FATTY ACID SOAP BARS PREPARED FROM OIL STOCK OF LOW IV COMPRISING POTASSIUM SOAP

Abstract

The present invention relates to predominantly (50% or greater) soap bars made from oil or oils of defined iodine value. Unexpectedly, it has been found that, when defined amounts of potassium soap are used, bars made from oils falling within the defined IV range have excellent extrusion rates (as defined by falling within defined hardness values) without exhibiting excessive cracking, while exhibiting wear and mush values associated with lower IV and surprising lather values not expected from bars made from lower IV oils. This is a unique and unexpected simultaneous accumulation of attributes. Further, unexpected perfume performance (e.g., bloom) is also found.

Claims

1. (canceled)

2. (canceled)

3. (canceled)

4. (canceled)

5. (canceled)

6. (canceled)

7. (canceled)

8. (canceled)

9. (canceled)

10. (canceled)

11. (canceled)

12. (canceled)

13. A method of forming a bar which method comprises the steps of: (a) selecting oil having an IV of from 0 to 37; (b) saponifying the oil with potassium to provide 5% to 15% by wt. of total bar potassium soap; and (c) extruding the soap of step (b) to form solid bar.

14. The method according to claim 13 wherein said bar hardness is within the range of 3.0 to 5.0 Kg when measured at 40 C. using 15 mm penetration.

15. The method according to claim 13, wherein the bar has a cracking value of 0 to 3.

16. The method according to claim 13, wherein the bar has wear and mush benefits associated with the use of starting oils having an IV of 0 to 37 and lather benefits associated with the use of starting oils having an IV of greater than 37.

17. The method according to claim 13, wherein the starting oil or oils is selected from the group consisting of tallow oil, coconut oil and mixtures thereof.

18. The method according to claim 13, wherein the fatty acid soap comprises 5 to 12% by wt. potassium soap based on wt. % of final composition and ratio of tallow to coconut is 78/22 to 82/18.

19. The method according to claim 13, wherein the starting oil or oils is selected from the group consisting of palm stearin oil (PSO), palm kernel oil (PKO) and mixtures thereof.

20. The method according to claim 13, wherein the fatty acid soap comprises 5 to 12% by wt. potassium soap based on overall wt. of bar composition and ratio of PSO to PKO is 78/22 to 82/18.

21. The method according to claim 13, wherein the fatty acid soap comprises 5 to 9% by wt. potassium soap based on wt. % of the bar composition and ratio tallow to coconut is 82/18 to 88/12.

22. The method according to claim 13 wherein the fatty acid soap comprises 8 to 12% by wt. potassium soap based on wt. % of the bar composition and ratio of tallow to coconut is 87/13 to 93/7.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0031] In FIG. 1 we see that saponification of oils having IV of 32 to produce bars having 7% or 10% potassium soap (Examples 5, 6, 8, 9, 11 and 12) resulted in bars with lather comparable or superior to the lather formed from bars produced from starting oils having IV 39 (Example A-C) and having no potassium soap (Examples 4, 7 and 10). Since bars with high unsaturates generally foam better than bars with high saturates (e.g., bars made from oils with starting IV 39 would be expected to foam better than those from oils with starting IV 32), this shows the truly unexpected nature of forming bars having 5 to 15% potassium soap when prepared from oil stock of low IV.

[0032] In FIGS. 2 and 3, it's possible to observe that, unexpectedly, the blend of oils with low unsaturates (e.g. bars with IV 32 or lower) generated potassium soap bars of our invention having lower rate of wear and lower mush. FIGS. 2 and 3 show that we can create bars with a hardness profile such as to have good high throughput production (e.g., falling within our defined hardness range and having acceptable cracking) even though bars are made from oils of IV 32 (Tables 1 and 2 in Examples); further, this is done while retaining the noted beneficial properties (good wear, low mush) associated with lower IV oils.

[0033] In other words, bars made from oils of this IV would normally have hardness value outside our defined desired level. According to our invention, we can reduce hardness (using specific amount of potassium soap) to ensure final bars have measured values which fall within our defined hardness window and have acceptable cracking, all while retaining lower wear and lower mush values associated with bars made from these oils of the lower IV.

[0034] FIG. 4 defines a cracking scale of 0 to 5 and accompanying photos showing cracks associated with defined numbers. It is noted the test is done following the rate of wear condition simulations defined in the protocol. Both are done directly following extrusion. As these tests simulate extremely heavy use and wear, which is activity most consumers may never match, cracking scores up to a level of 3 are considered acceptable for purpose of our invention.

DETAILED DESCRIPTION OF THE INVENTION

[0035] Except in the examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts of material or conditions of reaction, physical properties of materials and/or use are to be understood as modified by the word about.

[0036] As used throughout, ranges are used as shorthand for describing each and every value that is within the range. Any value within the range can be selected as terminus of the range.

[0037] The use of and/or indicates that any one from the list can be chosen individually, or any combination from the list can be chosen.

[0038] For the avoidance of doubt, the word comprising is intended to mean including but not necessarily consisting of or composed of. In other words, the listed steps or options need not be exhaustive.

[0039] Unless indicated otherwise, all percentages for amount or amounts of ingredients used are to be understood to be percentages by weight based on the weight of the material in the total weight of the composition, wherein total is 100%.

[0040] In one aspect, the invention relates to high (50 to 90%, preferably 55 to 85% by wt.) fatty acid soap bars wherein the level of soap with K+(potassium soap) is 5% up to about 15% by wt. final bar composition. At levels above 15%, the soap mass extruded is typically too soft. For example, at higher levels, potassium soap typically becomes extremely soluble. Depending on concentration, it can be liquid, paste or shaving cream/like.

[0041] Bars of the invention have hardness of 3 to 5 Kg when measured at 40 C. using 15 millimeter penetration and cracking values of 0 to 3.

[0042] Further, final bars preferably have water level of 13 to 25%, preferably 14 to 22%, more preferably 15 to 20%, even more preferably 16 to 18% by wt. of bar.

[0043] Preferably, the bar is extruded from soaps and the soaps are formed by saponification of starting oil or oils having an average iodine value of 0 to 37, preferably 2 to 37, preferably 10 to 35. Preferably IV is 25 to 35 and more preferably 30 to 35. At higher starting IV (e.g., 30-37) oils, the amount of potassium soap formed can be in the lower part of the range (5 to 9% potassium soap) and, in lower IV oils, the amount of potassium soap formed is generally in higher range (e.g., at IV 2-10, we can typically use 10-15% potassium soap). The exact amounts of potassium soap required, within range of 5 to 15%, can vary slightly depending on composition of the oil blend. Thus, for example, as previously noted, even if the IV is the same, if the ratio of tallow oil (or equivalent palm oil or palm stearine oil) to coconut oil (or equivalent palm kernel oil) is different (weight ratio of tallow to coconut 90/10 versus weight ratio of 80/20) level of potassium soap noodles in final bar may vary slightly. Thus a 90/10 ratio may result in slightly less plastic (more rigid) soaps on saponification and may require more potassium soap to be formed to obtain a plasticity of saponified soaps which, when extruded, will produce final bars of desired hardness range compared to the amount of potassium soaps required to bring bars made from 80/20 oils into the same preferred range. The exact amount of potassium soap (e.g., within the 5 to 15% range) can be readily determined by those skilled in the art by selecting a specific amount, extruding to form final bar, and measuring hardness of final bar (using hardness value test set forth in protocol). The results of this test can be used to calibrate and determine whether the amount of potassium soap produced should be slightly raised or lowered.

