Field of the invention
The present invention relates to improved combi-bar compositions comprising high levels of free fatty acid (FFAs) that can be easily processed at ambient temperature conditions.
Background and the prior art
Syndet bar (synthetic detergent bar/ synthetic surfactant bar) or combi-bar (soap + high syndet) making process is very sensitive due to the inherent property (viscoelastic property of syndets changes drastically with change in temperature at which the bar is plodded) of synthetic surfactant present in high level. High syndet concentrations make syndet bars and combi-bars rather coarse. Therefore organic oils are generally added to combi-bar compositions to achieve good skin sensorial.
However, addition of high concentrations of organic oils to combi-bar compositions leads to the formation of sticky mass which is very difficult to process and subsequently the formation of bar becomes difficult.
Further, addition of FFAs (which are again desirable ingredients in a combi-bar compositions as these help in improving skin feel) makes the combi-bar compositions even less processable.
Thus the maximum amount of FFAs which may be easily added to any given base of syndet, soap and organic oil without compromising on process ability of the formulation is not more than 5% in ambient process condition.
Even this addition of FFAs (C12-C18) requires high temperature conditions. It is also observed that at high temperature and high pH (alkaline) conditions, syndets (such as SCI) tend to destabilize. Particularly in a combi bars, comprising soap + SCI based combinations; stabilization of SCI becomes a challenge because SCI undergoes hydrolyzation (SCI converted to SI) in base media (i.e in the presence of soap). Yet again, high temperature is essential during syndet and combi-bar manufacturing process for proper mixing of syndet, soap and FFA, to get smooth surface and to remove grit formation in finished bar.

US 5294363 provides improved processable, mild personal cleansing syndet bar comprising: long chain C15 -C22 alkyl or acyl synthetic surfactant having essentially saturated, soap, free fatty acid, a lathering mild surfactant comprising C12 -C14 acyl (cocoyl) isethionate, a selected paraffin wax, and optionally, but preferably, a cationic polymer, preferably precomplexed with soap. The primary plastic binders used in this invention are free fatty acid and paraffin wax.
US 5683973 provides mild synthetic personal cleansing bars in which small amounts of polyalkylene glycol or mixtures of polyalkylene glycol, wherein the use of polyalkylene glycol or glycols has relatively low melting point, has been found to enhance extrusion of bars through a soap plodder. It has been found in this invention that when 0.1 to 10% by weight of a polyalkylene glycol or mixture of polyalkylene glycols with MP below 40◦C are added to compositions comprising (a)10% to 60% by weight of a synthetic non-soap detergent or mixture of synthetic non-soap detergents; (b) greater than 10% to 60% high molecular weight polyalkylene glycol having melting point (MP) greater than 40C, (c) 5% to 50% water insoluble structurant having MP greater than 40◦C, (d) 1 to 14% water; (e) 0 to 25% water soluble starch; and (f) 0 to 10% of a salt of C8 to C22 monocarboxylic acid. The addition of high molecular weight results in tremendous improvement in processing such that the bars are processed much more easily (i.e., extruded at significantly higher rate through a plodder) compared to if the lower melting point polyalkylene glycol or mixture of polyalkylene glycols had not been added.
US 6172026 relates to composition comprising (a) from about 30% to about 99% by weight of a mixture of an anionic surfactants comprising: i) an alpha sulfonated alkyl ester; and ii) a sulfonated fatty acid; (b) from about 0.5% to about 50% by weight of a fatty acid; and (c) from about 0.1% to about 50% by weight water; wherein the ratio of i) to ii) is from about 10:1 to about 0.5:1; and wherein the ratio of (a) to (b) is about 1:1 to about 11:1. The invention describe the unique synergism of alpha sulfonated alkyl esters and sulfonated fatty acids due to improved processability, increased surface tension reduction properties, increased foaming properties, improved color stability, and impart superior feel and after-feel properties to skin has been achieved. This invention uses paraffins and waxes as the further component which may be optionally present in an amount of 1.0% to about 15.0% by weight of wax, having a melting point of from about 54◦C to about 180◦C. The invention disclosed in US’026 teaches synergistic

