EP3820577A1 - Alkaline oleo-liniment - Google Patents

Abstract

The invention relates to a mechanically stable, more or less viscous liquid superfatted soap for cleansing delicate skin, said soap being obtained by a cold saponification reaction and comprising an oil phase, an aqueous alkaline phase, one or more mechanical stabilizers and one or more additives. The invention also relates to the use of a soap according to the invention for cleansing delicate human skin.

Description

 Oleo alkaline liniment

The present invention relates to the pharmaceutical and cosmetic field and more particularly to that of liquid or viscous compositions intended for cleaning the skin of any kind, normal, oily, sensitive, etc ... and this whatever age of the subject, prohibiting the use of any aggressive cleaning agent, in order to ensure the maintenance of the hydrolipidic film on the surface of the epidermis or to reinforce its protective properties in the case of a sebaceous-sweat imbalance.

 The skin is an organ covering the whole organism and acting as a protective barrier against any attack of any kind, physical, chemical or microbiological.

 It consists of 3 layers:

 - the epidermis

 - the dermis

 - and the hypodermis.

 The epidermis can be broken down into 5 layers from the inside to the outside:

 the basal stratum

 the stratum spinosum

 the stratum granulosum

 the stratum lucidum

 and the stratum corneum

The present invention focuses essentially on all of these 5 layers and among others the stratum corneum.

The stratum corneum, superficial part of the skin, associated with the epidermis, form a fine epithelial tissue in perpetual renewal. Despite this perpetual renewal, the rate of cell division remains low compared to its regeneration potential. This thus allows it to ward off aggressions requiring a major repair of the epithelial film in the case of major disorders such as an inflammatory process, a cut, etc. On the other hand it is good to point out that even if the stratum corneum is rich in corneocytes, cells producing the horn and leading to a relatively solid layer, the latter is nonetheless innervated, explaining a certain number of behaviors of the skin vis-à-vis external aggressive agents.

One of the important elements of the skin's regeneration and repair process is water.

 Physiologically, two major factors in cell multiplication (skin regeneration) will be controlled by water:

 - a calcium gradient within the epidermis and stratum corneum

- and the acid pH of the skin.

The pH on the surface of the stratum corneum is around 5-6, therefore slightly acidic due to the presence of lactic acid, the last waste product of the anaerobic metabolic activity of the epidermis.

 The stratum corneum is therefore considered as a protective barrier of the epidermis and intervenes in particular in:

 - control of incoming and outgoing water flows

 - protection against UV rays.

 - protection against microbiological agents, due to the acid pH

- protection against foreign molecules harmful to the body such as venoms

 - and protection against chemical stress: aggressive pH and irritants.

Thus the destruction of the stratum corneum and epidermis can lead to irreversible sequelae from simple increased sensitivity to the sun (destruction of the stratum corneum), death in the case of the ^3rd degree burns over 90% of the body (destruction of the stratum corneum and the epidermis).

As for the dermis, the deep layer, constitutes:

- a water reserve - a fabric of support and physical resistance to mechanical stress

- and an anchoring fabric for the blood network and skin appendages.

In the different layers of the dermis are located various glands:

 - the eccrine glands responsible for thermoregulation of the skin and sweating. These glands open directly on the surface of the skin. They release water, lactic acid and salts whose overall pH is around 4-6.

- the apocrine glands, a vestige of evolution without a well-defined role.

 Their channel ends at the base of the hair and their content mixes with sebum. They produce aloproteins, short-chain acids, odorous volatile matter. The pH of these secretions is greater than 7.

- The sebaceous glands responsible for waterproofing the skin. They are housed near the hair follicles, forming the pilosebaceous apparatus. The sebaceous glands make sebum, which is made up of squalane, triglycerides and cholesterol. Sebum is one of the major constituents of the hydrolipidic film.

Depending on the secretion rate of the different kinds of glands, stimulated by exogenous or endogenous factors, three types of skin will be distinguished:

 - oily skin

- dry skin

 - combination skin.

Oily skin is dominated by an increased secretion of sebum. The factors responsible for this disorder are of different types: physiological: basic hormonal imbalance which panics and stimulates the sebaceous glands

 lifestyle: stress, fatigue and unbalanced diet

chemical: tobacco, etc. The consequences of this imbalance is the retention of sebum at level of the sebaceous duct leading to the formation of comedones. The latter undergoes chemical modifications of its components such as peroxidation of squalene as well as other free fatty acids. At a final stage of peroxidation, a “comedonian” bag is formed containing a bacterial flora, sebum derivatives and cellular debris becoming an environment conducive to inflammation known as acne.

 Dry skin, on the other hand, is more under the dominance of exogenous factors such as:

 extreme climatic conditions: either temperatures too cold or climate too hot. In both cases the humidity of the atmosphere is reduced

 exposure to wind and sun. In these conditions there is drying of the skin.

 harsh chemicals or chemotherapy products

 increased consumption of alcohol, and tobacco

 etc ....

Endogenous factors have been identified, however, such as physiological changes: puberty, pregnancy, menopause.

 Apart from a decrease in the humidity of the outer layer of the skin, there is a reduced secretion of sebum promoting increased loss of water from the epidermis.

 The consequences of these disorders are thus the formation of a dull, scaly skin and rough to the touch due to a lack of water in the epidermis. In the ultimate case the skin becomes thinner and cracks can appear and become conducive to serious diseases such as atopic dermatitis and eczema.

 As for them, combination skin has the characteristics of the two previous types and in one place on the body. In the case of the face, it is generally the T zone defined by the forehead, the nose and the chin which has an oily tendency compared to the rest of the face, the cheekbones with a dry tendency.

Combination skin is less sensitive to temperature variations, however it is difficult to treat due to competition of the two types of skin in the same place such as the face. From an aesthetic point of view, combination skin is shiny with large pores leading to the formation of blackheads and, in extreme cases, pimples.

 Apart from normal, oily dry and combination skin, other types of skin have been identified:

 sensitive skin

 and skin at the extremes of life: babies and the elderly.

More than a skin type, these are skin conditions since, for example, oily skin can be sensitive skin.

 In the case of sensitive skin, it is difficult to give a definition. In fact, from a clinical point of view, sensitive skin has no apparent particular symptom. On the other hand, these are skins appearing to be very reactive with regard to a certain number of factors such as:

 intrinsic factors: age, heredity, hormones, etc.

 environmental factors: cold, sun, pollution

 factors linked to chemicals: soaps, perfumes, cosmetics

 and lifestyle factors: diet, alcohol, stress, etc.

Thus, if no secretory disturbance of the different glands of the dermis is highlighted, the sensations of tingling, itching, burning, tightness, etc. would be conveyed by the cutaneous neuronal C fibers present at the level of the sensory receptors of the skin, the nociceptors located at the base of the stratum corneum. They are polymodal receptors sensitive to pain as well as to extreme temperatures but also to chemical substances.

 For some dermatologists, sensitive skin is skin with a lower tolerance for pain.

 For others, real sensitive skin is characterized by:

- the finesse and transparency of the latter. The redness is almost permanent due to disturbances in the skin micro-circulation - clear skin sometimes associated with dermatoses: rosacea, seborrheic or atopic dermatitis, rosacea.

In this case, sensitive skin would be prone to eczema, scabs and, in an extreme case, psoriasis. There would be impairment of the barrier function allowing the penetration of irritating factors.

 However, it would seem that cases of real sensitive skin are rare and that it would be more judicious to speak of:

 - allergic skin

 - and reactive skins.

In the first case, the skin reacts excessively to an allergenic substance that the body considers to be an invader. This would cause redness, rashes, itchy eczema. The substances responsible for these disorders are generally perfumes, chemical filters, essential oils, antiseptics, chemical preservatives, etc.

 For so-called reactive skin, it is the pain tolerance threshold that is called into question: reduction of the latter. This decrease would cause an excessive but temporary reaction to external aggressions. The main cause is stress. Indeed anxiety acts on all physiological systems including the epidermis.

 Finally, the last types of skin identified are those corresponding to the extremes of life:

 - baby's skin,

 - and the skin of the elderly.

If the skins of babies are morphologically little different from that of an adult, on the other hand they are more immature, especially in premature babies, making them, therefore, more fragile.

 So on a functional level, baby's skin is, among other things:

- much finer, especially in premature babies (20 to 30% finer). The stratum corneum is more fragile. Consequently, the protective barrier function is almost zero, facilitating the penetration of any infectious or allergenic agent. - Much more permeable in the first days of life, making it more sensitive to external aggressions. This is how it dehydrates faster and certain products that are well tolerated by adults can be dangerous for the newborn.

- Close to neutral with regard to pH. It is around

7 while that of the adult is close to 5.5. Such a pH can:

 • change the baby's skin permeability

• cause irritation

 • and be a source of microbial development (bacteria) - Immature in terms of sweat secretions and sebum. If in the first days of life the baby's skin is much oily than that of the adult, it normalizes in a few months. It is then observed an absence of sweat secretion and sebum leading to a hydrolipidic film of poor quality. This contributes to increased water loss making the baby's skin dry.

It thus becomes vulnerable to chemical (poorly adapted products), mechanical (rubbing of layers and clothing), and climatic (cold, wind, sun) aggressions.

 - extremely sensitive to the sun due to almost non-existent protection.

Baby’s skin becomes mature around the age of 3.

 Its fragility will therefore lead to a number of problems.

 In the scalp, during the first days of life an excess of sebum is observed following stimulation of the sebaceous glands during pregnancy. There is the formation of crusts, called crusts of milk. This excess sebum can also be found in the folds of the neck, armpits, back of the ear, face and on the region covered by the diaper. This can lead to seborrheic dermatitis which usually goes away on its own.

 In the buttocks it is the fragility of the skin that is called into question because this part undergoes many irritations, either:

 mechanical by the friction of the layer on the buttocks,

or chemical due to stagnation of urine in the diaper as well as stool. Under these conditions a diaper rash appears (redness of the buttocks) due to wet and soiled diapers. The latter can be simple or Candida (C. Albicans, fungus) and is located mainly on the genital area and buttocks

On the whole body can appear:

 eczema due to dryness of the skin due to the poor quality of the hydrolipidic film making the skin drier. This eczema leads to a thicker and scaly skin or can cause the formation of small reddish bumps which gradually swell, ooze or become infected causing itching,

 or a contact dermatitis due in particular to the dyes of clothing. It appears in areas where the skin is rubbing or in areas where the baby is sweating. It is more like an allergy.

Finally it will be necessary to be very careful not to apply anything on the skin of a baby during his toilet because the cutaneous absorption at this age, is much more important than that of the adult and certain molecules could, without danger for adults, prove to be very toxic.

 If baby's skin becomes mature around the age of 10, that of an adult begins to degenerate around the age of 30. The main degeneration observed is a loss of collagen reducing the elasticity of the skin. This is observed at the facial level: widening of the wrinkle which goes from the corner of the nose to the corner of the lips.

