RU2080365C1 - Detergent in form of shaped solid body, bar-shaped detergent and method for producing bar-shaped detergent - Google Patents

Abstract

FIELD: organic chemistry, production of soaps and detergents. SUBSTANCE: detergent in form of shaped solid body has framework structure in form of open three-dimensional lattice formed by elongate crystals of neutralized mono- and/or dicarboxylic acid. Invention is directed to bar-shaped detergent consisting of at least two phases, namely: aqueous phase and solid phase with framework structure constituted by open lattice formed by elongate crystals of neutralized mono- and/or dicarboxylic acid, bar penetrating to depth of from 0 to 12 mm into sample 25 mm deep at temperature 25 C. Method involves shaping aqueous phase of melt containing 20 to 94% of water and 5 to 75% of neutralized carboxylic acid, casting into moulds and moulding by cooling. EFFECT: higher efficiency. 14 cl, 7 dwg, 12 tbl

Description

 The invention relates to molded solid compositions of neutralized carboxylic acid, especially cleaning bars, briquettes, soap bars, Synbars and the like.

 Products obtained in the form of molded solids, briquettes and whetstones are numerous. Cleaning bars are well known in the art.

 Reduced viscosity cleaning bars have been reported in the technical literature. For example, in US patent N 2988511, issued to Mills 06/03/61. describes a bar of low viscosity.

 A viscous bar, also called a lazy bar, is a soft solid or pulp that forms on the surface of the bar when it is immersed in water, consumers consider it dirty, unattractive and uneconomical.

 Products obtained in the form of molded solids, briquettes and whetstones are numerous. For example, some private cleaning bars of high humidity and low viscosity are described in US Pat. No. 4,606,839, issued to Harping on 08/19/86. Harping uses soap based on coconut oil and / or palm kernel oil.

 It was only necessary to examine the used cleaning bars for private use in the bathroom to see that there is still a need for improved cleaning bars with little or no viscosity.

 The production of hard fibers of hardened sodium laurate soap was reported by L. Marton et al. In a 1940 Journal of American Chemical Societry (Vol. 63, pp. 1990-1993). The message does not indicate the usefulness of hardened soap. Molded solids, as defined in this application, are not described by Marton, etc.

 Japanese Patent JP 7030-798, issued July 30, 1980, describes a transparent, solid, molded or cast bar of soap in which the fatty acids that make up the soap component are myristic, palmitic and stearic acids. A transparent soap is described where at least 90 weight. The fatty acids that make up the soap component are myristic, palmitic and stearic acids. It is reported that the product is a transparent solid soap with good foaming and curing properties, good storage stability and low irritation to human skin. It seems that the method and sample composition of the transparent bar of soap of Japan patent JP 7030-798 do not contain synthetic surfactants.

 It is also difficult to obtain solid non-sticky bars that have a relatively high moisture content (15-40%) (especially in the presence of most synthetic surfactants) of hygroscopic surfactants and / or higher levels of non-solid and soft solids, for example, water-soluble polyols and hydrocarbon fats.

 The present invention provides a molded three-dimensional skeleton structure containing a relatively rigid connecting network of a neutralized crystalline carboxylic acid. In another aspect, the present invention provides an improved cleansing bar that contains said skeleton structure, i.e. a rigid connecting network of neutralized carboxylic acid, preferably sodium soap fibers. Some cleaning bars that contain surprisingly large amounts of ash and other liquids retain their rigidity and excellent viscosity even when they are soaked in water overnight.

 In FIG. 1-8 are enlarged photographs of samples of bars of the present invention. In FIG. 9 and 10 show enlarged photographs of two different bars of ordinary soap.

в установке катодного распыления типа Пелко. Перед нанесением покрытия образец подвергают воздействию вакуума в течение периода времени, достаточного для адекватного удаления влаги из бруска, чтобы гарантировать приемлемое качество покрытия. После нанесения покрытия образец переносят в камеру растрового электронного микроскопа (SEM) и исследует в стандартных условиях работы растрового электронного микроскопа в растровом электронном микроскопе Хитачи модели S570 с целью наблюдения каркасной структуры (основы).Sample preparation for scanning electron microscopy (SEM) involves crushing a molded solid using simple pressure to create a fresh surface for examination. The crushed sample is reduced in size (razor blade) to a rectangle of approximately 10x15 mm and a thickness of approximately 5 mm. The sample is mounted on an SEM aluminum stage using silver adhesive paint. Mounted specimen is coated with 300 gold / palladium film

in a Pelco-type cathode sputtering apparatus. Before coating, the sample is exposed to vacuum for a period of time sufficient to adequately remove moisture from the bar to ensure acceptable coating quality. After coating, the sample is transferred to a scanning electron microscope (SEM) chamber and examined under standard operating conditions of a scanning electron microscope using a Hitachi S570 scanning electron microscope in order to observe the frame structure (base).

FIG. 1 and 2 are copies of photographs of a greatly enlarged frame structure containing a rigid connecting network of elongated fibers of neutralized carboxylic acid crystals. More specifically, FIGS. 1 and 2 show elongated fibers of C ₁₂ sodium soap having magnifications of 5000X and 2500X, respectively. The structure shown in figures 1 and 2, obtained with 5% soap, 94% water and 1% sodium chloride (example 10 in table. 7 of this application). Note that large fibers in the connecting network may consist of such fibers. In addition, we note the space of "voids" (Fig. 2).

FIG. 3 5 are copies of photographs of a frame structure obtained from 25% sodium soap C ₁₂ at 74% water, 1% sodium chloride. The crystalline fiber structure is shown at 3000X, 5000X, and 1000X magnifications, respectively.

 FIG. 6 is a copy of a photograph of a skeleton structure obtained from 20% disodium salt of 1,12-dodecandic acid. A crystalline fibrous structure is shown at 2000X magnification (Example 26).

FIG. 7 is a copy of a photograph of a frame structure containing a crystalline network of C ₁₄ carboxylic acid neutralized by lithium shown at 1500X magnification (Example 27).

FIG. 8 is a copy of a photograph of a cleaning bar (Example 1) containing coated fibers of C _14-16 sodium soap. The fibers are coated and / or mixed with other components of the bar. The magnification is 1500X.

 Figure 9 shows a sample of a purchased IVORY bar obtained by cooling the soap sodium / potassium coconut / solid animal fat at a magnification of 1000X. The air in the IVORY bar of soap makes it float.

 In FIG. 10 shows a sample of a NEUTROGENA purchased transparent bar at 1500X magnification.

 In figures 1 and 2, the samples were first melted on a hot plate, and then cooled on a glass slide (microscope). Other samples (Fig.3-10) are samples of the original structures of molded solids or ordinary bars, obtained as described in this application.

The invention provides a molded solid containing two phases or more. One phase is a crystalline skeleton structure containing a rigid connecting open three-dimensional network of elongated crystals of neutralized carboxylic acid. Another main phase is the aqueous phase, which softens or spreads at a temperature of 25 ^o C.

 More specifically, the frame structure is a relatively rigid, connecting, open, three-dimensional network of elongated crystals of neutralized mono- and / or dicarboxylic acid.

 Terms: wireframe structure, core structure, skeleton and wireframe are often used interchangeably here.

 The term “molded solid” as used herein includes configurations such as bars, briquettes, etc. The term “bar” as used herein includes similar configurations unless otherwise indicated.

 As used herein, the term "mesh" means connecting a crystalline wireframe lattice with voids or holes when considering magnification using a scanning electron microscope.

 In another aspect, the present invention provides an improved cleansing bar that has the specified frame structure. Some solids are in the form of cleaning bars that contain surprisingly large amounts of said aqueous phase containing water, other liquids and soft materials. Regardless of the presence of relatively large amounts of the aqueous phase, the preferred bars of the present invention retain their rigidity and excellent viscosity properties even after soaking in water overnight. It has been shown that a molded solid body containing these phases is similar to a relatively stiff, moist sponge.

 The crystalline phase contains crystals in the form of connecting plates and / or fibers, preferably fibers. These fibers preferably consist of sodium soap. The connecting network of these fibers and / or plates gives the three-dimensional structure strength even in the presence of relatively large amounts of water or other soft materials, even when soaking overnight in water.

 The strength of the carcass structure can be indirectly measured by measuring the hardness of the molded solid as the resistance to penetration into the solid body of a standard weight penetrometer probe. See further details in hardness test bar. The frame structure is sufficiently rigid so that the cleaning bar with a thickness of 20 mm or more has a penetration of from 0 to 12 mm, preferably from about 1 mm to about 10 mm, and more preferably from about 3 mm to about 8 mm.

 The presented bars differ from ordinary transparent bars in crystal size, as well as in other characteristics. The crystals or crystal beams that make up the structure of the connecting grid of the present invention are preferably of such a size as to refract light and, therefore, are larger than 400 nm either in diameter or in length. Conventional transparent bars, on the other hand, have transparency due to diameters or crystal lengths shorter than a white light wavelength that is greater than about 400 nm, and therefore do not refract light.

 After molding, a bar (molded solid body) containing the rigid frame structure of the present invention loses its rigidity when subjected to mechanical crushing forces, for example, forces in the conventional method of producing the bar using a screw machine or soap, as described in US Pat. No. 4,812,253 issued to Small et al. or in US Pat. No. 4,820,447 to Medcalf et al. This is due to the fact that the mechanical conditions of crushing cut and destroy the frame structure into small parts. Thus, when the bar of the present invention is cut in a screw machine for soap, it becomes much easier.

