Short chain free bar compositions comprising c18:3 soap

Abstract

A cleansing bar composition comprises: 3 to 20% by weight of C18:3 soap, based on the total weight of the cleansing bar composition, preferably 6 to 15% by weight C18:3 soap, more preferably 10 to 15% by weight C18:3 soap, based on the total weight of the cleansing bar composition, wherein the cleansing bar composition comprises less than 0.5% by weight C8 to 5 C14 soap, based on the total weight of the cleansing bar composition.

Description

[0001] SHORT CHAIN FREE BAR COMPOSITIONS COMPRISING C18:3 SOAP

[0002] Field of the invention

[0003] Disclosed herein is a cleansing bar composition. The cleansing bar comprises a composition that includes C18:3 soap. The cleansing bar is extrudable. The cleansing bar has desirable lather while being essentially free from short chain soap.

[0004] Background of the invention

[0005] There is always a need to provide skin cleansing formulations having desirable cleansing efficacy without being harsh, without causing problems to the skin, and having the ability to deliver benefit agents such as moisturizers, antibacterial actives, etc.

[0006] The soap in cleansing bar compositions is generally known to serve several purposes. First, it helps structure the bars, so they do not crumble when the bar is being finished (e.g., extruded, stamped) and as a final user bar. Fatty acid soap also provides some beneficial user properties such as good lather and a certain skin feel which can be desirable to consumers. In addition, soap is generally cheaper than most anionic surfactants and can provide cost savings.

[0007] It was believed that short chain soaps (e.g., C8-C14) were necessary for desirable lather in soap bars. Accordingly, commercial soap bars comprise various levels of short chain soap (e.g., 08- C14) soap made from either palm kernel or coconut oils that contain short chain triglycerides, or from fatty acids derived from these oils.

[0008] Short chain free bars have been disclosed in International Application No. WO 2021 / 164994. These bars comprise 018:2 soap and 018:1 soap, wherein a weight ratio of 018:2 soap to 018:1 soap in the composition must be higher than 0.7. Such a composition, although being free of short chain soap, provides bars that have good lather and can be made by a rapid extrusion process. To achieve the specific ratio of 018:2 to 018:1 , i.e., greater than 0.7, soap bars disclosed in International Application No. WO 2021 / 164994 are made from unconventional oils such as soya bean oil ( 018:2 / 018:1=2.4) and hydrogenated soya bean oils or a judicious mixture of these oils with conventional palm and palm stearin oils (018:2 / 018:1=0.24) or fatty acids derived from these oils. International Application No. WO 2021 / 164994 discloses that soap may also be prepared from other unconventional oil sources like corn, rice bran, cottonseed, and safflower oil. U.S. Patent No. 5,874,392 discloses a multipurpose soap bar that can be used for cleaning the human body and shampooing and conditioning the hair. The bar disclosed therein contains at least 11 % by volume C8 to C14 soap.

[0009] It would be greatly desirable to find other oils than those currently disclosed, which could be used in cleansing bar compositions that can be substantially short chain free, short chain free, or have a reduced amount of short chains to provide cleansing bars having a combination of good lather and good processability on high-speed extrusion and stamping soap manufacturing lines. It would also be desirable to find a cleansing bar composition that can be substantially short chain free, short chain free, or have a reduced amount of short chains to provide cleansing bars that would not have the constraint of the ratio C18:2 / C18:1 being greater than 0.7 and would allow for a greater use of conventional oils such as palm oil, which has the ratio C18:2 / C18:1 equal to 0.24.

[0010] As such, there is continually a need for cleansing bar compositions that can produce cleansing bars with lower soap content without a corresponding loss in desired cleansing bar properties, such as lather.

[0011] Summary of the invention

[0012] Disclosed in various aspects are cleansing bars and compositions thereof.

[0013] A cleansing bar composition comprises 3 to 20% by weight of C18:3 soap, based on the total weight of the cleansing bar composition, preferably 6 to 15% by weight of C18:3 soap, more preferably 10 to 15% by weight of C18:3 soap, based on the total weight of the cleansing bar composition, wherein the cleansing bar composition comprises less than 0.5% by weight C8 to C14 soap, based on the total weight of the cleansing bar composition.

[0014] These and other features and characteristics are more particularly described below.

[0015] Detailed description of the invention

[0016] Disclosed herein is a cleansing bar composition that include desirable lather despite containing substantially no or no short chain soap. Short chain as referred to herein generally refers to C8 to C14. “Substantially no”, “substantially free”, or “essentially free” as referred to herein means less than 0.5% by weight, and preferably, less than 0.3% by weight, and most preferably, less than 0.15% by weight or less than 0.1 % or 0.05% or 0.04 to 0.01% or 0.0% (none) by weight based on total weight of the cleansing bar composition. For example, substantially no, substantially free, or essentially free can refer to 0.00 to 0.5% by weight of the overall composition, for example, 0.0001 to 0.5% by weight, for example, 0.005 to 0.5% by weight, for example, 0.001 to 0.1 % by weight. The cleansing bar can be made by extrusion and stamping. It can be desirable to eliminate or reduce short chain soap in bars without compromising lather, because reduction of short chain soap can lead to enhanced bar mildness to the skin, improved deposition of skin benefit actives, and longer lasting fragrance benefits. Natural sources of these short chain feedstocks include coconut oil and palm kernel oil. Demand for these oils continues to rise as they are ubiquitous not just in bars, but in many personal care products such as body wash and shampoos. Accordingly, a cleansing bar with essentially no, no, or reduced short chain soap can be attractive from the sustainability point of view since it would alleviate some dependence on these highly sought after materials.

[0017] It was unexpectedly found that use of the compositions disclosed herein comprising 3 to 20% by weight of the cleansing bar composition of C18:3 soap, for example, 4 to 18% by weight of the cleansing bar composition of C18:3 soap, for example, 5 to 16% by weight of the cleansing bar composition of C18:3 soap, for example, 6 to 15% by weight of the cleansing bar composition of C18:3 soap to produce cleansing bars, for example, 10 to 15% by weight of the cleansing bar composition of C18:3 soap can provide cleansing bars with desirable lather and stability (e.g., shelf stable, color stability, etc.). The cleansing bars can be shelf stable even though they contain C18:3 chains with a high level of unsaturation (e.g., three double bonds in one molecule of soap). Moreover, with the cleansing bar compositions disclosed herein, methods of making cleansing bars can also be utilized that can allow for greater use of oils such as palm oil, palm oil stearin, or a combination thereof.

[0018] It was unexpectedly found that cleansing bars made from the cleansing bar compositions disclosed herein have desirable lathering properties. The cleansing bar compositions can comprise C18:3 soap that can be derived from linseed oil. For example, cleansing bars made using the cleansing bar compositions disclosed herein can comprise C18:3 soap made from linseed oil, hydrogenated oils, or a combination thereof. For example, the hydrogenated oils can comprise soya bean oil, palm oil, or a combination thereof. Bars made from such compositions can have desirable lather and hardness. Bars made from such compositions can also be processed via any bar making process including being processed on a rapid extrusion and stamping soap bar making line. Linseed (flaxseed) oil can promote skin smoothness and hydration. Linseed oil can also help to prevent skin irritation and redness. Without wishing to be bound by theory, it is believed that it is not just oil (e.g., triglycerides), but also fatty acids that are responsible for these effects. In a recent study, Kendall AC, Kiezel-Tsugunova M, Brownbridge LC, Harwood JL, Nicolaou A, Lipid functions in skin: Differential effects of n-3 polyunsaturated fatty acids on cutaneous ceramides, in a human skin organ culture model. Biochim Biophys Acta Biomembr. 2017 Sep; 1859(9 Pt B):1679-1689. doi: 10.1016 / j.bbamem.2017.03.016. Epub 2017 Mar 21. PMID: 28341437; PMCID: PMC5504780, polyunsaturated fatty acids such as C18:3 have been recognized as therapeutic agents in a number of inflammatory skin conditions, altering the lipid profile of the skin and production of bioactive cells. Skin converts triglycerides into fatty acids, which can be used in the production of ceramides. Skin, due to its low natural pH of about 5.5 and high buffering capacity, can convert deposited soaps into fatty acids. Conventional soap bars have only trace amounts of C18:3 soap, whereas bars made from the cleansing bar composition disclosed herein can comprise 3 to 20% by weight of the cleansing bar composition of C18:3 soap, for example, 4 to 18% by weight of the cleansing bar composition of C18:3 soap, for example, 5 to 16% by weight of the cleansing bar composition of C18:3 soap, for example, 6 to 15% by weight of the cleansing bar composition of C18:3 soap to produce cleansing bars, for example, 10 to 15% by weight of the cleansing bar composition of C18:3 soap. Bars made from the cleansing bar compositions disclosed herein can have comparable smoothness, increased hydration, and increase antiinflammatory effects as cleansing products in which linseed oil is incorporated as a neat oil.