[0044] In general, the term soap is used to mean an alkali metal or alkanol ammonium salts of aliphatic, alkane-, or alkene monocarboxylic acids derived from natural triglycerides. Sodium, potassium, magnesium, mono-, di and tri-ethanol ammonium cations, or combinations thereof, are typical counterions of the carboxylic acid. The criticality of using specific amounts of potassium soaps made, and the resulting effects on processing or properties, such as those of our invention, is not previously known. In typical bars used in the art, sodium soaps are generally used and, as noted, while potassium, magnesium or triethanolamine soaps are used, the particular criticalities of our invention are not known. In general, the soaps are 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 having about 8 to about 22 carbon atoms.

[0045] Soaps having the fatty acid distribution of coconut oil may provide the lower end of the broad molecular weight range. The term coconut oil as used herein, refers to fatty acid mixtures having an approximate carbon chain length distribution of 8% 08, 7% C.sub.10, 48% C.sub.12, 17% C.sub.14, 8% C.sub.16, 2% C.sub.18, 7% oleic and 2% linoleic acids (the first six fatty acids listed being saturated). Other sources having similar carbon chain length distributions, such as palm kernel oil (PKO) and babassu kernel oil, can be used in place of or together with coconut oil.

[0046] Soap having fatty acid distribution of tallow may present the upper end of the broad molecular weight range. Tallow oils define fatty acid mixtures which have approximate carbon chain length distribution of 2.5% C.sub.14, 29% C.sub.16, 23% C.sub.18, 8% palmitoleic, 41.5% oleic and 3% linoleic (the first three fatty acids listed being saturated). Other oils with similar distributions can be used in place of or together with tallow. This may include oils derived from various animal tallows and lard. For purposes of this invention, this may also include oils such as palm oil (PO) or palm stearine oil (PSO).

[0047] 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. For purposes of the present invention these classifications are:

[0048] Laurics soaps which encompass soaps which are derived predominantly from C.sub.12 to C.sub.14 saturated fatty acid, i.e. lauric and myristic acid, but can contain minor amounts of soaps derived from shorter chain fatty acids, e.g., C.sub.10.

[0049] Stearics soaps which encompass soaps which are derived predominantly from C.sub.16 to C.sub.18 saturated fatty acid, i.e. palmitic and stearic acid but can contain minor level of saturated soaps derived from longer chain fatty acids, e.g., C.sub.20.

[0050] Oleics soaps which encompass soaps which are derived from unsaturated fatty acids including predominantly oleic acid (C.sub.18:1), linoeleic acid (C.sub.18:2), myristoleic acid (C.sub.14:1) and palmitoleic acid (C.sub.16:1) as well as minor amounts of longer and shorter chain unsaturated and polyunsaturated fatty acids.

[0051] Coconut oil employed for the soap may be substituted in whole or in part by other high-laurics 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, ouricuri oil, tucum oil, cohune nut oil, murumuru oil, jaboty kernel oil, khakan kernel oil, dika nut oil, and ucuhuba butter.

[0052] When a solid mass which includes a mixture of laurics, stearics and oleics soaps is heated, the laurics and oleics soaps, which are more water soluble and have lower melting points than stearics soaps, combine with water and other components present in the composition to form a more or less fluid liquid crystal phase depending on water content and temperature. This transformation of laurics and oleics soaps form a solid to a liquid crystal phase provides plasticity to the mass which allows it to be mixed and worked under shear, i.e. the mass is thermoplastic.

[0053] In order for typical soap bars to be extruded and stamped at high rate (at least 200 bars per minute), the IV of starting oils (making soap noodles) has typically been observed to be around 39. If IV is lower (e.g., 32), it has often been observed that the typical bar will have a hardness value above 5 Kg, a range above which ideal high throughout extrusion of soap noodles was not previously associated. At such hardness range, bars produced will typically have excessive cracking (cracking value of 4 or 5). As far as applicants are aware, the specific window of potassium soaps we have identified, and ability to reduce hardness of soaps so they process well (at high speed), while simultaneously not demonstrating excessive cracking, is not known.

[0054] As noted, level of fatty acid soap in the bar is 50% or greater, preferably 55% or greater (e.g., 65-90% by wt.).

[0055] Surfactants other than soap (commonly known as synthetic surfactants or syndets) 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.

[0056] The bar may include structurants. These may include one or more polysaccharide structurants selected from the group consisting of starch, cellulose and their mixtures; one or more polyols; and optionally, a water insoluble particulate material. Structurants may, individually or combined, support 0 to 25% by wt. of bar composition.

[0057] 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. By the term natural starch, also known as raw or native starch, is meant starch which has not been subjected to further chemical or physical modification apart from steps associated with separation and milling.

[0058] A preferred starch is natural or native starch (commonly also known as raw starch) from maize (corn), cassava, wheat, potato, rice and other natural sources. 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.

[0059] 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.

[0060] Suitable cellulose materials include microcrystalline cellulose, hydroxyalkyl alkylcellulose ether and mixture thereof.

[0061] A preferred cellulose material is microcrystalline cellulose (a highly crystalline particulate cellulose made primarily of crystalline aggregates) which is obtained by removing amorphous fibrous cellulose regions of a purified cellulose source material by hydrolytic degradation. This is typically done with a strong mineral acid (e.g., hydrogen chloride). The acid hydrolysis process produces microcrystalline cellulose of predominantly coarse particulate aggregates, typically of mean size range 10 to 40 microns. One 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.

[0062] A preferred polysaccharide structurant is starch, most preferably a natural starch (raw starch), a pre-gelatinized starch, a chemically modified starch or mixtures thereof. Raw starch is preferred.

[0063] 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.

[0064] Many types of 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 maltodextrin, and polymeric synthetic polyols such as polyalkylene glycols, for example polyoxyethylene glycol (PEG) and polyoxypropylene glycol (PPG).

[0065] 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.

[0066] Especially preferred polyols are glycerol, sorbitol and their mixtures.

[0067] Preferred inorganic particulate material includes talc and calcium carbonate. Talc is a magnesium silicate mineral material, with a sheet silicate structure represented by the chemical formula Mg.sub.3Si.sub.4 (O).sub.1O(OH).sub.2, and may be available in the hydrated form. Talc has a plate-like morphology, and is substantially oleophilic/hydrophobic.

[0068] 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.

[0069] Commercially, 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. In this process the crystal type of calcium carbonate is calcite or a mixture of calcite and aragonite.

[0070] Examples of other optional insoluble inorganic particulate materials include alumino silicates, aluminates, silicates, phosphates, insoluble sulfates, borates and clays (e.g., kaolin, china clay) and their combinations.