 On the other hand, when a finished ordinary bar is processed in a soap auger or re-processed therein, the ordinary bar after re-processing is still very hard (for more information see Example 28 and Table 12).

 The frame structure contains significant areas of "voids" that are filled with soft and / or liquid aqueous phases. An amazing aspect of the present invention is that the physical properties of the bar, for example, the hardness of the bar and its low viscosity, are highly dependent on the crystal structure of the connecting network, even when other phases make up the majority of the materials presented. In ordinary bars, many components can affect the general physical properties of the bar, because these components either modify the phase and structure of soaps or components of a synthetic surfactant, which primarily determine the physical properties of the bar. The combination of two or more phases (for example, soap and an aqueous solution) dramatically changes the colloidal structure and, consequently, the physical properties of an ordinary bar.

 Thus, conventional bars are more limited in the type, amounts and compositions of soft phase materials that may be included in the bar than in the case of the present invention. Such phases include most materials that are either spreadable liquids or materials that are softer than the minimum hardness of an acceptable bar. These phases include aqueous solutions, liquid crystalline phases consisting of water and a surfactant, polymers, especially crystalline phases containing a surfactant and especially hygroscopic surfactants, which tend to become soft and sticky when mixed with water or other liquid phases, including water-soluble organic substances (e.g. propylene glycol and glycerin), hydrophobic materials (e.g. mineral oil, liquid triglycerides), and whether soft hydrophobic materials, for example, petroleum jelly, low-melting paraffin and low-melting triglycerides.

 In physical relations, these phases can be characterized as spreadable liquids or so soft substances that a standard-weight penetrometer probe, as defined in this application, will penetrate the entire 12 mm thick sample. These phases can be selectively incorporated into the structure of the present invention without losing the structure of the connecting network and some of the required physical properties.

 The present invention is a molded solid having a framework structure that is a relatively open three-dimensional network of elongated crystals of neutralized mono- and / or dicarboxylic acid.

A preferred embodiment is a cleansing bar (containing at least two phases: an aqueous phase having a penetration value of approximately 12 mm for a 12 mm deep sample, said aqueous phase being soft or spreadable; a hard crystalline phase containing a rigid crystalline structure of the crystalline phase, having a connecting, open three-dimensional grid of elongated crystals of neutralized mono- and / or dicarboxylic acid), in which the specified cleaning bar containing the specified the rigid crystalline structure of the crystalline phase and the specified aqueous phase, has a penetration value of 0 to 12 mm for a sample 25 mm thick, and in which the indicated penetration values are measured at a temperature of 25 ^o C using a standard probe penetrometer weighing 247 g, having a conical a needle attached to a nine-inch (22.9 cm) rod weighing 47 g with a load of 200 g from the top of the specified rod to replenish to the full specified weight of 247 g, and the specified conical needle has a top of 19/32 inches (1.51 cm) and a tip 1 / 32 inches (0.08 cm).

 The above cleansing bar is preferred when said neutralized carboxylic acid is selected from the group consisting of monocarboxylic acid (soap) and / or dicarboxylic acid neutralized with lithium and / or sodium, and mixtures thereof; wherein said monocarboxylic acid has a fatty alkyl (alkylene) chain of about 12-24 carbon atoms; wherein said dicarboxylic acid has a fatty alkyl (alkylene) chain of about 12-18 carbon atoms; in which at least about 80% of said carboxylic acid has saturated alkyl (alkylene) chains; in which the specified rigid frame structure of the crystalline phase occupies from about 3 to about 75 vol. a cleansing bar; in which the specified neutralized carboxylic acid contains from about 5 to about 75%; wherein said cleaning bar contains from about 15 weight. to about less than 94 weight. water.

,
где a + b от 8 до 20;
каждый a, b от 0 до 20;
X H, OR,

R или их смесь;
R C₁-C₃ алкил, H или их смесь;
M Na, Li или их смесь.The above cleansing bar is preferred when at least 80%, and more preferably 90%, of the carboxylic acid has the following general formula:

,
where a + b is from 8 to 20;
each a, b is from 0 to 20;
XH, OR,

R or a mixture thereof;
RC ₁ -C ₃ alkyl, H or a mixture thereof;
M Na, Li or a mixture thereof.

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

 The above cleansing bar is very preferred when said elongated crystals are composed of fibrous sodium fatty acid soap, of which at least about 25% of said saturated fatty alkyl chains have a single chain length; wherein said bar contains from about 15 to about 75% of said sodium soap; in which the ratio of said non-neutralized (free) carboxylic acid to soap is from about 1: 2 to 0, i.e. free fatty acid is not more than 50 weight. soap in the recipe.

The above cleansing bar is preferred when it contains the indicated sodium soap and water and from about 2 to about 60% of a synthetic surfactant selected from the group consisting of alkyl sulfates, paraffin sulfates, alkyl glyceryl ether sulfates, acyl sarcosinates, methyl acyltuorates, linear alkyl sulfonates -acylglutamates, alkyl glucosides, esters of alfasulfo fatty acid, acyl isethionates, alkyl sulfo succinates, carboxylates of alkyl ester, alkyl phosphate esters dimers, ethoxylated alkyl phosphate esters, methyl glucose esters, protein condensates, alkylamine oxides, alkyl betaines, alkyl sultaines, alkyl ether sulfates with a number of 1-12 ethoxy groups, mixtures thereof, where these surfactants contain C ₈ -C ₂₂ alkyl chains.

The above cleansing bar is preferred when said synthetic surfactant is hygroscopic, said hygroscopic surfactant is defined as a surfactant that absorbs at least 20% of its dry weight in water at a temperature of 26 ^° C. and 80% relative humidity after three days, and said bar is relatively non-swelling.

 The above cleansing bar is preferred when said surfactant is selected from the group consisting of alfasulfo fatty acid esters, alkyl sulfates; alkyl ether carboxylates; alkyl betaines; alkylsultaines; alkylamine oxides; alkyl ether sulfates and mixtures thereof.

The above cleansing bar is preferred when the ratio of said water to said soap is from about 1: 1 to about 5: 1; said water is present in an amount of from about 25 to about 60% in which said fatty acid chains are C ₁₄ -C ₂₂ , and said soap amount in said bar is from about 15 to about 35% in which at least 85% of said alkyl chains are saturated; in which the weight ratio of the specified neutralized (free) carboxylic acid to the specified soap is from about 1: 4 to 0; in which the specified amount of synthetic surfactant is from about 4 to about 25% of the weight of the bar, and the specified surfactant is selected from the group consisting of sodium acyl isethionates, sodium acyl sarcosinates, sodium alfasulfo fatty acid esters, paraffin sodium sulfonates, sodium alkyl sulfonates, sodium alkyl sulfates, linear linear sodium benzene sulfonates, alkyl betaines, alkyl sulfains and trialkylamine oxides.

The above cleansing bar is preferred when the ratio of said water to soap is from about 1.5: 1.0 to about 2: 1; the ratio of said non-neutralized (free) carboxylic acid to said soap is from about 1: 6 to 0; said amount of water is from about 30 to about 45%; said fatty alkyl chain is from about C ₁₄ to about C ₁₈ ; in which at least about 95% of these alkyl chains are saturated; the indicated amount of soap is from about 15 to about 30%, the indicated amount of synthetic surfactant is from about 8 to about 16%
The above cleansing bar is preferred when it contains from about 0.1 to about 40.0% hydrophobic material selected from the group consisting of microcrystalline wax, petroleum jelly, carnauba wax, palm wax, candelilla wax, sugarcane wax, plant triglycerides , beeswax, spermaceti, lanolin, wood wax, alkaline wax, triglycerides of animal origin, montage, ozokerite, ceresin and Fischer-Tropsch wax.

The above cleansing bar is preferred when it contains from about 2 to about 35% of said hydrophobic material selected from the group consisting of petrolatum and wax, said petrolatum and wax having a melting point in the range of 49 85 ^° C.

 The above cleansing bar is preferred when it contains from about 5 to about 25 weight. paraffin wax.

где R₁ H, C₁ C₄;
R₂ H, CH₃;
n 1 200,
C₂ C₁₀ алкандиолов, сорбита, глицерина, сахара, производных сахара, мочевин и
аминов общей формулы
(HOCH₂CH₂)_xNH_y,
где x 1 3; y 0 2; x + y 3
и их смеси.The above cleansing bar is preferred when it contains from about 1 to about 50% non-volatile, water-soluble, non-ionic organic material having a solubility of at least 5 parts in 10 parts of water; in which the specified water-soluble non-ionic organic material is selected from the group consisting of a polyol of the formula

where R ₁ H, C ₁ C ₄ ;
R ₂ H, CH ₃ ;
n 1 200,
C ₂ C ₁₀ alkanediols, sorbitol, glycerol, sugar, sugar derivatives, ureas and
amines of the general formula
(HOCH ₂ CH ₂ ) _x NH _y ,
where x 1 3; y 0 2; x + y 3
and mixtures thereof.

 The above cleansing bar is preferred when it contains from about 2 to about 40% of said non-volatile, water-soluble non-ionic organic material.

 The above cleaning bar is preferred when said non-volatile, water-soluble, non-ionic organic material is from about 5 to about 20 weight. bar; wherein said organic material is selected from the group consisting of propylene glycol, glycerin, sucrose and urea, and mixtures thereof.