 Around 40 years of age expression lines appear due to slower renewal of cells causing sagging of the epidermis: appearance of folds in the forehead and crow's feet at the ends of the eyes.

 At 50 the phenomenon increases with:

 - appearance of spots

- increased folds in the mouth and double chin - sagging corner of mouth and tip of nose

 - increased double chin

 - digging of the nasolabial folds.

At 60, the skin becomes thinner and more saggy, especially at the sagging eyelids. The spots are becoming more and more numerous.

 On the physiological level are observed among others:

 - a change in the epidermis:

 • decreased hydration of the stratum corneum

 • increase in the number of neoplastomas (cancerous tumors) under the potential influence of ultraviolet rays by exposure during life

 • flattening of the space between the dermis and the epidermis and even the complete erasure of the papillae of the dermis. This phenomenon leads to a predisposition of the elderly to blisters, scrapes and shear injuries

• 50% decrease in the renewal of epidermal cells which is dominated by too intense exposure to ultraviolet rays

 • decrease in melanocytes making melanin leading to the appearance of spots on the skin, especially on the hands

 • an increase in tumors following a decrease in the basic immune response of cells located in the skin.

 - a modification of the dermis

 • decreased vascularity leading to

 * pallor of the elderly,

 * a decrease in skin temperature. Elderly people have trouble regulating their body temperature,

* a decrease in the elimination of foreign toxins, leading to the appearance of dermatoses, among other things, contact dermatitis.

• decrease in the amount of collagen causing thinning of the skin and this from 20 years. In the elderly, this takes the form of the appearance of sores and tears due to the loss of flexibility of the links between the dermal cells between them.

 • decrease in the amount of hyaluronic acid and dermatam sulfate also participating in the elasticity of the skin.

• decrease in the number and quality of elastic fibers. Wrinkles appear and accentuate lesions of the dermis during a slight trauma.

 • decrease in the number of sweat glands and the quality of secretions accentuating the problem of thermoregulation

• increase in the volume of the sebaceous glands but decrease in secretions playing a role on the elasticity of the skin.

 • reduction in the number of sensory nerve receptors, which no longer allows the elderly to protect themselves against certain cutaneous aggressions. They become less skillful. All of these modifications are the cause of frequent skin tumors and pressure sores such as pressure sores.

Over time these different parameters can be influenced by a number of factors:

 - genetics

 - climatic: sun

 - mechanical: repeated muscle pulls

 - physical: gravity (aviators)

- environmental: tobacco, hormonal deficit, diet, stress, etc. All of these observations would be affected by "oxidative stress". Indeed for some authors, aging of the skin is due to a weakening of the immune system preventing the body from defending itself against the attack of germs. The latter are responsible for the formation of free radicals creating tissue damage. Indeed the mitochondria present in the cells, responsible destruction of the latter, see their oxidative phosphorylation capacity for these elements, decrease. There is an imbalance between free radicals and the lack of natural antioxidants. These very reactive elements due to the absence of an electron on their outer layer will by all means pick up one to stabilize. This recovery will be done at the expense of other molecules such as collagen, elastin, proteins of the extra cellular matrix, etc ... Thus it is observed:

 - cytotoxicity

 - depolymerization of macromolecules

 - an alteration of the structure such as the extracellular matrix

- and a structural and functional disorganization of the cell membrane.

If the body has its own defense system to neutralize the effects of free radicals, this over time unfortunately will decline.

 In the majority of cases, the literature on aging deals with the visible parts of the body, the face and the décolleté. But this process is found at the level of the whole body.

 Thus is observed:

 - intense dryness of the skin all over the body resulting in itching

 - loss of firmness in the stomach, neck, inside of the arms

 - a sagging of all tissues, among other things at the breast level

 - a decrease in the thickness of the skin

 - and a loss of elasticity and flexibility. If the fragility of the skin of an elderly person is linked to a progressive degeneration thereof, the effects linked to this degeneration are similar to those encountered with the immature skin of the baby.

This is how, at the end of their life, a bedridden elderly person will be faced with: - diaper rash by:

 • prolonged skin contact with urine and stool

 • mechanical friction due to changes and the lying position of the person.

 This erythema can be the source of a more serious problem, the appearance of bedsores. These appear when

4 factors are involved simultaneously:

 * a tissue compression point (reduced blood supply),

 * fragility of the skin (thinning),

 * shearing of the different layers of the skin by friction (rupture of blood capillaries and elastic fibers).

 * a decrease in skin sensitivity

 contact dermatitis due to:

 • the excessive use of occlusive creams which promotes maceration, microbial development

 • the stagnation of contaminants in the gluteal folds (stool, urine, cleaning products)

In addition, certain physiological parameters are disturbed such that the pH (increase) and the protective barrier of the skin becomes more permeable to certain molecules and to bacteria.

Thus it appears that the skin is a very complex organ on the physiological level and it plays an essential role in the protection of the human body: protective barrier against attacks of all kinds and allows to regulate the body temperature. Therefore its partial or total destruction will cause a number of problems that can go as far as death. Whatever the type of skin identified (dry, oily, combination, sensitive skin, etc.), it will change over time, from the immature stage (baby skin) to the age of 10 years and it will start to degenerate from 30 years. This degeneration appears gradually through the appearance of wrinkles, then a thinning of skin, pigmentation, etc ... and above all a decrease in the quality of the hydrolipidic film.

 Consequently, whatever the age, it is necessary to take care of the skin to maintain its protective barrier function at its optimum. One of the important parameters to take into account to reach this objective is the maintenance of a quality hydrolipidic film.

 Caring for your skin is a huge area. It goes from the simple daily toilet to skin care treatments in the case of dermatological problems like those mentioned above.

 In general, the daily grooming which the common of mortals calls for "soapy" products.

 The term “soapy products” means products which form foam to a greater or lesser extent either by simple contact of these said products with water (liquid soaps) or after rubbing them in the presence of water (soaps solids).

 This foam has the property of eliminating both solid impurities and more or less viscous liquids which have accumulated during the day on the skin and in the pores of the latter. These impurities can have a hydrophilic character (sweat) or a lipophilic character, such as an excess of sebum.

This foam is obtained from a number of products called soaps, which range from simple conventional soap to "syndets", including liquid soaps, bubble baths, breads, etc.

 The appearance of classic soap dates back to the dawn of time. It has existed in different forms for over 4,500 years. The first soaps were developed by the Sumerians. They were based on fats and potassium carbonate. They used it to protect the skin, against disease and to whiten hair.

 In the 11th century BC, the Arabs added ashes and substituted potassium carbonate with sodium hydroxide.

 In the 8th century sodium hydroxide was replaced by cooked lime, now known as slaked lime or calcium hydroxide, leading to harder soaps.

From the 9th to the 15th century, vegetable oils were used take the place of fats, such as Aleppo soap made up of a mixture of olive oil and bay leaf, combined with sodium hydroxide.

 In the 18th century, a new ingredient was obtained, obtained from vegetable oils and lead oxide, glycerin, which was later introduced into soaps.

 In the 20th century, between 1920 and 1930, the first synthetic surfactants appeared, giving rise to “soap-free soaps” or “syndets” (“syn” for synthetics and “det” for detergents). A certain craze for these products is emerging because a controversy appears concerning the potential that conventional soap would be dehydrating for the skin, except that containing glycerin. Thus appear on the market, shampoos and shower gels using surfactants of different natures. The latter being more or less aggressive for the skin.

So through this short history it is found that the soap is composed of two ingredients:

 - an alkali

 - and a fat.

Concerning the alkalis, it has been identified, potassium carbonate, ashes rich in sodium hydroxide, sodium hydroxide alone and slaked lime (or calcium hydroxide).

 Regarding the fatty phase, initially the soap was made from animal fats, then gradually these were replaced by vegetable oils, such as olive oil and bay oil. Then appeared other oils such as palm, coconut, walnut, rapeseed, carnation, sunflower, flax, shower almond, shea, etc. oils.

 Some authors have tried to classify soaps according to different criteria such as:

 - its geographical origin:

• Marseille soap made from shea, palm or coconut oil. Marseille soap must contain at least 72% fatty acids. Soap is used for cleaning babies' linen and for washing people with allergies

 • white Swiss soap, based on sunflower oil, for the toilet

 • Aleppo soap, based on olive oil and laurel

• Azul y Blanco soap from Portugal for cleaning linen and carpets

its use :

 • milk soap: pH close to that of the skin leading to use for sensitive, fragile skin (baby skin) and for certain skin diseases such as eczema and psoriasis

 • toilet soap based on tallow or coconut oil but very rich in fatty acids (76 to 78%)

 • household soap based on palm oil, glycerin

• surgras soap, containing sweet almond oil, shea oil, in excess

 • medicinal soap, containing antiseptics such as sulfur, phenol, ichthyol, etc ...

its shape :

 • liquid Marseille soap based on olive oil and copra, the fatty acid content of which is much lower than solid soap: 15 to 20%

 • black soap made from crushed black olive oil. It is a soap for all skin types. It removes impurities and dead skin

 • transparent soap based on glycerin and honey. It is a very mild, cleansing and moisturizing soap, with no feeling of tightness after use. Its very creamy foam is ideal for delicate skin

• antiseptic soap containing cationic detergents to destroy bacteria on the surface of the skin. In the majority of cases the surfactants used are quaternary ammoniums • dermatological bread or soap without soap or "syndet". The pH of these “soaps” is close to that of the skin.

 • etc.

Thus it appears, depending on the geographical place of manufacture, use and form, that there are a large number of soaps with different properties but whose manufacturing principle remains the same: saponification reaction between an oil and an alkali.

Chemically, a reaction takes place between the triglycerol esters of unsaturated fatty acids contained in oils (or fats) and an alkali such as sodium or potassium hydroxide, calcium hydroxide (slaked lime), and potassium carbonate and this according to principle (1) below:

CH _{2 -} OOC - R CH ₂ - OH

CH - OOC - R + 30H- -> 3R - COO + CH - OH

CH _{2 -} OOC - R CH ₂ - OH

Triglycerides alkali ion carboxylate glycerin fatty acid fatty acids where "R" represents a saturated or unsaturated fatty acid.

Consequently, in view of the reaction principle, the soap has an alkaline pH of the order of 8 - 9 and if the alkali during manufacture is not completely consumed, the pH evolves towards even more basic values incompatible with the pH of the skin. Therefore to limit this problem, an excess of oil is always present during manufacture.

 However, during the last century, to limit the aggression of the skin by a soap that did not respond to its neutrality, preference was given to chemical surfactants to clean it.

These ingredients have been used because of their foaming power similar to that of soap, this foaming power being more or less important depending on their chemical structure.

The role of a surfactant is to lower the surface tension between two components immiscible with each other (two phases) such as water and oil or water and air, to obtain a uniform phase after mixed.