effect of alpha sulfonated alkyl esters and sulfonated fatty acids which provides improved processability, increased surface tension reduction properties, increased foaming properties, improved color stability, and impart superior feel and after-feel properties to skin.
US 6218348 relates to process for making a bar having enhanced skin care properties (as measured by defined tests) by adding specifically defined protic acid salts to compositions comprising fatty acid soaps, free fatty acids, and polyalkylene glycol under mixing conditions carried out in a defined temperature range. The process of US’348 comprise the addition of 0.1 to 5% by wt of a salt of a protic acid having a pKa1 of less than 6, to the following components 25 to 85% by weight fatty acid soap; polyalkylene glycol having MW of 400 to 25,000, preferably 400 to 10,000 (an amount such to improve skin condition); and (c) 1 to 35 C8 -C22 free fatty acid (saturated and unsaturated). The resulting bar composition according to US’348 should have a molar equivalents ratio of fatty acid to protic acid salt that is preferably between 0.5:1 to 3:1.
US 6342470 provides personal washing bar that provides effective cleansing, and a refreshing experience while producing lower levels of visual dryness, retaining more moisture in the skin and maintaining a stronger protective barrier than ordinary soap. The composition comprises soap, polyalkalene glycol, fatty acid, and the salt of specific protic acids. The personal washing bar combines these benefits with excellent in-use sensory properties as well as good bar properties. Using the protic acids salts and in a defined ratio of the protic acid salts to free fatty acids, enhanced skin care properties has been obtained by the inventors of US’470 as measured by defined tests, while achieving good desirable bar properties (e.g., hardness, low grit) and desirable sensory properties (e.g., clean rinsing). The invention of US’470 comprises (a) 25 to 85% by weight fatty acid soap; (b) polyalkylene glycol having MW of 400 to 25,000, and (d) 0.1 to 5% by wt. of a salt of a protic acid having a pKa1 of less than 6, wherein the amount of polyalkylene glycol present in the bar must be sufficient to improve skin condition in Controlled Application Wash Tests either by reducing the barrier damage as measured by transepidermal water loss, increasing skin hydration as measured by skin conductivity/capacitance, and/or by reducing visual dryness as measured by objective grading. The ratio of free fatty acid to protic acid salt is preferably between 0.5:1 to 3:1 and the weight ratio of free fatty acid to the sum of

weights of PEG plus protic acid salt, i.e., (wt. % FA)/(wt. % PEG +wt. % protic acid salt) , should be between 1:2 to 2:1.
US 6849585 relates to soap/fatty acid based bars having high level of free fatty acid (greater than 35%); low level of synthetic surfactant (less than 25%) while retaining good user properties. US’585 teaches that addition of free fatty acids to either fatty acid soap or synthetic fatty soap bar in much greater amounts, the bar still retains excellent foaming properties. The bars thus comprise a minimum of about 65% of combination of fatty acid soap and free fatty acids.
WO9207931 discloses improved mild personal cleansing syndet bar comprising: long chain alkyl sulfate having essentially saturated C15-C22, preferably C16-C18, alkyl chains, more preferably cetearyl sulfate, combined with a selected plasticizer preferably selected from paraffin, fatty acids, and polyethylene glycols, and mixtures thereof. WO’931 discloses that a preferred syndet bar contains a mixture of free fatty acid (or polyethylene glycol) and paraffin at a ratio of from 3:1 to 1:1.
WO9213060 discloses a personal cleansing syndet bar composition which exhibits improved lather and reduced bar messiness, while not sacrificing the processability of the syndet bar. The improved mild personal cleansing syndet bar comprising: long chain alkyl sulfate having essentially saturated C15-C22, preferably C16-C18, alkyl chains, more preferably cetearyl sulfate, combined with a selected plasticizer binder system comprising selected free fatty acid, monoglyceride and polyethylene glycol which confers good processability and good bar-use properties on these products. The plasticizers according to WO’060 are selected from mixture of fatty acid monoglyceride, (b) fatty acid and (c) PEG. The syndet bar of this invention comprises from about 14-50% of total plasticizers.
WO93/06205 discloses mild personal cleansing syndet bar comprising long chain synthetic surfactant, a high lathering, mild synthetic surfactant, soap, fatty acids, sodium isethionate, paraffin wax and optionally but preferably cationic polymer. The bar of WO’205 has improved processability, good smear and in-use properties as well as improved mildness and rinsability without meaningful lather negatives. WO’205 discloses the use of long chain alkyl sulfates as a