The above cleansing bar is preferred when it contains said sodium soap, said water, said synthetic surfactant, and from about 0.1 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; from about 1 to about 15% of said triethanolammonium soap, from about 1 to about 60% of the smallest water-soluble materials selected from the group consisting of calcium carbonate and talc, from about 0.1 to about 20.0% of a polymer additive for sensitive skin, which selected from the group consisting of cationic polysaccharides, preferably cationic guar gum with a molecular weight of 1,000,000,000,000, cationic polyalkyleneimines, ethoxypolyalkyleneimines, and poly [N [-3 (dimatylammonium) propyl-] N'- [3-ethyleneoxyethylenedimethylamines ony / propyl -] - urea dichloride-1; silicone chambers and silicone fluids; JR polymers; Celgnat ^® ; from about 0.5 to about 25.0% aluminosilicate clay and / or other clays; wherein said aluminosilicates and clays are selected from the group consisting of zeolites, kaolin, kaolinite, montmorillonite, attapulgite, illite, bentonite, halloysite and calcined clays; about 1 to about 50% of their salts and salt hydrates and mixtures thereof; wherein said salt and salt hydrate has a cation selected from the group consisting of sodium, potassium, magnesium, calcium, aluminum, lithium, ammonium, monoethanolammonium, diethylammonium and triethanolammonium and wherein said salt and salt hydrate have an anion selected from the group consisting of chloride, bromide, sulfate, metasilicate, orthophosphate, pyrophosphate, polyphosphate, metaborate, tetraborate, carbonate, bicarbonate, hydrogen phosphate, methyl sulfate and mono- and polycarboxylate of 6 or less carbon atoms.

 The above cleansing bar is preferred when said elongated crystals contain wafers in which said soap consists of lithium neutralized monocarboxylic acid.

 The above cleansing bar is preferred when said elongated crystals are fibrous, in which said neutralized dicarboxylic acid is a disodium salt of 1,12-dodecandic acid and in which said neutralized dicarboxylic acid is about 20 to about 70 weight. specified bar.

The preferred method of manufacturing a bar
A method of manufacturing a preferred cleaning bar of the present invention comprises the following steps:
1) forming an aqueous liquid of a melt containing approximately 15 to 94 weight. water and from about 6 to about 75 weight. said neutralized carboxylic acid;
2) pouring said melt liquid into a profiled bar shape;
3) crystallization of the specified liquid melt by cooling to obtain the specified cleaning bar.

The above method is preferred when the aqueous melt liquid is obtained by neutralizing the aqueous mixture of the indicated carboxylic acid with sodium hydroxide or lithium hydroxide, stirring at a temperature of from about 50 ^° C (120 ^° G) to about 95 ^° C (205 ^° G).

 The above method is preferred when from about 2 to about 15 weight. said bar is a “crystallization enhancing salt” selected from the group consisting of sodium or lithium salt of sulfate, chloride, acetate and citrate, and mixtures thereof.

где R₁ H, C₁ C₄;
R₂ H, CH₃;
n 1 200;
C₂ C₁₀ алкандиолов, сорбита, глицерина, сахара, производных сахара, мочевины и
этаноламинов общей формулой
(HOCH₂CH₂)_xNH_y,
где x 1 3; y 0 2; x + y 3;
в) спиртов, содержащих от 1 до 5 атомов углерода;
c) синтетического поверхностно-активного вещества, выбранного из группы, состоящей из алкилсульфатов, сульфонатов парафина, сульфонатов алкилглицерилового эфира, анионных ацилсаркозинатов, метилацилтауратов, линейных алкилбензолсульфонатов, N-ацилглютоматов, алкилглюкозидов, эфиров альфасульфо жирной кислоты, ацилизетионатов, алкилсульфосукцинатов, карбоксилатов алкилового эфира, алкилфосфатных эфиров, этоксилированных эфиров алкилфосфата, эфиров метилглюкозы, конденсаторов белка, окислов алкиламина, алкилбетаинов, алкилсултаинов, сульфатов алкилового эфира, имеющих 1 12 этоксильных групп, и их смесей, в которой указанные поверхностно-активные вещества содержат C₈-C₂₂ цепи алкилена и их смеси, и в котором указанную добавку, превышающую растворимость, добавляют с целью увеличения количества указанной нейтрализованной карбоновой кислоты, растворенной в указанной водной фазе непрерывного расплава этапа 1.The above method is preferred when said aqueous phase of the aqueous melt liquid contains from about 2 to about 40% solubility enhancer selected from the group consisting of:
a) non-volatile, water-soluble non-ionic organic solvents selected from the group consisting of a polyol of the formula

where R ₁ H, C ₁ C ₄ ;
R ₂ H, CH ₃ ;
n 1,200;
C ₂ C ₁₀ alkanediols, sorbitol, glycerol, sugar, sugar derivatives, urea and
ethanolamines general formula
(HOCH ₂ CH ₂ ) _x NH _y ,
where x 1 3; y 0 2; x + y 3;
c) alcohols containing from 1 to 5 carbon atoms;
c) a synthetic surfactant selected from the group consisting of alkyl sulfates, paraffin sulfonates, alkyl glyceryl ether sulfonates, anionic acyl sarcosinates, methyl acyl taurates, linear alkyl benzenesulfonates, N-acyl glutosulfonic acid sulfates, alkyl glucosides, ethers, fatty acids alkyl phosphate esters, ethoxylated alkyl phosphate esters, methyl glucose esters, protein condensers, alkyl amine oxides, alkyl betaines, alkyl sultaines c, alkyl ether sulfates having 1 12 ethoxyl groups, and mixtures thereof, in which said surfactants contain C ₈ -C ₂₂ alkylene chains and mixtures thereof, and in which said additive exceeding solubility is added to increase the amount of said neutralized carboxylic acid dissolved in said aqueous continuous melt phase of step 1.

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

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

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

 The above method is preferred when said bar has various phases of non-carboxylic acid containing droplets or crystals selected from waxes, petroleum jelly, clays, etc.

A very preferred embodiment of the present invention is the composition of a cleaning bar for private use, containing a rigid, crystalline connecting network of elongated crystals of sodium soap, wherein said bar of soap contains from about 15 to about 50 weight. fatty acid sodium soap containing at least about 50% saturated alkylene fatty chains having 12 to 24 carbon atoms, of which at least about 25% of said saturated fatty alkyl chains are one-dimensional chain length; from about 15 to about 60 weight. water; from about 2 to about 60 weight. a hygroscopic synthetic surfactant that is selected from surfactants that absorb at least about 20% of their dry weight in water at a temperature of 26 ^° C. and 80% relative humidity after three days.

 The above very preferred partial use cleansing bar is more preferred when said hygroscopic synthetic surfactant is selected from the group consisting of alfasulfo fatty acid esters; alkyl sulfates; alkyl ether carboxylates; alkyl betaines; alkylsultaines; alkylamine oxides; alkyl ether sulfates; and mixtures thereof.

 This highly preferred private cleansing bar is more preferred when said bar contains from about 0.5 to about 40.0% salts and / or salt hydrates selected from the group consisting of sodium chloride, sodium sulfate, sodium hydrogen phosphate, sodium pyrophosphate, sodium tetraborate, sodium acetate, sodium citrate and other compatible salts of inorganic acids and short-chain organic acids.

 A very preferred cleansing bar contains various combinations of the skeleton structure of sodium soap fibers, water of soft synthetic surfactants, bar appearance stabilizers, skin softening additives and other additives. This preferred bar may have a composition that provides a bar that is substantially non-viscous.

 Some preferred bars of the present invention comprise a rigid netting framework of neutralized carboxylic acid fibers consisting essentially of sodium fatty acid soap containing at least 50% saturated fatty alkyl chains having 12 to 24 carbon atoms. Preferably, at least about 25% of said saturated alkyl chains are single chain length.

Some compositions of the present invention contain a rigid net as defined above with or without water. These compositions should be formed by water or other appropriate solvent system. Compositions can be obtained with large quantities of water, and the amount of water in the final composition can be reduced to about 1 or 2%
However, the main advantage of the structures described in this application is that they can be dehydrated without loss of mesh integrity. Some preferred molded solids can be dehydrated without a tangible change in their external dimensions. Other bars shrink, although they retain their bulk shape. Some bars have unique properties that are not destroyed by dehydration.

 Bars of the present invention of a more complex composition have a skeleton structure containing other salts of fatty acids selected from potassium, magnesium, triethanolammonium and / or calcium soaps used in combination with the selected contents of sodium and / or lithium soap. Cleansing bars of a more complex composition may contain surprisingly large amounts of water, soft synthetic surfactants, stabilizers of the appearance of the bar, additives to soften the skin and other activating additives of the cleansing bar; They are also soft and have a very good low viscosity.

 In the table. 1 to 3, some preferred bars are described that are prepared with sodium salts of fatty carboxylic acid (FA) soaps.

 If there are no special instructions, then in this application weight percentages, ratios and shares for the total weight of the composition are used.

 In the table. 1, all limit values are optionally shown. For example, some sodium soap may be used with a content of up to about 75%. Thus, the range is from about 5 to about 75%. Preferred contents and ratios may vary from cation to cation, etc. and from mono to polycarboxylic acid.

