WO2010089269A1 - Pains de savon extrudés à faible teneur en tmf comprenant un système structurant polysaccharide-polyol - Google Patents

Pains de savon extrudés à faible teneur en tmf comprenant un système structurant polysaccharide-polyol Download PDF

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Publication number
WO2010089269A1
WO2010089269A1 PCT/EP2010/051155 EP2010051155W WO2010089269A1 WO 2010089269 A1 WO2010089269 A1 WO 2010089269A1 EP 2010051155 W EP2010051155 W EP 2010051155W WO 2010089269 A1 WO2010089269 A1 WO 2010089269A1
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WIPO (PCT)
Prior art keywords
weight
soap
continuous phase
composition according
composition
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PCT/EP2010/051155
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English (en)
Inventor
Cristiane Aparecida Furtado Canto
Sérgio Roberto LEOPOLDINO
André Messias Krell PEDRO
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Unilever Plc
Unilever N.V.
Hindustan Unilever Limited
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Application filed by Unilever Plc, Unilever N.V., Hindustan Unilever Limited filed Critical Unilever Plc
Priority to CN201080016085.2A priority Critical patent/CN102388125B/zh
Priority to BRPI1005438A priority patent/BRPI1005438B8/pt
Publication of WO2010089269A1 publication Critical patent/WO2010089269A1/fr
Priority to ZA2011/05527A priority patent/ZA201105527B/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D13/00—Making of soap or soap solutions in general; Apparatus therefor
    • C11D13/14—Shaping
    • C11D13/18—Shaping by extrusion or pressing
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/007—Soaps or soap mixtures with well defined chain length
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22—Organic compounds, e.g. vitamins
    • C11D9/26—Organic compounds, e.g. vitamins containing oxygen
    • C11D9/262—Organic compounds, e.g. vitamins containing oxygen containing carbohydrates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22—Organic compounds, e.g. vitamins
    • C11D9/26—Organic compounds, e.g. vitamins containing oxygen
    • C11D9/265—Organic compounds, e.g. vitamins containing oxygen containing glycerol