base and is limited to the presence of specific alkyl sulfates (saturated) of specific constitution (C15-C22), use of fixed ratio of stearic acid to lauric acid, presence of isethionates and paraffin wax in the final formulation.
US 5300249 relates to an improved processable, mild personal cleansing syndet bar comprising: 4% to about 32% of long chain C15 -C22 alkyl or acyl synthetic surfactant having essentially saturated, preferably C16 -C18, alkyl chains, from 0% to about 15% soap; from about 2% to about 30% of free fatty acid, from about 20% to about 70% of a lathering mild surfactant comprising from about 2% to about 8% C12 -C14 alkyl (cocoyl) isethionate, and from about 4% to about 30% of paraffin wax; from 0% to about 2% sodium chloride; and from about 1.5% to about 10% water; wherein said bar has a pH of from about 4.0 to about 9.0. The bar of US’249 has improved procssability without a meaningful bar messiness or lather negative.
Prior art composition uses PEG for extrusion from plodder. The compositions disclosed in prior art essentially uses alpha sulfonated alkyl ester and a sulfonated fatty acid and requires addition of high amount of salts for preparation of syndet bar.
Although method of preparing a syndet bar is provided in prior art which include soaps as well as syndet bar; but still there is a need to provide an even simpler method of making syndet bars.
US 6342470 disclose a composition comprising ratio of free fatty acid & protic acids (0.5:1 to 3:1) and a ratio of fatty acid and Polyalkalene glycol (1:2-2:1).
However the invention of ‘470 is essentially limited to soap bars. This patent does not disclose compositions for syndet and combi bars.
WO9207931 essentially require the addition of long chain alkyl sulfate having essentially saturated C15-C22 alkyl chain surfactants in the syndet bars. Unlike the invention of WO’031, present invention provides combi-bars comprising high amounts of FFAs without any such limitations in compositions.

WO9213060 essentially require the addition of long chain alkyl sulfate having essentially saturated C15-C22 alkyl chain surfactants in the syndet bars. Moreover the ratio of FFAs containing C16-C20 chain length is also limited to 4:1 to 1:1 unlike the invention of WO’060 the present invention provides combi-bars comprising high amounts of FFAs without any such limitations in compositions.
WO93/06205 essentially require the addition of long chain alkyl sulfate having essentially saturated C15-C22 alkyl chain surfactants, use of fixed ratio of stearic acid to lauric acid and presence of isethionates in the syndet bars. Present invention provides combi-bars comprising high amounts of FFAs without any such limitations in compositions.
US 5300249 essentially require the addition of long chain C15 -C22 alkyl or acyl synthetic surfactant having essentially saturated, preferably C16 -C18, alkyl chains. Unlike the invention disclosed in US’249 present invention provides combi-bars comprising high amounts of FFAs without any such limitations in compositions.
Addition of synthetic surfactants at higher concentrations in bar format is a challenge for the formulators, since high concentrations of synthetic surfactants affects the processability of bar compositions adversely. Hence, formulators tend to add synthetic surfactants only at lower concentration levels.
A further challenge is the addition of ingredients such as organic oils, in particular paraffin wax; and FFAs in syndet and combi-bar formulations. Further addition of organic oils and FFAs at high concentrations, alone or in combinations thereof, leads to loss in ease of processability of syndet and combi-bars. Hence there is a need to provide bar compositions that include both the required ingredients in the formulation while maintaining the ease in its processability.
Present invention thereby overcome the problems of prior art by providing an improved combi-bar composition that can include soap bars as well as syndet bars providing an even simpler method of making combi-bars containing high FFAs by providing a specific range of ingredients i.e. protic acid, soap and water which form an integral part of all soap and combi bar

formulations and which may be incorporated to syndet bar formulations also. The present invention provides a method wherein high concentrations of synthetic surfactants may be added without limiting the processabaility of bar formulations.
Objects of the Invention
It is an object of the present invention to overcome the drawbacks of the prior art.
Another object of the present invention is to provide a unique blend of a) at least one fatty acid soap; b) at least one protic acid; and c)water which when added to any given syndet and combi-bar formulation, makes feasible the production of a combi-bar comprising high levels of FFAs while maintaining the ease of processability of combi-bar.
Yet another object of the present invention is to provide a stable combi-bar composition comprising high levels of FFAs that can be easily processed at ambient temperature conditions.
Still another object of the present invention is to provide a combi-bar comprising organic oils and high levels of FFAs in final bar formulation.
It is yet another object of the present invention is to provide combi-bar compositions wherein FFAs may be added at high levels (of at least about 15%) to any given base of syndet and organic oil and one which can be easily processed at ambient temperature and pH conditions, ensuring smooth process ability, stability of ingredients and good formation of bar.
Summary of the Invention
According to one aspect of the present invention, there is provided a combi-bar composition comprising a unique blend of:
a) at least one soap;
b) at least one protic acid; and
c) water