 The bars presented in table. 1 are obtained with the indicated water content, but the water content in the final bars can be reduced to provide bars having a reduced water content or even a low water content, or without water. The preferred water content is from about 20 to about 80 weight. bar.

 In the table. 2 shows some preferred FA single chain length soap contents. In the table. 3 shows some preferred unsaturations in FA used in the compositions of the present invention. Some compositions contain few or no FA short chains of ten or fewer carbon atoms.

 The terms “soap”, “fatty acid salts” (FA) and “monocarboxylic acid salts” used in this application are sometimes used interchangeably. The term “soap” is used because it is easier to operate on and is the preferred embodiment.

 In the table. 4 shows the limit values of some key preferred ingredients of the complex soap bar compositions of the present invention. None of these ingredients are essential to the main preferred framework structure of the bar. Zero is the bottom level for each optional ingredient. Some preferred bars may contain a total of about 0.1 to about 70.0% of such ingredients. The idea is that the main bars can contain large quantities of other ingredients besides soap and water. The contents are given in table. 4 are particularly indicative of bars containing from more than 5 to about 75% of the selected sodium soap and other ingredients.

 It must be understood that the forms of solids obtained from lithium soap or freshly neutralized carboxylic acid will necessarily differ in content and proportions from the contents and proportions given for sodium soaps.

 The soaps used in the present invention may be of the same alkyl chain lengths, i.e. consisting of 12-24 carbon atoms, as described in table. 2. The same chain lengths are applicable to other non-sodium soaps used in the bars of the present invention.

 Preferably, the sodium soap comprises at least 50% of the soap used in the bar.

 The content of potassium soap and / or triethanolammonium soap should not exceed half, preferably a third, more preferably less than a quarter of the content of sodium soap, the content of magnesium soap should not exceed approximately a third of the content of sodium soap, and preferably less than a quarter of the content of sodium soap.

 The total content of other soaps, with the exception of lithium soap, should preferably not exceed half, and more preferably, a third of the content of sodium soap.

 The synthetic detergent of the bar compositions of the present invention may be a detergent of the class consisting of anionic, nonionic, amphoteric and amphionic (zwitterionic) synthetic detergents. The limiting contents of soap-forming and water-soluble surfactants can be used in the bar compositions of the present invention.

 Examples for the use of the corresponding synthetic detergents here are the substances described in US Pat. No. 3,351,558, issued to Zimmerer on November 7, 67, column 6, line 70, column 7, line 74.

 Examples include water-soluble salts of organic, sulfonic acids and aliphatic sulfuric acid esters, i.e. water-soluble salts of organic sulfate reaction products, and having in their molecular structure an alkyl radical of 10-22 carbon atoms and a radical selected from the group consisting of sulfonic acid ester and sulfuric acid radicals.

 Synthetic sulphate detergents for special purposes are usually solid alkali metal salts of sulfuric acid of common primary aliphatic alcohols having 10-22 carbon atoms. Thus, the sodium and potassium salts of alkylsulfuric acids obtained from a mixture of higher alcohols by reduction of solid animal fat or coconut oil, palm oil, stearin, palm kernel oil, palm nut oil or other coconut group oils that can be used here.

 Other aliphatic sulfuric acid esters that may be used include water-soluble salts of the sulfuric acid esters of polyhydric alcohols which are not fully esterified with high molecular weight soap-forming carboxylic acids. Such synthetic detergents include water-soluble alkali metal salts of sulfuric acid esters of high molecular weight fatty acid monoglycerides, for example, sodium salt and potassium salt of coconut oil fatty acid monoester of 1,2-hydroxypropane-3-sulfuric acid ester, sodium sulfate and potassium monomyristoyl ethylene glycol and sodium sulfate and potassium monolauroyl diglycerol.

 Synthetic surfactants and other optional materials used in conventional cleaning products may also be used in the present invention. In fact, some ingredients, for example, some hygroscopic surfactants that are commonly used in liquids and which are very difficult to incorporate into conventional cleansing bars, are very compatible with the bars of the present invention. Thus, basically all known surfactants that have found use in cleaning products can be used in the compositions of the present invention. Patent literature related to cleaning products is full of descriptions of synthetic surfactants. The following references describe some preferred surfactants and other ingredients of cleaning products (Table 5).

 All of these patents are hereby incorporated by reference. Some preferred synthetic surfactants are shown in the examples given in this application. Preferred synthetic surfactant systems are separately developed for the stability of the appearance of the bar, the formation of soapy foam, cleansing action and softness.

It is noted that the softness of surfactants can be measured using a skin barrier destruction test, which is used to evaluate the irritant potential of surfactants. In this test, the softer the surfactant, the less the skin barrier is destroyed. The destruction of the skin barrier is measured using the relative amount of radioactive isotopes ( ³ HH ₂ O) introduced into the water, which comes from the test solution through the epidermis of the skin into a physiological buffer solution located in the diffuse chamber. This test is described by T.J. Franz in J. Invest. Dermetol, 1975, 64, pages 190-195 and US Pat. No. 4,673,525, issued June 16, 87 to Small and others, which describe a soft surfactant based on an alkyl glyceryl ether sulfonate (AGS) bar containing a “standard” mixture alkyl glyceryl ether sulfonate. The barrier break test is used to select mild surfactants. Some preferred mild synthetic surfactants are described in the above patents of Small et al. And Reese et al. Some specific examples of preferred surfactants are used in the examples given in this application.

 Some examples of surfactants for detergents that increase the formation of soap suds are, for example, sodium lauroyl sarcosinate, alkyl glyceryl ether sulfonate, sulfated fatty esters, paraffin sulfonates and sulfonated fatty acids.

 Numerous examples of other surfactants are described in the patents, which are referenced in this application. These include other alkyl sulfates, anionic acyl sarcosinates, methyl acyl taurates, N-acyl glutamates, acyl isethionates, alkyl sulfose seccinates, alkyl phosphate esters, ethoxylated alkyl phosphate esters, trideset sulfates, protein condensates, mixtures of ethoxylated alkyl sulfates and sulfates. The composition of surfactants includes sulfates of alkyl ether containing 1-12 ethoxyl groups, especially sulfates of laurylammonium ether and sodium.

The alkyl chains for these other surfactants are C ₈ -C ₂₂ preferably C ₁₀ -C ₁₈ . Alkyl glycosides and methyl glucose esters are preferred mild non-ionic substances that can be mixed with other mild anionic or amphoteric surfactants in the compositions of the present invention. Alkylpolyglycoside detergents are used to increase soap suds. The alkyl group can vary from about 8 to about 22, and the amount of glycosides per molecule can vary from about 1.1 to about 5.0 to ensure an adequate balance between the hydrophilic and hydrophobic parts of the molecule. Combinations of C ₈ -C ₁₈ , preferably C ₁₂ -C ₁₆ , alkyl polyglycosides with average degrees of glycosation in the range of from about 1.1 to about 2.7, preferably from about 1.2 to about 2.5, are preferred.

Preferred are sulfonated fatty esters in which the carboxylic acid chain length is C ₈ -C ₂₂ , preferably C ₁₂ -C ₁₈ , the ether alcohol chain length is C ₁ -C ₆ . These include sodium alfasulfomethyl laurate, sodium alfasulfomethyl cocoate and sodium alfasulfomethyl tolloate.

Amine oxide detergents increase soap suds well. Some preferred amine oxides are C ₈ -C _18, preferably C ₁₀ -C ₁₆ , alkyldimethylamine oxides and C ₈ -C ₁₈ , preferably C ₁₂ -C ₁₆ , fatty acylamidopropyl dimethylamine oxides and mixtures thereof.

Fatty acid alkanolamides increase soap suds well. Some preferred alkanolamides are C ₈ -C ₁₈ , preferably C ₁₂ -C ₁₆ , monoethanolamides, diethanolamides and monoisopropanolamides and mixtures thereof.

в которой R¹ H, C_1-4-алкильная группа, 2-гидроксиэтил, 2-гидроксипропил или их смеси;
R² C_5-31 гидрокарбил;
Z полигидроксигидрокарбил, имеющий линейную цепь гидрокарбила с по меньшей мере тремя гидроксильными группами, непосредственно соединенными с цепью, или их алкоксилирования производная.Other surfactants of the detergent are alkylethoxycarboxylites having the general formula
RO (CH ₂ CH ₂ O) _to CH ₂ COO ^- M ⁺ ,
in which R represents a C _8-22 alkyl group;
k is an integer in the range from 0 to 10;
M cation;
and polyhydroxyamide fatty acids having the General formula

in which R ¹ H, C _1-4 -alkyl group, 2-hydroxyethyl, 2-hydroxypropyl or mixtures thereof;
R ² C _5-31 hydrocarbyl;
Z is polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least three hydroxyl groups directly connected to the chain, or an alkoxylation derivative thereof.

Betaines increase soap suds well. Betaines, for example, C ₈ -C ₁₈ , preferably C ₁₂ -C ₁₆ , alkyl betaines, for example cocobetaines or C ₈ -C ₁₈ , preferably C ₁₂ -C ₁₆ , acylamidobetaines, for example cocoamidopropyl betoin, and mixtures thereof are preferred.

Some preferred surfactants that absorb at least about 20% of their dry weight at 26 ^° C. and 80% relative humidity after three days are hygroscopic synthetic surfactants. Hygroscopic surfactants help improve the bar's soapy foam. Some preferred hygroscopic synthetic surfactants are listed below. It should be noted that not all are hygroscopic.