[0019] When linseed oil is blended with oils such as palm oil or palm stearin oil, resulting soap bars can be excessively soft and deficient in lather. It was unexpectedly found that hardness and lather can be improved to desirable levels using a process that comprises neutralizing a first fat blend comprising 15% or greater of C18:3 chains in a first stream to produce a first long chain soap, for example, 15% to less than 50% of C18:3 chains in the first stream, for example, 20% to less than 50% of C18:3 chains in the first stream, for example, 25 to less than 50% of C18:3 chains in the first stream; neutralizing a second fat blend comprising saturated long chains, unsaturated long chains, or a combination thereof in a second stream to produce a second long chain soap; and combining and mixing the first long chain soap and the second long chain soap to produce a cleansing bar composition. The cleansing bar composition can then be made into a cleansing bar where the cleansing bar can have desirable lathering properties and desirable hardness. In an embodiment, the first fat stream can comprise 15% to 49.9% of C18:3 chains, for example, 20% to 49.9% of C18:3 chains, for example, 25 to 49.9% of C18:3 chains. The first fat blend can comprise greater than or equal to 50% C16 and C18 chains, for example, 50% to 85% C16 and C18 chains, for example, 50% to 80% C16 and C18 chains, for example, 50% to 75% C16 to C18 chains. The second fat blend can comprise 100% by weight of a combination of palm oil and palm stearin oil. In an embodiment, the second fat blend contains 100% by weight of a combination of palm oil and palm stearin oil. In the combination, palm oil can be present in an amount of 0% by weight to 50% by weight, for example, 25% by weight, for example, 30% by weight, for example, 35% by weight, for example, 40% by weight, for example, 45% by weight, for example, 50% by weight, including any and all ranges and combinations subsumed therein. Also in the combination, palm stearin oil can be present in an amount of 50% by weight to 100% by weight, for example, 50% by weight, for example, 55% by weight, for example, 60% by weight, for example, 65% by weight, for example, 70% by weight, for example, 75% by weight, for example, 80% by weight, for example, 85% by weight, for example, 90% by weight, for example, 95% by weight, for example, 100% by weight, including any and all ranges and combinations subsumed therein.

[0020] Bars made from the process disclosed herein can comprise substantially no C8 to C14 soap. Bars made from the process disclosed herein can comprise 0% by weight C8 to C14 soap.

[0021] In bars made from the above described process, in the cleansing bar composition, a total % by weight of C18:1 and C18:2 present in the cleansing bar composition can be greater than a total % by weight of C18:3 present in the bar and a ratio of (C18:3 plus C18:2) / C18:1 can be less than 0.7.

[0022] Cleansing bar as described herein refers to a cleansing bar composition comprising 3 to 20% by weight of the cleansing bar composition of C18:3 soap, preferably 6 to 15% by weight of the cleansing bar composition of C18:3 soap, where the cleansing bar composition is in the form of a shaped solid. The cleansing bar can be particularly useful for personal cleansing. The cleansing bar is a wash off product that generally contains an amount of surfactants that is used for cleansing the desired topical surface, for example, the body, hair, scalp, and / or the face. The cleansing bar is applied on the topical surface and left thereon for only a few seconds or minutes and thereafter washed off with copious amounts of water.

[0023] Soap as referred to herein means salt of fatty acid. The soap can be a soap of C8 to C24 fatty acids, preferably the soap is of greater than C14, for example, C16 to C24, for example, C18, for example, C18:3. The basic structure of soap includes a long hydrophobic (water-fearing) hydrocarbon "tail" and a hydrophilic (water-loving) anionic "head" with the following structure:

[0024] CH3(CH2)nCOO-

[0025] The length of the hydrocarbon chain ("n") varies with the type of fat or oil. The anionic charge on the carboxylate (COO-) head is usually balanced by either a positively charged potassium (K+) or sodium (Na+) cation. The cleansing bar composition disclosed herein generally comprise substantially no or no low molecular weight soap (C8 to C14 soap), which is generally water soluble. For example, the cleansing bar compositions can comprise substantially no C8 to C14 soap, for example, the cleansing bar compositions can comprise 0% by weight C8 to C14 soap.

[0026] The soap can be present in an amount of less than 20% by weight of the cleansing bar composition. For example, the soap can be present in an amount of 0, 2.5, 3, 5, 7.5, 10, 12.5, 15, 16, or 20% by weight, including any and all ranges subsumed therein and wherein % by weight refers to the weight percent present in the overall cleansing bar composition. For example, the soap can be present in an amount of 3 to 20% by weight, preferably, 4 to 18% by weight, more preferably, 5 to 17% by weight, and even more preferably, 6 to 15% by weight, including any and all ranges and values subsumed therein.

[0027] The cleansing bar compositions can comprise saturated long chain soap, unsaturated long chain soap, or a combination thereof.

[0028] The saturated long chain soap can comprise C16 soap, C18 soap, or a combination thereof. The unsaturated long chain soap can comprise C18:1 soap, C18:2 soap, or a combination thereof.

[0029] The cleansing bar composition disclosed herein can be extrudable and formed into bars. Bars can comprise the cleansing bar composition as disclosed herein. The cleansing bar composition and bars made therefrom can have a pH of 9.5 to 11 , for example, 10 to 11 , for example, 10.5 to 11.

[0030] The cleansing bar composition can additionally comprise a surfactant. The surfactant can be present in an amount of less than or equal to 40% by weight of the overall cleansing bar composition. For example, the surfactant can be present in an amount of less than or equal to 30% by weight of the overall cleansing bar composition, for example, less than or equal to 25% by weight of the overall cleansing bar composition, for example, 10% to 24% by weight of the overall cleansing bar composition.

[0031] The surfactant can comprise an anionic surfactant, an amphoteric surfactant, a zwitterionic surfactant, a cationic surfactant, a non-ionic surfactant, or a combination thereof.

[0032] When present, the anionic surfactant used can include aliphatic sulfonates, such as a primary alkane (e.g., C8-C22) sulfonate, primary alkane (e.g., C8-C22) disulfonate, C8-C22 alkene sulfonate, C8-C22 hydroxyalkane sulfonate or alkyl glyceryl ether sulfonate (AGS); or aromatic sulfonates such as alkyl benzene sulfonate. The anionic surfactant may also be an alkyl sulfate (e.g., C12- C18 alkyl sulfate) or alkyl ether sulfate (including alkyl glyceryl ether sulfates). Among the alkyl ether sulfates are those having the formula:

[0033] RO(CH2CH2O)nSO3M wherein R is an alkyl or alkenyl having 8 to 18 carbons, preferably 12 to 18 carbons, n has an average value of at least 1 .0, preferably less than 5, and most preferably 1 to 4, and M is a solubilizing cation such as sodium, potassium, ammonium, or substituted ammonium.