[0071] Organic particulate materials include: insoluble polysaccharides such as highly cross-linked 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.

[0072] The bars may comprise anti-cracking agents such as carboxymethylcellulose, acrylate polymers and their mixtures.

[0073] The bars comprise water at level of 10 to 25% by wt. Lower level of water may be 11 or 12 or 13% and upper level may be 24 or 22%.

[0074] In terms of possible optional ingredients, various additional electrolytes (in addition to the fatty acid soap and other charged surfactants which are electrolyte), especially those having alkali metal cations can be present in the bar. These electrolytes are present either as a result of saponification and neutralization of the fatty acids, e.g., NaCl generated from saponification with sodium hydroxide and neutralization with hydrochloric acid, or as added salts such as sodium or potassium sulfate which may be used to control hardness. Various electrolytes can be used in modest amounts as long as they are not strong detergent builders or otherwise interfere with the efficacy of the anti-cracking agents.

[0075] The level of electrolytes should be less than 2.0%, preferably less than 1.5%, preferably up to about 1.0%, preferably up to and including 0.8%, e.g., 0.1 to 0.8%. No extra electrolyte, other than sodium chloride (NaCl), is necessary for the formulation space in this case. In at least one form, no electrolyte, other than NaCl, is present in compositions of the invention.

[0076] 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.

[0077] The level of synthetic surfactant, individually or combined, 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 embodiment of the invention includes syndets at a level of about 2% to 10%, preferably about 4% to about 10%.

[0078] 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, individually or combined, at a level of 1% or less, preferably from 0.05 to 1% and more preferably from 0.05% to 0.5%.

[0079] 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 frictional drag on the skin). Although some consumers do not mind this sensory quality, while others dislike the sensation. In general, consumers prefer bars that are 20 perceived to glide easily over their skin and are perceived as being slippery.

[0080] It has been found that certain hydrophobic materials incorporated at low levels can dramatically reduce the wet skin frictional drag of bars containing higher levels of starch and/or insoluble particles to improve consumer acceptability.

[0081] Suitable slip modifier include petrolatum, waxes, lanolines, poly-alkane, -alkene, -polyalkalyene oxides, high molecular weight polyethylene oxide resins, silicones, polyethylene glycols and mixtures thereof.

[0082] Particularly suitable slip modifiers are high molecular weight polyethylene oxide homopolymer resins having molecular weights of from about 100,000 to about 7,000,000. The polymers have a degree of polymerization from about 2,000 to about 100,000. These polymers are available as white powders.

[0083] Preferably 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. Examples of suitable high molecular weight polyethylene oxide resins are water soluble resins supplied by Dow Chemical Company under the trade name POL VOX. An example is WSR N-301 (molecular weight 4,000,000 Daltons).

[0084] 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. Examples of adjuvants include but are not limited to: perfumes; opacifying agents such as fatty alcohols, ethoxylated fatty acids, solid esters, and Ti02; dyes and pigments; pearlizing agent such as Ti02 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 XL 1000), parabens, sorbic acid and the like; anti-oxidants such as, for example, butylated hydroxy toluene (BHT); chelating agents such as salts of ethylene diamine tetra acetic acid (EDTA) and trisodium etridronate (provided it is present at less than about 0.3%); emulsion stabilizers; auxiliary thickeners; buffering agents; and mixtures thereof.

[0085] The level of pearlizing agent, if present, 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.

[0086] 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.

[0087] Free fatty acids (FFA) up to 3% such as coconut fatty acid, PKO fatty acid, lauric acid are commonly used in soap bars for overall quality and process improvement. Free fatty acid higher than 3% will lead to soft and sticky mass and will negatively impact in bar quality. In at least one form, level of FFA in compositions of the invention is 0.05 to 3%, preferably 0.1 to 2%, more preferably 0.1 to 1.5% by wt.

[0088] 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; Impatiens balsamina, camu camu, Alpina leaf and other plant extracts such as witch-hazel, and mixtures thereof.

[0089] The composition can also include a variety of other active ingredients that provide additional skin (including scalp) benefits. Examples include anti-acne agents such as salicylic and resorcinol; sulfur-containing 0 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 agents such as terpolymers of vinylpyrrolidone, (meth)acrylic acid and a hydrophobic monomer comprised of long chain alkyl (meth)acrylates; anti-itch agents such as hydrocortisone, methdilizine and trimeprazine hair growth inhibition; 5-alpha reductase inhibitors; agents that enhance desquamation; anti-glycation agents; anti-dandruff agents such as zinc pyridinethione; hair growth promoters such as finasteride, minoxidil, vitamin D analogues and retinoic acid and mixtures thereof.

[0090] Regardless of the optional agent or agents employed, their level should be chosen such that the composition is an extrudable mass (penetrometer hardness of 3 to 5 Kg kPa measured at a temperature of 40 C.; preferably bars should have yield stress of 350 to 2000 kPa) and the bars derived from the composition conveniently have a Cracking Index of 3 or less. Cracking Index is based on a scale in which the degree of cracking can be visually observed (see FIG. 4) as described in the protocol. The yield stress referred to is the static yield stress. It is equivalent to extensional stress and is calculated, as set forth in the protocol section below, also using penetrometer device.

[0091] As mentioned, when starting oils are saponified, it is critical that 5 to 15% potassium soap be formed. The exact amount, within this range, is readily ascertainable by calibrating using the hardness value test. By ensuring correct window of production of potassium soap noodles (and more specifically, the correct range or amount within this window and which can be readily determined by those skilled in the art), this unexpectedly permits use of starting oil or oils having iodine value of 0 to 37, lower than would have been thought required in order to obtain bars having preferred hardness values as defined and without excessive cracking; further this is accomplished while retaining user benefits associated with the lower IV oils used. In addition, using lower IV oils we obtain lather comparable to use of high IV oils as well as unexpected enhancement in perfume performance. It is noted that a single and (rather than blend) can be theoretically used but blends are preferred. Also, oil of IV zero, for example, is not believed to exist in nature but distilled fractions can be prepared to obtain desired IV values.

[0092] The benefit agent bars of the invention further preferably comprise essential oils.

[0093] Essential oil is intended to encompass natural or synthetic fragrances, including natural oil synthetic perfumes. It may be a substance selected from perfume, terpene, terpenoid, various other essential oils (which may include antimicrobial essential oil or an active thereof, or a mixture thereof), or a synthetic compound having odoriferous properties, especially selected from aldehydes, esters, ketones, ionones, ethers and alcohols. If a perfuming substance, it can be a complex perfume composition containing a mixture of various terpenes, terpenoids, essential oils, synthetic odoriferous or more pure compounds. In solution, the weight percentage of said perfuming composition or substance may be between 1% to 10%, and especially from 3% to 10%, and being in particular approximately equal to 5% or approximately equal to 10% (wt. % of total bar).

[0094] Odoriferous means a detectable substance olfactively by a subject and/or by olfactormetry according to known principles of art. An exemplary method for the detection of an odoriferous substance is described in EP 0003088. Other detection techniques of an odoriferous substance are applicable as the chromatography techniques in a gas phase spectroscopy of Niasse or yet infrared absorption analysis.