 In the first case, the surfactant gives rise to emulsions of the water in oil or oil in water type, depending on the most important phase.

 In the second case, foaming occurs: stirring of air: dispersion of the air in a liquid phase. A multitude of air bubbles are separated from each other by a thin wall of soapy water.

 Whether for foam or for emulsions, the mechanism of action of surfactants is the same. It is due to its chemical structure which has two poles: a polar head (hydrophilic) and an apolar tail (lipophilic).

 The surfactants are therefore positioned at the interface of the two liquids, the polar head in the hydrophilic phase (water) and the apolar tail in the lipophilic phase making the two phases miscible by simple stirring. There is thus the formation of micelles (vesicles) from the phase of least importance in the phase of greatest importance.

 When one of the phases is gaseous, the apolar tail of the surfactant will position itself in this phase, such as air, and the mixture by simple stirring will give rise to air vesicles in the liquid phase.

Thus a surfactant is therefore characterized by two poles, a hydrophilic pole and a lipophilic pole. Depending on the chemical nature of these two poles, different types of surfactants are identified:

 - cationic surfactants

 - anionic surfactants

 - nonionic surfactants.

 - amphoteric surfactants

Chemically, anionics are represented as next: RX Y ⁺ . This category includes sulfonates and carboxylates (R-SO ₃ Na ⁺ and R-CO2 Na ⁺ ). The best known commercially are sodium lauryl sulfate and sodium laureth ethoxylate sulfate. They have a strong foaming power.

Among the cationic surfactants these are the best known quaternary ammonium salts and correspond to the following formula: R-NH ₄ ⁺ CL. Among these most used ammoniums we find cetrimide and benzalkonium chloride.

 The group of nonionic surfactants contains alcohols of the R-OH type whose foaming power is less and have the property of trapping calcium.

 The last group, amphoterics, are both anionic and cationic surfactants and their mode of action depends on the pH of the medium. The best known are the betaine derivatives. They have a significant foaming power and relatively little irritant.

Concerning soap, because of its foaming power, it has been classified, chemically, in the category of surfactants and more precisely, in the group of anionic surfactants.

Indeed, the reaction described in (1) shows the formation of a carboxylate (R-CO2) associated with a chemical element belonging to the class of alkalis (Na ⁺ , K ⁺ ) or alkaline earths (Ca ²⁺ ) according to Mendeleev's classification.

"R" represents the carbon chain of the unsaturated fatty acid used in the saponification reaction. This carbon chain consists of more than 10 carbon atoms such as palmitic acid (C15H _{3 1} COO) or oleic acid (C17H ₃₃ COO).

The polar pole is therefore constituted by the -COO part and the apolar part by the carbon chain (C15H _{3 1} , or C 17H ₃₃ ).

 These various surfactants are used in the composition of formulations intended for cleaning in the broad sense of the term, that is to say of all surfaces, as well for:

 - cleansing the body: washing and caring for delicate skin

- cleaning textiles: household linen, carpets, etc.

cleaning any surface such as house floors (tiles), cars, etc ...

 - etc ...

and generally to remove all grease stains in the same way as conventional soaps and this due to a similar behavior in contact with water: foaming.

Among these formulations we find a large majority, in terms of toiletries, bubble baths, shower gels and shampoos. The foaming effect, a priori identical to that of soap, meant that the surfactants were used for the treatment of delicate skin due to a more controllable pH. It is thus easier to obtain formulations having a pH close to that of the skin, 4 -5,

 “Delicate skin” is understood to mean all the types of skin which have been studied previously, oily skin, dry skin, sensitive skin, reactive skin, baby skin, aging skin.

 It therefore appeared on the market dermatological breads also called "syndets" for the cleaning of delicate skin.

 They are solid products of the same shape as conventional soaps, but totally devoid of soap. They contain various surfactants dissolved in a base of variable composition but generally containing a starch or derivative of starch such as starch of wheat, corn, oats, etc ... from where the name of "bread".

 However, if the pH of conventional soap is responsible for a potential drying out of the skin, resulting in a tightness of the latter, the surfactants are irritants, causing sensitization reactions by destroying the hydrolipidic film.

 The least irritant effect is observed in nonionic surfactants, then comes amphoterics, cationics and finally anionics.

 Generally dermatological breads contain amphoteric surfactants whose foaming power is moderate.

Unfortunately the cleaning action being linked in the minds of ordinary people, to the formation of foam, dermatological breads can also contain more aggressive surfactants with strong power foaming to compensate for the absence of foaming.

 Thus, if today dermatological breads use amphoteric surfactants, the fact remains that their composition is very complex (about 20 ingredients) and may contain surfactants with high foaming power, aggressive for the skin by destruction of the hydrolipidic film. . Formulas have been developed to compensate for this elimination of the hydrolipid layer by incorporating oils, giving rise to surgras breads.

 However, environmental policy means that chemical surfactants are in the crosshairs of consumers and a return to “natural” is more and more appreciated.

 So classic soaps are back in fashion and some dermatologists recommend their use, such as Marseille soap or Aleppo soap. They contain 72% olive oil, the latter being known for its nourishing, soothing and protective properties and gives its green color to soaps.

 “White” Marseille soap is obtained by substituting olive oil with peanut oil.

 Due to the absence of any coloring, fragrance and preservative, these soaps are considered hypoallergenic. Unlike industrial soaps and past claims, Aleppo and Marseille soap are gentle on the skin and do not irritate the skin when a good rinse after use is respected. They are generally used to wash clothes for infants because they reduce the risk of irritation and allergies.

 They would be suitable for all skin types and are even recommended in the case of dermatoses, eczema and acne. Some dermatologists also recommend them for the sensitive skin of babies.

 Liquid forms of Marseille soaps have also emerged. They implement the same manufacturing process as for solid soap, namely the cold process, the last step being the addition of glycerin, other than that formed during the saponification reaction, to liquefy the medium.

The cold process involves mixing olive oil or other oils with sodium hydroxide or another alkali. After obtaining a dough, it is poured into molds which are closed to allow the saponification reaction to continue for a minimum of 24 hours. After demolding, a drying time of 4 weeks is necessary.

 In the hot process, the oil and the alkali are brought to 00 ° C for a minimum of 45 minutes to accelerate the saponification reaction. The mass becomes very viscous (appearance of mash) and can be poured into a mold. The molds are stored cool without the need to close them. At the end of cooling the soaps can be used immediately, but a drying time of a few days would be welcome.

 In these two processes, all of the oil used is found in the finished product as well as the glycerin formed during the saponification step.

 On the other hand, in the industrial process, it is possible to remove the excess oil as well as the glycerin formed by washing in the presence of sodium chloride. Under these conditions the soap obtained is less mild than the previous one. Without eliminating the excess oil and glycerin, the soap obtained can be described as an overgrown soap.

 To obtain a liquid soap, the paste obtained during the cold process after 24 hours of rest (saponification), is diluted with water and glycerin is added increasing the softening power of this soap.

On the other hand, apart from artisanal products containing only natural components (olive oil or mixture of oils, sodium hydroxide, glycerin, water), industrial products contain preservatives and surfactants to increase the foaming power of liquid soap , hence a certain aggressiveness of the latter. This is the case of the brand “pure liquid soap ^® “ of “Petit Marseillais”. The composition of this includes 18 ingredients including two surfactants (polysorbate 60 and polysorbate 20), two preservatives and phosphates.

 However if we want to get as close as possible to naturalness, there is another liquid form of soap on the market, the manufacturing process of which is not only artisanal, the oleo-limestone liniment.

The term liniment comes from the Latin “linimentum” of “linire” which means “oindre” in old French. Translated into everyday French, “oindre” means “rub, coat with oil or other fatty matter”.

 Thus in its definition the term liniment uses an oily phase, such as vegetable oils.

 The French Pharmacopoeia VIII th edition defines liniment as a “liquid preparation containing various medicinal principles dissolved or suspended in an appropriate vehicle. It is generally constituted by a medicinal oil or by a mixture of fatty substances, sometimes simply by alcoholic or soapy liquids ”.

 The term “oleo-limestone” amplifies the fatty character of the preparation

(oleo) and the presence of another component, limestone. But chemically, “limestone” can only be introduced in aqueous form.

 Consequently even if throughout the literature concerning soaps in general (liquids or solids), the term oleo-limestone liniment has not been mentioned or very little, the fact remains that this preparation responds perfectly to the definition of a soap: an oily phase combined with an alkaline phase and obtained by a manufacturing process identical to that of soaps: cold mixing of the oily phase and the alkaline aqueous phase leading to the formation of a soapy phase more or less liquid dispersed within the excess oily phase.

 Thus we mean by “oleo-limestone liniment”, a more or less viscous preparation resulting from a saponification reaction between an olive oil and an alkaline aqueous solution of calcium hydroxide and whose proportions in oily and alkaline aqueous phase are identical, the oily phase being in excess with respect to the soapy phase formed, leading to the production of an overgrown liquid soap.

 “Liquid soap” is understood to mean, in the sense of the invention, a liquid soap at 25 ° C. and at atmospheric pressure, which can flow freely or following the application of a shearing force (inversion agitation, pressure on the bottle, etc.).

In a more general context, we mean by “oleo-alkaline liniment”, a more or less viscous preparation resulting from a saponification reaction between an oil other than olive oil and an alkaline aqueous phase other than calcium hydroxide, respecting same proportions between the two phases and the oily phase being in excess compared to the soapy phase, with the aim of preserving the surgras character of the soap.

 So in the case of the oleo-limestone liniment the oily phase is mainly virgin olive oil. But different types of olive oil can be used. For "oleo alkaline" liniments, olive oil is substituted for or in combination with other oils.

 Whether for the “oleo-limestone” or “oleo-alkaline” liniment, these preparations are defined by the concentration of the two phases. This must be identical in both cases. On the scientific level this is expressed in the following way: "50: 50".

 A third parameter qualifying an oleo-limestone liniment is the nature of the aqueous phase.

 Indeed, if in the manufacture of soaps the alkaline aqueous phase is constituted by sodium hydroxide (soda) or potassium hydroxide (potash), in this case this phase is based on calcium hydroxide .

 Even if the ionization constant (pKb = 2.43) is high and the water solubility of calcium hydroxide low compared to sodium hydroxide (pKb = 0.2) and potassium hydroxide (pKb = 0.5), in contact with the oil, a cold saponification reaction will take place, giving rise to a soap dispersed in the oily phase.

 In the case of “alkaline oleo” liniments, the alkaline aqueous solution consists of another basic substance whose ionization constant (pKb) is identical to or close to that of the aqueous calcium hydroxide solution.

Thus, in both cases, a whitish liquid soap with a certain viscosity is formed, but of which the “soap” part is relatively weak compared to the oily phase. Due to the low solubility of calcium hydroxide in water, or the very low concentration of alkali in the aqueous phase, characterized by a low pKb, all of the latter, dissolved in water, will be fully implemented during the saponification reaction. Consequently, these products are particularly interesting for the skin of babies and elderly people because they are not very aggressive for the latter.