Definitions

  • the invention relates to low TFM personal washing bars that are made by high speed extrusion and stamping and are suitable for the mass market.
  • the personal washing bars include a polysaccharide-polyol structuring system and fatty acids soaps which have a limited level of unsaturated soaps relative to their content of saturated soluble soaps.
  • Personal washing bars such as soap bars have played an important role in hygiene and their routine use has been critical in reducing the spread of communicable diseases. Manufacturers have continuously sought ways to improve the in-use sensory properties and skin compatibility of personal washing bars and to increase their affordability to consumers around the world.
  • TFM Total Fatty Matter
  • One strategy that has been used to reduce the soap content in bars is to replace part of the fatty acid soap by inorganic fillers and/or higher levels of water.
  • melt-cast technology yields bars that have lower surfactant content, the process is less efficient than high-throughput extrusion.
  • melt-cast bars have substantial levels of water and solvents, are subject to drying out and their rate of wear is much higher than milled toilet soaps. Consequently such bars are less economical in use than milled soaps.
  • WO 01/42418 to Chokappa et al discloses a detergent bar containing 0.5 to 30% amorphous alumina, one alkali metal salt of carboxylic/sulfonic acid, 5-70% detergent active and 10-55% water.
  • WO 2006/094586 to Gangopadhayay et al discloses a low TFM detergent bar including soap (15 % to 30 % TFM); 25 % to 70 % inorganic particulates including talc and calcium carbonate; 0.5 % to 10 % of alumino-silicate; and 3 % to 20 % water.
  • US 6,440,908 to Racherla discloses high moisture containing bar compositions that includes a borate compound which enables the retention of high amounts of moisture without compromising bar properties.
  • WO 96/35772 to Wise et al discloses laundry bar compositions including from about 20 % to about 70 % surfactant; from about 12 % to about 24 % water; from about 6.25 % to about 20 % calculated excess alkali metal carbonate; from about 2 % to about 20 % water-soluble inorganic strong-electrolyte salt; and various optional ingredients including whole-cut starch.
  • WO98/18896 to Rahamann et al discloses laundry bar composition including structured soap composition; from about 5 % to about 50 % starch; and about 25 % to about 45 % moisture.
  • US 2007/0021314 and US 2007/0155639 to Salvador et al disclose cleansing bar compositions that include (a) at least about 15%, water; (b) from about 40% to about 84% soap; and (c) from about 1 % to about 15%, inorganic salt.
  • the bar compositions further comprise a component selected from the group consisting of carbohydrate structurant, humectants, free fatty acid, synthetic surfactants, and mixtures thereof.
  • U.S. 6838420B2 to Sachdev et al discloses a translucent or transparent composition
  • US 4,808,322 to James McLaughlin discloses a non-foaming skin cleansing- conditioning bar consisting essentially of 14% to 18% of specific anionic surfactant materials; about 40% to 72% of specific water-insoluble emollients; 0% to 25% of a starch-derived filler; and 2% to 12% of water.
  • WO08055765 to Jagdish Gupta discloses soap prepared from fatty matter having 8 to 22, carbon atoms, 30 to 60%, total fatty matter (TFM). Of the total fatty matter it is preferred that 70 to 90% of the total fatty matter by weight is unsaturated. The soap bar has less than 30%, saturated fatty matter by weight of total fatty matter.
  • Previous work described in Patent Application GB 806340.6 identified lower TFM extrudable soap bar compositions that included starch, specific polyols and optionally water insoluble particles that did not require high levels of water and inorganic fillers. However, this technology was limited to compositions having a total level of fatty acid soap no lower than 45%. It was found that when the fatty acid soap level fell below about 45%, especially below 40%, the processing and in-use properties became progressively more sensitive to small changes in composition. This sensitivity increased as the total fatty acid soap level was reduced towards 20% soap made large scale production problematic.
  • compositions structured with polysaccharides such as starch and cellulose, polyols and optionally water insoluble particulate material at a soap level below 45% is surprisingly related to the types and relative proportions of the more water soluble and lower melting soap components which are present in the soap mixture.
  • the ratio of unsaturated soluble soaps such as oleate soap to the more water soluble and lower melting saturated soaps such as laurate soap and myristate soap was a key parameter in controlling the relative levels of starch and polyol required to achieve extrudable compositions with acceptable bar properties.
  • the optimal value of this ratio and its relationship to the optimal composition of the structuring system were found to depend upon the total fatty acid soap level in the composition and to some extent on the detailed composition of the structuring system which added additional levels of complexity to the composition.
  • This understanding has now allowed the definition of a composition space for soap bars having much lower soap content, e.g., 20-40% soap, which have highly acceptable in-use properties and can be manufactured by high speed extrusion.
  • the personal washing bars of the invention are extruded and preferably stamped bars suitable for mass market applications.
  • One embodiment of the invention is a personal washing bar that has a continuous phase that includes:
  • the fatty acid soap comprises at least 30% saturated fatty acid soaps based on the total weight of the soap and wherein the fatty acid soap has a ratio R OL , defined as the total weight of oleics fatty acids soaps divided by the total weight of the laurics fatty acid soaps which satisfies the inequality given in Eq (1 );
  • TS is the weight % of the total fatty acid soap in the continuous phase
  • a structuring system comprising: i) from 10% to 40% by weight of continuous phase of a polysaccharide structurant selected from the group consisting of starch, cellulose and a combination thereof, ii) from 8.0% to 30% by weight of continuous phase of a polyol selected from the group consisting of glycerol, sorbitol and their mixtures, and iii) 0 to 15% by weight of continuous phase of water insoluble particulate material; and
  • the weight of polysaccharide structurant divided by the weight of polyol, designated Rsp is in the range from 0.3 to 5.0, preferably 0.5 to 4.5, and wherein the continuous phase composition is an extrudable mass having a penetrometer hardness of 3 to 8 Kg and a yield stress of 350 to 2000 kPa measured at a temperature of 40° C.
  • the polysaccharide structurant is starch and the weight ratio of starch and polyol structuring components lies within a range which depends upon the weight % of the total fatty acid soap present in the continuous phase. Specifically, the weight of starch component divided by the weight of polyol component, designated Rsp, satisfies the inequality expressed by Eq (2)
  • the optional insoluble particulate material is present at a level of about 3 to 15%, preferably 5% to 10%.
  • the insoluble material is preferably an inorganic particulate material.
  • the bar composition includes a synthetic surfactant at a level of up to about 10% by weight of the bar, preferably between 2% and 8% by weight.
  • the continuous phase includes a slip modifier which greatly improves the feel of the wet bar when it is rubbed on the skin especially when the polysaccharide and/or insoluble particles are present in the bar at levels approaching the upper limits of their useful concentration ranges.
  • the continuous phase has a nominal water content of no more than 20% by weight, preferably between 14% and about 18% by weight when the bar is initially manufactured, i.e., immediately after it is extruded and stamped.
  • the continuous phase of the bar comprises 25% to 35% soap by weight
  • the polysaccharide is starch
  • Rsp is in the range from 0.5 to 3.7.
  • % or wt % refers to percent by weight of an ingredient as compared to the total weight of the composition or component that is being discussed (generally the composition of the continuous phase or the composition of the fatty acid soap).
  • composition will refer to the composition of the continuous phase of the bar.
  • the present invention relates to extruded personal washing bars in which the continuous phase of the bar comprises specific levels of fatty acid soaps, hereinafter designated simply as "soap"; from about 30% to about 60% of a structuring system; and various optional ingredients.
  • soaps hereinafter designated simply as "soap"
  • the compositions used to prepare the continuous phase of bars of the invention and the methods used to manufacture and evaluate the compositions and bars made from the compositions are described below.
  • the term "continuous phase of the bar” is used in a macroscopic sense to describe the predominant soft solid phase into which various macroscopic solid domains, the "dispersed phase” may be optionally dispersed or distributed.
  • the continuous phase is generally not a single phase in the microscopic sense but rather is a substantially uniform mixture (i.e., dispersion) of microscopic soap crystals and liquid crystalline or gel and liquid materials, components of the structuring system (e.g., starch, polyol, insoluble particulate material), and various optional ingredients.
  • the continuous phase generally comprises from 65% to 100% by weight of the personal washing bar. In the majority of applications, the continuous phase comprises 90% to 100% of the personal washing bar.
  • the optional dispersed phase can be in the form of stripes or variegations, bits (e.g., pieces or chunks of solid), plate like inclusions, veins, the like and mixtures thereof.
  • the dispersed phase generally has a different overall composition from the continuous phase but may only differ in the level or type of colorant.
  • the bar compositions of the invention are capable of being manufactured at high production rates by processes that generally involve the extrusion forming of ingots or billets, and stamping or molding of these billets into individual tablets, cakes, or bars.
  • the mass formed from the continuous phase composition and any dispersed phase is capable of being extruded at a rate in excess of 9 kg per minute, preferably at or exceeding 27 kg per minute and ideally at or exceeding 36 kg per minute.
  • Personal washing bars produced from compositions according to the invention in addition to being capable of being processed at high production rates also possess a range of desirable physical properties that make them highly suitable for every day use by mass market consumers.
  • the fatty acid soaps, optional surfactants and in fact all the components of the bar should be suitable for routine contact with human skin and preferably yield bars that are high lathering.
  • the preferred type of surfactant is fatty acid soap.
  • soap is used herein to mean an alkali metal or alkanol ammonium salts of aliphatic, alkane-, or alkene monocarboxylic acids usually derived from natural triglycerides.
  • Sodium, potassium, magnesium, mono-, di- and tri-ethanol ammonium cations, or combinations thereof, are the most suitable for purposes of this invention.