[0095] By terpenes is meant hydrocarbons wherein the base member is isoprene, their molecular formula comprising a multiple number of carbons 5, particularly terpenes particularly containing 10 to 15 carbon atoms, used in perfumery.

[0096] By terpenoid means derivatives of terpenes, for example, alcohols, phenols, ketones, aldehydes, esters, ethers.

[0097] The following list of odoriferous compounds provided for illustrative purposes, is by no means exhaustive:

[0098] terpenes pirene, camphene, limonene, cadinene, hull, caryophyliene,

[0099] alcohols: linolool, geraniol, menthol, citronellol, ketones, menthione, carvone, beta-ionone, thujone, camphor, cyclopertadecanone

[0100] aldehyde: citral, citrannal, citronellal, cinnamic alkehyde, lilial,

[0101] esters: linalyl acetate, methyl acetate, getranyl acetate, geranyl succinates, phenols, thymol, carvacrol, eugenol, isoeugenol,

[0102] ethers: anthole, eucalyptol, cineol, rose oxide.

[0103] Essential oils can be oils of yiang-yiang, bergamot, Eucalyptus, lavender, lavender, lemongrass, patchouli, peppermint, pine, rose, coriander, Shiu, of sage, geranium, palmarosa, Litsea cubeba, lemon, lemongrass, orange blossom, grapefruit, lime, mandarin, tangerine, orange, cajeput, camphor, rosemary, d anise, star anise, fennel, basil, tarragon, clove, pepper, thyme, sassafras, wormwood, mugwort, cedar, hyssop. Tagetes of street, elemi, Galbanum, juniper berries, cabreuva, guaiac wood, sandalwood, vetiver, ambrette, Angelica, orris rhizome, carrot, celery, cumin, lovage, parsley, cinnamon, cardamom, ginger, nutmeg, pepper, frankincense, myrrh, balsam of Peru, Styrax, buchu, chamomile or cistus (Jean Garnero, Essential oils engineering techniques, physic-chemical constants Treaty, K-345).

[0104] Typical perfumery material which may form part of, or possibly the whole of, the active ingredient include natural essential oils such as lemon oil, mandarin oil, clove leaf oil, petitgrain oil, cedar wood oil, patchouli oil, lavandin oil, neroli oil, ylang oil, rose absolute or jasmine absolute, natural resins such as labdalium resin or olibanun resin; single perfumery chemicals which may be isolated from natural sources or manufactured synthetically, as for example alcohols such as geraniol, nerol, citronellol, linalool, tetrahydro-geraniol, betaphenylethyl alcohol, methyl phenyl carbinol, dimethyl benzyl carbinol, -menthol or cedrol; acetates and other esters derived from such alcohols; aldehydes such as citral, citronellal, -hydroxy-citronellal, lauric aldehyde, undecylenic-aldehyde, cinnamaldehyde, amyl cinnamic aldeyde, vanillin or heliotropin; acetals derived from such aldehydes; ketones such as methyl hexyl ketone, the ionones and the methylionones; phenolic compounds such as eugenol and isoeu-genol; synthetic musks such as musk xylene, musk ketone and ethylene brassylate; and other materials commonly employed in the art of perfumery. Typically at least five, and usually at least ten, of such materials will be present as components of the active ingredient.

[0105] Besides fragrance material, volatile insecticides, bacteriocides, pheronones and fabric softeners can also usefully be incorporated.

[0106] As noted, antimicrobial essential oils and actives thereof, or mixture may be used.

[0107] Such antimicrobial essential oils include, but are not limited to, those obtained from thyme, lemongrass, citrus, lemons, orange, anise, clove, aniseed, pine, cinnamon, geranium, roses, mint, lavender, citronella, Eucalyptus, peppermint, camphor, ajowan, sandalwood, rosmarin, vervain, fleagrass, lemongrass, ratanhiae, cedar and mixtures thereof. Preferred antimicrobial essential oils to be used herein are thyme oil, clove oil, cinnamon oil, geranium oil, Eucalyptus oil, peppermint oil, citronella oil, ajowan oil, mint oil or mixtures thereof.

[0108] Actives of essential oils which may be used herein include, but are not limited to, thymol (present for example in thyme, ajowan), eugenol (present for example in cinnamon and clove), menthol (present for example in mint), geraniol (present for example in geranium and rose, citronella), verbenone (present for example in vervain), eucalyptol and pinocarvone (present in Eucalyptus), cedrol (present for example in cedar), anethol (present for example in anise), carvacrol, hinokitiol, berberine, ferulic acid, cinnamic acid, methyl salicylic acid, methyl salycilate, terpineol, limonene and mixtures thereof. Preferred actives of essential oils to be used herein are thymol, eugenol, verbenone, eucalyptol, terpineol, cinnamic acid, methyl salicylic acid, limonene, geraniol or mixtures thereof.

[0109] Thymol may be commercially available for example from AldrichManheimer Inc, eugenol may be commercially available for example from Sigma, SystemsBioindustries (S81)Manheimer Inc.

[0110] Preferably, the antimicrobial essential oil or active thereof or mixture thereof is present in the composition at a level up to 20% by weight of the total composition, preferably at a level of at least 0.003% to 10%, more preferably from 0.006% to 10%, even more preferably from 0.01% to 8% and most preferably from 0.03% to 3%.

[0111] The soap bars which comprise essential oils have compositions such as those noted in the first aspect of the invention.

[0112] The bars of the invention, made from oils having IV 0-37 saponified to form 5 to 15% potassium soaps (in turn extruded to form the final bars), provide unexpected enhancement in headspace over the bar or over diluted bar relative to bar made in which starting oil has higher IV (for example 39) and no potassium soap is formed.

Protocol

1) Hardness

Hardness Testing Protocol

Principle

[0113] A 30 conical probe penetrates into a soap/syndet sample at a specified speed to a pre-determined depth. The resistance generated at the specific depth is recorded. There is no size or weight requirement of the tested sample except that the bar/billet be bigger than the penetration of the cone (15 mm) and have enough area. The recorded resistance number is also related to the yield stress and the stress can be calculated as noted below. The hardness (and/or calculated yield stress) can be measured by a variety of different penetrometer methods. In this invention, as noted above, we use probe which penetrates to depth of 15 mm.

Apparatus and Equipment

[0114] TA-XT Express (Stable Micro Systems)

[0115] 30 conical probePart #P/30c (Stable Micro Systems)

Sampling Technique

[0116] This test can be applied to billets from a plodder, finished bars, or small pieces of soap/syndet (noodles, pellets, or bits). In the case of billets, pieces of a suitable size (9 cm) for the TA-XT can be cut out from a larger sample. In the case of pellets or bits which are too small to be mounted in the TA-XT, the compression fixture is used to form several noodles into a single pastille large enough to be tested.

Procedure

Setting Up the TA-XT Express

[0117] These settings need to be inserted in the system only once. They are saved and loaded whenever the instrument is turned on again. This ensures settings are constant and that all experimental results are readily reproducible.