 For babies, the oleo-limestone Uniment provides a good quality hydrolipidic film due to the presence of a high oil content. The product is cleaning because of its soapy phase playing the role of surfactants removing impurities. Contrary to what is said, this soapy phase being in small quantities, it is not necessary to rinse the baby's skin because there would be a decrease in the protective role of the lipid film provided by olive oil. In addition, the pH of 7 - 8 of this preparation is perfectly suited to that of baby's skin (pH 7), hence its use in diapers to neutralize the acid pH of urine.

 In the context of the elderly, apart from all the advantages mentioned above for baby's skin, it is good to note that olive oil has a very interesting healing effect in the presence of pressure sores on aging skin. So if we base ourselves on the National Form, the oleo-limestone Uniment answers to the following formula:

 100 virgin olive oil

 Lime water (calcium hydroxide solution) 100

corresponding after saponification reaction to the composition below:

 0.6% calcium carboxylate (soapy phase)

 0.7% glycerin (formed during the saponification reaction)

50% water

 48.7% olive oil

knowing that the lime water solution contains 1.69 g per liter of dissolved calcium hydroxide.

By simple stirring and in the cold, there is a whitish phase which, at rest, dephases a little, thus highlighting an excess of oil which did not react during saponification. Despite the formation of a soap, calcium carboxylate, this does not have sufficiently powerful surfactant properties to form a stable emulsion.

 Formerly made at the pharmacy this was not a problem and it was indicated on the bottle "shake before use".

 On the other hand, given the enthusiasm today for this 100% natural preparation, it is no longer possible to make such a preparation at the back of your pharmacy. A certain number of laboratories have therefore undertaken to manufacture this preparation industrially. However, from an aesthetic point of view, presenting a product that dries up is not a sign of quality for the consumer.

 Consequently, the laboratories have sought to stabilize this formulation and have used either natural thickeners or not and surfactants or a combination of the two.

 Among the natural products we find beeswax. But the stability of the product alone does not seem to be reached.

 Consequently, it has been associated with other molecules such as glycerol stearate, the latter belonging to the class of nonionic surfactants.

 Among the natural thickeners used in the Uniment we can find xanthan gum. Other less natural are cited in formulations such as sugar esters, stearic acid, cetyl alcohol, self-emulsifying waxes, etc.

The latter are more complex products, such as sorbitan olivaie (sorbitol + olive oil), cetearyl olivate (cetearyl alcohol + olive oil) and Polawax ^® (cetearyl alcohol + polysorbate 60).

 But the most common combination to stabilize the industrially manufactured oleo-limestone Uniment is the association of glyceryl monostearate with stearalkonium hectorite combined with propylene carbonate.

Even if the hectorite is of natural origin, smectite (clay), that used in oleo-limestone liniments, Bentone ^® , contains quaternary ammoniums inserted between the different strata of this material having a lamellar structure. Such a chemical transformation thus allows the hectorite to thicken oily media, therefore to stabilize in the presence of an aqueous phase all the more easily due to the presence of a surfactant distributed homogeneously within the raw material.

 However if we refer to the previous data, it turns out that these surfactants are aggressive for the skin and even toxic under certain conditions of use. Among other things, they destroy the lipid film causing skin irritations.

 Such products used to stabilize the oleo-limestone liniment at a rate of 10% in the preparation, can not be used for cleaning the skin of babies or the elderly without fear of risk of irritation if a rinse is not after use.

 If beeswax is used in industrial preparations of oleo-limestone liniment, to stabilize it, its thickening properties are not sufficient to obtain a physically stable preparation (absence of phase shift), at low concentrations. In addition, beyond a certain concentration, the liniment presents an unpleasant oily character during its application, or even at the limit of a phase shift in contact with the skin. Consequently, we have sought to increase the physical stability of the liniment without increasing the viscosity of the latter.

 A study of patents in the field of liniments shows that little has been protected concerning the stabilization of the preparation and does not correspond in any way to the present invention.

 Indeed, the majority of patents mentioning the term liniment based on olive oil among others, corresponds to the first definition of liniment cited above: oily preparations applied by friction on the body.

 Among these we can cite:

 - Chinese patents protecting:

 • CN 103479775: a mixture of olive oil and sweet almond, angelica essential oil, vitamin E, safflower oil and other ingredients to treat joint problems

 • CN 106728308: the manufacture of a paste based on corn starch, tea leaf oil containing a certain number of plant extracts, for the treatment of eczema

• CN 1990003: a preparation based on olive oil, isopropanol, mustard, camphor and menthol for athletes

 - the American patent US20088175933 protects a mixture based on olive oil (20%) and alcohol (49%) and other ingredients

 - Japanese patents protecting:

 • JPH09104623: a mixture of vitamins in a squalene / olive oil and isopropyl myristate base, intended for skin problems

 JPS5720922: an antibiotic (nanaomycin) dissolved in an oily phase such as olive oil, for the treatment of trycophytosis

 - the Korean patent, KR20030081848 protects a preparation for bleaching the hair and containing sodium persulfate dispersed in a mineral oil and a vegetable oil such as olive oil

 - Spanish patent ES228 1249 protects a mixture based on olive oil, camphor, menthol and methyl salicylate

 - the Philippine patents PH22017000624 and PH22017000601 protecting a manufacturing process for extracting a date oil and the mixture consisting of olive oil, eucalyptus essential oil and date oil.

 - European patent EP3 146969 protecting the calcipotriol and corticosteroid mixture in the form of a liniment consisting of paraffin oil

Other patents, on the other hand, use a saponification reaction as described above, but without seeking to stabilize the preparation. The alkaline solutions used are thus found:

- an ammonia solution as described in the following patents and protecting:

 • GB 190925743: a mixture based on olive oil, paraffin, ammonia, half an egg and 6 drops of lavender intended for rheumatism

GB502083: a mixture based on beef foot oil with olive oil saponified by ammonia to which essential oils and liquid soap are added

 • GB 190406487: a saponification reaction of rapeseed oil with ammonia combined with liquid soap giving liquid preparations identical in appearance to oleo-limestone liniments.

 • MXPA01008162: a mixture of essential oils and paraffin oil saponified by an ammonia solution, having analgesic and anti-inflammatory properties

a calcium hydroxide solution as mentioned in the following patents and protecting:

 • CN 106913746 and CN 106913745: a hot saponification reaction between tea leaf oil and a solution of calcium hydroxide. During this preparation a number of other ingredients are added.

 • CN 103800401: a saponification reaction between sesame oil and a solution of calcium hydroxide. After production, a certain number of other ingredients are introduced minerals, vitamins, sugars, etc. Mention is also made of the presence of glyceryl monostearate.

 • CN 1839898: saponification of sesame oil with a calcium hydroxide solution but different from the previous one in that the proportions of each phase are different: 30 to 65% (oil) and 35 to 70% (solution alkaline) and does not mention glyceryl monostearate

 • CN 103638075: a composition similar to the previous one but differentiated by the fact that the mass of the oily phase (sesame oil) is identical to that of the alkaline phase and does not contain glycerol monostearate

 • CN 1616059: a preparation similar to the previous patents but mentions an antibiotic added to the preparation. On the other hand the concentrations in oily and alkaline phase are not identical

• R0121586, R0121672, R0121673: a mixture based on lanolin, linseed oil, shark liver oil, stearin and beeswax saponified with a solution of calcium hydroxide

 • CN 101 103970, CN 101 103971, CN 101 1 12388: the formation of a calcium salt of fatty acid either from linoleic acid or glycerolinoleic acid, stearic or glycerostearic acid or oleic or glyceroolic acid in the presence of a solution of calcium hydroxide

 • KR100837796: a saponification reaction between an oil and calcium hydroxide, the latter of which is obtained from the oyster shells

 • KR20080087991: a saponification reaction between a vegetable or animal oil and calcium hydroxide in order to obtain calcium salts of fatty acids with less rancidity compared to the oils themselves.

 • CN 106883955: a saponification reaction of a mixture consisting of olive oil (5-10 parts), coconut oil oil (5-15 parts), tea leaf (1-5 parts) ) with an alkaline solution containing sodium hydroxide (2-5 parts) and calcium hydroxide (1 part). To the reaction product is added an algae extract (50-100 parts)

• CN 10585 1901 and CN 105901744: a saponification reaction between olive oil (10 to 20%) with a 1% solution of calcium hydroxide (10%) intended for the manufacture of fat substitutes for the food sector.

• R0121763: a cosmetic composition based on the saponification reaction between a mixture of sunflower oil and olive oil at a ratio of 39 to 44 parts and a solution of calcium hydroxide (50 parts). To this preparation is added glycerin (10 parts)

 • CN 102579483: a saponification reaction between olive oil and a solution of calcium hydroxide, the respective proportions are as follows: 2 to 8 parts for the alkaline phase and 8 to 2 parts for the oily phase

A potassium hydroxide solution as used in following and protecting patents:

 • CN 1061 1 8923: a saponification reaction between a mixture consisting of avocado oil, grape seed, olive, coconut, apricot oil and potassium hydroxide, to obtain a liquid soap for make-up removal

 • PH22015000466: a saponification reaction between a mixture consisting of olive oil and coconut, with a potassium hydroxide solution to which plant extracts are added in order to make a liquid soap

 • CN 107815366: a saponification reaction of a mixture consisting of coconut oil (100), palm (100), rice (100), sweet almond (100) and olive (100), with potassium hydroxide solution (92). To the product of this reaction is added an extract of fruit juice, this preparation being intended to treat acne

 • US2016376526: a saponification reaction between a fatty acid and potassium hydroxide in order to form a liquid soap whose viscosity is regulated by the addition of sodium chloride

 • etc ....

a sodium hydroxide solution as cited in the following patents and protecting:

 • GB 1915 18060: the manufacture of a soap based on essential oils, stearic acid and palmitic acid

 • CN 106867722, CN 106434055, CN 106467876: a mixture of several oils, including olive oil, saponified by a solution of sodium hydroxide

 • KR201 1004288, KR 20100028984: a saponification reaction between evening primrose oil and an alkaline solution of either sodium, potassium or lithium and defining a saponification rate, between 0.001 to 99.9%

 • GR1008293: the manufacture of a soap based on olive oil obtained from a saponification reaction by using sodium hydroxide.

• FR2992216: an exfoliating soap based on olive oil obtained from starting from a process similar to that described in the previous patent.

 • FR2963935: a liquid soap based on olive oil obtained by hot saponification reaction in the presence of sodium hydroxide, and hot dilution with water, of the soap obtained

• JP2003049199: a hot process for obtaining a soap by saponification reaction between olive or sweet almond oil, or palm or jojoba oil and a sodium hydroxide solution.