Hygroscopicity of some surfactants
As defined in this application, hygroscopic surfactants have a minimum 20% increase in total moisture after three days at 26 ^° C and 80% relative humidity.

Class: Nonionic
Sulfonates Total moisture percentage ^*
Sodium sulfonate C ₈ glyceryl ether 39.8
Sodium sulfonate C _12-14 glyceryl ether 22.9
Sodium sulfonate C ₁₆ glyceryl ether 71.4
Cocomonoglyceride Sodium Sulfonate 3.5
Sodium salt of sulfonates of C _8-16 alkyl glyceryl ether
Alphasulfoesters and acids Total moisture percentage ^*
Sodium Alfasulfomethyl Laurate / Myristate 39.3
Sodium Alfasulfomethyl Myristate 44.5
Sodium Alfasulfohexillaurate 23.2
Sodium Alfasulfomethyl / Hexillaurate or Myristate 26.3
Sodium Alphasulfomethyl Palmitate 3.7
Sodium Alfasulfomethyl Stearate 4.2
Sodium 2-sulfolauric acid 0.2
Sodium 2-sulfopalmitic acid 3.8
Sodium 2-sulfostearic acid 0.0
N + R ₁ -C (SO ₃ ^- ) -CO ₂ R ₂ R ₁ C _8-14 alkyl R ₂ C _1-8 alkyl
Sodium alkyl isethionates Total moisture percentage ^*
Sodium lauryl isethionate 31.7
Sodium alkyl isethionate 11.0
Sarcosinates Total moisture percentage ^*
Sodium lauryl sarcosinate 8.8
Sodium Stearyl Sarcosinate 13.3
Sodium cocoyl sarcosinate 18.7
Alkyl sulfates Total moisture percentage ^*
Sodium lauryl sulfate 28.2
Sodium laureth-1-sulfate 37.6
Sodium oleyl sulfate 20.3
Sodium acetyl aryl sulfate 4.7
Sodium Acetyl Sulfate 2.25
Na + R ₁ (OCH ₂ CH ₂ ) _n OSO ₃ ^- R ₁ C _8-14 alkyl, C _16-20 alkyl (en) with at least one double bond, n 0 18
Acylglutomats Total moisture percentage ^*
Sodium cocoyl glutomat 26.7
Sodium lauryl glutomat 17.8
Sodium myristyl glutomat 18.1
Sodium Steryl Glutomat 12.0
Alkyl ether carboxylates Total moisture percentage ^*
Sodium laureth-5-carboxylate 32.2
Sodium palmitil-20-carboxylate 50.2
Na + R ₁ - (O-CH ₂ CH ₂ ) _n CO ₂ ^- R ₁ C _8-18 alkyl, n 1 30
Sulfosuccinates Total moisture percentage ^*
Disodium laureth sulfosuccinate 33.6
Phosphates Total moisture percentage ^*
Sodium monoalkyl (70% C ₁₂ /30% C ₁₄ ) phosphate 21.1
Class: Amphoteric
Betaines Total moisture percentage ^*
Cocobetaine 70.0
Cococamidopropyl Betaine 48.2
Palmitilamidopropylbetaine 46.5
Isostearamidopropyl Betaine 44.3
Sultaines Total moisture percentage ^*
Cocoamidopropyl Hydroxy Sultaine 59.5
Amine oxides Total moisture percentage ^*
Palmityldimethylamine Oxide 34.0
Myristyldimethylamine oxide 46.0
Cocamide dipropylamine oxide 43.3
Protein Derivative Total Moisture Percent ^*
Na / TEA C ₁₂ Hydrolyzed Keratin 34.7
^* Three days at a temperature of 26 ^o C and a relative humidity of 80%
Polymer additives for skin softness are described in the patents of Small et al. And Medcalf et al. Cationic polysaccharides and cationic synthetic polymers are described. The cationic synthetic polymers of the present invention are cationic polyalkyleneimines, ethoxypolyalkyleneimines and poly [N- [3 - (dimethylammonium / propyl] -N '- [3 - (ethyleneoxyethylenedimethylammonium) propyl] urea dichloride, the latter being supplied from Miranol Chemical Company, Inc with the trade name Miranol A-15, CAS per. N 68555-36-2.

 Preferred cationic polymer skin conditioning polymer elements of the present invention are cationic polysaccharides of the cationic class of guar gum with molecular weights of 1,000 to 3,000,000. More preferred molecular weights are weights in the range of 2,550 to 350,000. These polymers have a polysaccharide backbone consisting of galactomanced sites, and the degree of cationic substitution is from about 0.04 per anhydroglucose unit to about 0.8 per anhydroglucose unit with a substitutional cationic group, which is an adduct of 2,3-epoxy optyltrimethylammonium chloride to the main chain of the natural polysaccharide. Examples are JAGUAR C-14-S, C-15 and C-17, supplied by Celanese Corporation.

 To achieve the constancy described in this invention, the polymer must have either structural or physical properties that would allow it to conform and fully hydrate and subsequently integrate well into the soap matrix.

 A soft skin cleansing bar of the present invention may contain from about 0.5 to about 20% a mixture of silicone gum and silicone fluid, in which the gum liquid ratio is from about 10: 1 to about 1:10, preferably from about 4: 1 to about 1: 4, most preferably from about 3: 2 to about 2: 3.

 Mixtures of silicone gums and liquids are described for use in shampoos and / or conditioners in US Pat. Nos. 4,906,459, issued March 6, 1990. Cobbu et al. N 4788006 issued to Bolich et al. 2911.88. N 4741855, issued to Groot and others 03.05.88g. N 4728454, issued to Filer et al. 03/01/88. N 4704272, issued by O and others 03.11.87g. and N 2826551, issued to Gene on 03/11/58. moreover, all of these patents are incorporated by reference.

The silicone component may be present in the bar in an amount that is sufficient to soften the skin, for example, from about 0.5 to about 20.0%, preferably from about 1.5 to about 16.0%, and most preferably from about 3 to about 12% of the composition. In the silicone fluid used in this invention, the viscosity of the silicone at a temperature of 25 ^° C. is in the range of from about 5 to 600,000 cSt, and most preferably from about 350 to about 100,000 cSt. The silicone used in this invention, silicone gum, has a viscosity of more than about 600,000 cSt and a molecular weight of from about 200,000 to about 1,000,000. The molecular weight and viscosity of the particular siloxanes selected will determine whether it is gum or liquid. Silicone gum and liquid are mixed together and incorporated into the compositions of the present invention.

 Other ingredients of the present invention are selected for various applications. For example, perfumes can be used in formulations for skin cleansing products, typically at a level of from about 0.1 to about 2.0% of the composition. Alcohols, hydrotropes, colorants and fillers, for example, talc, clay, water-insoluble fine calcium carbonate and dextrin can also be used. Ceteryl alcohol is a mixture of cetyl and stearic alcohols. Dispersion stabilizers, for example sodium ethylenediaminetetraacetate (EDTA), typically in an amount of less than 1% of the composition, can be incorporated into a cleaning product to prevent color and odor deterioration. Substances that destroy microbes can also be introduced usually in amounts of up to 1.5%. The above patents describe and link to such ingredients and formulations that can be used in the bars of the present invention.

 Some bars of the present invention contain from about 5 to about 75% of said fibers of fatty acid sodium soap; from about 10 to about less than 94% water and at least about 1% of another bar ingredient selected from another soap, moisturizers, dyes, fillers, synthetic detergent surfactants, polymer additives that give a pleasant sensation and softness, fragrances, dispersion stabilizers and mixtures thereof.

 Some bars of the present invention contain from more than 5 to 50% fibers of sodium fatty acid soap, comprising at least about 50% saturated fatty alkyl chains having 12-24 carbon atoms, of which at least about 25% of said saturated fatty alkyl chains are single chain length.

 Some bars of the present invention include these fibers, which occupy from about 3 to about 75% and preferably from about 15 to about 40% of the volume of the bar structure.

 Some bars contain a rigid, low viscosity structure having more than 5-75% sodium fatty acid soap, consisting of at least 50% saturated fatty alkyl chains having 12-24 carbon atoms, of which at least about 25% is a single chain length from about 10 to about 94% water and from about 0 to a total of about 70% of other ingredients selected from the group described in table. 4.

Some particular soap cleansing bar compositions contain a stiff, combining grid of sodium soap fibers in which the fatty acid sodium soap consists of at least about 50% saturated fatty alkyl chains having 12-24 carbon atoms, of which at least 25% are single chain lengths; and from about 2 to about 40 weight. hydroscopic synthetic surfactant selected from surfactants that absorb at least about 20% of their weight in the zone at a temperature of 26 ^o and a relative humidity of 80% after three days.

Bar appearance additives
Additives of the appearance of the bar (preventing water retention and / or shrinkage) are preferably selected from the group consisting of:
compatible salt and salt hydrates;
water soluble organic substances, for example, polyols, urea;
aluminosilicates and clays;
their mixtures described in table. 4.

 Water-soluble organic substances are also used to stabilize the appearance of the soap bars of the present invention. Some preferred water-soluble organic substances are propylene glycol, glycerin, ethylene glycol, sugars, urea and other compatible polyols.