wherein at least one soap, at least one protic acid and water is present in a ratio of from about 30:1:0.5 to about 5:1:1.
According to another aspect of the present invention, there is provided a process for preparation of combi-bar compositions comprising:
a) preparing a mixture of at least one fatty acid soap; along with protic acid; water and optional ingredients such as opacifiers, preservatives and structurants in a mixer;
b) adding syndets, fatty acids, humectants to the mixture of a) to form a blend of soap and syndets;
c) preparing a pre-blend, preferably hot, of polymers and oils and adding it to the blend of b) to obtain combi-bar mass; and
d) milling, plodding and stamping combi-bar mass of c) to obtain the final combi-bar.
Detailed description of the Invention
In one of its embodiments the present invention provides a combi-bar composition comprising a unique blend of:
a) at least one soap;
b) at least one protic acid; and
c) water
wherein at least one soap, at least one protic acid and water is present in a ratio of from about 30:1:0.5 to about 5:1:1.
The blend of the present invention when added to any given base of syndet bars or combi bars comprising syndets and organic oil increases the total content of FFAs present in the final soap/syndet/combi bars while maintaining its processabilty at ambient temperature conditions.
In another embodiment, the present invention provides an improved combi-bar composition comprising syndets, organic oil and a blend of at least one fatty acid soap; at least one protic acid; and water wherein the ratio of soap, protic acid and water is 30:1:0.5 to 5:1:1.

The inventors of present invention have found that invention solves the problems of syndet bars and combi-bars known in prior arts by providing a blend of soap, protic acid and water which when added to any given base of syndets and organic oil provides a composition that is processable at ambient temperature conditions.
In yet another embodiment the invention discloses a process for preparation of combi-bar compositions comprising:
d) preparing a mixture of at least one fatty acid soap; along with protic acid; water and optional ingredients such as opacifiers, preservatives and structurants in a mixer;
e) adding syndets, fatty acids, humectants to the mixture of a) to form a blend of soap and syndets;
f) preparing a pre-blend, preferably hot, of polymers and oils and adding it to the blend of b) to obtain combi-bar mass; and
g) milling, plodding and stamping combi-bar mass of c) to obtain the final combi-bar.
Accordingly a stable combi-bar composition is provided comprising high levels of FFAs that can be easily processed at ambient temperature conditions.
The percentages, ratios and parts herein are on a total composition weight basis, unless otherwise specified. All levels and ranges herein are approximations unless otherwise specified.
The term “free fatty acids” as used herein are selected from fatty acids with alkyl chain lengths of from C8 – C18. These may be selected from group of linear chained fatty acids, branched chain fatty acids, saturated and unsaturated fatty acids such as Caprylic, Capric, Lauric, Myristic, Palmitic, Stearic, Oleic, etc and mixtures thereof. Fatty acid is a plasticizer in the present combi-bar composition. The challenge is to increase the amount of FFA that can be incorporated into any syndet bar or combi-bar composition.
The term “syndet bar” as used herein means synthetic detergent bar or synthetic surfactant bar or “combi bar” (having high syndet). These are primarily bathing bars which contain high concentrations of synthetic surfactants in their composition.

The combi-bar compositions of present invention comprise free fatty acids (FFAs) that may be added at high levels (of at least about 15%) to any given base of syndet and organic oil and one which can be easily processed at ambient temperature and pH conditions, ensuring smooth processability, stability of ingredients and good formation of bar.
The desired properties like smooth processability, stability of ingredients (high amounts of FFAs) and good formation of bar are achieved from the blend of three essential ingredients i.e. soap, protic acid and water added within specific amounts to the soap /combi bar/ syndet bar composition.
The present invention also provides a method of increasing or enhancing FFA levels in syndet based formulation by providing a unique blend of soap, protic acid and water; wherein soap, protic acid and water are added in a predetermined ratio. Typically the ratio of soap, protic acid and water is 30:1:0.5 to 5:1:1.
The first essential element of the combi-bar composition of present invention is fatty acid soap.
Fatty acid soap according to the present invention includes alkali metal salts of fatty acids such as sodium palmitate and sodium oleate (i.e. anionic surfactants). Among the soaps that are used herein may be saponified glycerides from plant or animal sources such as sodium palmate, sodium palm kernelate, sodium cocoate, sodium tallowate, potassium tallowate, sodium lardate and other alkali metal salt of C8-C22 single chained and branched carboxylic acids. The soaps that are used in the combi-bar compositions of the present invention may be present in an amount from 1 to 30% by weight; preferably from 5 to 15% by weight.
A second essential component of combi-bar of the present invention is protic acid.
Non-limiting examples of protic acid that may be added to the composition of the present invention comprise acetic acid, lactic acid, oxalic acid, citric acid, malic acid and combinations thereof. Protic acid may be present in the composition of the present invention at concentration of about 0.5 to10% by weight, preferably at concentrations of about 1 to 3% by weight.