 · W02017 / 192109 describes a preparation giving rise to a soap obtained by saponification of vegetable oils of different types with a solution of sodium or potassium hydroxide, these oils are mixed with a defined acid solution of “vinegar” serving as support for certain plants. The addition of this acid phase, containing a certain level of acetic acid, is intended to form salts with the calcium or magnesium present in the washing water. The pH of such preparations is around 9 to 10, not acceptable for babies' skin. On the other hand the proportions of the aqueous and oily phases do not meet the criterion of the liniment “oleo limestone”

Among all the cited patents using either calcium hydroxide or another alkaline solution, only 3 patents mention the use of beeswax (R0121586, R0121672, R0121673) and only 1 of l use of glyceryl stearate as a stabilizer.

 Similarly, in the case of patents using potassium hydroxide leading to liquid soaps by saponification reaction, none of them mentions a stabilizing agent for the preparation.

Thus after an in-depth study of the literature in the field of liniments as defined in the National Form, or the manufacture of liquid soaps, it was not possible to highlight an effective solution to avoid the phase shift of such preparation, apart from the use of chemicals potentially dangerous for the skin of babies or the elderly.

On the basis of this state of affairs and to remedy it, the subject of the invention is in particular liquid soaps, more or less viscous, more or less viscous, mechanically stable, intended for the cleaning of delicate skin, obtained by cold saponification reaction, comprising:

i) an oily phase, consisting of fatty materials whose fatty acids in the form of triglycerides, have carbon chains having a number of carbon atoms between 12 and 18 (C1 2 to C i ₈ )

 ii) an alkaline phase, consisting of hydroxides or salts of alkaline or alkaline earth ions, the concentration of which in aqueous solution results in a pH of between 10 and 13 and a pKb of between 0.2 and 4.0, preferably a pKb between 0.75 and 2.5

 iii) one or more mechanical stabilizing agents, at a concentration greater than 5% by mass relative to the total mass of the finished product and belonging to the family of native or modified starches insoluble cold in an aqueous medium, the particle size of which is between 1 and OOpm, preferably between 1 and 20 pm

 iv) one or more additives chosen from the class of natural structuring agents, acids, buffer systems, preservatives and antioxidants, active principles and their mixtures,

 the proportion of each phase being identical and at most each representing 50% by mass of the final mass of the final product, the saponification reaction carried out when cold is such that the carboxylates formed are dispersed in the oily phase in excess, the medium viscosity ranging from 1000 mPa.s (cPs) to 40,000 mPa.s (cPs), preferably from 1000 mPa.s (cPs) to 30,000 mPa.s (cPs), measured at a temperature of 20 ° C, the pH from 4 to 8 and the size of the oily globules from 5 to 15 pm.

The proportion of the oily and aqueous phases being identical and at most representing each, 50% by mass, of the final mass of the final product, The saponification reaction carried out cold is such that the carboxylates formed are dispersed in the oily phase in excess, the viscosity of the medium possibly ranging from 1000 mPa.s (cPs) to 40,000 mPa.s (cPs) measured at the temperature of 20 ° C., the pH of 4 to 8 and the size of the oily globules from 5 to 15 μm.

 Thus the present invention aims to develop liquid preparations, more or less viscous, consisting of an oily phase representing at most 50% of the final mass of the preparation and an alkaline aqueous phase also representing at most 50% of the mass of the finished product, the mixture of these two phases leading to the formation of a soap by saponification reaction between the fatty acids of the oily phase and the alkali solubilized in the aqueous phase. The saponification reaction is carried out cold. The amount of alkali used is such that the saponification of the oily phase is not complete, thus leading to the formation of fatty acid carboxylates (products of the saponification reaction) dispersed in the oily phase. The dispersion of these carboxylates is perfect by adding a substance having the role of a mechanical surfactant to the medium.

 The term “mechanical surfactant” is intended to mean a substance capable of stabilizing a preparation without carrying out electrophilic reactions, as is observed with anionic, cationic or amphoteric surfactants. The product obtained is mechanically stable under the effect, for example, of centrifugation or any other mechanical process capable of normally deteriorating the product.

 The preparations resulting from the present invention have properties:

 - cleansers due to the presence of a protective soapy phase (carboxylates) due to an excess of oil in the medium, making it possible to maintain the balance of the hydrolipidic film on the surface of the skin during cleaning

 - And caregivers by incorporating active substances to prevent certain skin problems such as erythema, dermatitis, etc.

The preparation thus obtained is considered to be an overgrown liquid soap, the pH of which can be adjusted to approach physiological pH. of the skin, 7-8 for the skin of babies and 4-5 for adults.

 Such a soap can therefore be used for all types of skin and, among other things, "delicate skin".

 This invention is based on the fact that certain substances insoluble in oily and aqueous medium, exhibit in an lipophilic environment, unexpected physical properties giving rise to oily solutions of non-negligible viscosity (100 to 200 mPa.s (cPs)) while their thickening power by swelling or gelation, in this same environment is completely zero and this whether cold or after heating.

 Thus, for defined concentrations of these substances dispersed in the oily phase, it is possible to stabilize the preparation containing fatty acid carboxylates resulting from the saponification reaction, the latter not being in sufficient quantity to themselves ensure the physical stability of the finished product. The solutions thus produced remain sufficiently liquid to be packaged in bottles with or without a pump, in single doses or in tubes.

 The term "stabilizing substances" or "stabilizing agents" means any product which avoids the phase shift of an emulsion (appearance of two phases), either by sedimentation (formation of a deposit) or by creaming.

(formation of a solid phase on the surface of the product) of particles in suspension in a medium.

 The stabilizing substances used in the present invention are raw materials of natural origin widely used in the pharmaceutical, cosmetic and dietetic and food fields.

 Obtaining said cleaning preparations which are the subject of the present invention make use of substances known as stabilizing substances which in oily solution lead, after the saponification reaction, to preparations of low viscosity, stable over time.

 The term “preparations stable over time” means preparations which, after 3 months of storage or more, at ambient temperature, do not exhibit any phase shift phenomenon.

These so-called stabilizing substances can be used alone or as a mixture (combination of several stabilizing substances) in the phase oily, at a concentration greater than or equal to 5% relative to the total mass of the finished product, giving rise, after cold saponification reaction between the oily phase and the alkaline aqueous phase, to a stable solution of low viscosity containing carboxylate fatty acid dispersed in excess unreacted oil.

 “Low viscosities” are understood to mean viscosities of between 1,000 and 10,000 mPa.s (cPs), determined at 20 ° C. using the rotating mobile technique defined in the European Pharmacopoeia (Pharm. Europ. (2.2 . 10)).

 Thus these stabilizing substances, by their weak influence on the viscosity of the finished product, ensure packaging in bottles or in single doses and allow easy use by the consumer. Apart from this low viscosity, it was observed that the final mixture obtained exhibited a certain thixotropy amplifying the physical stability of the product over time.

 The term “thixotropy” is understood to mean the property that a mixture has to take a gelled appearance at rest and which by manual agitation (inversion of the bottle) resumes its liquid form.

 The stabilizing substances making it possible to obtain said liquid preparations and playing the role of "mechanical surfactants (or mechanical stabilizing agents)" belong to the class of natural polymers, polysaccharides:

 The polysaccharides used in the context of this invention are starches and in particular native starches.

 The term "native starch" means starches as they are contained in cereals, legumes, tubers, roots and fruits, during their extraction, the latter having undergone no structural modification whatsoever. physical, chemical or enzymatic.

 Native starches are polymers of glucose. The glucose molecules are linked either:

 linear: amyloidosis

 branched: amylopectin

Generally the so-called native starches, starches as they are extracted from plants, are formed by the mixture of these two structures. On the physical level, the starch grain is formed by different layers of these two molecules and are positioned identically to the structure of an onion: formation of strata between amylose and amylopectin within the same grain.

 Depending on their botanical origin, the proportion of these two polymers varies as shown in Table I below.

 Table I: physico-chemical characteristics of different types of starches

As is, native starches do not have thickening properties

 It is only by heating the starch grains in the presence of water that their thickening properties are enhanced.

 The grains swell up to a temperature called gelatinization temperature, specific to each type of starch. This is the starch gelation step (see Table II). By continuing the heating in an aqueous medium, the hydration of the starch grains is maximum. The latter burst (separation of the different layers), thereby releasing amylopectin and amylose and leading to the formation of a colloidal solution.

This hydration is concretized on the physical level by an increase in the viscosity of the solution which by cooling gives rise over time to a gel. This is the phenomenon of demotion.

 Table II: gelatinization temperature of different native starches

If in an aqueous medium the behavior of starches is well defined, it is not the same in oily medium as indicated by Miroslaw M. Kasprzak and All. (Foods hydrocolloïds, 81 [2018], pp 409-418, ISSN 1 873- 7137). Little has been described concerning the behavior of native starches in such media and even less as a mechanical stabilizer of particles (solid or liquid) in oily media.

 In accordance with the preceding comments, the study of the patents has not led to the identification of applications similar to that making the object and of the present invention.

 Indeed, no patent mentions the use of starches in the native state, as stabilizers (chemical or mechanical) of emulsions of water in oil type (W / O or W / O, "W" for water and "O" for oil) .or oil in water (O / W or O / W) during a saponification reaction.

Certain patents such as the American patent US2015337120 mentions an emulsifying system consisting of cellulose, hemicellulose and starch in the form of fibers dispersed in an oily phase and an aqueous phase in which the oily phase represents 60% of the total mass. of the preparation. The viscosity of this system is such that it can lead to chewable or skin-like forms (solid forms), therefore of viscosity greater than that defined in the present invention. On the other hand, no mention is made of the oils which can be used in this system, nor of any aqueous alkaline phase giving rise to a saponification reaction.

 Another US patent US5676994 protects an emulsifier system obtained from a solution of starch brought to the boil and gradually introduced into the oily phase. In this case, the starch undergoes gelatinization: destruction of the starch grain releasing amylopectin and amylose in the medium. After the emulsion obtained has cooled, a gel forms which becomes liquid again under the effect of heat. The last step described in this patent is to obtain a dry form which is easily redispersible in an aqueous or oily medium. Thus, this patent differs from the present invention by the fact that:

 no aqueous alkaline phase is used

 the proportions of the two phases are not defined

 and it is necessary to heat the preparation to reach its objective of emulsion stabilizer. In the present case, stabilization is obtained by swelling of the starch up to the gelation stage under the effect of heat.

Regarding patents W0201208206 and W02008 / 104591, if these use, certainly starches to stabilize emulsions, but these are modified starches and in particular in the form of a salt of starch octenyl succinate. It is considered a chemical surfactant in the same way as anionic, cationic and amphoteric surfactants, the polar part being constituted by the octenyl succinate group.