  • sodium soaps are used in the compositions of the invention, but from about 1 % to about 25 wt% of the soap may be potassium, magnesium or triethanolamine soaps.
  • the soaps useful herein are the well known alkali metal salts of natural or synthetic aliphatic (alkanoic or alkenoic) acids having about 8 to about 22 carbon atoms, preferably about 10 to about 18 carbon atoms. They may be described as alkali metal carboxylates of saturated or unsaturated hydrocarbons having about 8 to about 22 carbon atoms.
  • Soaps having the fatty acid distribution of coconut oil and palm kernel oil may provide the lower end of the broad molecular weight range.
  • Those soaps having the fatty acid distribution of peanut or rapeseed oil, or their hydrogenated derivatives may provide the upper end of the broad molecular weight range.
  • soaps having the fatty acid distribution of coconut oil or tallow, or mixtures thereof since these are among the more readily available triglyceride fats.
  • the proportion of fatty acids having at least 12 carbon atoms in coconut oil soap is about 85%. This proportion will be greater when mixtures of coconut oil and fats such as tallow, palm oil, or non-tropical nut oils or fats are used, wherein the principle chain lengths are Ci ⁇ and higher.
  • Preferred soap for use in the compositions of this invention has at least about 85% fatty acids having about 12 to 18 carbon atoms.
  • the preferred soaps for use in the present invention should include at least about 30% saturated soaps, i.e., soaps derived from saturated fatty acids, preferably at least about 40% saturated soaps by weight of the soap.
  • Soaps can be classified into three broad categories which differ in the chain length of the hydrocarbon chain, i.e., the chain length of the fatty acid, and whether the fatty acid is saturated or unsaturated.
  • these classifications are:
  • Laurics soaps encompass soaps which are derived predominantly from C12 to Ci 4 saturated fatty acid, i.e. lauric and myristic acid, but can contain minor amounts of soaps derived from shorter chain fatty acids, e.g., Ci 0 . Laurics soaps are generally derived in practice from the hydrolysis of nut oils such as coconut oil and palm kernel oil
  • Steps soaps encompass soaps which are derived predominantly from C16 to C18 saturated fatty acid, i.e. palmitic and stearic acid, but can contain minor levels of saturated soaps derived from longer chain fatty acids, e.g., C2o- Stearics soaps are generally derived in practice from triglyceride oils such as tallow, palm oil and palm stearin.
  • Oleics soaps encompass soaps which are derived from unsaturated fatty acids including predominantly oleic acid (Ci 8 1), linoeleic acid( (Ci 8 2), myristoleiic acid (Ci 4 1 ) and palmitoleic acid (Ci 6 1 ) as well as minor amounts of longer and shorter chain unsaturated and polyunsaturated fatty acids.
  • Oleics soaps are generally derived in practice from the hydrolysis various triglceride oils and fats such as tallow, palm oil, sunflower seed oil and soybean oil.
  • Coconut oil employed for the soap may be substituted in whole or in part by other "high-lauhcs” or “laurics rich” oils, that is, oils or fats wherein at least 45% of the total fatty acids are composed of lauric acid, myristic acid and mixtures thereof.
  • These oils are generally exemplified by the tropical nut oils of the coconut oil class. For instance, they include: palm kernel oil, babassu oil, ouhcuri oil, tucum oil, cohune nut oil, murumuru oil, jaboty kernel oil, khakan kernel oil, dika nut oil, and ucuhuba butter.
  • a preferred soap is a mixture of about 10% to about 40% derived from coconut oil, palm kernel oil or other laurics rich oils and about 90% to about 60% tallow, palm oil, palm stearin or other stearics rich oils or a combination thereof provided the ratio of oleics and laurics soaps, R 0 L, satisfies the above criteria.
  • Soaps may be made by the classic kettle boiling process or modern continuous soap manufacturing processes wherein natural fats and oils such as tallow, palm oil or coconut oil or their equivalents are saponified with an alkali metal hydroxide using procedures well known to those skilled in the art.
  • Two broad processes are of particular commercial importance.
  • the SAGE process where triglycerides are saponified with a base, e.g., sodium hydroxide, and the reaction products extensively treated and the glycerin component extracted and recovered.
  • the second process is the SWING process, where the saponification product is directly used with less exhaustive treatment and the glycerin from the triglyceride is not separated but rather included in the finished soap noodles and/or bars.
  • the soaps may be made by neutralizing fatty acids (e.g., distilled fatty acids), such as lauric (Ci 2 ), myristic (Ci 4 ), palmitic (Ci 6 ), stearic (Ci 8 ) and oleic acid (Cis i) acids and their mixtures with an alkali metal hydroxide or carbonate.
  • fatty acids e.g., distilled fatty acids
  • the level of fatty acid soap in the continuous phase of the bar can range from 20% to less than 45%, preferably 20% to about 40% and more preferably about 25% to 35% based on the total weight of the continuous phase composition.
  • Surfactants other than soap can optionally be included in the bar at levels generally up to and including about 10%, preferably at levels between about 2% to about 7% by weight of the bar. Examples of suitable syndets are described below under OPTIONAL INGREDIENTS.
  • the structuring system includes one or more polysaccharide structurants selected from the group consisting of starch, cellulose and their mixtures; one or more polyols; and optionally, water insoluble particulate material.
  • the total level of the structuring system used in the composition should be greater than 30% by weight, preferably 30% to 70% and most preferably 35% to about 55% based on the total weight the continuous phase.
  • total level of the structuring system is meant the sum of the weights of the starch/cellulose, polyol, and optional insoluble particle material.
  • Suitable starch materials include natural starch (from corn, wheat, rice, potato, tapioca and the like), pregelatinzed starch, physically and chemically modified starch and mixtures thereof.
  • natural starch starch which has not been subjected to chemical or physical modification - also known as raw or native starch.
  • a preferred starch is natural or native starch from maize (corn), cassava, wheat, potato, rice and other natural sources of it.
  • Raw starch with different ratio of amylose and amylopectin include: maize (25% amylose); waxy maize (0%); high amylose maize (70%); potato (23%); rice (16%); sago (27%); cassava (18%); wheat (30%) and others.
  • the raw starch can be used directly or modified during the process of making the bar composition such that the starch becomes either partially or fully gelatinized.
  • Another suitable starch is pre-gelatinized which is starch that has been gelatinized before it is added as an ingredient in the present bar compositions.
  • Various forms are available that will gel at different temperatures, e.g., cold water dispersible starch.
  • One suitable commercial pre-gelatinized starch is supplied by National Starch Co. (Brazil) under the trade name FARMAL CS 3400 but other commercially available materials having similar characteristics are suitable.
  • Suitable cellulose materials can come from various sources for example wood, cotton, and various grasses such as switch grass and sugar cane (Bagasse).
  • the plant biomass can be processed by a range of physico-chemical techniques and purified as required.
  • Particularly suitable cellulose have a particle size less than 100 microns, preferably less than 50 microns and preferably 45 microns or less.
  • Suitable celluloses include microcrystalline cellulose, hydroxyalkyl alkylcellulose ether and mixture thereof.
  • a preferred cellulose material is microcrystalline cellulose which is generally made from alpha cellulose and is highly crystalline particulate cellulose made primarily of crystalline aggregates. This is typically done with a strong mineral acid (e.g., hydrogen chloride). Such an acid hydrolysis process produces microcrystalline cellulose of predominantly coarse particulate aggregates, typically of mean size range 10 to 40 microns.
  • a suitable commercial microcrystalline cellulose is supplied by FMC Biopolymer (Brazil) under the trade name AVICEL GP 1030 but other commercially available materials having similar characteristics are suitable.
  • a preferred polysaccharide structurant is starch, most preferably a natural starch (raw starch), a pre-gelatinized starch, a chemically modified starch or mixtures thereof.
  • the amount of the polysaccharide (e.g., starch and/or cellulose) component in the continuous phase can range from about 10% to about 40%, preferably 20% to 40% and more preferably 30% to 40% by weight of the composition.
  • a second critical component of the structuring system is a polyol or mixture of polyols.
  • Polyol is a term used herein to designate a compound having multiple hydroxyl groups (at least two, preferably at least three) which is highly water soluble, preferably freely soluble, in water.
  • polyols are available including: relatively low molecular weight short chain polyhydroxy compounds such as glycerol and propylene glycol; sugars such as sorbitol, manitol, sucrose and glucose; modified carbohydrates such as hydrolyzed starch, dextrin and maltodexthn, and polymeric synthetic polyols such as polyalkylene glycols, for example polyoxyethylene glycol (PEG) and polyoxypropylene glycol (PPG).
  • PEG polyoxyethylene glycol
  • PPG polyoxypropylene glycol
  • Preferred polyols are relatively low molecular weight compound which are either liquid or readily form stable highly concentrated aqueous solutions, e.g., greater that 50% and preferably 70% or greater by weight in water. These include low molecular weight polyols and sugars.
  • Especially preferred polyols are glycerol, sorbitol and their mixtures.
  • the level of polyol is critical in forming a thermoplastic mass whose material properties are suitable for both high speed manufacture (27 - 36 Kg/min) and for use as a personal washing bar. It has been found that when the polyol level is too low, the mass is not sufficiently plastic at the extrusion temperature, typically 4O 0 C to 45 0 C. Conversely, when the polyol level is too high, the mass becomes too soft to be efficiently formed into bars by extrusion at normal process temperatures.
  • the level of polyol should be between 8% and 30%, preferably 10 to 20% and preferably about 10% to about 15% by weight of composition.
  • the weight ratio of starch and/or cellulose to polyol in the continuous phase is critical to forming compositions that can be extruded at high speed and provide bars having good in-use properties such as a low level of mush and a low rate of wear.
  • the weight of polysaccharide structurant to the weight of polyol, designated Rsp, should be in the ranged from about 0.3 to about 5, preferably 0.7 to about 4.5 based on the total weight of the continuous phase. It has been found that the exact ratio required to achieve acceptable compositions depends primarily on the total level of soap employed in the continuous phase and to some extent on R 0 L-
  • the structuring system may optionally include one or a combination of insoluble particulate materials.