[0034] The anionic surfactant may also be alkyl sulfosuccinates (including mono- and dialkyl, e.g., Ce- C22 sulfosuccinates); alkyl and acyl taurates (often methyl taurates), alkyl and acyl sarcosinates, sulfoacetates, C8-C22 alkyl phosphates and phosphonates, alkyl phosphate esters and alkoxyl alkyl phosphate esters, acyl lactates, C8-C22 monoalkyl succinates and maleates, sulphoacetates, alkyl glucosides and acyl isethionates, and the like.

[0035] Sulfosuccinates may be monoalkyl sulfosuccinates having the formula:

[0036] R1OC(O)CH2CH(SO3M)CO2M; and amide-MEA sulfosuccinates of the formula:

[0037] R1CONHCH2CH2OC(O)CH2CH(SO3M)CO2M wherein R1ranges from C8-C22 alkyl. Sarcosinates are generally indicated by the formula:

[0038] R2CON(CH3)CH2CC>2M, wherein R2ranges from C8-C20 alkyl.

[0039] Taurates are generally identified by formula:

[0040] R3CONR4CH2CH2SO3M wherein R3is a C8-C20 alkyl, R4is a C1-C4 alkyl.

[0041] M is a solubilizing cation as previously described.

[0042] The cleansing bar composition disclosed herein may contain Cs-Cis acyl isethionates. These esters are prepared by a 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.

[0043] The acyl isethionate may be an alkoxylated isethionate such as is described in llardi et al., U.S. Pat. No. 5,393,466, entitled "Fatty Acid Esters of Polyal koxylated isethonic acid; issued Feb. 28, 1995; hereby incorporated by reference. This compound has the general formula:

[0044] R5C— (0)0— C(X)H— C(Y)H— (OCH2— CH2)m— SO3M wherein R5is an alkyl group having 8 to 18 carbons, m is an integer from 1 to 4, X and Y are each independently hydrogen or an alkyl group having 1 to 4 carbons and M is a solubilizing cation as previously described.

[0045] In an aspect of the cleansing bar composition, the anionic surfactant used is 2-acrylamido-2- methylpropane sulfonic acid, ammonium lauryl sulfate, ammonium perfluorononanoate, potassium lauryl sulfate, sodium alkyl sulfate, sodium dodecyl sulfate, sodium laurate, sodium laureth sulfate, sodium lauroyl sarcosinate, sodium stearate, sodium sulfosuccinate esters, sodium lauroyl isethionate, or a combination thereof. Such anionic surfactants are commercially available from suppliers like Galaxy Surfactants, Clariant, Sino Lion, Stepan Company, and Innospec. Optionally, amphoteric surfactants can be included in the cleansing bar compositions disclosed herein. Amphoteric surfactants (which depending on pH can be zwitterionic) include sodium acyl amphoacetates, sodium acyl amphopropionates, disodium acyl amphodiacetates and disodium acyl amphodipropionates where the acyl (i.e., alkanoyl group) can comprise a C7-C18 alkyl portion. Illustrative examples of amphoteric surfactants include sodium lauroamphoacetate, sodium cocoamphoacetate, sodium lauroamphoacetate, or a combination thereof.

[0046] As to the zwitterionic surfactants employed in the present cleansing bar composition, such surfactants include at least one acid group. Such an acid group may be a carboxylic or a sulphonic acid group. They often include quaternary nitrogen, and therefore, can be quaternary amino acids. They should generally include an alkyl or alkenyl group of 7 to 18 carbon atoms and generally comply with an overall structural formula:

[0047] R6— [— C(O)— NH(CH2)q— ],— N+(R7)(R8)-A— B where R6is alkyl or alkenyl of 7 to 18 carbon atoms; R7and R8are each independently alkyl, hydroxyalkyl or carboxyalkyl of 1 to 3 carbon atoms; q is 2 to 4; r is 0 to 1 ; A is alkylene of 1 to 3 carbon atoms optionally substituted with hydroxyl, and B is — CO2— or — SO3 — .

[0048] Desirable zwitterionic surfactants for use in the cleansing bar composition disclosed herein and within the above general formula include simple betaines of formula:

[0049] R6— N+(R7)(R8)-CH2CO2‘ and amido betaines of formula:

[0050] R6— CONH(CH2)t— N+(R7)(R8)-CH2CO2- where t is 2 or 3.

[0051] In both formulae R6, R7and R8are as defined previously. R6may, in particular, be a mixture of Ci2and C14 alkyl groups derived from coconut oil so that at least half, preferably at least three quarters of the groups R6have 10 to 14 carbon atoms. R7and R8are preferably methyl.

[0052] A further possibility is that the zwitterionic surfactant is a sulphobetaine of formula: R6— N+(R7)(R8)-(CH2)3SO3- or

[0053] R6— CONH(CH2)U— N+(R7)(R8)-(CH2)3SO3- where u is 2 or 3, or variants of these in which — (CH2)3SO3‘ is replaced by — CH2C(OH)(H)CH2SO3-.

[0054] In these formulae, R6, R7and R8are as previously defined.

[0055] Illustrative examples of the zwitterionic surfactants desirable for use include betaines such as lauryl betaine, betaine citrate, cocodimethyl carboxymethyl betaine, cocoamidopropyl betaine, coco alkyldimethyl betaine, and laurylamidopropyl betaine. An additional zwitterionic surfactant suitable for use includes cocoamidopropyl sultaine, for example, cocamidopropyl hydroxysultaine. Preferred zwitterionic surfactants include lauryl betaine, betaine citrate, sodium hydroxymethylglycinate, (carboxymethyl) dimethyl-3-[(1 -oxododecyl) amino] propylammonium hydroxide, coco alkyldimethyl betaine, (carboxymethyl) dimethyloleylammonium hydroxide, cocoamidopropyl betaine, (carboxymethyl) dimethyloleylammonium hydroxide, cocoamidopropyl betaine, (carboxylatomethyl) dimethyl(octadecyl)ammonium, cocamidopropyl hydroxysultaine, or a combination thereof. Such surfactants are made commercially available from suppliers like Stepan Company, Solvay, Evonik and the like and it is within the scope of the cleansing bar compositions disclosed herein to employ mixtures of the aforementioned surfactants.

[0056] Nonionic surfactants may optionally be used in the cleansing bar composition. When used, nonionic surfactants are typically used at levels as low as 0.5, 1 , 1 .5 or 2% by weight and at levels as high as 6, 8, 10 or 12% by weight. The nonionic surfactants which may be used include in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkylphenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic surfactant compounds are alkyl (Ce-C22) phenols, ethylene oxide condensates, the condensation products of aliphatic (Cs-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 nonionic surfactants include long chain tertiary amine oxides, long chain tertiary phosphine oxides, dialkyl sulphoxides, and the like. In an aspect, nonionic surfactants can include fatty acid / alcohol ethoxylates having the following structures a) HOCH2(CH2)s(CH2CH2O)cH or b) HOOC(CH2)v(CH2CH2O)d H; where s and v are each independently an integer up to 18; and c and d are each independently an integer from 1 or greater. In an aspect, s and v can be each independently 6 to 18; and c and d can be each independently 1 to 30. Other options for nonionic surfactants include those having the formula HOOC(CH2)i — CH=CH — (CH2)k(CH2CH2O)zH, where i, k are each independently 5 to 15; and z is 5 to 50. In another aspect, i and k are each independently 6 to 12; and z is 15 to 35.

[0057] The nonionic surfactant may also include a sugar amide, such as a polysaccharide amide. Specifically, the surfactant may be one of the lactobionamides described in U.S. Pat. No. 5,389,279 to Au et al., entitled "Compositions Comprising Nonionic Glycolipid Surfactants issued Feb. 14, 1995; which is hereby incorporated by reference or it may be one of the sugar amides described in U.S. Pat. No. 5,009,814 to Kelkenberg, titled "Use of N-Poly Hydroxyalkyl Fatty Acid Amides as Thickening Agents for Liquid Aqueous Surfactant Systems" issued Apr. 23, 1991 ; hereby incorporated into the subject application by reference.

