4. Stamp these plugs into bricks, cool to room temperature (at least 12 hours) and evaluate.

The hardness of the plotter / stamped bars is shown as bar 2 in Table 12 for each test bar. Bar hardness test is as described herein.

While not wishing to be bound by theory, the floated bars having a delta value of 4 or more strongly suggest that they have a skeletal structure that is crushed or destroyed upon original floating. The hard bars of the present invention will form soft, dirty bars when floating in a conventional bar process. The bar of Example 28 is first formed using the freezer process. The bars of Example II are first formed using the frame bar process described above. Approximately 5-10 kg of each bar is floated and stamped.

Commercial bars consist of tallow and coconut natural soap. Floated SAFEGUARD And ZEST The hardness of the soap is approximately the same as the original. IVORY And LAVA Floated soap 2 is slightly softer than the original bar.

On the other hand, the floated bar 2 of Example 28 is much softer than the original bar 1 of Example 28. More dramatically, the floating bar 2 of Example II is broken when floating and is too soft to be stamped. The hardness after floating is that of the soft aqueous phase, suggesting that the hardness of the skeletal structure is inherently destroyed.

Claims (31)

Molded solid comprising an open three-dimensional relatively hard interlocking mesh skeleton structure of neutralized mono-carboxylic or di-carboxylic acid stretched crystals. At least two phases: an aqueous phase having a penetration value of 12 mm for a 12 mm thick sample that is soft or flowable at 25 ° C .; A hard crystalline phase backbone structure comprising an open three-dimensional interlocking mesh of neutralized mono-carboxylic or di-carboxylic acid stretched crystals, and 200 g of conical needles on top of a 47 g weight 9 inch (22.9 cm) shaft. 12 mm for 25 mm thick samples when measured at 25 ° C using a total weight of 247 g standard penetrometer probe combined with top 19/32 inch (1.51 cm) and vertex value 1/32 inch (0.08 cm) Cleansing bar with penetration value below. 3. The method of claim 2 wherein said neutralized carboxylic acid is selected from the group consisting of lithium or sodium neutralized monocarboxylic acids (soaps) or dicarboxylic acids and mixtures thereof; The monocarboxylic acid has a fatty alkyl (ene) chain having 12 to 24 carbon atoms; The dicarboxylic acid has a fatty alkyl (ene) chain having 12 to 18 carbon atoms; At least 80% of said carboxylic acids have a saturated alkyl chain; The hard crystalline phase backbone structure comprises 3 to 75% by volume of the cleansing bar; Said neutralized carboxylic acid comprises from 5 to 75% by weight of the cleaning bar; A cleaning bar wherein said cleaning bar contains 15 to 94% water. A cleaning bar as set forth in claim 2 wherein at least 80% of said carboxylic acids have the following general formula; Wherein a + b is 8-20, a and b are each 0-20, X is H, OR, Or a combination thereof, R is C _1-3 alkyl, H or a combination thereof, and M is Na, Li or a combination thereof. The cleaning bar of claim 4, wherein a + b is 10-16, each of a and b is 0-16, X is H or OR, R is H, and M is Na. Sodium fatty acid soap 15-50% consisting of at least 50% saturated fatty alkylene chains of C _12-24 having at least 25% a single chain length; Water 15-60%; Hard crystallinity of elongated sodium soap crystals comprising from 2 to 60% of a hygroscopic synthetic surfactant selected from surfactants which absorb at least 20% of its dry weight of water for 3 days at 26 ° C. and 80% relative humidity. A cleansing bar composition for a human body comprising an interlocking mesh. 4. The method of claim 3 wherein said elongated crystals comprise at least 25% of said saturated fatty alkyl chains consisting of fiber-like sodium fatty acid soaps having a single chain length; The bar contains 15-75% of the sodium soap; Cleansing bar, wherein the bar contains up to 50% by weight of unneutralized (free) carboxylic acid. 8. The method of claim 7, wherein the bar comprises: the sodium soap and water; And alkyl sulfates, paraffin sulfonates, alkyl glycerylether sulfonates, acyl sacosinates, methylacyl taurates, linear alkyl benzene sulfonates, N-acyl glutamate, alkyl glucosides, alpha sulfo fatty acid esters, acyl isethionates, alkyls Sulfosuccinates, alkyl ether carboxylates, alkyl phosphate esters, ethoxylated alkyl phosphate esters, methyl glucose esters, protein condensates, alkyl amine oxides, alkyl betaines, alkyl steines, alkylethers with 1 to 12 ethoxy groups A cleansing bar containing 2 to 60% of a synthetic surfactant containing a C _8-22 alkyl chain selected from the group consisting of sulfates and mixtures thereof. The cleansing bar of claim 8, wherein the synthetic surfactant is a hygroscopic surfactant that absorbs at least 20% of its dry weight of water for three days at 26 ° C. and 80% relative humidity, and the bar is relatively non-swellable. 