  • insoluble particulate material is meant materials that are present in the continuous phase as finely divided solid particles and are suitable for personal washing applications.
  • the particulate material can be inorganic or organic or a combination as long as it is insoluble in water.
  • the insoluble particulate material should not be perceived as scratchy or granular and thus should have a particle size less than 300 microns, more preferably less than 100 mircons and most preferably less than 50 microns.
  • Preferred inorganic particulate material include talc and calcium carbonate.
  • Talc is a magnesium silicate mineral material, with a sheet silicate structure represented by the chemical formula Mg 3 Si 4 (O)i 0 (OH) 2 , and may be available in the hydrated form.
  • Talc has a plate-like morphology, and is substantially oleophilic/hydrophobia
  • Calcium carbonate or chalk exists in three crystal forms: calcite, aragonite and vaterite.
  • the natural morphology of calcite is rhombohedral or cuboidal, acicular or dendritic for aragonite and spheroidal for vaterite.
  • calcium carbonate or chalk (precipitated calcium carbonate) is produced by a carbonation method in which carbon dioxide gas is bubbled through an aqueous suspension of calcium hydroxide.
  • the crystal type of calcium carbonate is calcite or a mixture of calcite and aragonite.
  • optional insoluble inorganic particulate materials include alumino silicates, aluminates, silicates, phosphates, insoluble sulfates, borates and clays (e.g., kaolin, china clay) and their combinations.
  • Organic particulate materials include: insoluble polysaccharides such as highly crosslinked or insolubilized starch (e.g., by reaction with a hydrophobe such as octyl succinate); synthetic or natural polymers such as various polymer lattices and suspension polymers and mixtures thereof.
  • the structuring system can comprise up to and including about 15% insoluble particulate material, preferably 4% to about 10%, based on the total weight of the composition.
  • Equations 1 and 2 are meant as targets to greatly reduce experimentation.
  • the equations are approximate as they relate to compositions at the boundary values of the inequalities (i.e., the end points of each equation).
  • other components such as perfumes, emollient oils, electrolytes as well as the variability in the fatty acid distribution and starch/cellulose component can affect the material properties of the composition (e.g., yield stress and hardness). It is preferable to target the ratios to be within the boundaries.
  • the overriding limitation on composition is that the composition be an extrudable mass having a penetrometer hardness of 3 to 8 Kg and a yield stress of 350 to 2000 kPa measured at a temperature of 40° C.
  • the bar compositions of the invention do not comprise an especially high level of water compared to typical extruded and stamped soap bars which typically can range from about 13 to about 18% water when freshly made, i.e., after extrusion and stamping.
  • the water content of the freshly made bar should be less than 20%, and preferably be between 14% and 18% based on the total weight of the bar.
  • the water level of the freshly made bars of the invention is lower than the water content of freshly made melt and pour or melt-cast bars, i.e., the nominal water content based on the formulation as made in a factory, which typically exceeds 25% by weight in melt- cast compositions. It is stressed that the preferred water levels quoted above refers to freshly made bars.
  • This quantity “initial water level” or “initial water content” of the freshly made bar” is also designated as the “nominal water content” or “nominal water level” of the composition.
  • soap bars are subject to drying out during storage, i.e., water evaporates from the bar when the relative humidity is lower than the partial vapor pressure of water in equilibrium with the bar composition although the amount of evaporation depends on the rate of diffusion of water from the bar.
  • the actual water content of the bar at the moment of sampling can obviously differ significantly from the nominal water content of the bar immediately after manufacture.
  • added soluble salt is meant one or more salts that are introduced in the bar in addition to the salts which are present in the bar as a result of saponification and neutralization of the fatty acids, e.g., NaCI generated from saponification with sodium hydroxide and neutralization with hydrochloric acid.
  • water soluble salts could potentially be used.
  • the preferred salts are water soluble salts that do not contain cations which precipitate with soap, i.e., which form insoluble precipitates with fatty acid carboxylates.
  • water soluble salts containing divalent ions such as calcium, magnesium and zinc and trivalent ions such as aluminum should be avoided.
  • highly insoluble calcium salts such as calcium carbonate may be used as optional insoluble particulate material as part of the structuring system as discussed above.
  • Especially preferred soluble salts comprise monovalent cations that form soluble fatty acid soaps (such as sodium, potassium, alkylanolammonium but not lithium) and divalent anions (e.g., sulfates, carbonates, and isethionates), trivalent anions (e.g., citrates, sulfosuccinates, phosphates) and multivalent anions (e.g., polyphosphates and polyacylates).
  • soluble fatty acid soaps such as sodium, potassium, alkylanolammonium but not lithium
  • divalent anions e.g., sulfates, carbonates, and isethionates
  • trivalent anions e.g., citrates, sulfosuccinates, phosphates
  • multivalent anions e.g., polyphosphates and polyacylates.
  • Especially preferred salts are sodium and potassium sulfates, carbonates, phosphates, citrates, sulfosuccinates and isethionates and mixtures thereof.
  • the added salts have been found to be useful in reducing wear rate and mush. Without wishing to be bound by theory, it is believed that a limited amount of the one or more water soluble salts reduces the level of liquid crystal phase (e.g., lamellar phase) in the bar and therefore allow the bar to accommodate a composite structuring system that itself comprises some liquid. However, the incorporation of too much salt reduces the liquid crystal phase to a level where the bar becomes insufficiently pliable and may exhibit excessive cracking.
  • liquid crystal phase e.g., lamellar phase
  • the level of added salt (i.e., excluding salts generated during saponification like NaCI) should be less than 2.0% (e.g. 1.5% to 2%), preferably less than 1.5%, preferably up to about 1.0%, preferably up to and including 0.8%. In some circumstances a level of salt from about 0.3% to about 0.8% is useful.
  • salts are not used in the present invention to lower water activity so as to accommodate very high levels of water in the bar which are characteristic of some low TFM bars described in the prior art, i.e. the use of electrolytes to prevent or slow the drying out of the bar.
  • the bars of the current invention have water levels that are not especially high (up to about 20%) compared with normal commercial soap bars which can range from about 13 to about 15-18% nominal water content.
  • levels of salts in the range of 2.5 to 8% typical of the high water content bars of the prior art would be detrimental to the bars described herein.
  • a useful optional ingredient is fatty acid and /or triglycerides which are useful for improving lather, as well as modifying the rheology at low levels incorporated in composition to increase plasticity.
  • fatty acids are C 8 -C 22 fatty acids.
  • Preferred fatty acids are Ci 2 - Ci8, preferably predominantly saturated, straight-chain fatty acids.
  • some unsaturated fatty acids can also be employed.
  • the free fatty acids can be mixtures of shorter chain length (e.g., C10-C14) and longer chain length (e.g., Ci 6 -Ci 8 ) chain fatty acids.
  • one useful fatty acid is fatty acid derived from high-lauhcs triglycerides such as coconut oil, palm kernel oil, and babasu oil.
  • the fatty acid can be incorporated directly or they can be generated in-situ by the addition of a protic acid to the soap during processing.
  • suitable protic acids include: mineral acids such as hydrochloric acid and sulfuric acid, adipic acid, citric acid, glycolic acid, acetic acid, formic acid, fumaric acid, lactic acid, malic acid, maleic acid, succinic acid, tartaric acid and polyacrylic acid.
  • the level of fatty acid having chain lengths of 14 carbon atoms and below should generally not exceed 5.0%, preferably not exceed about 1 % and most preferably be 0.8% or less based on the total weight of the continuous phase.
  • the bar compositions can optionally include non-soap synthetic type surfactants (detergents) - so called "syndets".
  • Syndets can include anionic surfactants, nonionic surfactants, amphoteric or zwitterionic surfactants and cationic surfactants.
  • the level of synthetic surfactant present in the bar is generally not greater than about 10% in the continuous phase although inclusion of higher levels in the bar may be advantageous for some applications.
  • Some embodiments of the invention include syndets at a level of about 2% to 10%, preferably about 4% to about 10%.
  • Especially preferred syndets include anionic surfactants (non-soap), amphoteric surfactants and nonionic surfactants.
  • the toilet bar compositions of the present invention may contain one or more non-soap anionic syndet surfactants (simply designated “anionic syndets”) at a level up to about 20%, preferably 0 to 10% and more preferably 2% to 5% based on the total weight of the continuous phase.
  • anionic syndets non-soap anionic syndet surfactants
  • Suitable anionic syndets may be, for example, an aliphatic sulfonate, such as a primary alkane (e.g., C8-C22) sulfonate, primary alkane (e.g., C8-C22) disulfonate, C8-C22 alkene sulfonate, C 8 -C 22 hydroxyalkane sulfonate or alkyl glyceryl ether sulfonate (AGS); or an aromatic sulfonate such as alkyl benzene sulfonate.
  • Alpha olefin sulfonates are another suitable anionic surfactant.
  • the anionic syndet may also be an alkyl sulfate (e.g., Ci 2 -Ci 8 alkyl sulfate), especially a primary alcohol sulfate or an alkyl ether sulfate (including alkyl glyceryl ether sulfates).
  • alkyl sulfate e.g., Ci 2 -Ci 8 alkyl sulfate
  • a primary alcohol sulfate e.g., a primary alcohol sulfate or an alkyl ether sulfate (including alkyl glyceryl ether sulfates).
  • the anionic syndet can also be a sulfonated fatty acid such as alpha sulfonated tallow fatty acid, a sulfonated fatty acid ester such as alpha sulfonated methyl tallowate or mixtures thereof.
  • a sulfonated fatty acid such as alpha sulfonated tallow fatty acid
  • a sulfonated fatty acid ester such as alpha sulfonated methyl tallowate or mixtures thereof.
  • the anionic syndet may also be alkyl sulfosuccinates (including mono- and dialkyl, e.g., C 6 -C 22 sulfosuccinates); alkyl and acyl taurates, alkyl and acyl sarcosinates, sulfoacetates, C 8 -C 22 alkyl phosphates and phosphates, alkyl phosphate esters and alkoxyl alkyl phosphate esters, acyl lactates or lactylates, C 8 -C 22 monoalkyl succinates and maleates, sulphoacetates, and acyl isethionates.
  • Another class of anionic syndets is Cs to C20 alkyl ethoxy (1 -20 EO) carboxylates.