For its part, the US patent US2005214432 protects a process for manufacturing white sauce used in cooking, consisting of an oily phase and an aqueous phase stabilized by the use of native starches, wheat starch, starch rich in protein derivatives. The emulsion of the medium is carried out using an ultrasound system of frequency included between 20 and 200 Hz. On the other hand, unlike the present invention, the proportion of the two phases is completely different. Indeed the oily phase represents only 15% at most, of the total mass of the finished product and the aqueous phase can go up to 95%. The probability of obtaining a stable emulsion under such conditions is much greater than in the case of the present invention because even if the temperature of the medium is maintained at 20 ° C. during mixing, the ultrasound can cause in situ heating of the molecules leading to a slight hydration of the starch molecules more easily stabilizing such preparations. On the other hand, there is no mention whatsoever of the use of an alkaline aqueous phase and even less of a cold saponification reaction.

 Japanese patent JO2007274983 seeks to stabilize the manufacture of sauces (roux) by the use of starches without adding chemical surfactants. But in the present case, all of the manufacture is carried out hot and at very high temperatures close to the gelation temperature of the starch.

 Similarly, patent HU9603,157 implements a technique similar to that described in the preceding patent, for the manufacture of light butter in the absence of any chemical surfactants, these being substituted by a mixture of starch and pectin, the starch can be a modified starch.

 If the previous patents do not implement the saponification reaction, the patent GB305742 describes the production of solutions with emulsifying properties intended for road bitumens and other types of materials of this kind, by implementing this said reaction. These solutions are obtained from oils, oil resins and by-products from the paper industry. These oils are mixed with corn starch and water. The whole is heated to 50 ° C., the gelatinization temperature of this starch. To this solution is added concentrated sodium hydroxide and the whole is brought to 96 ° C. After cooling, the product of this reaction is used as an emulsifier.

 If this patent comes as close as possible to the present invention, it is distinguished by the fact that:

- the proportion of the alkaline and oily aqueous phases is not mentioned

 the saponification agent is concentrated sodium hydroxide and heating is necessary to produce such an emulsifying solution.

Among the native starches that can be the subject of the present invention, the native starches of cereals, legumes, roots, tubers, and fruits are retained, among other things, starch from rice, corn, wheat, potato, tapioca.

 Provided that they remain insoluble in an aqueous and oily medium when cold, modified starches of these different botanical origins can be the subject of the present invention.

 This is how the cold-insoluble modified modified starches are obtained by chemical modifications, physical and enzymatic modification being prohibited because of the production of cold-soluble modified starches in an aqueous medium.

The chemical reactions that native starches can undergo are: substitution reactions leading to starches:

 · Crosslinked: creation of bonds between two polymer chains

 • esterified and etherified: substitution of an OH group in the polymer chain by hydroxypropyl, hydroxyethyl or acetyl groups

- hydrolysis reactions leading to starches with short polymer chains:

• Dextrins: starch which has undergone depolymerization and then recombined into branched short chain polymers. These starches do not exhibit the phenomenon of retrogradation · Hydrolysed starches leading to unbranched polymers of short chains. These starches have a strong retrograding power. Subsequently, they can undergo substitution reactions as defined above. Oxidation reactions lead to the substitution of the hydroxyl groups by COOH or CO groups. then oxidation reactions there is depolymerization of starches giving rise to molecules having short polymer chains. These starches do not exhibit a demotion phenomenon due to the steric hindrance of the COOH and CO groups, thus preventing the formation of hydrogen bonds between the polymer chains.

Regardless of the plant origin, whether native or modified starch, insoluble when cold, retained, the size of the starch grains is essential for the latter to act as a "mechanical surfactant" or "mechanical stabilizer".

 FIG. 1 corresponds to a photograph by electron microscope of native rice starch suspended in the oily phase. There is no grain swelling. Their size is of the order of 9 pm.

 FIG. 2 corresponds to a photograph by electron microscope of native rice starch suspended in the liniment after the saponification reaction, at the start of the homogenization process. We observe the distribution of starch grains on the surface of the oil globules, without swelling of the latter. The microscopic photos (Fig 1 and Figure 2) of the emulsions obtained at the industrial stage show that the starch grains are positioned on the surface of the oil globules. The smaller the starch particles, the better their role as a "mechanical surfactant". The starch grains being essentially hydrophilic, their positioning on the surface of the oil globule makes it "hydrophilic" at the periphery facilitating its integration into the aqueous medium. It is assumed that this mechanism is related to the composition of the starch grain.

 Indeed being made up of layers of amylopectin (little soluble in water) and amylose (soluble in water), the grain will be positioned in such a way that the amylopectin part will be in contact with the oily phase and the part amylose will be turned towards the aqueous phase, such as a conventional surfactant having a hydrophilic pole, here amylose and a lipophilic pole, here amylopectin.

Even if the preparation is not heated to hydrate starch, the latter can gradually absorb water causing it to swell, further stabilizing the preparation by giving it the appearance of a thixotropic structure.

 The particle size of the native starches and of the modified starches must be between 1 and 10 μm and preferably between 1 and 20 μm.

 Since the amylose and amylopectin concentrations are responsible for a good distribution of the grains at the oil / water interface, the ratio of these two components within the starch grain must be between 1: 3 and 1: 5 (amylose: amylopectin).

 Following stabilization tests of oleo-limestone liniments obtained cold and in accordance with the definition of the National Form, it was possible to define the concentration in mechanical stabilizer (s), and preferably in native rice starch, in the medium, between 5 and 30% by mass relative to the final mass of the mixture and preferably between 7 and 15% relative to the final mass of the mixture.

 Under such conditions, the preparations obtained have a size of oily globules less than 25 μm (FIG. 3) and between 5 and 15 μm. This is highlighted in the photograph obtained by electron microscope, of the rice starch suspended in the Uniment after 3 hours of homogenization. It is observed that the sizes of the globules are between 5 and 15 microns and surrounded by starch grains. (figure 3)

A centrifugation test of such preparations (N) obtained on an industrial scale, shows that they are as stable as preparations (A) containing chemical surfactants and an oily phase thickener, hectorite (Bentone®) (Figure 4). This is highlighted in FIG. 4, the 4 test tubes containing the preparations (N) and (A) as defined above, were subjected to centrifugation, 15 minutes at 4000 rpm. Fes preparations (A) representing the old formula based on Bentone ^® are much more unstable (phase shift) than, preparations (N), new formula based on native rice starch.

The starches, native or modified, insoluble in cold, are introduced into the oily phase before the cold saponification reaction.

This oily phase in the case of oleo-limestone liniment, in the sense strict of the definition, is constituted by olive oil.

 Different olive oils exist on the market and are characterized by the content of oleic acid (Table III)

 Table III: different types of olive oil

The fatty acid composition, from C 14 to C24, is identical regardless of the type of oil, but they differ in terms of "trans" fatty acids. The values are listed in the following table IV:

Table IV: fatty acid composition of olive oils Oils are characterized by:

 the saponification index corresponding to the following definition: amount of potassium hydroxide, expressed in milligrams, necessary for the neutralization of free fatty acids and for the saponification of the esters present in l g of substances

(European Pharmacopoeia (2.5. 1)),

 the iodine index corresponding to the following definition: quantity of halogen (iodine), expressed in milligrams, capable of being fixed by 100 g of substances. This index makes it possible to determine the content of unsaturated fatty acids (European Pharmacopoeia (2.5.4)), the unsaponifiable: rate of non-volatile substances at l 00 ° - l 05 ° C, expressed as a percentage, obtained by extraction in organic medium (European Pharmacopoeia (2.5.7)) In the case of olive oils these three parameters are listed in the following table (table Y)

 Table IV: chemical characteristics of olive oils

Each of these oils can be used pure or as a mixture in the present invention.

 In the pure state, the quantity used must be equal to that of the alkaline aqueous phase and represented at most 50% by mass of the final mass of the finished product and preferably between 30% and 50% by mass, preferably between 40% and 50% by mass, relative to the final mass of the finished product.

When mixed, the concentration of virgin olive oil must be between 5% and 95% relative to the mass of the oily phase. The term “oleo” in Uniment oleo-limaire broadly means “fat”. Therefore in view of the bibliographic study of patents, it is possible to introduce other fats other than olive oil into the preparation provided that the proportion between the alkaline aqueous phase and the oily phase is respected. .

 In fact, during the patent study, a preparation obtained by the saponification reaction of an oily phase other than olive oil was not highlighted with an alkaline aqueous solution and stabilized by addition a native or modified starch which is cold insoluble in the medium.

 "Fat" means any substance containing saturated, mono and polyunsaturated fatty acids and / or in trans form, whether in liquid form (oil) or in semi-solid form (butters and fats). These fats can be of vegetable or animal origin.

 The fats which can be the subject of this present invention are numerous and are obtained from the fruits of certain trees. They are defined by a composition of fatty acids, the number of carbon atoms on the carbon chain of which can range from C8 (caprylic acid) to C26 (cerotic acid) and more. These oils are in fact mixtures of triglycerides of fatty acids corresponding to the structure described above in equation (1), thus leading after the saponification reaction to the in situ formation of glycerin and carboxylates, soapy phase.

 In the present invention, oils containing mainly triglycerides of fatty acids with carbon chain ranging from C 12 to C 18 are retained.

 These fatty acids can be:

 saturated such as palmitic acid (C 16), stearic acid (C 18), arachnic acid (C20)

 mono unsaturated such as palmitoleic acid (C 16 - 1), oleic acid

(C 1 8 - 1)

and poly unsaturated such as linoleic acid (C 18-2) and linolenic acid (C 1 8-3). The fatty acid composition of the oils used for the present invention is as follows:

 content of saturated fatty acids from C 12 to C 18 between 10 to 95% by mass relative to the total mass of the oil

- content of mono-saturated fatty acids from C 12 to C 18 between 15 and

95% by mass based on the total mass of the oil

 content of polyunsaturated fatty acids from C 12 to C 18 between 5 and 60% by mass relative to the total mass of the oil A list of these different oils is given below in Table VI but is not in in no case a limitative list of fats which can be used in the present invention.

 Table VI: fatty acid profile of certain oils

These oils can largely replace Uniment olive oil oleo-limestone either:

 partially and whose proportion in olive oil is between 5 and 95% by mass, of the total mass of the oily phase in totality, thus representing at most 50% by mass, of the total mass of the finished product, this phase oily can be a mixture of different oils other than olive oil, of variable proportions but respecting the final maximum rate of 50% in the finished product. The cold saponification of the oily phase, whether it contains whole olive oil, or a mixture of olive oils of different types, or a mixture of olive oil and another oil and / or another oil or mixture of other oils, other than olive oil, is obtained by adding an alkaline solution to the medium. According to the National Form, this alkaline solution for the oleo-limestone liniment, is obtained from a saturated solution of calcium hydroxide, or lime water.

 The saturated calcium hydroxide solution leads to a content of 1.69 g / liter of calcium hydroxide dissolved in the medium.

 Such a solution has a pH of 12.4 and a pKb of 2.43.