A third essential component of combi-bar of the present invention is water. Water may be present in the composition of the present invention at concentration of about 0.2 to about 3.5% by weight, preferably at concentrations of about 0.5 to 2.5% by weight.
The combi-bar of the present invention may further comprise adjuvants including but not limited to organic oils, syndet and other conventional ingredients as are present in cleansing formulations. The invention does not require any specific syndet, oil or combinations thereof for its functioning. Hence without limitation any syndets and oil can be used in the present invention.
Non-limiting examples of organic oils that may be added to the compositions of the present invention comprise paraffin wax, paraffin oil (the blends of C8 to C28) and combinations thereof. Oils may be present in the composition of the present invention at concentration of about 0.5% by weight to about 30% by weight, preferably at concentrations of about 3% by weight to about 15% by weight.
Examples of syndets that may be added to the compositions of the present invention may be selected from anionic surfactants, amphoteric surfactants, nonionic surfactants and cationic surfactants and combinations thereof. As it is well known in the art that surfactant materials can also be an emulsifier, the term “surfactant” does not exclude materials which also have emulsification properties. Syndets may be present in the composition of the present invention at concentration of about 10% by weight to about 70% by weight, preferably at concentrations of about 35%by weight to about 60% by weight.
The anionic surfactants that may be used in the present invention include but are not limited to acyl isethionates, Sodium cocoyl isethionate, sodium isethionate, sodium lauroyl isethionate, Sodium lauroyl methyl isethionate, sodium methyl cocoyl taurate, and the series, sodium alkyl sulfate, alkyl sulfates, anionic acyl sarcosinates, methyl acyl taurates, N-acyl glutamates, acyl isethionates, alkyl ether sulfates, alkyl sulfosuccinates, alkyl phosphate esters, ethoxylated alkyl phosphate esters, trideceth sulfates, protein condensates, mixtures of ethoxylated alkyl sulfates and the like. Alkyl chains for these surfactants are C8-22, preferably C10-18 and, more

preferably, C12-14 alkyls. More preferably, SCI (65%) may be used for making the combi-bar of the present invention. This SCI (65%) may comprise about 65% SCI and from about 25 to about 30% FFA.
The amphoteric surfactants which can be used in the compositions of the present invention are those which can be broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. Examples of compounds falling within this definition are CDMA, sodium 3-dodecylaminopropionate, sodium 3-dodecylaminopropane sulfonate. Other amphoterics such as betaines are also useful in the present composition. Examples of betaines useful herein include the high alkyl betaines such as coco dimethyl carboxymethyl betaine, lauryl dimethyl carboxy-methyl betaine, lauryl dimethyl alpha-carboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis-(2-hydroxyethyl)carboxy methyl betaine, stearyl bis-(2-hydroxypropyl)carboxymethyl betaine, oleyl dimethyl gamma-carboxypropyl betaine, lauryl bis-(2-hydro-xypropyl)alpha-carboxyet-hyl betaine, etc. The sulfobetaines may be represented by coco dimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, amido betaines, amidosulfobetaines, and the like.
The nonionic surfactants useful in this invention can be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. Non-limiting examples of preferred nonionic surfactants for use herein are those selected form the group consisting of glucose amides, alkyl polyglucosides, sucrose cocoate, sucrose laurate, alkanolamides, ethoxylated alcohols and mixtures thereof. In a preferred embodiment the nonionic surfactant is selected from the group consisting of glyceryl monohydroxystearate, isosteareth-2, trideceth-3, hydroxystearic acid, propylene glycol stearate, PEG-2 stearate, sorbitan monostearate, glyceryl laurate, laureth-2, cocamide monoethanolamine, lauramide monoethanolamine, decyl glucoside and mixtures thereof. The composition of the present invention may also comprise one or more sugar based surfactants selected from but not limited to condensation products of long chain alcohols with sugar or starch polymers (e.g. decyl