[0058] Illustrative examples of nonionic surfactants that can optionally be used in the cleansing bar compositions disclosed herein include, but are not limited to, polyglycoside, cetyl alcohol, decyl glucoside, lauryl glucoside, octaethylene glycol monododecyl ether, n-octyl beta-d- thioglucopyranoside, octyl glucoside, oleyl alcohol, polysorbate, sorbitan, stearyl alcohol, or a combination thereof.

[0059] In an aspect, cationic surfactants may optionally be used in the cleansing bar composition of the present application.

[0060] One class of cationic surfactants includes heterocyclic ammonium salts such as cetyl or stearyl pyridinium chloride, alkyl amidoethyl pyrrylinodium methyl sulfate, and lapyrium chloride.

[0061] Tetra alkyl ammonium salts are another useful class of cationic surfactants for use. Examples include cetyl or stearyl trimethyl ammonium chloride or bromide; hydrogenated palm or tallow trimethylammonium halides; behenyl trimethyl ammonium halides or methyl sulfates; decyl isononyl dimethyl ammonium halides; ditallow (or distearyl) dimethyl ammonium halides, and behenyl dimethyl ammonium chloride. Still other types of cationic surfactants that may be used are the various ethoxylated quaternary amines and ester quats. Examples include PEG-5 stearyl ammonium lactate (e.g., GENAMIN® KSL manufactured by Clariant), PEG-2 coco ammonium chloride, PEG-15 hydrogenated tallow ammonium chloride, PEG 15 stearyl ammonium chloride, dipalmitoyl ethyl methyl ammonium chloride, dipalmitoyl hydroxyethyl methyl sulfate, and stearyl amidopropyl dimethylamine lactate.

[0062] Still other useful cationic surfactants include quaternized hydrolysates of silk, wheat, and keratin proteins, and it is within the scope of the cleansing bar composition to use mixtures of the aforementioned cationic surfactants.

[0063] If used, cationic surfactants will make up no more than 1 .0% by weight of the cleansing bar composition. When present, cationic surfactants typically make up from 0.01 to 0.7%, and more typically, from 0.1 to 0.5% by weight of the cleansing bar composition, including all ranges subsumed therein.

[0064] The cleansing bar can additionally include up to 30% by weight skin benefit agents. The term “skin benefit agent” is defined as a substance which softens or improves the elasticity, appearance, and youthfulness of the skin (stratum corneum) by either increasing its water content, adding, or replacing lipids and other skin nutrients, or both, and keeps it soft by retarding the decrease of its water content. Included among the suitable skin benefit agents are emollients, including, for example, hydrophobic emollients, hydrophilic emollients, or blends thereof. Preferred benefit agents include moisturizers, emollients, sunscreens, and anti-aging compounds.

[0065] Desirably the optional skin benefit agents used in the cleansing bar composition disclosed herein include niacinamide (vitamin B3), tocopherol (Vitamin E), aloe vera, alpha-hydroxy acids and esters, beta-hydroxy acids and esters, hydroxyethyl urea, polyhydroxy acids and esters, creatine, hydroquinone, t-butyl hydroquinone, mulberry, hyaluronic acid and salts thereof (including, but not limited to, Na+ and K+ salts of the same), extract, liquorice extract, resorcinol derivatives, or a combination thereof. For example, the skin benefit agent can be sodium hyaluronate. Such benefit agents, including sodium hyaluronate can be present in an amount of 0.0001 to 10%, for example, 0.001 to 6.5%, for example, 0.01 to 3.5%, and for example, 0.01% by weight, based on total weight of the cleansing bar composition including all values and ranges subsumed therein. Further optional water-soluble skin benefit agents include acids, such as amino acids like arginine, valine or histidine. Other vitamins can be used such as vitamin B2, picolinamide, panthenol (vitamin B5), vitamin Be, vitamin C, a combination thereof or the like. Derivatives (generally meaning something that has developed or been obtained from something else), and especially, water soluble derivatives of such vitamins can also be employed. For instance, vitamin C derivatives such as ascorbyl tetraisopalmitate, magnesium ascorbyl phosphate and ascorbyl glycoside may be used alone or in combination with each other. Niacinamide derivatives such as nicotinamide adenine dinucleotide (NADH) and nicotinamide adenine dinucleotide phosphate (NADPH) may be used alone or in combination with each other. Other skin benefit agents that can be used include 4-ethyl resorcinol, extracts like sage, aloe vera, green tea, sugar cane, citrus, grapeseed, thyme, chamomile, yarrow, cucumber, liquorice, rosemary extract, or a combination thereof. Electrolytes such as NaCI and / or KOI, MgCh may also be used. The total amount of optional water-soluble benefit agents (including mixtures) when present in the composition disclosed herein can be 0.0001 to 10%, preferably, 0.001 to 6.5%, and most preferably, 0.01 to 3.5% by weight, based on total weight of the cleansing bar composition, including all values and ranges subsumed therein.

[0066] It is also within the scope of the cleansing bar composition to optionally include oil soluble benefit agents. Illustrative examples of the types of oil soluble benefit agents that can optionally be used in the cleansing bar composition disclosed herein include components like stearic acid, vitamins like vitamin A, D, E and K (and their oil soluble derivatives).

[0067] Other optional oil soluble benefit agents for use include resorcinols and resorcinol derivatives like 4-hexyl resorcinol, 4-phenylethyl resorcinol, 4-cyclopentyl resorcinol, 4-cyclohexyl resorcinol 4- isopropyl resorcinol or a combination thereof. Also, 5-substituted resorcinols like 4-cyclohexyl-5- methylbenzene-1 ,3-diol, 4-isopropyl-5-methylbenzene-1 ,3-diol, combination thereof or the like may be used. The 5-substituted resorcinols and their synthesis are described in commonly assigned U.S. Published Patent Application No. 2016 / 0000669A1.

[0068] Even other oil soluble benefit agents that can be used include omega-3 fatty acids, omega-6 fatty acids, climbazole, magnolol, honokiol, farnesol, ursolic acid, myristic acid, geranyl geraniol, oleyl betaine, cocoyl hydroxyethyl imidazoline, hexanoyl sphingosine, 12-hydroxystearic acid (12HSA), petroselinic acid, conjugated linoleic acid, stearic acid, palmitic acid, lauric acid, terpineol, thymol essential components, the dissolution auxiliary selected from limonene, pinene, camphene, cymene, citronellol, citronellal, geraniol, nerol, linalool, rhodinol, borneol, isoborneol, menthone, camphor, safrole, isosafrole, eugenol, isoeugenol, tea tree oil, eucalyptus oil, peppermint oil, neem oil, lemon grass oil, orange oil, bergamot oil, or a combination thereof.

[0069] Another optional oil soluble benefit agent that may be used is a retinoic acid precursor. The retinoic acid precursor can be retinol, retinal, retinyl ester, retinyl propionate, retinyl palmitate, retinyl acetate or a combination thereof. Retinyl propionate, retinyl palmitate and combinations thereof are typically preferred. Still another retinoic acid precursor for use is hydroxyanasatil retinoate made commercially available under the name REXEXTRA® as supplied by Molecular Design International. The same may be used in a combination with any of the oil soluble benefit agents described herein.

[0070] When an optional (i.e., 0.0 to 1.5% by weight) oil soluble benefit agent is used in the cleansing bar composition, it typically is present in an amount of 0.001 to 1.5% by weight of the overall cleansing bar composition including all values and ranges subsumed therein, and for example, 0.05 to 1.2% by weight, for example, 0.2 to 0.5% by weight of the total weight of the cleansing bar composition.