Set Test Method

[0118] Press MENU

[0119] Select TEST SETTINGS (Press 1)

[0120] Select TEST TPE (Press 1)

[0121] Choose option 1 (CYCLE TEST) and press OK

[0122] Press MENU

[0123] Select TEST SETTINGS (Press 1)

[0124] Select PARAMETERS (Press 2)

[0125] Select PRE TEST SPEED (Press 1)

[0126] Type 2 (mm s.sup.1) and press OK

[0127] Select TRIGGER FORCE (Press 2)

[0128] Type 5 (g) and Press OK

[0129] Select TEST SPEED (Press 3)

[0130] Type 1 (mm s.sup.1) and press OK

[0131] Select RETURN SPEED (Press 4)

[0132] Type 10 (mm s.sup.1) and press OK

[0133] Select DISTANCE (Press 5)

[0134] Type 15 (mm) for soap billets or 3 (mm) for soap pastilles and press OK

[0135] Select TIME (Press 6)

[0136] Type 1 (CYCLE)

Calibration

[0137] Screw the probe onto the probe carrier.

[0138] Press MENU

[0139] Select OPTIONS (Press 3)

[0140] Select CALIBRATE FORCE (Press 1)the instrument asks for the user to check whether the calibration platform is clear

[0141] Press OK to continue and wait until the instrument is ready.

[0142] Place the 2 kg calibration weight onto the calibration platform and press OK

[0143] Wait until the message calibration completed is displayed and remove the weight from the platform.

Sample Measurements

[0144] Place the cut billet after the extrusion (maximum 30 min) onto the test platform.

[0145] Place the probe close to the surface of the billet (without touching it) by pressing the UP or DOWN arrows.

Press RUN

[0146] Take the readings (g or kg) at the target distance (Fin).

[0147] After the run is performed, the probe returns to its original position.

[0148] Remove the sample from the platform and record its temperature.

Calculation & Expression of Results

Output

[0149] The output from this test is the readout of the TA-XT as force (R.sub.T) in g or kg at the target penetration distance, combined with the sample temperature measurement. (In the subject invention, the force is measured in Kg at 40 C. at 15 mm distance)

[0150] The force reading can be converted to extensional stress, according to Equation 2.

[0151] The equation to convert the TX-XT readout to extensional stress is

[00001]$=\frac{1}{C}.Math.\frac{R_T.Math.g_c}{A}$ [0152] where: =extensional stress [0153] C=constraint factor (1.5 for 30 cone) [0154] G.sub.c=acceleration of gravity [0155] A=projected area of cone=(d tan ).sup.2 [0156] d=penetration depth [0157] =cone angle

[0158] For a 30 cone at 15 mm penetration Equation 2 becomes

(Pa)=R.sub.T (g)128.8

[0159] This stress is equivalent to the static yield stress as measured by penetrometer.

[0160] The extension rate is

[00002]$\stackrel{.}{\mathrm{.Math.}}=\frac{V}{d.Math..Math.\tan \left(\frac{1}{2}.Math.\right)}$ [0161] where {acute over ()}=extension rate (s.sup.1) [0162] V=cone velocity [0163] For a 30 cone moving at 1 mm/s, {acute over ()}=0.249 s.sup.1

Temperature Correction

[0164] The hardness (yield stress) of skin cleansing bar formulations is temperature-sensitive. For meaningful comparisons, the reading at the target distance (R.sub.T) should be corrected to a standard reference temperature (normally 40 C.), according to the following equation:

R.sub.40=R.sub.Texp[(T40)] [0165] where R.sub.40=reading at the reference temperature (40 C.) [0166] R.sub.T=reading at the temperature T [0167] =coefficient for temperature correction [0168] T=temperature at which the sample was analyzed.

[0169] The correction can be applied to the extensional stress.

Raw and Processed Data

[0170] The final result is the temperature-corrected force or stress, but it is advisable to record the instrument reading and the sample temperature also.

2) Lather volume (FIG. 1)

Definitions

[0171] Lather volume is related to the amount of air that a given soap bar composition is capable of trapping when submitted to standard conditions.

Principle:

[0172] Lather is generated by trained technicians using a standardized method. The lather is collected and its volume measured.

Apparatus and Equipment:

[0173] Washing up bowl1 per operator capacity 10 liters

[0174] Soap drainer dishes1 per sample

[0175] Surgeons' rubber glovesBritish Standard BS 4005 or equivalent (see Note 14ii).

[0176] Range of sizes to fit all technicians

[0177] Tall cylindrical glass beaker400 mL, 25 mL graduated (Pyrex n 1000)

[0178] ThermometerMercury types are not approved

[0179] Glass rodSufficiently long to allow stirring in the glass beaker

Procedure:

Tablet Pre-Treatment:

[0180] Wearing the specified type of glove well washed in plain soap, wash down all test tablets at least 10 minutes before starting the test sequence. This is best done by twisting them about 20 times through 180 under running water.

[0181] Place about 5 liters of water at 30 C. of known hardness (hardness should be constant through a series of tests) in a bowl. Hardness can be measured, for example, in units of French degrees ( fH or f), which may also be defined as 10 mg/Liter of CaCO.sub.3, equivalent to 10 parts per million (ppm). Hardness may typically range from 5 to 60 fH. Tests of the subject invention were conducted at 18 fH. Change the water after each bar of soap has been tested.

[0182] Take up the tablet, dip it in the water and remove it. Twist the tablet 15 times, between the hands, through 180. Place the tablet on the soap dish (see Note).

[0183] The lather is generated by the soap remaining on the gloves.

[0184] Stage 1: Rub one hand over the other hand (two hands on same direction) 10 times in the same way (see Note).

[0185] Stage 2: Grip the right hand with the left, or vice versa, and force the lather to the tips of the fingers.

[0186] This operation is repeated five times.

[0187] Repeat Stages 1 and 2

[0188] Place the lather in the beaker.

[0189] Repeat the whole procedure of lather generation from paragraph iii, twice more, combining all the lather in the beaker.

[0190] Stir the combined lather gently to release large pockets of air. Read and record the volume.

Calculation & Expression of Results:

[0191] The data obtained consists of six results for each bar under test.

[0192] Data analysis is carried out by two way analysis of variance, followed by Turkey's Test.

Operators:

[0193] Experienced technicians should be able to repeat lather volumes to better than 10%. It is recommended that technicians be trained until they are capable of achieving reproducible results from a range of different formulation types.

Notes:

[0194] Water hardness, as noted above, should be constant for a series of tests and should be recorded. Where possible, it is preferable to adhere to suitable water hardness. For example, bars which will be used in soft water markets should ideally be tested with soft water (e.g., lower end of French hardness scale).

[0195] It is important to keep the number of rubs/twists constant.

3) Wear (FIG. 2) and Cracking (FIG. 4)

Definitions

[0196] The rate of wear (RoW) relates to the amount of material which is lost by a soap bar product under controlled conditions. These conditions for use, mimic approximately the way consumers use the product.

[0197] Cracking can be defined as the physical damage which may result (or not) from the sequence of washdown and drying of the bar, as per the protocol bellow.