  • Cs-Cis acyl isethionates Another suitable anionic syndet is Cs-Cis acyl isethionates. These esters are prepared by reaction between alkali metal isethionate with mixed aliphatic fatty acids having from 6 to 18 carbon atoms and an iodine value of less than 20. At least 75% of the mixed fatty acids have from 12 to 18 carbon atoms and up to 25% have from 6 to 10 carbon atoms.
  • the acyl isethionate may also be alkoxylated isethionates
  • the anionic syndet will comprise a majority of the synthetic surfactants used in the composition.
  • Amphoteric surfactants which may be used in this invention include at least one acid group. This may be a carboxylic or a sulphonic acid group. They include quaternary nitrogen and therefore are quaternary amido acids. They should generally include an alkyl or alkenyl group of 7 to 18 carbon atoms. Suitable amphoteric surfactants include amphoacetates, alkyl and alkyl amido betaines, and alkyl and alkyl amido sulphobetaines.
  • Amphoacetates and diamphoacetates are also intended to be covered in possible zwittehonic and/or amphoteric compounds which may be used.
  • Suitable nonionic surfactants include the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols or fatty acids, with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
  • alkylene oxides especially ethylene oxide either alone or with propylene oxide.
  • Examples include the condensation products of aliphatic (C 8 - Cis) primary or secondary linear or branched alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine.
  • Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
  • the nonionic may also be a carbohydrate or sugar based, ethers, esters or amides, such as alkyl (poly)sacchahdes and alkyl (poly)sacchahde amides.
  • cationic detergents are the quaternary ammonium compounds such as alkyldimethylammonium halides.
  • slip modifiers Very useful optional ingredients are slip modifiers.
  • the term "slip modifier” is used herein to designate materials that when present at relatively low levels (generally less than 1.5% based on the total weight of the bar composition) will significantly reduce the perceived friction between the wet bar and the skin.
  • the most suitable slip modifiers are useful at a level of 1 wt% or less, preferably from 0.05 to 1 % and more preferably from 0.05% to 0.5%.
  • Slip modifiers are particularly useful in bar compositions which contain starch/ cellulose and/or insoluble particles whose levels approach the higher end of the useful concentration range for these materials, e.g., 30-40% for starch with 5-10% insoluble particulate material. It has been found that the incorporation of higher levels of starch and/or insoluble particles increases the wet skin friction of the bar and the bars are perceived as "draggy" (have a high perceived level of fhctional "drag" on the skin). Although some consumers do not mind this sensory quality, other dislike it. In general, consumers prefer bars that are perceived to glide easily over their skin and are perceived as being slippery.
  • Suitable slip modifier include petrolatum, waxes, lanolines, poly-alkane, -alkene, - polyalkalyene oxides, high molecular weight polyethylene oxide resins, silicones, poly ethylene glycols and mixtures thereof.
  • a particularly suitable slip modifier is high molecular weight polyethylene oxide resin.
  • the molecular weight of the polyethylene oxide resin is greater than 80,000, more preferably at least 100,000 Daltons and most preferably at least 400,000 Daltons.
  • suitable high molecular weight polyethylene oxide resins are water soluble resins supplied by Dow Chemical Company under the trade name POLYOX.
  • An example is WSR N-301 (molecular weight 4,000,000 Daltons).
  • Adjuvants are ingredients that improve the aesthetic qualities of the bar especially the visual, tactile and olefactory properties either directly (perfume) or indirectly (preservatives).
  • a wide variety of optional ingredients can be incorporated in bars of the current invention.
  • adjuvants include but are not limited to: perfumes; opacifying agents such as fatty alcohols, ethoxylated fatty acids, solid esters, and TiO 2 ; dyes and pigments; pearlizing agent such as TiO 2 coated micas and other interference pigments; plate like mirror particles such as organic glitters; sensates such as menthol and ginger; preservatives such as dimethyloldimethylhydantoin (Glydant XL1000), parabens, sorbic acid and the like; anti-oxidants such as, for example, butylated hydroxytoluene (BHT); chelating agents such as salts of ethylene diamine tetra acetic acid (EDTA) and thsodium etidronate;
  • the level of pearl izing agent should be between about 0.1 % to about 3%, preferably between 0.1 % and 0.5% and most preferably between about 0.2 to about 0.4% based on the total weight of the composition.
  • Adjuvants are commonly collectively designated as "minors” in the soap making art and frequently include at a minimum, colorant (dyes and pigments), perfume, preservatives and residual salts and oils from the soap making process, and various emotive ingredients such as witch-hazel. Minors generally constitute 4 to 10% by weight of the total continuous phase composition, preferably 4 to 8%, and often about 5-7% of the continuous phase.
  • a particular class of optional ingredients highlighted here is skin benefit agents included to promote skin and hair health and condition.
  • Potential benefit agents include but are not limited to: lipids such as cholesterol, ceramides, and pseudoceramides; antimicrobial agents such as TRICLOSAN; sunscreens such as cinnamates; exfoliant particles such as polyethylene beads, walnut shells, apricot seeds, flower petals and seeds, and inorganics such as silica, and pumice; additional emollients (skin softening agents) such as long chain alcohols and waxes like lanolin; additional moisturizers; skin-toning agents; skin nutrients such as vitamins like Vitamin C, D and E and essential oils like bergamot, citrus unshiu, calamus, and the like; water soluble or insoluble extracts of avocado, grape, grape seed, myrrh, cucumber, watercress, calendula, elder flower, geranium, linden blossom, amaranth, seaweed, gingko, ginseng, carrot
  • the composition can also include a variety of other active ingredients that provide additional skin (including scalp) benefits.
  • active ingredients include anti-acne agents such as salicylic and resorcinol; sulfur-containing D and L amino acids and their derivatives and salts, particularly their N-acetyl derivatives; anti-wrinkle, anti-skin atrophy and skin-repair actives such as vitamins (e.g., A, E and K), vitamin alkyl esters, minerals, magnesium, calcium, copper, zinc and other metallic components; retinoic acid and esters and derivatives such as retinal and retinol, vitamin B3 compounds, alpha hydroxy acids, beta hydroxy acids, e.g.
  • salicylic acid and derivatives thereof skin soothing agents such as aloe vera, jojoba oil, propionic and acetic acid derivatives, fenamic acid derivatives; artificial tanning agents such as dihydroxyacetone; tyrosine; tyrosine esters such as ethyl tyrosinate and glucose tyrosinate; skin lightening agents such as aloe extract and niacinamide, alpha-glyceryl-L-ascorbic acid, aminotyroxine, ammonium lactate, glycolic acid, hydroquinone, 4 hydroxyanisole, sebum stimulation agents such as bryonolic acid, dehydroepiandrosterone (DHEA) and orizano; sebum inhibitors such as aluminum hydroxy chloride, corticosteroids, dehydroacetic acid and its salts, dichlorophenyl imidazoldioxolan (available from Elubiol); anti-oxidant effects, protease inhibition; skin tightening
  • the extruded bars according to the invention can include various types of optional macroscopic domains generally having a different composition from the continuous phase which are dispersed or distributed either uniformly or non- uniformly in the continuous phase of the bar.
  • the composition of domains can differ from the composition of the continuous phase in for example colorant, surfactant level and type, benefit agents, structurants or matrix.
  • Optional dispersed domains can include one or a combination of stripes or variegations such as described in U.S. Patents 4,634,564, 3,673,294, 3,884,605 and 6,383,999, chucks or bits as described in U.S. Patent 6,730,642, veins as described in U.S. Patent Application no. 2008/214430, plate like inclusions, and surface inclusions such as is described in U.S. Patent Application no. 2008/188388.
  • the domains can be included during extrusion by injection, co-extrusion, dispersion and post-extrusion by surface impaction.
  • extruded mass is meant that the bars are made by a process which involves both the intensive mixing or working of the soap mass while it is in a semi-solid plastic state, and its forming into a cohesive mass by the process of extrusion.
  • the intensive mixing can be accomplished by one or more unit operations known in the art which can include roller milling, refining, and single or multistage extrusion.
  • Such processes work (shear) the composition at a temperature between about 3O 0 C and about 5O 0 C to form a homogeneous network of insoluble solid materials dispersed in a viscous liquid and/or liquid crystalline phase containing the lower melting, more soluble surfactants (e.g., laurics and oleics soaps and other water soluble/dispersible materials).
  • soluble surfactants e.g., laurics and oleics soaps and other water soluble/dispersible materials.
  • An extruded mass must be thermoplastic within the process temperature of extrusion which is generally between about 30 0 C and about 45°C, preferably at a temperature between about 33°C to about 42°C.
  • the material must soften within this process temperature window but remain highly viscous, i.e., the material should not soften excessively to form a sticky mass.
  • the material must regain its structure and harden quickly as the temperature is lowered below its softening point. This means that the internal structure must reform quickly generally by re-solidification of structure forming units, e.g., crystals.
  • the softened mass although pliable must be sufficiently viscous so that it does not stick to the surfaces of the extruder in order to be capable of conveyance by the extruder screws but not bend excessively when exiting the extruder as a billet.
  • the mass if the mass is too viscous it will not be capable of extrusion at reasonable rates.
  • the hardness of the mass should fall within limits within the process temperature window to be capable of high rates of production as defined above.
  • Personal washing bars formed by extrusion also commonly known as milled soaps
  • high temperature e.g. 7O 0 C
  • the one or more key properties that serve as characteristic "finger-prints" of an extruded mass are structural anisotropy, the level of high melting point materials such as stearics soaps, high melting point and thermal reversibility, and rapid recovery of hardness after heating and shear. These characteristics are briefly described below.
  • Bars made by extrusion typically have a characteristic anisotropic internal structure both with respect to the alignment of crystals and overall macro- structure.
  • the liquid (crystalline) phase generated at the extrusion temperature has a relatively lower viscosity and is expected to preferentially flow to the surface of the candles during the plodder compression stage.
  • melt-cast bars have a predominantly isotropic structure because crystallization occurs during quiescent cooling and thus the alignment of crystals is minimal and there is no candle structure.