[0071] Other useful skin benefit agents include the following:

[0072] (a) silicone oils and modifications thereof such as linear and cyclic polydimethylsiloxanes; amino, alkyl, alkylaryl, and aryl silicone oils;

[0073] (b) fats and oils including natural fats and oils such as jojoba, soybean, sunflower, rice bran, avocado, almond, olive, sesame, persic, castor, coconut, and mink oils; cacao fat; beef tallow and lard; hardened oils obtained by hydrogenating the aforementioned oils; and synthetic mono, di and triglycerides such as myristic acid glyceride and 2-ethylhexanoic acid glyceride;

[0074] (c) waxes such as carnauba, spermaceti, beeswax, lanolin, and derivatives thereof;

[0075] (d) hydrophobic and hydrophilic plant extracts;

[0076] (e) hydrocarbons such as liquid paraffin, petrolatum, microcrystalline wax, ceresin, squalene, pristan and mineral oil; (f) higher fatty acids such as lauric, myristic, palmitic, stearic, behenic, oleic, linoleic, linolenic, lanolic, isostearic, arachidonic and poly unsaturated fatty acids (PLIFA);

[0077] (g) higher alcohols such as lauryl, cetyl, stearyl, oleyl, behenyl, cholesterol and 2-hexydecanol alcohol;

[0078] (h) esters such as cetyl octanoate, myristyl lactate, cetyl lactate, isopropyl myristate, myristyl myristate, isopropyl palmitate, isopropyl adipate, butyl stearate, decyl oleate, cholesterol isostearate, glycerol monostearate, glycerol monolaurate, glycerol distearate, glycerol tristearate, alkyl lactate, alkyl citrate and alkyl tartrate;

[0079] (i) essential oils and extracts thereof such as mentha, jasmine, camphor, white cedar, bitter orange peel, ryu, turpentine, cinnamon, bergamot, citrus unshiu, calamus, pine, lavender, bay, clove, hiba, eucalyptus, lemon, starflower, thyme, peppermint, rose, sage, sesame, ginger, basil, juniper, lemon grass, rosemary, rosewood, avocado, grape, grapeseed, myrrh, cucumber, watercress, calendula, elder flower, geranium, linden blossom, amaranth, seaweed, ginko, ginseng, carrot, guarana, tea tree, jojoba, comfrey, oatmeal, cocoa, neroli, vanilla, green tea, penny royal, aloe vera, menthol, cineole, eugenol, citral, Citronelle, borneol, linalool, geraniol, evening primrose, camphor, thymol, spirantol, penene, limonene and terpenoid oils;

[0080] (j) polyhydric alcohols, for example, glycerine, sorbitol, propylene glycol, and the like; and polyols such as the polyethylene glycols, examples of which are: Polyox WSR-205 PEG 14M, Polyox WSR-N-60K PEG 45M, or Polyox WSR-N-750, and PEG 7M;

[0081] (k) lipids such as cholesterol, ceramides, sucrose esters and pseudo-ceramides as described in European Patent Specification No. 556,957;

[0082] (l) vitamins, minerals, and skin nutrients such as milk, vitamins A, E, and K; vitamin alkyl esters, including vitamin C alkyl esters; magnesium, calcium, copper, zinc and other metallic components;

[0083] (m) sunscreens such as octyl methoxyl cinnamate (Parsol MCX) and butyl methoxy benzoylmethane (Parsol 1789);

[0084] (n) phospholipids; and (o) anti-aging compounds such as alpha-hydroxy acids and beta-hydroxy acids.

[0085] Preferred skin benefit agents include fatty acids, hydrocarbons, polyhydric alcohols, polyols, and mixtures thereof, with emollients that include at least one C12 to C18 fatty acid, petrolatum, glycerol, sorbitol, and / or propylene glycol being of particular interest in one or more embodiments. The agents may be added at an appropriate step during the process of making the cleansing bars. Some benefit agents may be introduced as macro domains.

[0086] Other optional ingredients like antioxidants, perfumes, polymers, chelating agents, colorants, deodorants, dyes, enzymes, foam boosters, germicides, anti-microbials, lathering agents, pearlescers, skin conditioners, stabilizers, or superfatting agents, may be added in suitable amounts in the process of making the bars. Preferably, the ingredients are added after the saponification step. Sodium metabisulphite, ethylene diamine tetra acetic acid (EDTA), borax, or ethylene hydroxy diphosphonic acid (EHDP) can be added to the formulation.

[0087] Additional optional ingredients which may be present in the cleansing bar compositions are, for example: fragrances; sequestering and chelating agents such as tetrasodium ethylenediaminetetraacetate (EDTA), ethane hydroxyl diphosphonate (EHDP), and etidronic acid, aka 1-hydroxyethylidene diphosphonic acid (HEDP); coloring agents; opacifiers, and pearlizers such as zinc stearate, magnesium stearate, TiC>2, ethylene glycol monostearate (EGMS), ethylene glycol distearate (EGDS) or Lytron 621 (Styrene / Acrylate copolymer), and the like; pH adjusters; antioxidants, for example, butylated hydroxytoluene (BHT), pentaerythrityl tetra-di-t- butyl hydroxyhydrocinnamate (e.g., TINOGARD® commercially available from BASF), and the like; stabilizers; suds boosters, such as for example, coconut acyl mono- or diethanol amides; ionizing salts, such as, for example, sodium chloride and sodium sulfate, and other ingredients such as are conventionally used in cleansing bar compositions. The total amount of such additional optional ingredients is typically from 0 to 10% by weight, more particularly from 0.1 to 5% by weight, based on the total weight of the personal cleansing formulation.

[0088] The cleansing bar composition disclosed herein can be used to deliver antimicrobial benefits. Antimicrobial agents that can be included to deliver these benefits include oligodynamic metals or compounds thereof. Preferred metals are silver, copper, zinc, gold, aluminum, or a. Silver is particularly preferred. In the ionic form it may exist as a salt or any compound in any applicable oxidation state. Preferred silver compounds are silver oxide, silver nitrate, silver acetate, silver sulfate, silver benzoate, silver salicylate, silver carbonate, silver citrate, silver phosphate, or a combination thereof, with silver oxide, silver sulfate and silver citrate being of particular interest in one or more embodiments. In at least one aspect, the silver compound is silver oxide. Oligodynamic metal or a compound thereof can be included in an amount of 0.0001 to 2%, preferably 0.001 to 1% by weight of the composition. Alternately an essential oil antimicrobial active may be included in the cleansing bar composition. Essential oil actives which can be included are terpineol, thymol, carvacol, (E) -2(prop-1-enyl) phenol, 2- propylphenol, 4- pentylphenol, 4-sec-butylphenol, 2-benzyl phenol, eugenol, or a combination thereof. Furthermore, preferred essential oil actives are terpineol, thymol, carvacrol, thymol, or a combination thereof, with the most preferred being terpineol or thymol, or a combination thereof. When present, essential oil actives can be included in an amount of 0.001 to 1 %, preferably 0.01 to 0.5% by weight of the composition.

[0089] Even other ingredients which may be used include octopirox (piroctone), zinc pyrithione, chloroxylenol, triclosan, cetylpyridinium chloride, as well as silver compounds including silver oxide, nitrate, sulfate, phosphate, carbonate, acetate, benzoate, a combination thereof or the like. If used, these other components typically make up from 0.001 to 1.6% by weight of the overall cleansing bar composition including all values and ranges subsumed therein, and preferably, from 0.01 to 1.2% by weight.

[0090] Optionally, preservatives can be used in the cleansing bar composition disclosed herein. When used, illustrative preservatives for use include sodium benzoate, iodopropynyl butyl carbamate, phenoxyethanol, hydroxyacetophenone, ethylhexylglycerine, methyl paraben, propyl paraben, imidazolidinyl urea, sodium dehydroacetate, dimethyl-dimethyl (DMDM) hydantoin, and benzyl alcohol, or a combination thereof. Other preservatives suitable for use include sodium dehydroacetate, chlorophenesin, and decylene glycol. Preservatives are preferably employed in amounts of 0.01% to 2.0% by weight of the total weight of cleansing bar composition, including all values and ranges subsumed therein. Also preferred is a preservative system with hydroxyacetophenone alone or in a mixture with other preservatives.