Principle:

[0198] Soap tablets are washed down in a controlled manner, 6 times per day for 4 days. The tablets are stored in controlled conditions after each washdown, and the weight loss is determined after a further 2 or 3 days drying out.

[0199] Visual cracking assessments is made after 3 days of drying out under ambient conditions.

Apparatus and Equipment:

[0200]

TABLE-US-00001 Soap trays, with drainers preferably rigid plastic 1 sample per condition Soap trays, without drainers preferably rigid plastic area of approximately 15 10 cm flat bottom 1 sample per batch Washing bowl 10 liter capacity (approx.) Gloves waterproof, disposable gloves (plastic or rubber)

Procedure:

[0201] Start the test on first morning (e.g., a Monday).

[0202] Weigh 4 tablets of each of the batches to be tested and put them on soap trays that have been coded as follows:

TABLE-US-00002 Drainers? Wash temperature ( C.) Yes 25 Yes 40 No 25 No 40

[0203] Measure 10 mL of water (room temperature and appropriate hardness) and pour into the tray without drainers (25 and 40 C.).

[0204] Carry out washdowns on each tablet of soap as follows:

[0205] (a) Fill washing bowl with about 5 liters of water with appropriate hardness, and at the desired temperature (25 C. or 40 C.).

[0206] (b) Mark the tablet to identify top face (e.g. make small hole with a needle).

[0207] (c) Wearing waterproof gloves, immerse the tablet in the water, and twist 15 times (180 each time) in the hands above water.

[0208] (d) Repeat (c).

[0209] (e) Immerse the tablet in the water again in order to wash off the lather.

[0210] (f) Place the tablet back on its soap tray, ensuring that the opposite face is uppermost (i.e. the unmarked face).

[0211] Carry out the full washdown procedure 6 times per day for 4 consecutive days, at evenly spaced intervals during each day (e.g. hours in day: 8.00, 09:30, 11.00, 12.30, 14.00, and 15.30. Alternate the face placed down after each washdown.

[0212] Between washdowns the soap trays should be left on an open bench or draining board, at controlled room conditions. (See Note 14.1.iii) After each washdown cycle, change the position of each soap tray/tablet on the bench, to minimize variability in drying conditions. At the end of each day: [0213] rinse and dry each soap tray with drainer [0214] drain and refill the soap tray without drainer (25 C. and 40 C.) with 10 mL water (ambient temperature). Consider the appropriate water hardness.

[0215] After the last wash down (afternoon of fourth day, e.g., Thursday), rinse and dry all soap trays, and place each tablet on its soap tray.

[0216] On 5th day afternoon, turn the samples so they can dry both sides.

[0217] On the eighth day (e.g., following Monday), weigh each tablet

Cracking:

[0218] The visual assessment of the degree of cracking is carried out with the same samples used in the rate of wear test. Some cracking may occur during the first 5 days of the test, but for maximum level can be only observed after the final length of the test (i.e. on the 8th or 9th day).

Calculation & Expression of Results:

Rate of Wear:

[0219] Rate of wear is defined as the weight loss in grams or percentage. One shall bare in mind that the results are relative to the test conditions.

[00003]$\mathrm{Wear}.Math..Math.\left(\%\right)=\frac{\left(\mathrm{initial}.Math..Math.\mathrm{weight}-\mathrm{final}.Math..Math.\mathrm{weight}\right)*100}{\mathrm{Initial}.Math..Math.\mathrm{weight}}$$\mathrm{Wear}.Math..Math.\left(g\right)=\left(\mathrm{initial}.Math..Math.\mathrm{weight}-\mathrm{final}.Math..Math.\mathrm{weight}\right)$

[0220] A team of expert technicians must be able to attain less than 10% differences between duplicates.

Cracking

[0221] A trained assessor examines the tablets and records separately the degree of cracking in each of the following areas:

TABLE-US-00003 Both faces all types of tablets Both ends band-type tablets Both sides band-type tablets Periphery capacity die tablets

[0222] The degree of cracking is graded using the following 0-5 scale:

[0223] 0No cracking

[0224] 1Small and shallow cracking: [0225] 1.1minimum degree [0226] 1.2maximum degree

[0227] 2Small and medium deep cracking: [0228] 2.1minimum degree [0229] 2.2maximum degree

[0230] 3Medium and deep cracking: [0231] 3.1minimum degree [0232] 3.2maximum degree

[0233] 4Big and deep cracking: [0234] 4.1minimum degree [0235] 4.2maximum degree

[0236] 5Very big and very deep cracking: [0237] 5.1minimum degree [0238] 5.2maximum degree

[0239] 4) Objective Mush (FIG. 3)

Definitions

[0240] Mush is defined as the jelly, creamy material that forms when toilet soap bars absorbs water.

[0241] The Mush Immersion Test described here gives a numerical value for the amount of mush formed on a bar. The Mush by Immersion value does not distinguish between different types of mush; these aspects are assessed by the Subjective Mush Test.

Principle:

[0242] Soap tablets are cut down to give a rectangular block, which is immersed in demineralized water at 20 C. for 2 hours. The soap mush formed is scraped off and its weight determined.

Apparatus and Equipment:

[0243]

TABLE-US-00004 250-ml beakers 1 per sample Sample holders 1 per sample Water bath Thermostatically controlled at 20 C. + 0.5 C. Large enough to accommodate all beakers Tablet cutter size plane, knife or cutting jig designed to cut samples to predetermined Scraper preferably plastic (e.g. laboratory spatula) must have a straight corner

Procedure:

[0244] Cut a rectangular billet from the soap tablet to the required dimensions using a plane, knife or cutting jig.

[0245] Measure the width and depth of the cut billet accurately (0.1 cm).

[0246] Measure 5 cm from the bottom of the billet, and draw a line across the billet at this point. This is the immersion depth.

[0247] Attach the billet to the sample holder and suspend the billet in an empty beaker.

[0248] Add demineralized (or distilled) water at 20 C. to the beaker until the level reaches the 5 cm mark on the billet.

[0249] Place the beaker in a water bath at 20 C. (0.5 C.) and leave for exactly 2 hours.

[0250] Remove the soap-holder+billet, empty the water from the beaker, and replace the soap-holder+billet on the beaker for 1 minute so that excess water can drain off.

[0251] Shake off extraneous water, remove the billet from the soap-holder, and weigh the billet (WM), standing it on its dry end.

[0252] Carefully scrape off all the mush from all 5 faces of the billet, and remove any remaining traces of mush by wiping gently with a tissue.

[0253] Weigh the billet within 5 minutes of scraping (WR).

Calculation & Expression of Results:

[0254] Weight of mush (grams)

Surface area (cm.sup.2)=A=10 (width+thickness)+(widththickness)

[0255] NBthis equation presumes 5 cm immersion

[00004]$\mathrm{Mush}.Math..Math.\left(g.Math.\text{/}.Math.50.Math..Math.{\mathrm{cm}}^2\right)=\frac{\left(W_M-W_R\right).Math.50}{A}$$\mathrm{Lost}.Math..Math.\mathrm{mass}.Math..Math.\left(g.Math.\text{/}.Math.50.Math..Math.{\mathrm{cm}}^2\right)=\frac{\left(W_O-W_R\right).Math.50}{A}$$\mathrm{Absorbed}.Math..Math.\mathrm{water}.Math..Math.\left(g.Math.\text{/}.Math.50.Math..Math.{\mathrm{cm}}^2\right)=\frac{\left(W_M-W_O\right).Math.50}{A}$ [0256] initial weight (Wo) [0257] weight after mushing (WM) [0258] weight after removing mush (WR)

[0259] 5) Head Space

[0260] Fragrance performance was measured by evaluating three key fragrance attributes.