10. The cleaning according to claim 9, wherein the hygroscopic surfactant is selected from the group consisting of alpha sulfo fatty acid esters, alkyl sulfates, alkyl ether carboxylates, alkyl betaines, alkyl sulfines, alkyl amine oxides, alkyl ether sulfates and mixtures thereof. bar. The method of claim 8, wherein the ratio of water to the soap is 1: 1 to 5: 1; The water is present in an amount from 25% to 60%; The soap has a C ₁₄ to C ₂₂ fatty alkyl chain and the amount of soap in the bar is 15% to 35%; At least 85% of the soap alkyl chain is saturated; The non-neutralized (free) carboxylic acid is 25% by weight or less of the soap; The amount of the synthetic surfactant is 4 to 25% by weight of the bar, the surfactant is sodium acyl isethionate, sodium acyl sacosinate, sodium alpha sulfo fatty acid ester, sodium paraffin sulfonate, sodium alkyl ether sulfate, sodium alkyl sulfide Cleansing bar selected from the group consisting of tate, sodium linear alkyl benzene sulfonate, alkyl betaine, alkyl steine and trialkyl amine oxide. The method of claim 11, wherein the ratio of water to soap is from 1.5: 1 to 2: 1; The non-neutralized (free) carboxylic acid is no more than 17% by weight of the soap; The amount of water is 30% to 45%; The soap fatty alkyl chain is C ₁₄ to C ₁₈ ; At least 95% of said alkyl chains are saturated; The amount of soap is 15% to 30%; Cleansing bar is the amount of the synthetic surfactant 8% to 16%. The method of claim 8 wherein the bar is microcrystalline wax, mineral oil, carnauba wax, palm wax candelilla wax, sugar cane wax, plant derived triglycerides, beeswax, spermaceti, lanolin, wood wax, shellac wax, animal A cleansing bar containing from 0.1% to 40% of a hydrophobic material selected from the group consisting of triglyceride montar, ozocarite, ceresin and Fischer-Tropsch waxes derived from. The method of claim 13, wherein the bar contains 2% to 35% of the hydrophobic material selected from the group consisting of mineral oil and wax, wherein the mineral oil and wax and mixtures thereof have a melting point of 49 ° C. (120 ° F.) to 85 ° C. (185 ° F.). Cleansing bar having a. The method of claim 8, wherein the bar contains 1% to 50% of a nonvolatile water soluble nonionic organic material having a solubility of at least 5 parts in 10 parts of water; The water-soluble nonionic organic material is a polyol of the following structural formula; Wherein R ₁ is H or C _1-4 alkyl, R ₂ is H or CH ₃ and n is from 1 to 200; C _2-10 alkanediols; sorbitol; glycerin; sugars; Sugar derivatives; urea; And ethanol amines of the formula: (HOCH ₂ CH ₂ ) _x NH _y (Wherein x is 1 to 3, y is 0 to 2 and x + y is 3), and a cleaning bar selected from the crowd consisting of mixtures thereof. 16. The cleaning bar of claim 15, wherein the bar contains 2-40% of a nonvolatile water soluble nonionic organic material. The method of claim 16, wherein the nonvolatile water soluble nonionic organic material comprises 5-20% by weight of the bar; A cleaning bar wherein said organic material is selected from the group consisting of propylene glycol, glycerin, sucrose, and urea, and mixtures thereof. The method of claim 8, wherein the bar comprises the sodium soap, the water and the synthetic surfactant, and 1% to 10% of the potassium soap; 1% to 35% of the magnesium soap; 1% to 35% of the calcium soap; 1% to 15% triethanol ammonium soap; Micro water-insoluble material selected from 1% to 60% calcium carbonate and talc; 0.1% to 20% of a polymeric skin feel aid; Aluminosilicate clay and / or other clay selected from the group consisting of 0.5% to 25% zeolite, kaolin, kaolinite, montmorillonite, attapulgite, elite, bentonite, halosite and sintered clay; And 1% to 50% of a cation selected from the group consisting of sodium, potassium, magnesium, calcium, aluminum, lithium, ammonium, monoethanol ammonium, diethanol ammonium and triethanol ammonium, and chloride, bromide, sulfate, metasilicate, ortho With salts and salt hydrates with anions selected from the group consisting of phosphates, pyrophosphates, polyphosphates, metaborates, tetrabolite carbonates, bicarbonates, hydrogen phosphates, methyl sulfates and mono- and polycarboxylates having up to 6 carbon atoms A cleansing bar containing 0.1 to 70% of the other ingredients selected from the group consisting of. 3. The cleaning bar of claim 2, wherein said elongated crystals contain a plate and said soap consists of lithium neutralized