polyglucoside and lauryl polyglucoside), amides (e.g. cocoamide diethanolamine and cocoamide monoethanolamine), alkylene oxide derived surfactants (e.g. ceteth-6, ceteareth-6, steareth-6, PEG-12 stearate, and PEG-200 glyceryl tallowate), Maltooligosyl Glucoside/Hydrogenated Starch Hydrolysate and mixtures thereof.
Other adjuvants that may be present in the combi-bar composition of the present invention includes binders, emollient, preservatives, color, fragrance, emotives, pH Regulator, Water, secondary emulsifier, active ingredients and the like.
Binders according to the present invention includes high molecular weight PEGs like PEG 6000, PEG 8000, poly acrylates, high molecular weight poly-ox, silicates, fatty alcohols, lanolin, sugars, tallow alcohol ethoxylates, and mixtures thereof. Other plastic binders are identified in the published literature, such as J. Amer. Oil Chem. Soc. 1982, 59, 442.Binders can be present in amounts 0.2 to 4 % by weight in the final product.
Emollients are substance which soften or improve the elasticity, appearance, and youthfulness of the skin (stratum corneum) by increasing its water content, and keeps it soft by retarding the decrease of its water content. Emollients that may be used in the present invention include but are not limited to silicone oils and modifications thereof such as linear and cyclic polydimethylsiloxanes; polyols such as glycerol, sorbitol; amino, alkyl, alkylaryl, and aryl silicone oils; fats and oils including natural fats and oils such as jojoba, soybean, sunflower, rice bran, avocado, almond, olive, sesame, persic, castor, coconut, mink oils; cacao fat; beef tallow, 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; waxes such as carnauba, spermaceti, beeswax, lanolin, and derivatives thereof; hydrophobic plant extracts; hydrocarbons such as liquid paraffin, petrolatum, microcrystalline wax, ceresin, squalene, pristan and mineral oil; higher fatty acids such as lauric, myristic, palmitic, stearic, behenic, oleic, linoleic, linolenic, lanolic, isostearic, arachidonic and poly unsaturated fatty acids (PUFA); higher alcohols such as lauryl, cetyl, stearyl, oleyl, behenyl, cholesterol and 2-hexydecanol alcohol; 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 distearate, glycerol tristearate, alkyl

lactate, alkyl citrate and alkyl tartrate; 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; and mixtures of any of the foregoing components, and the like. Advantageously emollients may be used from about 0.5 to about 3 % by weight in the final product.
Preservatives according to the present invention include BHT, EDTA, phenoxy ethanol. Preservatives can be present in amounts 0.01 to 0.2 % by weight in the final product.
pH regulator according to the present invention includes citric acid, lactic acid, oxalic acid, acetic acid etc. pH regulator can be present in amounts 0.5 to 5 % by weight in the final product.
Further the composition of the present invention may comprise 0.5 to 1.5 % by weight of fragrance, 0.005 to 0.5 % by weight of emotives.
Further the composition of the present invention may comprise secondary emulsifiers. Secondary emulsifiers that may be added to compositions of the present invention can be of the W/O type or O/W type. The addition of an emulsifier allows the incorporation of hydrophilic components or agents into the wax phase. Preferred are non-ionic emulsifiers which typically have good skin compatibility. Non-ionic emulsifiers of the present invention may be selected from group comprising addition products of 2 to 50 moles of ethylene oxide and/or 0 to 20 moles propylene oxide to linear fatty alcohols having 8 to 40 C-atoms, to fatty acids with 12 to 40 C-atoms and to alkylphenols with 8 to 15 C-atoms in the alkyl rest; C12-18-fatty acid mono- and -diesters of addition products of 1 to 50 moles of ethylene oxide and glycerine; glycerine mono-and -diesters and sorbitan mono- and -diesters of saturated and unsaturated fatty acids with 6 to 22 C-atoms and their ethylene oxide addition products; alkyl mono- and -oligoglycosides with 8 to 22 C-atoms in the alkyl rest and their ethoxylated analogs; addition products of 7 to 60 moles of ethylene oxide to castor oil and/or hardened castor oil; Polyol- and in particular polyglycerine esters, such as e.g. polyol poly-12-hydroxystearate, polyglycerine polyricinoleate, polyglycerine