[0261] The first attribute is the concentration of fragrance in the static headspace above a neat samplesolid soap. This measurement evaluates the amount of fragrance that a consumer smells when they sniff the bar. It is referred to as the initial impact assessment. The soap bar was shaved to half of the total bar volume from one side, and the shaved bar flakes were mixed well before 2 grams were weighed into a 20 ml GC (gas chromatography) vial to ensure an even sampling of the outer and inner portion of the bar. The air above soap is allowed to come to equilibrium with the soap sample by leaving the sealed GC vial in room temperature for at least 24 hours. After equilibrium is achieved, the relative fragrance concentration in the air of the GC vial is measured by GC/MS (gas chromatography/mass spectrometer). Samples are made in triplicates.

[0262] The second attribute measured is the amount of fragrance in the static headspace above a diluted soap slurry. The fragrance concentration above the 30 times diluted soap correlates well with the fragrance intensity that a consumer experiences during a shower (blooming) when using the bar. For this measurement, soap was diluted 30 times with water. Again, 2 gram of the diluted soap is sealed in a 20 ml GC vial. The air above the diluted body wash is allowed to come to equilibrium with the soap dilution by leaving the sealed GC vial in room temperature for at least 24 hours. After equilibrium is achieved, the relative fragrance concentration in the air of the GC vial is measured by GC/MS (gas chromatography/Mass spec). Triplicate GC samples were made and measured for each diluted sample.

[0263] For measurement of both attributes, GC (e.g., column used was HP-5MS model number: Agilent 19091S-433) conditions were as follows: Injector was in splitless mode using helium as carrier gas. Injection port was heated to about 250 degrees centigrade, Pressure 12.01 psi, purge flow 8.1 mL/min at 1.0 minute, total flow 17.1 mL/min. Column was in constant flow mode with 1.3 ml/min flow rate. Oven temperature ramp: hold at 70 degrees centigrade for 2 minutes, then increase oven temperature at a rate of 3 degrees centigrade/min to 125 degrees centigrade, 15 degrees centigrade/min to 280 degrees centigrade and hold for 2 minutes. Fragrance samples were run in scan mode with mass range set at 35-300 amu. Hygiene actives were run using SIM mode targeting ions having m/z 59, 135, and 136. Autosampler's conditions were: No incubation (all experiments done in room temperature). SPME (solid phase micro-extraction) fiber was inserted into the sample headspace for a 5 minute extraction and then injected to the injector for a 15 minute desorption.

[0264] The third attribute is the amount of fragrance deposited on Vitroskin washed with soap. A 3 cm6 cm piece of Vitro Skin (N19 IMS inc.) is washed with 0.5 g of sample. Water temp is controlled at 95F and flow rate is controlled at 3-4 L/min. A watch glass (or other rigid, nonabsorbent, non porous substrate) is used as a base for washing the Vitro skin. The Vitroskin is held on the watch glass with the thumb rough side up. The Vitroskin is rinsed for 30 seconds prior to treatment and excess water is poured off of the Vitroskin. 0.5 g of sample is dosed onto wet skin, lathered with forefinger for 30 seconds (out of the stream of water), and rinsed for 15 seconds (making sure to rinse both sides of the Vitroskin in case any sample was trapped under the Vitroskin). Treated Vitroskin was then patted dry between the layers of a folded paper towel for 10 pats (hand held palm facing down so that both surfaces of the Vitroskin are dried), Samples were placed into GC vial immediately and allowed to equilibrate for 24 hours at room temperature. The Vitroskin can be rolled carefully with tweezers, using a forefinger to keep the Vitroskin from unrolling. The tighter the Vitroskin is rolled the easier it is to place in the vial. The vial is allowed to equilibrate for 24-48 hours. Additionally, an incubation step is included prior to SPME to increase volatiles in the headspace. The samples are incubated for 25 minutes at 45 C, then sampled as described in the previous method depending on the actives delivered.

Examples 1-3

[0265] In order to demonstrate the effect of potassium soap on high throughput processing, applicants first set forth Table 1 below.

TABLE-US-00005 TABLE 1 Fat Charge Example 1 (80/20) Example 2 (85/15) Example 3 (90/10) Sample 0% 7% 10% 0% 7% 10% 0% 7% 10% K Soap K Soap K Soap K Soap K Soap K Soap K Soap K Soap K Soap Total fatty matter, % 69.25 69.01 68.91 69.39 69.16 69.06 69.58 69.35 69.25 Saponification NaOH, % 100.00 93.00 90.00 100.00 93.00 90.00 100.00 93.00 90.00 KOH, % 7.00 10.00 7.00 10.00 7.00 10.00 Na Soap 75.13 69.64 67.29 75.29 69.79 67.44 75.49 69.79 67.44 K Soap 5.52 7.68 5.53 7.89 5.75 8.11 Glycerine 8.19 8.16 8.15 7.83 7.65 7.79 7.55 7.36 7.55 Other Ingredients Up to Up to Up to Up to Up to Up to Up to Up to Up to 20% 20% 20% 20% 20% 20% 20% 20% 20% IV 32.00 32.00 32.00 32.00 32.00 32.00 32.00 32.00 32.00 Oil Blend PO PSO 80 80 80 85 85 85 90 90 90 PKO 20 20 20 15 15 15 10 10 10 PO = palm oil (triglyceride blend within IV of 55) PSO = palm stearine oil (triglyceride blend within IV of 33 to 35) PKO = palm kernel oil (triglyceride blend within IV of 18)

[0266] For purposes of our invention, tallow could be used in place of PO and/or PSO; and coconut could be used in place of PKO.

[0267] In each of Examples 1-3, 0% potassium soap is used as a baseline value. Bars with some potassium soap (7% and 10%) potassium hydroxide used to make potassium soaps within ranges of the invention were also tested. The IV value remains constant within each example.

[0268] The effect of potassium soap substitution on bar hardness (and on ability to obtain desired hardness range) is shown in Table 2 below:

TABLE-US-00006 TABLE 2 80/20 85/15 90/10 IV (cg l.sub.2/g) 32 32 32 KOH (%) 0% 7% 10% 0% 7% 10% 0% 7% 10% NaOH (%) 100% 93% 90% 100% 93% 90% 100% 93% 90% Hardness (Kg @ 40 C.) 5.21 4.48 3.72 5.83 4.81 2.86 6.39 5.23 3.85

[0269] The 80/20, 80/15 and 90/10 figures refer to the composition of the oils as set forth at bottom of Table 1. This 80/20 refers to oil blend derived from 80% PSO (IV 33 to 35) and 20% PKO (IV of 18). That is, weight ratio is 80% PSO to 20% PKO.