[0091] Fragrances, fixatives, opacifiers (like titanium dioxide or glycol distearate), and chelating agents may optionally be included in the cleansing bar composition. Possible chelating agents include, but are not limited to, ethylyene diaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), ethylene diamine disuccinic acid (EDDS), pentasodium diethylenetriaminepentaacetate, trisodium N-(hydroxyethyl)-ethylenediaminetracetate, an acid form of EDTA, sodium thiocynate, trisodium salt of methylglycinediacetic acid, tetrasodium glutamate diacetate and phytic acid, preferably wherein the chelating agent is ethylene diaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), ethylene diamine disuccinic acid (EDDS), or a combination thereof. Each of these substances may be present in an amount of about 0.03 to about 3% by weight of the overall cleansing bar composition including all values and ranges subsumed therein, preferably, about 0.1 to about 2.6% by weight.

[0092] Bars made from the cleansing bar composition can have a hardness value of greater than or equal to 2.0 kilograms (kg) (measured at 40°C), for example, the bars can have a hardness value of greater than or equal to 2.5, for example, the bars can have a hardness value of greater than or equal to 3, for example, greater than or equal to 4, , measured by a TA.XT texture analyzer described herein in the protocol. Such hardness values indicate that the bars can be processed via a high throughput extrusion process.

[0093] The cleansing bar disclosed herein has a moisture level of 10 to 20%, preferably 12 to 16% as measured by Karl Fischer titration.

[0094] The cleansing bar composition can be in the form of a shaped solid, for example, a bar. The cleansing bar composition can be a wash off product that generally has a sufficient amount of surfactants included therein such that it can be used for cleansing a desired surface such as a topical surface, e.g., the whole body, the hair, scalp, and / or the face. The cleansing bar composition can be applied on the topical surface and left thereon only for a few seconds or minutes and washed off thereafter with copious amounts of water. Alternately, it may be used for laundering clothes. In such an instance, the composition or bar can be usually rubbed onto wet clothes, optionally brushed, and then rinsed with water to remove the residual soap and dirt.

[0095] In one embodiment, bars can be produced by the following method:

[0096] Through several processes, all the ingredients, less the perfume, are combined in a mixer suitable for mixing viscous materials. The process is run at a temperature which ensures homogeneity of the batch, generally between 180° to 240°F (80° to 120°C). When the target moisture has been achieved, the product is removed from the mixer and cooled forming either chips or noodles. The cooled material is then optionally combined with perfume and tumbled to ensure an even distribution of perfume throughout the product. The optionally perfumed material is then transported to a hopper which feeds a refiner, which in turn feeds a plodder. The billet which exits the plodder is then cut, stamped into a bar, and packaged. It can be difficult to stamp billets that are too soft (e.g., do not have a hardness of at least 1.0 kg (measured at 40°C) into bars.

[0097] State more simply, the cleansing bar composition can be made into bars by a process that first involves saponification of the fat charge with alkali followed by extruding the mixture in a conventional plodder. The plodded mass can then be optionally cut to a desired size and stamped with desirable indicia.

[0098] In another embodiment, when linseed oil is blended with oils such as palm oil or palm stearin oil, resulting soap bars can be excessively soft and deficient in lather. This problem was able to be overcome by using a process that comprises neutralizing a first fat blend comprising 15% or greater of C18:3 soap in a first stream to produce a first long chain soap; neutralizing a second fat blend comprising saturated long chain soap, unsaturated long chain soap, or a combination thereof in a second stream to produce a second long chain soap; and combining and mixing the first long chain soap and the second long chain soap to produce a cleansing bar composition. The cleansing bar composition can then be made into a cleansing bar where the cleansing bar can have desirable lathering properties and desirable hardness.

[0099] The total level of the adjuvant / filler materials used in the cleansing bar composition should be in an amount not higher than 50%, preferably 1 to 50%, more preferably 3 to 45% by weight of the cleansing bar composition.

[0100] Structurants can be included in the cleansing bar composition. Suitable starchy materials which may be used include natural starch (from corn, wheat, rice, potato, tapioca, and the like), pregelatinized starch, various physically and chemically modified starch, and combinations thereof. By the term natural starch is meant starch which has not been subjected to chemical or physical modification - also known as raw or native starch. The raw starch can be used directly or modified during the process of making the cleansing bar composition such that the starch becomes gelatinized, either partially or fully gelatinized. The starch can assist in adding structure to bars produced from the cleansing bar composition.

[0101] Silica gel can also be used as a structurant. Silica gel can be pre-formed silica gel, or the generation of silica gel may be in-situ during the process to make cleansing bars. It is understood that silica gel is a porous form of silicon dioxide. Silica gels are amorphous solids. The partial dipole in the Si-0 bond allows silica gel to hydrogen bond with water molecules while the porous nature and large surface area of silica gel enables the material to readily adsorb water. In accordance with the cleansing bar compositions disclosed herein and bars made therefrom, metal silicates can form silica gel in-situ during the manufacture of the cleansing bar compositions.

[0102] The silica gel can be formed in-situ by acidulation of an alkaline metal silicate salt. Any metal silicate that can convert to silica gel can be used. For example, alkali metal silicates such as sodium silicate, potassium silicate, lithium silicate, calcium silicate, or any combination thereof can be used. The alkaline metal silicate can be added by itself (in a solid form) or in a wet form, such as a slurry or solution. The alkaline metal silicate component is preferably sodium silicate or alternatively, sodium silicate in combination with another metal silicate. Sodium silicate is a basic inorganic compound which is readily soluble in water, sodium silicate is often sold as an aqueous solution.

[0103] An opacifier may be optionally present in the cleansing bar composition. When opacifiers are present, the cleansing bar is generally opaque. Examples of opacifiers include titanium dioxide, zinc oxide, and the like. A particularly preferred opacifier that can be employed when an opaque soap composition is desired is ethylene glycol mono- or di-stearate, for example in the form of a 20% solution in sodium lauryl ether sulphate. An alternative opacifying agent is zinc stearate.

[0104] Bars made from the cleansing bar composition disclosed herein can have a pH of 9.5 to 11 , for example, 10 to 11 , for example, 10.5 to 11.

[0105] Except 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.” All amounts are by weight of the final composition, unless otherwise specified.

[0106] It should be noted that in specifying any range of concentration or amount, any particular upper concentration can be associated with any particular lower concentration or amount as well as any subranges consumed therein. In that regard, it is noted that all ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other (e.g., ranges of “up to 25% by weight, or, more specifically, 5% by weight to 20% by weight, in inclusive of the endpoints and all intermediate values of the ranges of 5% by weight to 25% by weight, etc.). “Combination is inclusive of blends, mixtures, alloys, reaction products, and the like. Furthermore, the terms “first,” “second,” and the like herein do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The terms “a” and “an” and “the” herein do not denote a limitation of quantity and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The suffix “(s)” as used herein is intended to include both the singular and the plural of the term it modifies, thereby including one or more of the term (e.g., the film(s) includes one or more films). Reference throughout the specification to “one embodiment”, “one aspect”, “another embodiment”, “another aspect”, “an embodiment”, “an aspect” and so forth means that a particular element (e.g., feature, structure, and / or characteristic) described in connection with the embodiment or aspect is included in at least one embodiment or aspect described herein and may or may not be present in other embodiments or aspects. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments or aspects.

[0107] All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in the present application contradicts or conflicts with a term in the incorporated reference, the term from the present application takes precedence over the conflicting term from the incorporated reference. While particular aspects have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications, variations, improvements, and substantial equivalents.

[0108] 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, options, or alternatives need not be exhaustive.

[0109] The disclosure of the invention as found herein is to be considered to cover all aspects as found in the claims as being multiply dependent upon each other irrespective of the fact that claims may be found without multiple dependency or redundancy. Unless otherwise specified, numerical ranges expressed in the format "from x to y" are understood to include x and y. In specifying any range of values or amounts, any particular upper value or amount can be associated with any particular lower value or amount. All percentages and ratios contained herein are calculated by weight unless otherwise indicated. The various features of the present invention referred to in individual sections above apply, as appropriate, to other sections mutatis mutandis. Consequently, features specified in one section may be combined with features specified in other sections as appropriate. Any section headings are added for convenience only and are not intended to limit the disclosure in any way.