diisostearate or polyglycerine dimerate. Also applicable are mixtures of compounds of several of these substance classes; addition products of 2 to 15 moles of ethylene oxide to castor oil and/or hardened castor oil; partial esters derived from linear, branch chained, unsaturated or saturated C6-C22-fatty acids, ricinoleic acid as well as 12-hydroxystearic acid and glycerine, polyglycerine, pentaerythrite, dipentaerythrit, sugar alcohols (e.g. sorbitol), alkylglucosides (e.g. methylglucoside, butylglucoside, laurylglucoside), as well as polyglucosides (e.g. cellulose), or mixed esters such as e.g. glyceryl stearate/citrate and glyceryl stearate/lactate;Wool wax alcohols; Polysiloxane-polyalkyl-polyether-copolymers and derivatives thereof; Mixed esters from pentaerythrite, fatty acids, citric acid and fatty alcohols and/or mixed esters of fatty acids with 6 to 22 C-atoms with methylglucose and polyols, respectively glycerine or polyglycerine; Polyalkylene glycols. Emulsifiers can be present in amounts 0.5 to 5 % by weight in the final product.
Active ingredients according to the present invention include lipophilic or hydrophilic active ingredients. As used herein an 'active ingredient' is meant to comprise a compound that has a cosmetic or therapeutic effect on the skin, hair, or nails, e.g., lightening agents, darkening agents such as self-tanning agents, anti-acne agents, shine control agents, anti-microbial agents, anti-inflammatory agents, anti-aging agents, in particular anti-wrinkle agents, anti-mycotic agents, anti-parasite agents, external analgesics, sunscreens, photoprotectors, antioxidants, keratolytic agents, detergents/surfactants, moisturizers, nutrients, vitamins, energy enhancers, anti-perspiration agents, astringents, deodorants, hair removers, firming agents, anti-callous agents, and agents for hair, nail, and/or skin conditioning.
Examples of active ingredients are hydroxy acids, benzoyl peroxide, sulfur resorcinol, ascorbic acid, D-panthenol, hydroquinone, octyl methoxycinnimate, titanium dioxide, octyl salicylate, homosalate, avobenzone, polyphenolics, carotenoids, free radical scavengers, spin traps, retinoids such as retinol and retinyl palmitate, ceramides, polyunsaturated fatty acids, essential fatty acids, enzymes, enzyme inhibitors, minerals, hormones such as estrogens, steroids such as hydrocortisone, 2-dimethylaminoethanol, copper salts such as copper chloride, peptides containing copper such as Cu:Gly-His-Lys, coenzyme Q10, peptides such as those disclosed in WO-00/15188, lipoic acid, amino acids such a proline and tyrosine, vitamins, lactobionic acid, acetyl-coenzyme A, niacin, riboflavin, thiamin, ribose, electron transporters such as NADH and FADH2, and other botanical extracts such as aloe vera and soy, and derivatives and mixtures

thereof. The cosmetically active agent will typically be present in the formulation of the invention in an amount of from about 0.001 % to about 20% by weight of the formulation, e.g., about 0.01% by weight to about 10% by weight, more preferably0.1% to about 5%.
Examples of vitamins include, but are not limited to, vitamin A, vitamin Bs such as vitamin B3, vitamin B5, and vitamin B12, vitamin C, vitamin K, and vitamin E and derivatives thereof.
According to another embodiment of the present invention, a method of preparing combi-bar composition is provided. The method involves preparation of a blend of soap, protic acid and water in a predefined ratio of 30:1:0.5 to about 5:1:1. The blend when added to a base of syndet and organic oil provides a composition that is processable at ambient temperature and pH conditions.
Ambient temperature conditions in reference to the present invention refer to 26˚C-32˚C. pH conditions in reference to the present invention refers to from about 6 to about 8.
Advantages of combi-bars of present invention:
It is noted that the addition of blend of the present invention to syndet / soap / combi bar formulations enhances the FFA (such as palmitic acid and stearic acid) content of the combi-bar. The blend thus helps in addition of more FFAs in the formulation at ambient temperature and provides advantages like:
a) Grit free soap/syndet/combi bars
b) Increased FFA content in soap;
c) Improved skin hydration
d) Low pH soap/syndet/combi
e) Creamy lather
f) Cost effective formulation
The present invention is now being illustrated by means of non-limiting examples.
Example 1
A non- limiting example of the combi-bar composition of the present invention is stated herewith.

Combi-bar compositions comprising soap, protic acid and water in the range of 30-5:1:0.5-1


Positive example:
Observation: Good process excellent skin sensorial. The final product bar surface obtained was excellent. Moreover excellent in-use sensorial was achieved.
“Skin sensorial” means that during application of soap the skin should get moisturized and become smooth (i.e improved surface feel) and soft (i.e improved overall texture of skin). So the post wash desired outcomes are enhanced moisturization of skin, enhanced skin smoothness and enhanced skin softness.