 PKb is a constant used to calculate the strength of an alkaline solution, corresponding to the number of OH ions present in the medium. The lower this constant, the stronger the alkaline solution.

 By adding this solution to the oily phase containing native starch and by simple cold stirring of the medium, there is formation of calcium carboxylates (soapy phase of the liniment) and glycerin.

The study of patents in the field of the manufacture of soaps, whether liquid or solid, or even liniments other than those meeting the definition of the National Form, has shown that this soapy phase or the soap itself, could be obtained from different alkaline solutions other than a calcium hydroxide solution. These can be based on sodium (sodium hydroxide or carbonate), potassium (hydroxide or carbonate) or ammonia. In addition, this study has shown that none of the preparations from these saponification reactions was the subject of a stabilization of the finished product by the addition of native or modified starch insoluble cold in the oily phase before reaction.

 Consequently, the present invention can be applied to the formation of an “oleo-alkaline” unit obtained from aqueous alkaline solutions which have a pH of between 10 and 13 and a pKb of between 0.2 and 4.0, preferably a pKb between 0.75 and 2.5. These different solutions can be obtained by dissolving another substance other than calcium but belonging to the class of alkalis and alkaline-earths such as sodium, potassium, lithium (alkalines), calcium, and magnesium (alkalines earth).

 Among these solutions having a pH between 10 and 13, we can cite:

 solutions based on magnesium hydroxide (saturated solution),

 solutions of magnesium oxide, pH 10.5;

 solutions based on potassium carbonate at a concentration of 1.30% m / V ± 5%, pH 11.5;

 solutions based on potassium hydroxide at a concentration of 0.06% m / V ± 5%, pH 12;

 solutions based on sodium carbonate at a concentration of 1.06% m / V ± 5%, pH 11.6;

 solutions based on sodium hydroxide at a concentration of 0.04% m / V ± 5%, pH 12;

 - solutions based on trisodium phosphate at a concentration of 1.63% m / V ± 5%, pH 12.

Thus the concentrations of alkaline substances in the aqueous phase are such that when these solutions are added in an amount equal to that of the oily phase, carboxylates dispersed in an excess oil do not form by simple cold stirring having not been saponified.

In accordance with the definition of the National Form, the concentration in alkaline aqueous solution in the present invention must therefore be equal to that of the oil phase and represent at most 50% by mass of the final mass of the finished product and preferably included between 30% and 50% by mass, more preferably between 40% and 50% by mass, relative to the final mass of the finished product.

Even if the pH of the final preparation after the saponification reaction drops, it remains relatively high and cannot be used as it is for cleaning the skin of babies or the elderly.

 Consequently, it is possible to disperse in the oily phase, that is:

 an acid such as sorbic, citric, malic, lactic, etc ... - or an acid buffer system of disodium phosphate / monosodium phosphate monohydrate, sodium acetate / acetic acid, monopotassium phosphate / disodium phosphate, etc ....

reducing the pH of the preparation to the physiological pH of baby's skin (7-8) or of the adult (4-5).

The concentration of these substances in the medium depends on the desired pH and between 4 and 8

The finished product obtained from this reaction has a viscosity of the order of 1100 mPa.s (cPs). In this form, the product can be used as a treatment lotion for sensitive skin.

By cons for a more thorough cleaning of damaged skin, bedsores, or baby skin in contact with diapers, a more consistent product is necessary.

Thus it is possible to add to the medium substances acting on the viscosity of the finished product, and in particular natural structuring agents such as:

- natural waxes such as, for example, beeswax, carnauba, jojoba, candellia, rice bran, etc. However, it was found that there was a ratio to be respected between the oil concentration and the wax. Thus in the presence of beeswax, even if the product seems physically stable over time, during its application, the fatty character of the preparation is very pronounced on contact with the skin. A kind of phase shift is observed when it is applied to the skin. Therefore a ratio should preferably be respected and between 1: 15 and 1: 90 (wax: oil)

- thickening agents such as modified cold-soluble starches, gums, etc.

 We understand by “cold soluble modified starches” unlike “cold insoluble modified starches”, all starches having undergone a modification

 * physical, such as pregelatinization

 * chemical and physical, such as a substitution reaction (fixing of hydroxypropyl groups on the starch grain) combined with a physical modification of pre-gelatinization

 Among these starches we will retain the native pregelatinized cold-soluble starches in the aqueous phase, such as rice starch, potato starch, tapocia corn, legumes, etc ... and the corresponding hydroxypropyl starches having also undergone a pre-gelatinization.

 Compared with native starches and modified cold insoluble starches, these thickening agents are no longer in the form of grains of defined size, dispersed in the oily phase. The pregelatinization phase made it possible to break the shell of these so-called grains, thus releasing amylose and amylopectin in aqueous medium, facilitating their hydration. This hydration leads to a thickening of the aqueous phase in which these molecules are found.

A certain similarity appears between the present invention and that protected in the American patent application US2009 / 0232856 A1 where an emulsion is dispersed in a gel. However, the present patent is distinguished by the fact that the gel consists of a cold-soluble modified starch, preferably a native pregelatinized starch or a pregelatinized hydroxypropyl starch. Nothing of the sort is specified in the American patent apart from the quotation of polysaccharides and gums in the broad sense. In addition, the American patent mentions a certain number of surfactants which can be used for the formation of a three-phase emulsion which have the characteristic of being all chemical. There is no mention of the use of native starch as a “mechanical surfactant” to stabilize this ternary system.

 Finally, no saponification reaction is involved during the development of this three-phase emulsion

 The concentration of thickening agents, other than natural waxes, will depend on the viscosity desired for the finished product and on the feel of the latter when it is applied to the skin. It is a maximum of 5% by mass relative to the total mass of the finished product.

 The viscosity of such preparations is between 20,000 cPs and 40,000 cPs.

 In addition, these preparations have a very interesting rheological property: they are called “rheo-thickeners”. The viscosity of the medium increases despite the application of a shear force. This property is all the more important as the product, under certain conditions, must have a covering power. This is the case for products with high levels of active ingredients with protective power such as zinc oxide.

 Such viscosity allows tube packaging

The primary definition of liniment given above mentions “various medicinal principles dissolved or suspended in an appropriate vehicle”. Consequently, the “oleo-alkaline” liniments obtained from the present invention can serve as a vehicle for certain active agents, such as:

 vitamins (vitamin A, B vitamins, vitamin PP, etc.)

- protective agents: zinc oxide, titanium oxide, sun filters

 minerals: copper, zinc, scale, etc ....

 repair agents: resveratrol, centella asiatica, hyaluronic acid, allantoin, etc.

anti inflammatory drugs: enoxolone plant extracts with repairing, emollient, nourishing properties, etc.

 In the context of therapeutic use, these same preparations may contain active ingredients called curative, used in skin problems such as eczema, psoriasism, acne, dermatitis, etc.

 Their concentration in the finished product varies depending on the desired effect: comfort product or product with a therapeutic aim. The presence of water in the medium and natural compounds such as starch, involve the introduction into the medium of preservatives so as to ensure microbiological cleanliness over time.

 Natural preservatives such as sorbic acid, potassium sorbate, benzoic acid, sodium benzoate, or caprylyl glycol ethylhexylglycerin combinations can be used.

To avoid any rancidity of the oily phase, it is possible to add to the medium antioxidants of the tocopherol type, or ascorbic acid and ascorbic acid salts such as ascorbyl palmitate, or the combination of the two ; preferably tocopherol and / or its derivatives.

The manufacturing process used to obtain these so-called oleo-limestone or "oleo-alkaline" liniments includes:

 cold dispersion of native or modified starch insoluble in cold in the oily phase containing or not an acid or a buffer system in order to bring the pH of the finished product to physiological values

 The solubilization of the alkali in the aqueous phase the introduction, with stirring, of the alkaline aqueous phase, in the oily phase

 and the homogenization of said liniment for a fixed period of time, depending on the size of the batch.

In the case of the need for a thickener of the medium by a natural wax, this is introduced into the oily phase which is brought to a temperature corresponding to the melting point of the latter. After melting, the temperature of the medium is brought back to a value not exceeding 60 ° C.

 Similarly, if the need to increase the viscosity of the medium using a thickening agent, this is done by introducing modified cold soluble starch into the alkaline aqueous phase.

Another object of the present invention relates to the use of a soap as defined above, for cleaning delicate human skin.

The present invention also relates to the following subject:

 Surgras liquid soaps, mechanically stable, intended for the cleaning of delicate skins, obtained by cold saponification reaction, comprising:

 i) an oily phase, consisting of fatty materials, the fatty acids of which in the form of triglycerides, have carbon chains having a number of carbon atoms between 12 and 18 (C1 2 to C 1 s) iijune alkaline aqueous phase, consisting by hydroxides or salts of alkaline or alkaline earth ions whose concentration in aqueous solution leads to a pH between 10 and 13 and a pKb between 0.75 and 2.5

 iii) one or more mechanical stabilizers, at a concentration greater than 5% by mass relative to the total mass of the finished product and belonging to the family of native or modified starches insoluble cold in an aqueous medium, including the particle size is between 1 and OOpm

 iv) one or more additives chosen from the class of natural thickeners, acids, buffer systems, preservatives and antioxidants, and mixtures thereof,

 the proportion of each phase being identical and at most each representing 50% by mass, of the final mass of the final product,

the saponification reaction being such that the carboxylates formed are dispersed in the oily phase in excess, the viscosity of the medium possibly ranging from 1000 mPa.s (cPs) and 30,000 mPa.s (cPs) measured at the temperature of 20 ° C., the pH from 4 to 8 and the size of the oily globules from 5 to 15 μm.

Preferably according to this object and, the proportion of oily phase in the finished product is between 30% and 50% by mass, more preferably between 40 and 50% by mass relative to the mass of the finished product.

 Preferably according to this object, the fats of the oily phase are oils and butters of vegetable origin.

Preferably according to this object, the fats of the oily phase consist of virgin olive oil, olive oil, olive-pomace oil or a mixture of at least two of these components.

 More preferably according to this object, the concentration of virgin olive oils is between 5% and 95% relative to the total mass of the oily phase.

 Preferably according to this object, fats other than olive oils have a defined fatty acid composition.

 Preferably according to this object, the fatty acid composition of fatty substances other than olive oils, comprises from 10 to 95% of saturated fatty acids from C 12 to Cis, from 15 to 95% of monounsaturated fatty acids from C 12 to Cis and from 5 to 60% of polyunsaturated fatty acids from C1 2 to Cis.

 Preferably, according to this object, fats other than olive oils are used alone within the oily phase or as a mixture with olive oils or as a mixture between them.

 Preferably according to this object, the alkaline and alkaline-earth ions constituting the aqueous alkaline solutions are sodium, potassium, lithium, calcium and magnesium.

 Preferably, according to this object, the alkaline or alkaline-earth ions are in the form of hydroxides, carbonates or phosphates.