[0110] The following examples are merely illustrative of the cleansing bar compositions disclosed herein and are not intended to limit the scope hereof.

[0111] Examples

[0112] The following examples are merely illustrative of the cleansing bar compositions disclosed herein and are not intended to limit the scope hereof.

[0113] In the following examples, bars were prepared according to the following process: fats / oils were added to a mixer. The mixer was heated to a temperature of 85 to 90°C. Caustic was slowly added to fully convert the starting materials to a soap mixture. The soap mixture was mixed for approximately 10 minutes after full caustic addition creating a final mixture. The final mixture was then chill rolled into flakes and extruded, forming an extrudate. The extrudate was stamped into a cleansing bar.

[0114] The cleansing bars were tested for various properties including lather, grittiness, cracking, hardness, and pH, as described in the test protocol. The bar moisture was measured by Karl Fischer titration. Table 1 lists the cleansing bar compositions for Examples 1 to 3. All amounts are listed in % by weight of the cleansing bar composition. POLYOX™ refers to a water-soluble polyethylene glycol (PEG-45M) commercially available from Dow Chemical. Acceptable bars had both a hardness value of greater than or equal to 2.0 kg and a lather value of at least 3.

[0115] Bar appraisal protocol

[0116] Hardness Testing Protocol

[0117] Principle

[0118] A 30° conical probe penetrates into a soap / syndet sample at a specified speed to a predetermined depth. The resistance generated at the specific depth is recorded. This number can be related to the yield stress.

[0119] Hardness (or yield stress) can be measured by a variety of different penetrometer methods.

[0120] Apparatus and Equipment TA-XT Express (Stable Micro Systems)

[0121] 30° conical probe - Part #P / 30c (Stable Micro Systems)

[0122] 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.

[0123] Procedure

[0124] Setting up the TA-XT Express

[0125] These settings need to be inserted in the system only once. They are saved and loaded whenever the instrument is turned on again.

[0126] Set test method

[0127] Press MENU

[0128] Select TEST SETTINGS (Press 1)

[0129] Select TEST TPE (Press 1)

[0130] Choose option 1 (CYCLE TEST) and press OK

[0131] Press MENU

[0132] Select TEST SETTINGS (Press 1)

[0133] Select PARAMETERS (Press 2)

[0134] Select PRE TEST SPEED (Press 1)

[0135] Type 2 (mm s-1) and press OK

[0136] Select TRIGGER FORCE (Press 2)

[0137] Type 5 (g) and Press OK

[0138] Select TEST SPEED (Press 3)

[0139] Type 1 (mm s-1) and press OK

[0140] Select RETURN SPEED (Press 4) Type 10 (mm s-1) and press OK Select DISTANCE (Press 5)

[0141] Type 15 (mm) for soap billets or 3 (mm) for soap pastilles and press OK

[0142] Select TIME (Press 6)

[0143] Type 1 (CYCLE)

[0144] Calibration

[0145] Screw the probe onto the probe carrier.

[0146] Press MENU

[0147] Select OPTIONS (Press 3)

[0148] Select CALIBRATE FORCE (Press 1) - the instrument asks for the user to check whether the calibration platform is clear

[0149] Press OK to continue and wait until the instrument is ready.

[0150] Place the 2kg calibration weight onto the calibration platform and press OK

[0151] Wait until the message “calibration completed” is displayed and remove the weight from the platform.

[0152] Sample Measurements

[0153] Place the billet onto the test platform.

[0154] Place the probe close to the surface of the billet (without touching it) by pressing the UP or DOWN arrows.

[0155] Press RUN

[0156] Take the readings (g or kg) at the target distance (Fin).

[0157] After the run is performed, the probe returns to its original position.

[0158] Remove the sample from the platform and record its temperature.

[0159] Calculation & Expression of Results

[0160] Output

[0161] The output from this test is the readout of the TA-XT as “force” (RT) in g or kg at the target penetration distance, combined with the sample temperature measurement.

[0162] Temperature Correction The hardness (yield stress) of skin cleansing bar formulations is temperature sensitive. For meaningful comparisons, the reading at the target distance (RT) should be corrected to a standard reference temperature (normally 40°C), according to the following equation:

[0163] R40 — RT x exp[a(T-40)] where R40 = reading at the reference temperature (40°C)

[0164] RT = reading at the temperature T a = coefficient for temperature correction

[0165] T = temperature at which the sample was analyzed.

[0166] The correction can be applied to the extensional stress.

[0167] Raw and Processed Data

[0168] The final result is the temperature-corrected force or stress, but it is advisable to record the instrument reading and the sample temperature also.

[0169] Lather Test

[0170] Cleansing bars were evaluated by trained assessors under defined water hardness at constant temperature.

[0171] The test apparatus and conditions were as follows:

[0172] - Controlled running water flow: 2.5 L / min or bowl

[0173] - Ten-liter bowl with water at 30°C (hardness of the local country)

[0174] - Metronome set at 160 / 0 and stopwatch

[0175] - Thermometer

[0176] - Grittiness and Sandiness mock-ups - used to help the assessments on comparison of samples and definition of scores.

[0177] - Assessments conducted by trained operators without gloves

[0178] The Procedure of lather assessment: i. Pre-treatment: Before starting the assessment, the bar was wetted under running water, twisted 20 times between hands at 180° to remove the dried out surface layer. Then the bar was replaced on the tray. ii. The bar was taken, dipped into a bowl and rotated out of the water 12 times at the pace of the metronome in 5 seconds counted on the chronometer. iii. The bar was placed on the tray. iv. The back of the left hand was swept with the right hand one single time to collect the lather that has been generated in both hands. v. The hands were twisted three times. vi. The lather amount was analyzed.

[0179] Attributes of lather quantity were measured according to the scale below.

[0180] Lather quantity of “good” and “excellent” are taken as good lathering properties where a score of 4 would be considered as consumer acceptable and representative of a marketed bar. Scores of 3 and 5 would be consumer noticeably less or more acceptable, respectively.

[0181] Comparative Samples 1 to 4 (C1-C4) and Samples 1 to 6 were prepared by the process previously disclosed herein in the example section. Iodine value (IV) is a measure of the relative degree of unsaturation in oil components, determine by the uptake of halogen. Since melting point and oxidative stability are related to the degree of unsaturation, the IV value provides an estimation of these factors. The greater the iodine value, the more unsaturation and the higher the susceptibility to oxidation.

[0182] Table 1. Fat Charge of Bars made in process where oils blended before saponification

[0183] 1: palm oil

[0184] 2: palm stearin oil

[0185] 3: palm kernel oil

[0186] 4: refined bleached deodorized soybean oil

[0187] 5: mixture of stearic and palmitic fatty acids in a 1 :1 ratio

[0188] 6: hydrogenated soybean oil

[0189] Comparative Sample 5 (C5) was made according the same process as C1 to C3. Samples 7 to 9 were made by splitting the soap making into two streams: a first stream comprising high C18:3 soap stream; and a second stream comprising a short chain free palm-based stream. The individual soap streams were processed under the conditions mentioned previously. Both streams were very roughly combined by Sigma mixing for 2 to 3 minutes at 40°C, followed by the addition of minors such as fragrance, and mixed for an additional 5 minutes. This mixture was then chill rolled into flakes, extruded, and stamped similar to the cleansing bar process previously described herein in the example section.

[0190] Table 2. Fat Charge of Bars made in process where oils not blended before saponification

[0191] 1: palm oil

[0192] 2: palm stearin oil

[0193] 3: mixture of stearic and palmitic fatty acids in approximately a 1 :1 ratio

[0194] Sample 7 had the same composition as C5 made by the conventional process in which all oils were blended prior to saponification. Sample 7, however, had greater hardness and higher lather as shown in Table 2. Without wishing to be bound by the theory, it is believed that greater hardness and higher lather in Sample 7 compared to C5 could be attributed to C18:3 soap being in separate domains rather than being mixed on the molecular level with other soaps, whereby being more available during use for lather generation, and not softening the composition by mixing with C18:2 / C18:1 soap.