  • an extruded mass In order to achieve the rheological properties required for milling and extrusion, an extruded mass must have a sufficient level of solid particles to adequately structure the mass at the process temperature, i.e., the bar contains materials whose melting point is above the extrusion temperature.
  • these high melting solids are provided in at least part by the stearic soaps which include the C16 and C18 saturated soaps.
  • the level of high melting solids e.g. melting point greater than the extrusion temperature
  • the level of high melting solids is generally greater than 20%, and typically greater than 30% based on the total level of fatty acid soap present in the continuous phase.
  • the level of stearics soaps is generally between about 25% and about 60%, preferably between 30% to about 45% based on the total weight of the fatty acid soap.
  • Other sources of solid particles are also present in the bars described herein.
  • extruded masses Because of the presence of significant high melting solids (e.g. stearics-hch soaps) and the lower levels of liquids relative to cast soaps, extruded masses have melting points that are generally above 8O 0 C, typically above 9O 0 C and usually above 100 0 C. In contrast, cast soaps generally melt at temperature between 7O 0 C and 8O 0 C.
  • high melting solids e.g. stearics-hch soaps
  • an extruded mass regains its structure and harden quickly as the temperature is lowered below its softening point.
  • This rapid re-solidification is generally observed as thermal reversibility in differential scanning calohmetry (DSC).
  • thermal reversibility is meant that increasing and decreasing temperature sweeps tend to be superimposible albeit offset by a temperature difference characteristic of the composition.
  • cast soaps require much longer periods of time to reform the solid structural units and exhibit lower thermal reversibility, e.g., increasing-decreasing temperature sweeps are either not super-imposable or are offset by much larger temperatures than is found with an mass.
  • An extruded mass must soften when it is heated to the extrusion process temperature, which is typically in the range of about 35° C to about 45° C.
  • the hardness of the mass should generally be at least about 3 Kg, preferably at least 4 Kg but generally not greater than about 8 Kg, preferably between 4.5 Kg and 6.5 Kg when measured by the Hardness Penetration Test described in the TEST
  • An extruded mass also remains cohesive after its has been subjected to shear at the extrusion temperature without exhibiting excessive pliability or stickiness.
  • retention cohesive is meant when compacted under pressure the mass should be capable of sintering together to form a single cohesive unit that has mechanical integrity.
  • an extruded mass quickly recovers its yield stress (as measured by its penetrometer hardness) when it is subjected to shear at the extrusion temperature (e.g., 4O 0 C) and allowed to cool.
  • the extrusion temperature e.g. 4O 0 C
  • the mass should recover at least about 75%, preferably at least about 85% and more preferably at least about 95% of the initial hardness before it was sheared, by for example, extrusion through an "orifice" extruder.
  • an "orifice" extruder which provides a controlled extensional flow similar to that encountered by the mass during extrusion through an eye plate.
  • This device comprises a thermal jacketed barrel (e.g. 350 mm length by 90 mm in diameter) ending in a narrow opening (typically 2-4 mm) and a plunger which is coupled to a drive unit e.g., lnstron Mechanical Tester. The plunger forces the mass through the orifice to form an extrudate. The extrudate can be assessed at the process temperature.
  • the extrudate can be placed in the barrel of the orifice extruder, compressed under different loads and removed to determine its cohesivity or extent of cohesion, its stickiness and its ability to recover its hardness after it has been sheared at the extrusion temperature (e.g., 4O 0 C) and cooled (e.g., 25 0 C).
  • the extrusion temperature e.g., 4O 0 C
  • cooled e.g., 25 0 C
  • melt and pour compositions such as those used to make glycerin soaps that require casting in molds in order to form bars are not extrudable masses when they are initially formed from the melt and are not suitable.
  • melt and pour compositions such as those used to make glycerin soaps that require casting in molds in order to form bars are not extrudable masses when they are initially formed from the melt and are not suitable.
  • the bar mass should also be sufficiently hard to be stamped with conventional soap making dies.
  • the stamping process involves placing a billet or ingot of the extruded mass into a split mold comprised of generally two moveable halves (the dies). These dies when closed compress the billet ("stamp" the billet), squeezing out excess mass and defining the ultimate shape of the bar.
  • the mold halves meet at a parting line which becomes visible as a line on the edge perimeter of the molded finished bar (stamped bar).
  • a stamped personal washing bar can be characterized as comprising top and bottom stamped faces meeting at a parting line.
  • stamping can be achieved by ensuring that an extruded billet of the bar mass (also known as an ingot) has a minimum hardness of at least about 3.0 Kg at the stamping temperature which is typically in the range 25° to 45 0 C.
  • a variety of methods are known in the art to measure the hardness and yield stress of soft solids such as toilet soaps.
  • the techniques used in the current work is the Penetration Test which measures the penetration of a needle or tapered rod under load. The distance traveled (penetration of the needle into the test mass) under a constant load or the load required to produce a given distance of penetration can be measured. In the test method used in the present work, the latter measurement approach is employed, i.e., variable load to achieve fixed penetration depth.
  • Hardness penetration measurements were made using finished toilet soap bars using the TA-XT Plus Texture Analyzer supplier by Stable Micro Systems.
  • the rheological parameters of the finished bars were determined by measuring the weight necessary for the test probe to penetrate the sample to a distance of 15 mm (see table below).
  • the 30° conical test probe is made from X2 stainless steel and the dimensions are: Length, 60.4 mm; Diameter 30 mm.
  • the instrument parameters used in hardness analyses with TA-XT Express are given in the table below
  • the TA-XT Plus Texture Analyser allows for various preset probe speeds.
  • the rheological parameters other then hardness were carried out at various speeds (minimum 10), ranging from 0.01 to 10 mm/sec and the forces measured accordingly. Shear stresses and shear rates were calculated and rheological charts were built. The rheological parameters were finally calculated by least-squares utilizing the Herschel-Bulkley equation:
  • ⁇ is the shear stress
  • ⁇ o is the yield stress
  • k stands for the consistency index
  • n is the flow index
  • ⁇ is the shear rate
  • Soap bar compositions suitable for the present invention should have a yield stress and penetrometer hardness (or simply "hardness") which falls within the following ranges:
  • Hardness from 3 to 8 Kg when measured at a temperature of 4O 0 C, preferably from 4.5 Kg to 6.5 Kg
  • thermoplastic soap composition not only depend upon the soap composition (e.g., oleics to laurics ratio), the structuring system and water content but also upon the optional ingredients that are included in the bar composition.
  • the soap composition e.g., oleics to laurics ratio
  • optional ingredients that are included in the bar composition.
  • inclusion of excessive amounts of low melting point emollients, e.g., mineral oil and/or liquid nonionic surfactants can lead to excessive softening of the bar composition at temperatures within the extrusion process window.
  • electrolyte(s) or particulate material can produce a mass which is highly brittle and non-cohesive.
  • Measurements of yield stress and hardness provide a means for determining whether particular optional ingredients at the levels contemplated can be included in the bar composition without excessively compromising the extrusion and stamping rates of the composition.
  • optional ingredients can be incorporated in the continuous phase composition provided that the mass has a penetrometer hardness of 3 to 8 Kg and a yield stress of 350 to 2000 kPa measured at a temperature of between 35 and 45, preferably around 4O 0 C.
  • the wear rate of the bar was measured by the following procedure. Four weighed samples of each test bar are placed on soap trays. Two types of soap trays are employed: those that have drainers or raised grids so the water left on the bar after rinsing is drained away; and no drainers so that water can be added to the tray to allow the bars to become "water-logged".
  • the trays are coded as follows:
  • each soap tray with drainer is rinsed and dried. Soap trays without drainers are refilled with 10 ml distilled water (ambient temperature). After the last washdown (4 th day), all soap trays are rinsed and dried. Each washed bar is placed in its tray and allowed to dry for up to a period of 9 days. On the 5 th day afternoon, the samples are turned so that both sides of the tablet dry. On the 8 th day, each tablet is weighed.
  • the rate of wear is defined as the percent weight loss as follows:
  • Mush is a paste or gel of soap and water, formed when soap is left in contact with water as in a soap-dish. Soluble components of the soap move into solution, and water is absorbed into the remaining solid soap causing swelling, and for most soaps, also recrystallization. The nature of the mush depends on the balance of these solution and absorption actions. The presence of a high level of mush is undesirable not only because it imparts an unpleasant feel and appearance to the soap, but also especially because the mush may separate from the bar and leaves a mess on the wash basin. Residual mush or soap residue is a known consumer negative.
  • the Mush Immersion Test described herein gives a numerical value for the amount of mush formed on a bar.
  • the test is carried out as follows: A rectangular billet from the soap tablet is cut to the required dimensions using a plane, knife or cutting jig. The width and depth of the cut billet are accurately measured (+/- 0.1 cm). A line is drawn across the billet 5 cm from the bottom of the billet. This line represents the immersion depth.
  • the billet is attached to a sample holder and suspend in an empty beaker.
  • Demineralised (or distilled) water at 20 0 C is added to the beaker until the water level reaches the 5 cm mark on the billet.
  • the beaker is placed in a water bath at 20 0 C (+/- 0.5°C) and left for exactly 2 hours.
  • the soap-holder + billet is removed, the water emptied from the beaker, and the soap-holder + billet is replaced on the beaker for 1 minute so that excess water can drain off. Extraneous water is shaken off, the billet is removed from the soap- holder, and the weight of the billet standing it on its dry end is recorded (W M ).
  • the quantitative amount of mush is calculated as follows:
  • Mush( g l5Qcm 2 ) ⁇ W -W Lx 50
  • A is the surface area:
  • the potential of bars to crack in use is assessed by washing the bars in a controlled manner 6 times per day for 4 days, storing the bars between washes under different conditions to simulate different consumer habits and then allowing the bars to dry for different periods of time to induce cracking.