mono carboxylic acid. 3. The cleaning according to claim 2, wherein the elongated crystals are fibrous, the neutralized dicarboxylic acid is a disodium salt of 1,12-dodecanedioic acid, and the neutralized dicarboxylic acid comprises 20 to 70% by weight of the bar. bar. At least two phases; Aqueous phase with a penetration value of 12 mm for a 12 mm thick sample that is soft or flowable at 25 ° C .; 200 g on top of a 47 g weight 9 inch (22.9 cm) shaft comprising a hard crystalline phase comprising an open three-dimensional relatively hard interlocking mesh framework of neutralized mono-carboxylic or di-carboxylic acid stretched crystals 25 mm thick when measured at 25 ° C using a total 247 g standard-weight penetrometer probe combined with the cone's needle (top 19/32 inch (1.51 cm) and vertex value 1/32 inch (0.08 cm)) A process for the preparation of a cleansing bar having a penetration value of less than 12 mm for a sample of I. Molten aqueous comprising 20 to 94% water and 5 to 75% by weight of said neutralized carboxylic acid. Preparing a liquid; II. Pouring the molten liquid into a bar forming mold; And III. Crystallizing by cooling the molded molten liquid to provide a cleaning bar comprising the step of providing a cleaning bar. The hydroxide of claim 21 wherein the molten aqueous liquid is selected from the group consisting of sodium hydroxide or lithium hydroxide and mixtures thereof at temperatures between 50 ° C. (120 ° F.) and 95 ° C. (205 ° F.) with stirring the aqueous mixture of carboxylic acids. Prepared by neutralizing with a. 22. The process of claim 21 wherein 2-15% by weight of said bar is a crystallinity enhancing salt selected from the group consisting of sodium or lithium salts of sulfate, chloride acetate and citrate and mixtures thereof. Containing C _8-22 alkylene chains selected from the group consisting of _cos esters, protein condensates, alkyl amine oxides, alkyl betaines, alkyl sultanes, alkyl ether sulfates having 1 to 12 ethoxy groups and mixtures thereof 2 to 40% solubilization aid selected from the group consisting of synthetic surfactants; A method of adding the solubilizing aid to increase the amount of neutralized carboxylic acid dissolved in the applied aqueous continuous phase in step I. The method of claim 21 wherein said aqueous phase contains 20 to 100 weight percent water. The method of claim 21, wherein the crystalline phase contains 75 to 100 weight percent of the neutralized carboxylic acid. The method of claim 21, wherein the bar has a penetration value of 3 mm to 9 mm for the bar sample of 25 mm. 22. The method of claim 21, wherein the bar has other non-carboxylic acid phases comprising crystals or droplets selected from waxes, mineral oils and clays. 7. The method of claim 6, wherein the hygroscopic synthetic surfactant is selected from the group consisting of alpha sulfo fatty acid esters, alkyl sulfates, alkyl ether carboxylates, alkyl betaines, alkyl steines, alkyl amine oxides, alkyl ether sulfates, and mixtures thereof. Cleansing bar for humans. 7. The salt or salt hydrate of claim 6 wherein the bar is selected from the group consisting of sodium chloride, sodium sulfate, disodium hydrogen phosphate, sodium pyrophosphate, sodium tetraborate, sodium acetate, sodium citrate and other compatible salts of inorganic and short-chain organic acids. Cleansing bar for humans containing 0.5 to 40%. 31. The method of claim 30, wherein the molten aqueous liquid phase comprises (a) a polyol of the formula: Wherein R ₁ is H or C _1-4 alkyl, R ₂ is H or CH ₃ and n is 1 to 200; C ₂ -C ₁₀ alkane diol; sorbitol; glycerine; sugars; sugar derivatives; urea; And ethanol amines of the formula: A nonvolatile water soluble nonionic organic solvent selected from the group consisting of (HOCH ₂ CH ₂ ) _x NH _y (where x is 1 to 3, y is 0 to 2 and x + y is 3); (b) alcohols having 1 to 5 carbon atoms; (c) alkyl sulfates, paraffin sulfonates, alkyl glyceryl ether sulfonates, anionic acyl sacosinates, methyl acyl taurates, linear alkyl benzene sulfonates, N-acyl glutamate, alkyl glucosides, alpha sulfo fatty acid esters, acyl ises Thionates, alkyl sulfosuccinates, alkyl ether carboxylates, alkyl phosphate esters, ethoxylated alkyl phosphate esters, methyl glucosesters, protein condensates, alkyl amine oxides-alkyl betaines, alkyl sulfines, 1 to 12 e 2 to 40% solubilization aid selected from the group consisting of synthetic surfactants containing C _8-22 alkylene chains selected from the group consisting of alkyl ether sulfates with oxy groups and mixtures thereof; The method of adding the solubilizing aid to increase the amount of the neutralized carboxylic acid dissolved in the molten aqueous continuous phase in step I.