Preferably according to this object and, the proportion of alkaline aqueous phase in the finished product is between 30% and 50% by mass, more preferably between 40% and 50% by mass, relative to the final mass of the finished product.

Preferably according to this object, the mechanical stabilizing agent is a native or modified starch insoluble cold in the aqueous phase, obtained from cereals, roots, tubers, fruits and legumes.

 Preferably according to this object, the mechanical stabilizing agent is native rice starch.

 Preferably according to this object, the concentration of mechanical stabilizing agent (s) is between 5 and 30% of the total mass of the finished product and preferably between 7 and 15%.

 Preferably according to this object, the particle size of the mechanical stabilizing agent is between 1 and 20 μm.

 Preferably according to this object, the concentration of acids and buffer systems leads to a pH of between 4 and 8.

 Preferably according to this object, the natural thickening agents are waxes such as beeswax, carnauba, jojoba, candellia, rice bran.

 Preferably according to this object, the concentration of natural thickening agents is between 0.5 and 5% by mass relative to the total mass of the finished product.

 Preferably according to this object, the antioxidants are preferably chosen from the group of tocopherols.

 Another object of the present invention relates to the use of a soap as described in the object above, for cleaning delicate human skins. Examples of oleo-limestone liniments obtained from the present invention are presented below but do not in any way constitute a limiting list of formulations.

EXAMPLE 1:

 Virgin olive oil 200 g

Saturated solution of filtered calcium hydroxide 200 g

Rice starch 20 g

Place 200g of virgin olive oil and 20g of rice starch in a beaker with a capacity of 500 ml. Subject the mixture to stirring for 3 minutes at 20,000 rpm using an Ultra Turrax.

 Then gradually add 200g of saturated calcium hydroxide solution with stirring.

 Perfect agitation for 5 hours.

 The Oleo limestone Uniment obtained has a pH of 9.0 and a viscosity of 1100 mPa.s (cPs).

EXAMPLE 2:

 Virgin olive oil 445, 70 g

Vitamin E 0.10 g

Calcium hydroxide solution 444.44 g

Beeswax 15.00 g

 Sorbic acid 1.00 g Rice starch 100.00 g

Sensiva ^® SC 10 12.50 g

In a beaker with a capacity of 1500 ml, introduce:

 - 222.85g of virgin olive oil

 - 15.00 g of beeswax

 Bring the mixture to 75 ° C to melt the beeswax. Stop heating after melting.

 Once melted, with stirring add:

 - 222.85 g of olive oil

 - 0.10 g of vitamin E

 - the rice starch OOg

 - 1.00 g of sorbic acid

 Mix at 20,000 rpm using an Ultra Turrax for 5 minutes.

 Introduce the calcium hydroxide solution with stirring.

 Homogenize for 5 minutes at 20,000 rpm using an ultra Turrax.

Add Sensiva ^® SC 10 and perfect the homogenization for 3 minutes. The Oléo limestone Uniment obtained has a pH of 7.3 and a viscosity of 12000 mPa.s (cPs).

EXAMPLE NO.3:

Virgin olive oil 222.85 g

Pomace oil 222.85 g

Vitamin E 0.10 g

Calcium hydroxide solution 444.44 g Beeswax 15.00 g

Sorbic acid 1.00 g

Rice starch 100.00 g

Sensiva ^® SC 10 12.50 g

In a beaker with a capacity of 1500 ml, introduce:

 - 222.85g of virgin olive oil

 - 15.00 g of beeswax

 Bring the mixture to 75 ° C to melt the beeswax. Stop heating after melting

 Once melted, with stirring add

 - 222.85 g of pomace oil

 - 0.10 g of vitamin E

 - the rice starch OOg

 - 1.00 g of sorbic acid

 Mix at 20,000 rpm using an Ultra Turrax for 5 minutes

 Introduce the calcium hydroxide solution with stirring

 Homogenize for 5 minutes at 20,000 rpm using an ultra Turrax

Add Sensiva ^® SC 10 and perfect the homogenization for 3 minutes.

The oleo limestone liniment obtained has a pH of 7.4 and a viscosity of 1100 mPa.s (cPs). EXAMPLE # 4:

 Pomace oil 445, 70 g

Vitamin E 0.10 g

Calcium hydroxide solution 444.44 g Beeswax 15.00 g

Sorbic acid 1.00 g

Rice starch 100.00 g

Sensiva ^® SC 10 12.50 g In a beaker with a capacity of 1500 ml, introduce:

 - 222.85g of pomace oil

 - 25, 00 g of beeswax

 Bring the mixture to 75 ° C to melt the beeswax. Stop heating after melting

 Once melted, with stirring add

 - 222.85 g of pomace oil

 - 0.10 g of vitamin E

 - the rice starch OOg

 - 1.00 g of sorbic acid

 Mix at 20,000 rpm using an Ultra Turrax for 5 minutes

 Introduce the calcium hydroxide solution with stirring

 Homogenize for 5 minutes at 20,000 rpm using an ultra Turrax

Add Sensiva ^® SC 10 and perfect the homogenization for 3 minutes.

The oleo limestone liniment obtained has a pH of 7.5 and a viscosity of 9000 mPa.s (cPs). EXAMPLE 5:

 Virgin olive oil 393.00g

Vitamin E 0.10 g

Calcium hydroxide solution 393.00 g Beeswax 20.00 g

Sorbic acid 1.00 g

Rice starch 100.00 g

Sensiva ^® SC 10 7.50 g

Chamomile extract 4.00 g Pregelatinized rice starch 20.00 g

In a beaker with a capacity of 1500 ml, introduce:

 - 196.5 virgin olive oil

 - 20.00 g of beeswax

 Bring the mixture to 75 ° C to melt the beeswax. Stop heating after melting. Once melted, with stirring add:

 - 196.5 g of olive oil

 - 0.10 g of vitamin E

 - the rice starch OOg

 - 1.00 g of sorbic acid

 - 100 g of zinc oxide

 - 4.00 g of chamomile extract

Mix at 20,000 rpm using an Ultra Turrax for 5 minutes

 Add 20.00 g of pregelatinized rice starch to the calcium hydroxide solution.

 Mix using a paddle shaker for 60 minutes at 200 rpm.

 Introduce the starch calcium hydroxide solution with stirring into the oily phase.

 Homogenize for 5 minutes at 20,000 rpm using an ultra Turrax

Add Sensiva ^® SC 10 and perfect the homogenization for 3 minutes.

Claims

1. Liquid soaps, mechanically stable, for cleaning delicate skin, obtained by cold saponification reaction, comprising:

 i) an oily phase, consisting of fatty materials whose fatty acids in the form of triglycerides, have carbon chains having a number of carbon atoms between 12 and 1 8 (C1 2 to Cis)

ii) an alkaline phase, consisting of hydroxides or salts of alkaline or alkaline earth ions, the concentration of which in aqueous solution results in a pH between 10 and 13 and a pKb between 0.2 and 4.0

iii) one or more mechanical stabilizers, at a concentration greater than 5% by mass relative to the total mass of the finished product and belonging to the family of native or modified starches insoluble cold in an aqueous medium, the particle size of which is between 1 and 20 pm

iv) one or more additives chosen from the class of natural structuring agents, acids, buffer systems, preservatives and antioxidants, active principles and their mixtures,

 the proportion of each phase being identical and at most each representing 50% by mass of the final mass of the final product, the saponification reaction carried out when cold is such that the carboxylates formed are dispersed in the oily phase in excess, the viscosity of the medium ranging from 1000 mPa.s (cPs) to 40,000 mPa.s (cPs) measured at a temperature of 20 ° C, the pH from 4 to 8 and the size of the oily globules from 5 to 15 pm.

 2. Soaps according to the preceding claim, characterized in that the proportion of oily phase in the finished product is between 30 and 50% by mass, relative to the final mass of the finished product.

3. Soaps according to any one of the preceding claims, characterized in that the fats of the oily phase are oils and butters of vegetable origin. 4. Soaps according to any one of the preceding claims, characterized in that the fats of the oily phase consist of virgin olive oil, olive oil, pomace oil d olive or a mixture of at least two of these components.

 5. Soaps according to the preceding claim, characterized in that the concentration of virgin olive oils is between 5% and 95% relative to the total mass of the oily phase.

 6. Soaps according to any one of the preceding claims, characterized in that the fats other than olive oils have a defined fatty acid composition.

 7. Soaps according to any one of the preceding claims, characterized in that the fatty acid composition of fatty materials other than olive oils, comprises from 10 to 95% of saturated fatty acids from C12 to C is, from 15 to 95% of mono-saturated fatty acids from C 12 to C is and from 5 to 60% of polyunsaturated fatty acids from C 12 to Cis.

 8 ° Soaps according to any one of the preceding claims, characterized in that the fats other than olive oils are used alone within the oily phase or as a mixture with olive oils or as a mixture between them.

 9. Soaps according to any one of the preceding claims, characterized in that the alkaline and alkaline-earth ions constituting the aqueous alkaline solutions are sodium, potassium, lithium, calcium and magnesium.

 10 ° Soaps according to any one of the preceding claims, characterized in that the alkali or alkaline earth ions are in the form of hydroxides, carbonates, oxides or phosphates.

1 1 ° Soaps according to any one of the preceding claims, characterized in that the mechanical stabilizing agent is a native or modified starch insoluble cold in the aqueous phase, obtained from cereals, roots, tubers, fruits and legumes. 12 ° Soaps according to any one of the preceding claims, characterized in that the mechanical stabilizing agent is native rice starch.

 13 ° Soaps according to any one of the preceding claims, characterized in that the concentration of mechanical stabilizing agent is between 5 and 30% of the total mass of the finished product and preferably between 7 and 15%.

 14. Soaps according to any one of the preceding claims, characterized in that the concentration of acids and buffer systems leads to a pH of between 4 and 8.

 15. Soaps according to any one of the preceding claims, characterized in that the natural structuring agents are waxes and thickeners.

 16. Soaps according to any one of the preceding claims, characterized in that the waxes are chosen from beeswax, carnauba, jojoba, candellia, bran, rice.

 17. Soaps according to any one of the preceding claims, characterized in that the wax: oil ratio must be between 1: 15 and 1: 90.

 18 ° Soaps according to claim 15, characterized in that the thickeners are native pregelatinized starches and hydroxypropyl pregelatinized cold soluble starches.

 19 ° Soaps according to claim 1 8, characterized in that the concentration of pregelatinized starches is at most 5% by mass relative to the final mass of the finished product.

 20 ° Soaps according to any one of the preceding claims, characterized in that the antioxidants are chosen from the group of tocopherols.

21. Soaps according to any one of the preceding claims, characterized in that the active principles are vitamins, protective agents, minerals, repairing agents, anti-inflammatory agents, plant extracts. 22 ° Use of a soap as defined according to any one of claims 1 to 21, for cleaning delicate human skins.