A particularly suitable water soluble organic substance is propylene glycol. Other compatible organic substances include polyols, for example, ethylene glycol or 1,7-heptanediol, respectively mono- and polyethylene and propylene glycols with a molecular weight of up to about 8000, any of mono-C _1-4 alkyl esters, sorbitol, glycerol, glucose, diglycerol, sucrose, lactose, dextrose, 2-pentanol, 1-butanol, mono-, di- and triethanolammonium, 2-amino-1-butanol, etc. especially polyhydric alcohols.

As used herein, the term “polyol” includes non-reducing sugar, for example, sucrose. Sucrose will not regenerate Feling's solution and is therefore classified as a “non-reducing” disaccharin. Unless otherwise specified, the term “sucrose” as used in this application includes sucrose, its derivatives, such non-reducing sugars and side polyols, which are substantially stable at a soap processing temperature of up to about 210 ^° F (98 ^° C), for example, trialose, raffinose and stachiosis: sorbitol, lactitol and maltitol.

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

 Commonly used co-salts and salt hydrates include sodium, potassium, magnesium, calcium, aluminum, lithium, and ammonium salts of inorganic acids and small (6 carbon atoms or less) carboxylic or other organic acids, corresponding hydrates, and mixtures thereof. Inorganic salts include chloride, bromide, sulfate, metasilicate, orthophosphate, pyrophosphate, polyphosphate, metaborate, tetraborate and carbonate. Organic salts include acetate, format, methyl sulfate and citrate.

 Water soluble amine salts may also be used. Salts of methanolamine, diethanolamine and triethanolammonium chloride (TEM) are preferred.

 Aluminosilicates and other clays are used in the present invention. Some preferred clays are described in US Pat. Nos. 4,605,509 and 4,274,975.

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

 Waxes include petroleum-based waxes (paraffin, polycrystalline paraffin and petroleum jelly), plant waxes (carnauba wax, palm wax, candelilla wax, sugarcane wax and plant triglycerides), animal waxes (beeswax, spermaceti, wool wax, shellac wax and triglycerides of animal origin), mineral waxes (Montar, ozokerite and ceresin) and synthetic waxes (Fischer-Tropsch).

A preferred wax was used in the examples. The wax used has a melting point of from about 120 to about 185 ^° F (49 to 85 ^° C), preferably to about 125 to about 175 ^° F (52 to 79 ^° C). A preferred wax is a fully refined wax (paraffin wax) from petroleum having a melting point in the range of about 130 to about 140 ^° F. (49 ^{° to} 60 ^° C.). This wax is odorless and tasteless and meets the FDA's requirements for use as coatings for food and food packaging. Such paraffins can be easily purchased. A very acceptable paraffin can be supplied, for example, from Standard Oil Comp. of Ohio under the trade name Factowax R-133.

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

 Preferably, paraffin is presented in the bar in an amount of from about 5 to about 20 weight.

 The paraffin ingredient is used in the product to give softness to the skin, plasticity, strength and workability. It also adds gloss and smoothness to the bar.

The paraffin ingredient is randomly administered using microcrystalline wax. Suitable microcrystalline wax has a melting point, for example, in the range of from about 140 (60) to about 185 ^° F (85 ^° C), preferably from about 145 (62) to about 175 ^° F (79 ^° C). Preferably, the wax necessarily meets the FDA requirements for microcrystalline waxes used for food. A very acceptable microcrystalline wax is obtained from Witro Chemical Company under the trade name Multiwax X-145A. Microcrystalline wax is preferably presented in a bar in an amount of from about 0.5 to about 5.0 weight. The microcrystalline wax ingredient gives the bar ductility at room temperature.

 The following examples are illustrative, but not limiting, of the scope of the present invention. Unless otherwise noted, the non-neutralized or “free” fatty acids used in the examples are of the same chain lengths as the acids used to make soaps. Unless otherwise noted, all quantities, ranges, temperatures, results, etc. used in this application. are approximate.

A method of producing bars of the present invention by molding
Unless otherwise noted, the cleaning bars in the present examples are prepared using the following procedure:
1. The starting fatty acid, propylene glycol, sodium chloride and water (excluding water coming from other starting materials) are mixed and heated to 71 ^o C.

2. A caustic solution (50% sodium hydroxide) is added and the mixture is stirred until a homogeneous aqueous melt liquid is formed containing 15 94% water and 5.5 75.0% soap (neutralized carboxylic acid). The temperature in the process of neutralizing the liquid melt increases to about 95 ^o .

3. Other ingredients are added preferably in the following order while maintaining a temperature of about 88 ^° : cocobetaine, sodium lauroyl sarcosinate; or sodium alfasulfomethyl cocoate, kaolin clay; or hydrated zeolite (synthetic sodium aluminosilicate); and paraffin. Fragrance is added last.

 4. The mixture of melt liquid is poured into a profiled form.

 5. The liquid melt crystallizes (solidifies) by cooling to room temperature and the resulting bars are removed from the molds.

 Unless otherwise noted, the bars in the above examples are obtained using the general procedure described above.

 It is important to note that when the formulations used in the examples of the present invention are subjected to conventional processing with a screw machine for soap or cooling in a heat exchanger, very soft bars are formed or not formed at all. Example II (table. 6) is a very preferred common bar.

Description of sample test examples
Hardness Test
The hardness of the bar is determined by measuring at a temperature of 25 ^o C the depth of penetration (in mm) into the bar of a standard probe of a centrometer weighing 247 g, having a conical needle attached to a 22.9 cm (nine-inch) rod weighing 47 g with a load of 200 g on top of the specified rod. A measured hardness of 5 mm or less indicates a very hard block; 5 10 mm per block of medium hardness; 10 12 indicates a soft bar at the limit of acceptability, and values greater than 12 mm indicate that the bar is very soft, which is unacceptable for most applications. Unless otherwise noted, this value limits the "hardness" used in this application.

Bar viscosity test
The degree of viscosity is determined by:
placing a bar of soap on a milestone in a round plate with a diameter of 1400 mm;
adding 200 ml of room temperature water to the plate so that the bottom 3 mm of the bar is immersed in water;
enabling the bar to soak throughout the night (15 hours);
overturning the bar and a qualitative assessment of the magnitude of the degree of viscosity and viscosity characteristics, the depth of viscosity at the scale, where 10 is the absence of viscosity, 8.0 9.5 low viscosity, 5.0 7.5 average viscosity, like most purchased bars, 4.5 or less very poor viscosity.

 Purchased bars of soap, for example, SAFEGUARD, ZEST, IVORY and LAVA, have a viscosity of approximately equal to 5, 6, 6 and 6, respectively. More detailed data are given in table. fourteen.

Shrinkage bar test
Shrinkage is measured by placing a freshly prepared unwrapped bar for one week in a room in which a temperature of 26 ^° C. and 15% relative humidity is maintained. The amount of shrinkage from the initial form of the bar is determined by the quality scale, where 0 indicates the absence of shrinkage, + slight shrinkage, ++ average shrinkage, +++ large shrinkage.

In the table. Figures 7 and 8 describe bars of soap 1 10 indicating hardness, viscosity and shrinkage for soaps of the C ₁₀ , C ₁₂ , C ₁₄ , C ₁₆ , C ₁₆ and C ₁₈ alkyl chains. Preferred alkyl chain soaps of the present are described previously in table. 1 and 2.

 The term “X” means that this example is comparative.

Note that Example 1 has a very poor viscosity, regardless of hardness of 8.9, since the C ₁₀ soluble soap dissolves during the implementation of the viscosity test methodology.

 Example 10 has a rigid structure, but is not preferred since its hardness is 14.

 Examples 12 to 16 are excellent bars of the present invention (Tables 9 and 10).

 Examples 17-19 (table. 11) obtained with more complex mixtures of soaps than other examples. They form very good bars of the present invention, have little or no viscosity. A comparison of their hardness and viscosity with soaps obtained on the basis of solid animal fat and coconut soap is given in table. 12.

In these comparative examples X.20, X.21 and X.22, the rigid structure of the present invention is not formed. Note that they are obtained with ordinary purchased soaps and are mild soaps with terrible viscosity. Compare with example 15 of the present invention, which is obtained with 65% water and C ₁₆ and C ₁₈ saturated soap and forms a solid inviscid bar.

 Example 23 is a bar of the present invention that contains more synthetic surfactant than soaps. It has low viscosity and good soap suds. Example 24 is a bar of the present invention that contains a polymer and other soap bar ingredients.

Example 23. An example of a bar of synthetic detergent
Ingredient Weight.

Sodium Palmitate 20
Sodium lauroyl sarcosinate 9 ^*
Sodium laureth-3-sulfate 7 ^*
Sodium petearyl sulfate 5 ^*
Free fatty acid (palmitic) 1
Sodium Chloride 3
Propylene glycol 14
Hydrated Zeolite A 3
Fragrance 1
Water 37
^* The total content of synthetic surfactant is 21%
Example 24. Example with the addition of polymer
Ingredient Weight.

Sodium palmitate 20.0
Sodium Alfasulfomethyl Cocoate 8.7
Cocobetaine 4.65
Jagnar C376 1.5
Propylene glycol 15.0
Kaolin clay 5.0
Paraffin (melting point 55 ^o C) 4,5
Sodium Chloride 3.0
Fragrance 1.0
Water 35.5
Examples 23 and 24 are similar to example IV of the table. 6. Example 24 soft bar recipe with a polymer addition of skin softness.