Example 2: Negative example:


Observation: Sticky mass: difficult to process. Quality of final product bar surface obtained was poor. Stamping is not proper.
Example 3: Negative example Table 3

Observation: Process is good, but skin sensorial property is very poor. The bar so obtained was not mild enough on skin. The pH of this bar so obtained was more than 8.
Skin sensorial means that during application of soap the skin should get moisturized and become smooth (i.e improved surface feel) and soft (i.e improved overall texture of skin). So the post

wash desired outcomes are enhanced moisturization of skin, enhanced skin smoothness and enhanced skin softness.
As shown in examples 1 to 3 the amounts of soap, protic acid and water are as follows:

In example 1 it is observed that even with 2.5% protic acid desired results can be achieved. The ratio is defined such that a higher limit of water is shown. If the level of water is decreased and protic acid level is increased (for example, if 4wt% protic acid was added), even better result would be obtained.
In example 1 the ratio of water: protic acid is 1:1. However the soap present is within the specified limits of the invention. Hence an improved bar is obtained which is processable and provides all desirable product attributes.
The negative examples are provided to show the non-working of the invention when the three ingredients are added outside the specified ratios. Here the ratio of each of the three ingredients to one another is of the prime importance.
In example 2, the amount of water is outside the specified range of the present invention, hence the final formulation is not workable/processable.
In example 3 the ratio of water: protic acid is 1:1. However the ratio of soap present is outside the specified range. Hence even though the bar is processable, the desired product characteristics (such as mildness, creaminess, sensorials) are not obtained.
Example 4
Non-limiting process of preparing syndet bar of present invention

Step 1: Firstly, Soap / soap noodles along with optional ingredients such as opacifiers,
preservatives and structurants are mixed together in a mixer to form a mixture.
Step 2: A blend of protic acid and water are added to the mixture of step 1 and mixed further.
Step 3: Glycerin is added at slightly higher temperature 50-60˚C to the mixture of Step 2 to
obtain a softened mass.
Step 4: Thereafter syndets (such as sodium cocoyl isethionate, CAPB etc) and fatty acids (such
as freely available FFAs or those from pre blend of Syndet-FFA in powder form) are added to
the softened mass of step 3 to form a blend of soap and syndets. The mass temperature at this
point should preferably be 35˚C due to heat of mixing.
Step 5: A hot melt pre-blend of polymers (PEGs) and oils (Paraffins) is prepared at
predetermined temperature conditions and added to the blend of step 4 to obtain syndet –polymer
-oil mass.
Step 6: At least one viscosity modifier and remaining adjuvants are added to the syndet –
polymer -oil mass of step 5 to achieve syndet mass of desired visco elasticity.
Step 7: Syndet mass of step 6 is milled, plodded and stamped to obtain the final syndet bar of the
present invention.

WE CLAIM:
1. An improved combi-bar composition comprising a blend of:
a) at least one fatty acid soap;
b) at least one protic acid; and
c) water,
wherein at least one fatty acid soap, at least one protic acid and water is added in a ratio of 30:1:0.5 to 5:1:1.
2. The combi-bar composition as claimed in claim 1, wherein said fatty acid soap is selected
from group comprising alkali metal salts of fatty acids such as sodium palmitate, sodium
stearate and sodium oleate, sodium palm kernelate, sodium cocoate and mixtures thereof.
3. The combi-bar composition as claimed in claim 1, wherein said fatty acid soap is present
in the composition in an amount from 1 to 30% by weight; preferably from 5 to 15% by
weight.
4. The combi-bar composition as claimed in claim 1, wherein said protic acid is selected from group comprising acetic acid, lactic acid, oxalic acid, citric acid, malic acid and mixtures thereof.
5. The combi-bar composition as claimed in claim 1, wherein said protic acid is present in the composition in an amount from 0.5 to10% by weight, preferably 1 to 3% by weight.
6. The combi-bar composition as claimed in claim 1, wherein water is present in an amount of 0.2 to about 3.5% by weight, preferably 0.5 to 2.5% by weight.
7. The combi-bar composition as claimed in claim 1 further comprising adjuvants selected from the group comprising but not limited to syndets, oils, binders, emollient, preservatives, color, fragrance, emotives, pH regulator, secondary emulsifier and active ingredients.

8. A method of preparing combi-bar compositions of claim 1 comprising:
a) preparing a mixture of at least one fatty acid soap; along with protic acid; water and optional ingredients such as opacifiers, preservatives and structurants in a mixer;
b) adding syndets, fatty acids, humectants to the mixture of a) to form a blend of soap and syndets;
c) preparing a pre-blend, preferably hot, of polymers and oils and adding it to the blend of b) to obtain combi-bar mass; and
d) milling, plodding and stamping combi-bar mass of c) to obtain the final combi-bar.