  • the procedure is as follows: Four weighed of each test bar are placed on soap trays in an identical arrangement as described above in the Wear Rate Test. 10 ml of distilled water (ambient temperature) are poured into the undrained tray (25° and 40 0 C).
  • a subjective assessment of the degree of cracking is carried out on each bar. Some cracking may occur during the first 5 days of the test, but for maximum sensitivity and realism it is best to assess the cracking after drying out (i.e. on the 8th or 9th day).
  • a trained assessor examines the tablets and records separately the degree of cracking in each of the following areas: Both faces - all types of tablets; both ends - band-type tablets; both sides - band-type tablets periphery - capacity die tablets
  • the degree of cracking is graded using the following 0-5 scale:
  • compositions used to prepare the personal washing bars of examples Ex 1 - Ex 3 are set forth in Table 5 and contain about 33-43% soap (about 30-40% TFM).
  • Ex1 and Ex2 include starch (native corn starch) as the polysaccharide while Ex3 is based on cellulose (microcrystalline).
  • the continuous phase compositions and bars were prepared at pilot plant scale using conventional equipment used in the manufacture of extruded soap. In summary, the compositions were prepared by combining soap noodles with the remaining ingredients in Table 5 in a Z-blade mixer and passing the mixture through a 3-roll mill and a refiner.
  • compositions of the soap noodles are given in the second row of the table and were composed of a mixture of fatty acids derived from palm kernel oil (PKO - laurics-rich soap) and a mixture derived from of palm oil (PO) and palm stearin (POS), sources of stearics-rich and oleics soaps, using the weight ratios set forth in the table.
  • the compositions so processed were added to the hopper of a two stage extruder and extruded at a temperature of 35 0 C to 45 0 C at an extrusion rate of 1.2 - 4.0 Kg/min through an eyeplate having a 3.5 x 3.5 cm cross section to form billets that were cut to about 12 cm in lengths.
  • the billets were then transferred to a manual soap stamper and stamped to form the finished personal washing bar utilizing a die set defining a mold having a volume of approximately 79 to 80 cm 3 .
  • the polyol used in these examples was glycerin and no insoluble particulate material was used in the structuring system.
  • the second column from the left under physical properties provides the "ideal range" for these properties to achieve a bar that combines excellent manufacturability (high throughput extrusion and stamping on a commercial scale) and highly acceptable overall in-use properties.
  • compositions have both a ratio of Oleics soap to Laurics soap, R 0 L and a starch (or cellulose) to polyol ratio, R S p which are within the limits required by Eq (1 ) and (2) at the soap level employed in each composition subject to the error limits at the boundary values as described above.
  • the compositions not only exhibit hardness and yield stress that allows high throughput manufacture (e.g., 36 Kg per minute) but also provides excellent in-use properties as judged from acceptably low values of bar cracking, wear rate and mush. Table 5. Soap compositions of Examples 1-3 (TFM)
  • compositions used to prepare the personal washing bars of example Ex 4 and comparative examples C1 -C3 are shown in Table 6 and contain about 27% soap (25% TFM).
  • the bars were prepared according to the methods described in Examples 1 -3.
  • the organization and form of the Table 6 and the meanings of the various parameters are the same as described above in Examples 1 -3.
  • Ex 4 composition has both a Oleics soap to Laurics soap ratio and a starch to polyol ratio within the limits required by Eq 1 and 2 at this TFM level.
  • This composition not only provides a hardness and yield stress that allows high throughput manufacture (e.g. 36 Kg per minute) but also provides excellent in-use properties as judged from acceptably low values of bar cracking, wear rate and mush.
  • the comparative composition C1 to C3 which have either one or both of the critical ratios outside the required ranges, do not provide bars that either allow high throughput extrusion and/or have optimal in-use properties.
  • compositions of example Ex 5 and comparative examples C4-C6 are set forth in Table 7 and correspond to bars having 37.5% soap by weight (35% TFM). The bars were prepared according to the methods used to produce the bars of
  • Ex 5 The first point to note from Table 7 is that only the Ex 5 composition has both an Oleics soap to Laurics soap ratio (R 0 L.) and a starch to polyol ratio (Rps) within the limits required by Eqs 1 and 2 at the soap content employed.
  • This composition not only provides hardness and yield stress that allows high throughput manufacture (e.g. 36 Kg per minute) but also provides excellent in-use properties as judged from acceptably low values of bar cracking, wears rate and mush.
  • the comparative composition C4 to C6 which have either one or both of the ratios outside the optimal ranges, do not provide bars that either allow high throughput extrusion and/or have optimal in-use properties.
  • compositions of example Ex 6 and comparative examples C7-C9 are set forth in Table 8 and contain about 42% soap by weight (40% TFM).
  • the bars were prepared according to the methods used to produce the bars of Examples 1 -3.
  • the organization and form of the Table 8 and the meanings of the various parameters are the same as described above in Examples 1 -3.
  • the Ex 6 composition has both an Oleics soap to Laurics soap ratio (R OL ) and a starch to polyol ratio (Rps) within the limits required by Eqs 1 and 2 at the total soap content employed.
  • This composition not only provides hardness and yield stress that allows high throughput manufacture (e.g. 36 Kg per minute) but also provides excellent in-use properties as judged from acceptably low values of bar cracking, wears rate and mush.
  • the comparative composition C7 to C9 which have either one or both of the ratios outside the optimal ranges, do not provide bars that either allow high throughput extrusion and/or have optimal in-use properties.
  • compositions of example Ex 7 and comparative examples C10-C12 are set forth in Table 9 and contain about 22.5% soap by weight (20%TFM).
  • the bars were prepared according to the methods used to produce the bars of Examples 1 - 3.
  • the organization and form of the Table 9 and the meanings of the various parameters are the same as described above in Examples 1 -3.
  • the Ex 7 composition has both an Oleics soap to Laurics soap ratio (R OL ) and a starch to polyol ratio (Rsp) within the limits required by Eqs 1 and 2 at the soap content employed.
  • This composition not only provides hardness and yield stress that allows high throughput manufacture (e.g., 36 Kg per minute) but also provides acceptably low values of bar cracking, wears rate and mush.
  • the comparative composition C10 to C12 which have either one or both of the ratios outside the optimal ranges, do not provide bars that either allow high throughput extrusion and/or have optimal in-use properties.
  • compositions of example Ex 8 and comparative examples C13-C15 are set forth in Table 10 and contain about 32 % soap by weight (30%TFM).
  • the bars were prepared according to the methods used to produce the bars of Examples 1 - 3.
  • the organization and form of the Table 10 and the meanings of the various parameters are the same as described above in Examples 1 -3.
  • the Ex 8 composition has both an Oleics soap to Laurics soap ratio (R OL ) and a starch to polyol ratio (Rps) within the limits required by Eqs 1 and 2 at the soap content employed.
  • This composition not only provides a hardness and yield stress that allows high throughput manufacture (e.g. 36 Kg per minute) but also provides acceptably low values of bar cracking, wear rate and mush.
  • the comparative composition C13 to C15 which have either one or both of the ratios outside the optimal ranges, do not provide bars that either allow high throughput extrusion and/or have optimal in-use properties.
  • compositions of Examples Ex 9-11 and comparative examples C16-C18 are set forth in Table 11.
  • the bar compositions have 20% to 30% TFM.
  • the bars were prepared according to the methods used to produce the bars of Ex 1 and C1 -C3.
  • the organization and form of the Table 11 and the meanings of the various parameters are the same as described above in Examples 1 -3.
  • the Ex 9-11 composition have both an Oleics soap to Laurics soap ratio (R OL ) and a starch to polyol ratio (Rps) within the limits required by Eqs 1 and 2 at the soap content employed.
  • R OL Oleics soap to Laurics soap ratio
  • Rps starch to polyol ratio
  • the comparative composition C16 to C18 had a starch/polyol ratio that was above the maximum range, i.e., they contained too much starch relative to the polyol component. Although the bars could be extruded they were too hard and brittle (above the ideal hardness limit of about 8). All of these bars exhibited to high a level of cracking, rate of wear and mush generation.
  • compositions of example Ex 12 and comparative examples C19-C20 are set forth in Table 12.
  • the polysaccharide in this case is microcrystalline cellulose.
  • the bar compositions have about 30% TFM.
  • the bars were prepared according to the methods used to produce the bars of Ex 1 and C1 -C3.
  • the organization and form of the Table 11 and the meanings of the various parameters are the same as described above in Examples 1 -3.
  • the Ex 12 composition has both an Oleics soap to Laurics soap ratio (R OL ) and a polysaccharide to polyol ratio (Rsp) within the limits required by Eqs 1 and 2 at the soap content employed.
  • This composition provides bars having the hardness and yield stress in the desired range for high speed extrusion and also provides bars that were acceptable in terms of cracking, wear rate and mush generation.
  • the comparative composition C19 and C20 had either an R 0 L or an Rsp ratio that was outside the preferred ranges. Although the bars could be extruded they were too soft for high throughput extrusion. All of these bars exhibited to high a rate of wear and mush generation.
  • Especially preferred personal washing bars are extruded bar consisting essentially of the ingredients listed in Table 13 with the constraints that: i) the sum of the ingredients can not exceed 100% so that all or some of the individual ingredients can not be simultaneously present at their maximum levels; ii) the ratio of oleic soaps to lauric soaps satisfies Eq 1 within the error limits of about 15% and iii) the composition is an extrudable mass having a penetrometer hardness of 3 to 8 Kg and a yield stress of 350 to 2000 kPa measured at a temperature of 40°; and iv) the finished bars have physical properties close to the ideal values as set forth in preceding tables (e.g. Table 5).
  • the term "essentially” is used to encompass ingredients that can be included to confer benefits to soap bars provided the ingredients are safe for routine contact with skin and do not cause the composition to exhibit physical properties outside the boundaries set forth under item iii) and iv) above which insure high speed manufacturing and acceptable in-use properties.