 Examples 25-27 are given in table. 13.

For example 25, the formulation was obtained by heating the starting fatty acid to a temperature of 71 ^° C, lithium hydroxide was added separately to water, and then the fatty acid and lithium hydroxide solution were mixed together, mixed for 30 min, heating was maintained at least at a temperature of 71 ^° C, and added lithium chloride salt and stirred for an additional 5 minutes, then poured into a mold and allowed to cool and harden. Got a solid bar with excellent viscosity properties.

For examples 26 and 27, dibasic acid is melted at a temperature of 150-180 ^° C and a hot (90 ^° C) caustic solution (for NaOH equivalent) is added. The mixture is stirred for about 5 minutes.

 For example 27, sodium lauroyl sarcosinate is pre-dissolved in the solution by hardening, which occurs during the destruction, for example, to about 35 to 40 weight. water in the bar.

 Example 25 shows the ability to form bars of high humidity, strength in the absence of viscosity without the need for sodium soap. Examples 26 and 27 show the ability to form a product completely free of soap, and still get a relatively rigid structure of a connecting network of fibers.

Example 28 of a bar obtained by freezing in a heat exchanger
The following example 28 relates to a bar obtained using the method of cooling (freezing) in a heat exchanger described in application for US patent N 07/731163 Teineri and others filed July 15, 91. This method provides a private cleansing bar containing a skeleton structure having a relatively rigid, mating, semi-continuous, open, three-dimensional crystal net of neutralized carboxylic acid soap obtained by the following steps:
1) mixing the melt mixture containing the weight parts of the ingredients of said bar from about 15 to about 85% of said soap and from about 15 to about 40% of water;
2) cooling said mixture to a semi-solid state in the refrigerator of a screw mold-heat exchanger;
3) extruding said semi-solid substance in the form of a soft rod;
4) further cooling and crystallization of the specified soft rod to a solid state in order to obtain the specified cleaning bar private use.

Stage 1. Mixing
The soap defined in the formulation is obtained by mixing the required fatty acids consisting essentially of C ₁₂ -C ₂₄ chain lengths with an appropriate base or a mixture of bases consisting mainly of sodium, lithium, magnesium, calcium, potassium and triethanolamine. The fatty acid, base and water are mixed at a temperature of from about 170 to about 200 ^° F (76 ^{° to} 93 ^° C) to form a soap. In Example 28, a temperature of 180 ^° F. (82 ^° C.) was used. A sufficient amount of water is used to mix the mixture. Other ingredients are added while maintaining a temperature in the range of about 180 to about 200 ^° F. (82 ^{° to} 93 ^° C.). Example 28 temperature 180 ^o F (82 ^o C). Optimum mixing temperatures may vary depending on the particular formulation.

Step 4. Optional Ventilation, Minor Additives and Thermal Drying
Venting (optional) the specified mixture, adding perfume (only if dried) and other minor additives using a piston pump or other built-in mixer. In example 28, there is no ventilation or drying. The mixture of step (1) is randomly dried to reduce the water content to the desired level, preferably 20 to 40% water. The drying temperature is from about 225 to about 315 ^o F (135 157 ^o C) at a pressure of from about 30 to about 100 psi (115 517 mmHg).

Stage 3. Refrigerator
Cooling the mixture using a screw crystallizer-heat exchanger (refrigerator) to partially crystallize the components from an initial temperature of about 180,200 ^° F (82 93 ^° C) or 200,220 ^° F (93,104 ^° C), drying to a final temperature, preferably about 135,180 ^o F (57 82 ^o C), more preferably 145 180 ^o F (63 82 ^o C), and most preferably approximately 155 175 ^o F (63 79 ^o C). This final temperature, also referred to as exit temperature (FOT), is usually the maximum temperature at which an even rod forms that retains its shape when extruded onto a moving belt (step 4). FOT in example 28 is 175 ^o F (79 ^o C).

Stage 4. Extrusion
The cooled mixture of step 3 is extruded onto a moving rod in the form of a soft rod, which is then cooled, completely crystallized, then stamped and packaged. Preferably, the rods are molded by an extrusion operation as described in US Pat. No. 3,853,059. Some compositions crystallize in a refrigerator (step 3) to provide a semi-solid state in which they have sufficient viscosity to fit on the tape, although further crystallization takes place after extrusion, leading to curing the bar. Upon final crystallization in sodium soap, a connecting, semi-continuous, open mesh structure is formed.

Example 28
Ingredient Weight.

Sodium Soap C ₁₄ 27.99
Magnesium Soap C ₁₄ 5.00
Sodium Lauroyl Sarcosinate 3.00
Cocobetaine 10.00
Propylene glycol 3.50
Vaseline 22.49
Sodium Chloride 2.58
Free fatty acid C ₁₄ 0.50
Fragrance 0.50
Water 24.44
Hardness test of stamped bar after auger soap machine
The hardness test of the stamped bar after the auger for soap can be used to identify differences between the bars of this invention from other bars. Four purchased bars were selected to represent the various methods of preparation: SAFEGUARD bar of ground soap; ZEST bar of ground substance of the composition soap / synthetic substance; Ivory whetstone obtained by cooling in a heat exchanger; LAVA molded block. Samples of these purchased bars and bars obtained in Example 28 and Example II were processed in a soap auger using the procedure described below.

 In general, the purchased bars after the screw machine are much harder and have better viscosity than the bars of Example 28 and Example II after the screw machine. These data are given in detail in table. 14. Such a test is certainly an excellent way to distinguish between bars having a rigid frame structure from other bars. The bars of the present invention will be much softer after reprocessing in a soap auger machine than conventional bars.

The procedure is as follows:
1. Molded bars (approximately 2.5 kg or more) are placed in a single-feed auger with a 4 inch / 10, 16 cm lid without vacuum and passed through a noodle plate. The noodle plate has 19 holes with a diameter of 0.93 cm in a plate with a thickness of 8 cm. The drum temperature is set to 120 ^o F (49 ^o C), and the neck 110 ^o F (43.5 ^o C).

 2. Step 1 is repeated with noodles.

3. The noodles of stage 2 are placed in a single-feed auger machine with a cover of 4 inches / 10, 16 cm with vacuum and passed through a nozzle of the form of a bar. An extruded bar-shaped rod having an approximate dimension of 1.88 inches (4.6 cm) (height) x 1.16 inches (3 cm) (width) x 3 inches (7.6 cm) (length). These rods should have an internal temperature of 90 105 ^o F (32 41 ^o C).

 4. The rods are stamped in the form of bars and allowed to cool to room temperature (at least 12 hours) before testing.

 The "hardness" of the bars, after processing the screw-machine, stamping is indicated as bar 2 in the table. 12 for each bar test. Hardness testing of bars is described elsewhere.

 Without resorting to theory, a delta value of 2 or more bars processed in a soap auger machine strictly indicates that the original sample had a skeleton structure that was fragmented or destroyed in a screw machine. The solid bars of the present invention will form soft viscous bars when processed in a soap auger during a standard process.

 The bars of Example 28 were first prepared using the cooling method of a heat exchanger refrigerator described above. The bars of Example II were first prepared using the above-described bar casting.

 It is processed in a screw machine and stamped approximately 5 10 kg of each bar.

 Purchased bars were obtained on the basis of natural soaps with the basis of solid animal fat and coconut. The hardness of SAFEGUARD and ZEST bars processed in the screw machine is approximately equal to the hardness of the original bars. The bars IVORY and LAVA after processing in the screw machine (2) are slightly softer than the original bars.

 On the other hand, the bar 2 processed in the screw machine in Example 28 is much softer than the original bar 1 in Example 28. A greater difference in the hardness of the processed and the original bars occurs in the case of bars of Example II. The hardness of the bar after processing in the screw machine corresponds to the hardness of the aqueous phase, indicating that the rigidity of the frame structure is essentially destroyed.

Claims (12)

 1. Detergent in the form of a molded solid containing a skeleton structure, characterized in that the skeleton structure is an open three-dimensional network of elongated crystals of neutralized mono- and / or dicarboxylic acid. 2. A detergent in the form of a bar containing at least two phases: an aqueous phase and a phase containing a frame structure, characterized in that the aqueous phase is taken with a penetration value of 12 mm for a sample with a depth of 12 mm and soft and spreadable at a temperature of 25 ^o C, the frame structure is an open three-dimensional network of elongated crystals of neutralized mono- and / or dicarboxylic acid, and the bar has a penetration value from 0 to 12 mm for a sample with a depth of 25 mm, while the penetration value is measured at a temperature of 25 ^o With the power of the penetrometer probe of a standard weight of 247 g having a conical needle attached to a 22.9 cm rod having a weight of 47 g with a load of 200 g on top of the specified rod to provide a total indicated weight of 247 g, and the specified conical needle has 1.51 cm top and 0.08 cm tip. 3. The tool according to claim 2, characterized in that the neutralized carboxylic acid is selected from the group consisting of neutralized lithium and / or sodium monocarboxylic acid and / or dicarboxylic acid and mixtures thereof, where the monocarboxylic acid has a fatty alkyl chain of 12 to 24 carbon atoms , dicarboxylic of 12 to 18 carbon atoms, and at least 80% of the carboxylic acid has saturated alkyl chains, the skeleton structure of the crystalline phase is 3 75% of the bar, the neutralized carboxylic acid is 5 75% of the bar, and the water is 15 94%
4. The tool of claim 2, characterized in that at least 80% of the carboxylic acid has the following general formula:

where a + b 8 20, each a, b 0 20;
X H OR

R or mixtures thereof;
R ₁ C ₃ -alkyl, H or mixtures thereof;
M Na, Li or mixtures thereof.  5. The tool according to p. 2, characterized in that a + b 10 16, each of the specified a, b 0 16, and X H, OR, and R H and M Na. 6. The tool according to p. 3, characterized in that the elongated crystals consist of fibrous sodium fatty acid soap, of which at least 25% of the saturated fatty alkyl chains are single chain length, the bar contains 15 75% of the specified sodium soap and non-neutralized carboxylic acid no more than 50 weight. sodium soap, preferably the bar contains sodium soap and water and 2 to 50% of a synthetic surfactant selected from the group: alkyl sulfates, paraffin sulfonates, alkyl glyceryl ether sulfonates, acyl sarcosinates, methyl acyl taurates, linear alkyl benzene sulfonates, alkyl alcohyl glucosyl sulfonates acids, acyl isethionates, alkyl sulfosuccinates, alkyl ether carboxylates, alkyl phosphate esters, ethoxylated alkyl phosphate esters, methyl glucose esters, protein condensates, oxides alkylamine, alkyl betaines, alkyl sultaines, the alkyl ether sulfates containing from 1 to 12 ethoxy groups, and mixtures thereof, wherein said surfactants contain C ₈ chain C ₁₂ alkyl. 7. The tool according to claim 6, characterized in that the synthetic surfactant is hygroscopic, wherein the hygroscopic surfactant is selected from surfactants that absorb at least 20% of their dry weight in water at a temperature of 26 ^{° C.} and 80% relative humidity after three days, and preferably said surfactant is taken from the group: esters of alpha-fatty acid, alkyl sulfates, carboxylates of alkyl ether, alkyl betaines, alkyl sultaines, alkylamine oxides, sul Veils alkyl ether and mixtures thereof. 8. The tool according to claim 6 or 7, characterized in that the ratio of water to soap is from 1: 1 to 5: 1, water is present in an amount of 25-60%, and the soap has chains of fatty C ₁₄ C ₂₂ -alkyl and the soap content in the specified bar is 15 to 35% where at least 85% of the alkyl chains of the soap are saturated, in which the non-neutralized carboxylic acid is 0 to 25 weight. soap and in which the content of synthetic surfactant is 4 to 25 weight. the bar and surfactant are selected from the group: sodium acyl isethionates, sodium acyl sarcosinates, sodium alfasulfo-fatty acid esters, sodium paraffin sulfonates, sodium alkyl sulfates, sodium alkyl sulfates, sodium sulfonates, alkyl alkynes, and trilates from 1.5 1 to 2: 1, and non-neutralized carboxylic acid is 0 to 17 weight. soap, the water content is 30 45% and the fatty alkyl chain of the soap is from C ₁₄ to C ₁₈ , in which at least 95% of the alkyl chains are saturated, the soap content is 15 30% and the synthetic surfactant is 8 16 %
9. The tool according to claim 7 or 8, characterized in that it contains 0.1 to 40% hydrophobic material selected from the group: microcrystalline wax, petroleum jelly, carnauba wax, palm wax, candelilla wax, sugarcane wax, plant triglycerides, bee wax, spermaceti, lanolin, wood wax, slag wax, triglycerides of animal origin, Montar, ozokerite, ceresin and Fischer-Tropsch wax, and the bar contains 2 35% hydrophobic material selected from the group: petrolatum and wax, and petrolatum and wax and their mixtures have a tamper the melting point in the range 49 - 85 ^o C, the bar contains 5 25 weight. paraffin wax and which contains 1 50% non-volatile water-soluble, non-ionic organic material having a solubility of at least 5 parts in 10 parts of water, wherein the water-soluble non-ionic organic material is selected from the group consisting of a polyol of the formula

where R ₁ H, C ₁ C ₄ -alkyl;
R ₂ H, CH ₃ ;
n 1 200,
C ₂ C ₁₀ alkanediols, sorbitol, glycerol, sugar, derivatives of sugar, urea and ethanolamines of the general formula
(NOSH ₂ CH ₂ ) _x NH _y ,
where x 1-3;
y 0 2;
x + y 3,
and mixtures thereof, and in which non-volatile, water-soluble, non-ionic organic material is 5 to 20 weight. bar, and the organic material is selected from the group: propylene glycol, glycerin, sucrose, urea, and mixtures thereof.  10. The tool according to paragraphs. 7, 8 or 9, characterized in that it contains sodium soap, water and a synthetic surfactant and 0.1 - 70% of other ingredients selected from the group: 1 10% potassium soap, 1 35% magnesium soap, 1 35 % calcium soap, 1 15% triethanolammonium soap, 1 60% of the smallest water-insoluble materials selected from the group consisting of calcium carbonate and talc, 0.1 20% polymer skin-sensitive additives, 0.5 25% aluminosilicate clay and / or other clays, in which aluminosilicates and clays are selected from the group: zeolite, kaolin, kaolinite, montmorillonite, and tapulgite, illite, bentonite, gallousite and calcined clays, 1 50% salt and salt hydrates and mixtures thereof, and in which the salt and salt hydrate have a cation selected from the group: sodium, potassium, magnesium, calcium, aluminum, lithium, ammonium, monoethanolammonium, diethanolammonium and triethanolammonium, and said salt and salt hydrate have an anion selected from the group: chloride, bromide, sulfate, metasilicate, orthophosphate, pyrophosphate, polyphosphate, metaborate, tetraborate, carbonate, bicarbonate, hydrogen sulfate and methyl phosphate, methyl 6 or less carbon atoms. 11. A method of obtaining a detergent in the form of a bar, comprising molding an aqueous liquid of the melt, pouring the melt into a profiled form of the bar and crystallizing the liquid of the melt by cooling, characterized in that the aqueous liquid of the melt containing 20 94% water and 5 75 weight is molded. a bar of neutralized carboxylic acid, wherein the molten aqueous liquid is obtained by neutralizing the aqueous carboxylic acid mixture with a hydroxide selected from the group: sodium hydroxide or lithium hydroxide and their mixture with stirring at a temperature of 50 to 95 ^o C and the melt liquid contains 2 to 15 weight. bar and is a salt that increases crystallization, selected from the group: sodium or lithium salt of sulfate, chloride, acetate and nitrate and mixtures thereof, and the aqueous phase of the aqueous liquid of the melt contains 2 40% solubility enhancer selected from the group consisting of non-volatile water-soluble nonionic organic solvents selected from the group consisting of a polyol of the formula

where R ₁ H, C ₁ C ₄ -alkyl;
R ₂ H, CH ₃ ;
n 1 200,
C ₂ C ₁₀ alkanediols, sorbitol, glycerol, sugar, derivatives of sugar, urea and ethanolamines of the general formula
(NOSH ₂ CH ₂ ) _x NH _y ,
where x 1 3;
y 0-2;
x + y 3,
alcohols containing from 1 to 5 carbon atoms and a synthetic surfactant selected from the group: alkyl sulfates, paraffin sulfonates, alkyl glyceryl ether sulfonates, anionic acyl sarcosinates, methyl acyl taurates, linear alkyl benzenesulfonates, alkyl acyl sulfonates, alkyl sulfonates , alkyl ether carboxylates, alkyl phosphate esters, ethoxylated alkyl phosphate esters, methyl glucose esters, protein condensates, alkyl amine oxides, alkyl betaines, alkyl sultaines, alkyl ether sulfates having 1 12 ethoxyl groups, and mixtures thereof, wherein said surfactants contain C ₈ C ₂₂ alkylene chains, and mixtures thereof, wherein a solubility improver is added to increase the content of said neutralized carboxylic acid, dissolved in said aqueous phase of a continuous melt. 12. The method according to p. 11, characterized in that the aqueous phase contains 20 to 100 weight. water of said aqueous phase, and the hard crystalline phase contains 75
100% neutralized carboxylic acid by weight of the crystalline phase, the bar having a penetration value of 3 to 9 mm for a bar sample of 25 mm. 13. The tool according to p. 2, characterized in that it contains a rigid crystalline connecting network of elongated crystals of sodium soap, the bar contains 15 to 50% sodium soap of a fatty acid containing at least 50% saturated chains of fatty alkylene having 12 to 24 carbon atoms, of which at least 25% of these saturated fatty alkyl chains are single chain length, 15-60% water and 2-60 weight. hygroscopic synthetic surfactant, which is selected from surfactants that absorb at least 20% of their dry weight in water at a temperature of 26 ^o C and 80% relative humidity after three days.  14. The tool according to p. 13, characterized in that the hygroscopic synthetic surfactant is selected from the group: esters of alpha-fatty acid, alkyl sulfates, carboxylates of alkyl ether, alkyl betaines, alkyl sultaines, alkylamine oxides, alkyl ether sulfates, and a mixture thereof, and which contains 0.5 to 40% of salts and / or hydrates of a salt selected from the group: sodium chloride, sodium sulfate, sodium hydrogen phosphate, sodium pyrophosphate, sodium tetraborate, sodium acetate, sodium citrate and other compatible salts of inorganic acids and organic short chain anic acids. Priority on points:
11/26/90 by claims 1, 13, 14;
11/01/91 for PP. 2 12.

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