[0270] As seen in Table 2, when 7 or 10% potassium hydroxide is added to various oil blends, hardness (as measured in final extruded bars) can be controlled in order to obtain desired value (e.g., 3 to 5 Kg measured at 40 C.). If potassium levels are too high, it can be seen that bars will become too soft (e.g., below 3 Kg). Because some blends are harder than others (e.g., 90/10 is harder than 80/20), the exact range or amount (within 5 to 15% potassium soap range of final bar) varies but can be readily determined by one skilled in the art as demonstrated from Table 2 (by varying amount of potassium hydroxide used to form soaps). Specifically, the hardness value is measured and used to calculate whether potassium hydroxide level (and resulting soap level) should be moved slightly up or down.

[0271] For example, at a uniform IV of 32, slightly different amounts of potassium hydroxide are needed depending on composition of oils (e.g. 80/20 versus 90/10. Thus, 90/10 oils typically will have longer chain oils than 80/20 and make the resultant bar slightly harder. As such, more potassium soap (as percent of final bar) is needed to bring 90/10 bar into preferred hardness range.

[0272] In preferred embodiments, the fatty acid soap (50% to 90% of bar) comprise 5 to 15% potassium soap, based in weight of the bar; and the soaps are formed from oil or oil blend which has average IV of 0 to 37, wherein said oil or oil blend is selected from the group consisting of palm oil (PO), palm stearine oil (PSO to PKO) and palm kernel oil (PKO). In one preferred embodiment, ratio of PSO to PKO is about 78/22 to 82/18.

[0273] In one preferred bar, potassium soap is at a level of 5 to 12% by wt. and ratio of oils used (e.g., PSO to PKO) to form soap is 78/22 to 82/18. In another preferred bar, level of potassium soap is 5 to 9% and ratio of tallow to coconut used to make the bar is 82/18 to 88/12. In another preferred bar, level of potassium soap is 8 to 12% by wt. and ratio of tallow to coconut (or PSO to PKO) is 87/13 to 93/7.

[0274] As seen in FIGS. 1, 2 and 3, the use of potassium soap enhances lather and does not affect rate of wear value or objective mush values. With improved lather, oils with lower IV can be used. Thus, we obtain bars which have long wear and have mush attributes associated with low IV starting oil and good lather correlated with high IV bars. As previously indicated, such bars extrude well (defined by hardness) but without excessive cracking,

[0275] In FIG. 1, for example, we used soaps made from oils having various chain length distribution (80/20, 85/15, 90/10), all having IV of 39 as control examples A, B, and C. Typically, compared to bars made from oils of lower IV but no potassium saponification (Ex. 4, 7, 10), lather was a bit lower. However, when saponified with 7 or 10% potassium ions, resulting bars (5-6 vs. A; 8-9 vs. B; 11-12 vs. C) all surprisingly showed lather far more comparable to the control bars made from oils of higher IV which would be expected to have far more lather.

[0276] A summary of the Examples shown in the FIG. 1 is seen in Table 3 below:

TABLE-US-00007 TABLE 3 Examples Fat Blend IV KOH Example A 80/20 39 0% Example 4 32 0% Example 5 32 7% Example 6 32 10% Example B 85/15 39 0% Example 7 32 0% Example 8 32 7% Example 9 32 10% Example C 90/10 39 0% Example 10 32 0% Example 11 32 7% Example 12 32 10%

[0277] Similar to FIG. 1, FIG. 2 shows that when same bars as shown in Table 3 are saponified with 7 or 10% potassium salt, the resulting bars (14-15 vs. D; 17-18 vs. E; 20-21 vs. F) showed lower/better results in the Rate of Wear test compared to the control bars made from oils of higher IV.

[0278] Again, similar to FIG. 1, FIG. 3 shows that when bars as shown in Table 3 are saponified with 7 or 10% potassium salt, the resulting bars (23-24 vs. G; 26-27 vs. H; 29-30 vs. I) showed lower/better results compared to the control bars made from oils of higher IV, with lower Objective mush values.

Example 31-38

[0279] In order to assess the performance of fragrance of bars of the invention, applicants prepared the following bars as set forth in Table 4 below.

TABLE-US-00008 TABLE 4 J 31 32 K 33 34 L 35 36 Soap 80/20 80/20 80/20 85/15 85/15 85/15 90/10 90/10 90/10 base IV 39 30 20 39 30 20 39 30 20 KOH, % 0 5.5 6.5 0 6.2 7.3 0 6.5 7.5 Fragrance 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 (Chiffon Petal), % HS over 12.1 13.4 17.2 12.3 15.1 17.2 14.5 17.5 18.5 bar 0.9 1.0 1.1 1.1 1.0 1.2 0.90 0.08 1.1 HS over 3.5 4.0 5.7 3.2 4.3 6.5 3.1 4.0 6.6 30 0.25 0.30 0.55 0.25 0.35 0.45 0.40 0.35 0.65 dilution HS over n/a n/a n/a n/a n/a n/a 1.35 1.60 2.4 vitro-skin 0.08 0.11 0.11

[0280] Bars 31, 32, 33, 34, 35, 36 were prepared as per invention wherein the IV values are 30 and 20 and the saponification (or neutralisation) was conducted with a mixture of sodium hydroxide and potassium hydroxide. Bars J, K, and L are comparative bars having IV value 39 and no potassium soap. As seen from the data above the bars of the invention show higher fragrance head space over bar, and over the 30 bar dilution, which implies greater bloom during the use. Applicant also measured the head space over vitro-skin washed with bars L, 35, and 36. One can see that bars 35 and 36 according to the invention deliver more fragrance to vitro-skin as compared to comparative (conventional) bar L.

[0281] In order to compare the performance of essential oils, in particular, used for anti-bacterial bars, applicants prepared bars with thymol and terpineol. Bars 37 and 38 are prepared according to the invention, and bar M is a comparative bar. One can see that the head space over 30 times diluted bars is significantly higher in bars with lower IV value according to the invention.

TABLE-US-00009 TABLE 5 M 37 38 Soap base 90/10 90/10 85/15 IV 39 32 32 KOH 0 7.0 7.0 Terpineol, % 0.25 0.25 0.25 Thymol, % 0.10 0.10 0.10 HS over 30x Terpineol 1.12 0.08 1.56 0.06 1.40 0.07 dilution, r.u. Thymol 0.23 0.03 0.43 0.03 0.34 0.03

Example 39

[0282] Applicants saponified bars of varying IV to determine the level of potassium hydroxide needed to achieve preferred hardness range. Oil blends used for all bars were 85/15 PSO/PKO. Results were set forth in Table 6 below:

TABLE-US-00010 TABLE 6 IV 5 10 15 20 25 30 KOH % 13.00 10.70 10.20 9.50 9.00 8.10 Hardness 4.70 4.38 3.80 4.74 4.53 4.06

[0283] As seen, using bars from starting 85/15 oils, bars of measured IV 5 to 30 achieved preferred hardness values at KOH level ranging from 8.10 to 13.00.