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Abstract

L'invention porte sur un pain de lavage personnel extrudé à faible teneur en TFM ayant une phase continue comprenant : a. de 20 % à moins de 45 % de savon à base d'acides gras, le savon à base d'acides gras comprenant au moins 30 % de savon à base d'acides gras saturés par rapport au poids total du savon et le savon à base d'acides gras ayant un rapport ROL, défini comme étant le poids total des savons à base d'acides gras oléiques divisé par le poids total des savons à base d'acides gras lauriques, qui satisfait à Eq (1) : ROL ≤ (-0,00063(TS2) + 0,297(TS) – 1,95) ± 15 % (1) où TS est le pourcentage en poids de savon à base d'acides gras dans la composition ; b. un système structurant comprenant : i) de 10 % à 40 % en poids d'une phase continue constituée d'un structurant polysaccharide choisi dans le groupe constitué par l'amidon, la cellulose et un mélange de ceux-ci, ii) de 8,0 % à 30 % en poids d'une phase continue constituée d'un polyol choisi dans le groupe constitué par le glycérol, le sorbitol et leurs mélanges et iii) de 0 à 15 % en poids d'une phase continue constituée d'une matière particulaire insoluble dans l'eau, le rapport du poids du structurant polysaccharide sur le poids du polyol, appelé Rsp, se trouvant dans la plage de 0,3 à 5,0 et la phase continue étant une masse apte à l'extrusion ayant une dureté mesurée par pénétromètre de 3 à 8 Kg et une limite apparente d'élasticité de 350 à 2000 kPa mesurée à une température de 40 °C.
PCT/EP2010/051155 2009-02-09 2010-02-01 Pains de savon extrudés à faible teneur en tmf comprenant un système structurant polysaccharide-polyol WO2010089269A1 (fr)

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CN201080016085.2A CN102388125B (zh) 2009-02-09 2010-02-01 包含多糖-多元醇结构化体系的低tmf挤出皂条
BRPI1005438A BRPI1005438B8 (pt) 2009-02-09 2010-02-01 barra de limpeza pessoal extrudada de baixa matéria graxa total (tfm)
ZA2011/05527A ZA201105527B (en) 2009-02-09 2011-07-27 Low tmf extruded soap bars comprising polysacharide-polyol structuring system

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GBGB0901953.0A GB0901953D0 (en) 2009-02-09 2009-02-09 Low TMF extruded soap bars comprising polysacharide-polyol structuring system

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Cited By (9)

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US7981852B2 (en) 2009-12-16 2011-07-19 Conopco, Inc. Method of enhancing perfume retention during storage using low total fatty matter extruded bars having starch polyol structuring system
US7989410B2 (en) 2009-12-16 2011-08-02 Conopco, Inc. Method of enhancing perfume bloom in extruded diluted bars having low total fatty matter and using starch polyol structuring system
DE102012019981A1 (de) * 2012-10-11 2014-04-17 Sheng-Chun Technology Co., Ltd. Detergentienzusammensetzung
GB2562510A (en) * 2017-05-17 2018-11-21 Reckitt Benckiser Llc Composition
EP3074498B1 (fr) 2013-11-25 2019-04-17 Unilever Plc. Formulations de pains de savon améliorant la douceur de la peau comprenant un système de structuration de polymère non ionique
US10758750B2 (en) 2015-07-29 2020-09-01 Conopco, Inc. Cleansing composition with improved availability of benefit agent
US11352594B2 (en) 2019-02-19 2022-06-07 Conopco, Inc. Extruded soap bar with high water content
EP3927804B1 (fr) * 2019-02-19 2022-06-22 Unilever IP Holdings B.V. Barres dures à teneur en eau élevée comprenant une combinaison de type et de quantité d'électrolytes
WO2022258605A1 (fr) 2021-06-10 2022-12-15 Unilever Ip Holdings B.V. Barres de savon en gel de silice à teneur élevée en agent d'humidité et leur procédé de préparation

Families Citing this family (3)

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Publication number Priority date Publication date Assignee Title
CN104327974A (zh) * 2014-11-15 2015-02-04 柳州市康小乐牛奶有限公司 一种马奶护肤香皂
DE102020102483A1 (de) * 2020-01-31 2021-08-05 Kennametal Inc. Verdampferschiffchen
CA3167306A1 (fr) * 2020-02-20 2021-08-26 Unilever Global Ip Limited Composition de savon

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US5264144A (en) 1991-05-30 1993-11-23 The Procter & Gamble Company Freezer personal cleansing bar with selected fatty acid soaps for improved mildness and good lather
US20070155639A1 (en) * 2005-06-18 2007-07-05 Salvador Charlie R Cleansing bar compositions comprising a high level of water
US20090005290A1 (en) * 2007-06-26 2009-01-01 Conopco, Inc., D/B/A Unilever Extruded Personal Washing Bars With Plate-Like Inclusions

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CN101198687A (zh) * 2005-06-18 2008-06-11 宝洁公司 包含高含水量的清洁条皂组合物

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Publication number Priority date Publication date Assignee Title
US5264144A (en) 1991-05-30 1993-11-23 The Procter & Gamble Company Freezer personal cleansing bar with selected fatty acid soaps for improved mildness and good lather
US20070155639A1 (en) * 2005-06-18 2007-07-05 Salvador Charlie R Cleansing bar compositions comprising a high level of water
US20090005290A1 (en) * 2007-06-26 2009-01-01 Conopco, Inc., D/B/A Unilever Extruded Personal Washing Bars With Plate-Like Inclusions

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7981852B2 (en) 2009-12-16 2011-07-19 Conopco, Inc. Method of enhancing perfume retention during storage using low total fatty matter extruded bars having starch polyol structuring system
US7989410B2 (en) 2009-12-16 2011-08-02 Conopco, Inc. Method of enhancing perfume bloom in extruded diluted bars having low total fatty matter and using starch polyol structuring system
DE102012019981A1 (de) * 2012-10-11 2014-04-17 Sheng-Chun Technology Co., Ltd. Detergentienzusammensetzung
EP3074498B1 (fr) 2013-11-25 2019-04-17 Unilever Plc. Formulations de pains de savon améliorant la douceur de la peau comprenant un système de structuration de polymère non ionique
US10758750B2 (en) 2015-07-29 2020-09-01 Conopco, Inc. Cleansing composition with improved availability of benefit agent
GB2562510A (en) * 2017-05-17 2018-11-21 Reckitt Benckiser Llc Composition
US11352594B2 (en) 2019-02-19 2022-06-07 Conopco, Inc. Extruded soap bar with high water content
EP3927804B1 (fr) * 2019-02-19 2022-06-22 Unilever IP Holdings B.V. Barres dures à teneur en eau élevée comprenant une combinaison de type et de quantité d'électrolytes
US11473038B2 (en) 2019-02-19 2022-10-18 Conopco, Inc. High water hard bars comprising combination of type and amount of electrolytes
WO2022258605A1 (fr) 2021-06-10 2022-12-15 Unilever Ip Holdings B.V. Barres de savon en gel de silice à teneur élevée en agent d'humidité et leur procédé de préparation

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CN102388125B (zh) 2014-06-11
SA110310104B1 (ar) 2015-04-29
BRPI1005438A2 (pt) 2020-08-18
TR201107813T2 (tr) 2012-06-21
GB0901953D0 (en) 2009-03-11
CO6410244A2 (es) 2012-03-30
AR075376A1 (es) 2011-03-30
BRPI1005438B1 (pt) 2021-04-27
CN102388125A (zh) 2012-03-21
ZA201105527B (en) 2012-10-31
BRPI1005438B8 (pt) 2021-06-29

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