[0195] Table 3. Chain Composition of Bars made in process where oils blended before saponification

[0196] Table 4. Chain Composition of Bars made in process where oils not blended before saponification

[0197] Comparative Sample 1 (C1) was a bar that had a composition similar to a commercially available bar. C1 produced very good lather and also had hardness that allowed for extruding and stamping at high speed. This bar was made from blends of conventional for bar making oils: long chain oils - palm oil and palm stearin oil, and short chain oil - palm kernel oil (see Tables 1 and 3). Comparative Sample 2 (C2) was a bar made with no short chains using only palm and palm stearin oils. It produced very poor lather. Comparative Sample 3 (C3) was made from a blend of soybean oil, hydrogenated soybean oil, and palm oil. It had no short chains, but because the ratio C18:2 / C18:1 is greater than 0.7 and the total content of a C18:2 plus C18:1 is about 25% of soap, the bar produces very good lather. C3 was made according to International Application No. WO 2021 / 164994). The bars of C1 to C3 contained very small amounts of C18:3 chains - below 2%. Sample 1 was a bar made from a blend of hydrogenated soybean oil and linseed oil in the ratio of 88 / 12. The bar had good lather, parity to C1 , and acceptable hardness for high-speed extrusion and stamping. This bar comprised 7.1 % C18:3 soap, which provided both lather and acceptable rheological properties for extrusion and stamping. Sample 2 had slightly less C18:3 soap - 6.1%, but still provided good lather and desirable rheological properties for extrusion and stamping. To illustrate the lowest acceptable range for C18:3 soap, Sample 6 was prepared which was made from the blend of hydrogenated soybean oil and linseed oil in the ratio of 94:6. This composition had 3.64% C18:3 soap and it provided some lather.

[0198] Sample 3 illustrated the upper range of the C18:3 soap in the cleansing bar compositions disclosed herein. Sample 3 was made from the blend of ASAD and linseed oil in the ratio 75:25. Comparative Sample 4 was made from the blend of ASAD and linseed oil in the ratio 50:50. In these examples ASAD could be replaced with fully hydrogenated palm oil. Sample 3 had 15.1 % C18:3 soap. Sample 3 had acceptable hardness and produced lather similar in volume to Samples 1 and 2 and C1 . The hardness in C4, being under 2.0, was not acceptable.

[0199] Samples 4 and 5 illustrated the effect of the ratio of the long saturated chain soap C16 and C18 on the hardness and lather of linseed oil bars. Sample 4 was made from the blend of ASAD (or hydrogenated palm oil) and linseed oil in the ratio 86:14. Sample 5 was made from the blend of hydrogenated soybean oil and linseed oil in the same ratio 86:14. The difference between Samples 4 and 5 was in the composition of long saturated chains C16 and C18. Sample 4 with a C16 / C18 ratio close to 1 :1 had higher hardness and lower lather compared to Sample 5, that had a C 16 / C 18 ratio about 1 :7.

[0200] Comparative Example 5 (C5) illustrated the case when the blend of linseed oil with other long chain oils comprised a high fraction (60% wt.) of conventional (non-hydrogenated) oils like palm oil and palm oil stearin. In this case, due to high levels of oleic and linoleic chains at 25.8% by weight, the composition became unacceptably soft for extrusion and stamping. Also, because the ratio of C18:2 / C18:1 was less than 0.7, it produced very poor lather.

[0201] Unexpectedly, it was found that if a similar composition having the same chain distribution was made by combining two separate streams of soap, one of them being 75 / 25 ASAD / linseed oil (similar to Sample 3), and another one being 25 / 75 palm oil / palm oil stearin (similar to C2), the resulting bar in Sample 7, which comprised streams C2 and Sample 3 in the ratio of 60:40, had greater hardness and produced good lather. Sample 8 was made similarly to Sample 7 by combining two streams of soap: another high linseed oil stream - 50 / 50 ASAD / linseed oil (similar to C4) and long chain soap 25 / 75 palm oil / palm oil stearin (similar to C2). Sample 7 comprised steams of C2 and C4 in the ratio of 80:20. Although the total fraction of conventional oils was 80% and the ratio of C18:2 / C18:1 equaled to 0.24 , this composition produced good lather and had desirable hardness for extrusion and stamping. Sample 9 illustrated the lower range of C18:3 soap for desirable lather when C18:3 bars were made according to the new process described herein. Sample 9 was made by combining soap streams corresponding to C2 and Sample 3 in the ratio of 76:24, so that the fraction of C18:3 soap in the final composition was 3.8%. Sample 9 had acceptable hardness for extrusion and stamping hardness. Tables 5 and 6 show more details for the bars made in the examples described herein.

[0202] Table 5. Bar Compositions of Bars made in process where oils blended before saponification

[0203] Table 6. Bar Compositions of Bars made in process where oils not blended before saponification

Claims

CLAIMSWhat is claimed is:1 . A cleansing bar composition, comprising:3 to 20% by weight of C18:3 soap, based on the total weight of the cleansing bar composition, preferably 6 to 15% by weight of C18:3 soap, more preferably 10 to 15% by weight of C18:3 soap, based on the total weight of the cleansing bar composition, wherein the cleansing bar composition comprises less than 0.5% by weight C8 to C14 soap, based on the total weight of the cleansing bar composition.

2. The cleansing bar composition of Claim 1 , wherein the cleansing bar composition comprises 0.0001 to 0.5% by weight C8 to C14 soap, based on the total weight of the cleansing bar composition.

3. The cleansing bar composition of Claim 1 or Claim 2, comprising 0.005 to 0.5% by weight C8 to C14 soap, based on the total weight of the cleansing bar composition.

4. The cleansing bar composition of any of the preceding claims, further comprising saturated long chain soap, unsaturated long chain soap, or a combination thereof.

5. The cleansing bar composition of any of the preceding claims, wherein the saturated long chain soap comprises C16 soap, C18 soap, or a combination thereof.

6. The cleansing bar composition of any of the preceding claims, wherein the unsaturated long chain soap comprises C18:1 soap, C18:2 soap, or a combination thereof.

7. The cleansing bar composition of any of the preceding claims, wherein the cleansing bar composition is extrudable.

8. A bar comprising the cleansing bar composition of any of the preceding claims.

9. A process for making a cleansing bar composition, wherein , wherein in the cleansing bar composition:(a) a total % by weight of C18:1 and C18:2 present in the cleansing bar composition is greater than a total % by weight of C18:3 present in the bar; and(b) a ratio of (C18:3 plus C18:2) / C18:1 is less than 0.7; wherein the process comprises: neutralizing a first fat blend comprising 15% or greater of C18:3 chains in a first stream to produce a first long chain soap; neutralizing a second fat blend comprising saturated long chain soap, unsaturated long chain soap, or a combination thereof in a second stream to produce a second long chain soap; and combining and mixing the first long chain soap and the second long chain soap to produce a cleansing bar composition.

10. The process of Claim 9, wherein the saturated long chain soap comprises C16 soap, C18 soap, or a combination thereof and wherein the unsaturated long chain soap comprises C18:1 soap, C18:2 soap, or a combination thereof.11 . The process of any Claim 9 or Claim 10, wherein the first fat blend comprises greater than or equal to 50% C16 and C18 soap.

12. The process of any of Claims 9-11 , wherein the second fat blend comprises 0 to 50% by weight of palm oil and 50 to 100% by weight of palm stearin oil.

13. A bar made from the process of any of Claims 9-12, wherein the bar comprises less than 0.5% by weight, based on the total weight of the cleansing bar composition , preferably 0.0001 to 0.5% by weight by weight C8 to C14 soap, based on the total weight of the cleansing bar composition.

Images