WO2004065533A1

WO2004065533A1 - Novel lanolin substitutes, production method thereof and applications of same

Info

Publication number: WO2004065533A1
Application number: PCT/FR2003/003759
Authority: WO
Inventors: Pierre Charlier De Chily; Mikaële RAYNARD
Original assignee: Aldivia Sa
Priority date: 2002-12-23
Filing date: 2003-12-17
Publication date: 2004-08-05
Also published as: EP1576077A1; AU2003300641A1; FR2849053A1; FR2849053B1

Abstract

The present applicant has already developed a method of obtaining a substitute of lanolin and derivatives (lanolin alcohol, etc.) which can absorb up to at least twice the weight thereof in water or aqueous solution or aqueous suspension. Said substitute of lanolin and derivatives (lanolin alcohol, etc.) forms real emulsions which are stable over time, which have a water retention power greater than that of lanolin and which possess the known emollient, hydrating and occlusive properties of lanolin. The invention relates to the production of novel substitutes of lanolin and derivatives (lanolin alcohol, etc.) which also have other organoleptic and physicochemical characteristics of lanolin, such as the feel, colour, iodine number and melting point thereof. The novel substitutes of lanolin and derivatives (lanolin alcohol, etc.) are obtained by hemi-synthesis from a mixture of saturated and/or unsaturated fatty acids, saturated and/or unsaturated fatty acid esters, saturated and/or unsaturated hydrocarbons or saturated and/or unsaturated derivatives of same and compounds comprising or generating hydroxyl functions, such as glycerol, preferably without a catalyst and in an oxygen-depleted atmosphere. In addition, the invention involves standard heat treatment or, preferably, dielectric heating. Said substitutes are suitable for use in any current or future lanolin application in cosmetics, pharmaceutics, veterinary medicine, dermatology and in industrial applications (waxes, lubricants, etc.), etc.

Description

New lanolin substitutes and derivatives (lanolin alcohol ...),

their production process and their applications

Technical sector of the invention and problem posed:

Lanolin, fat extracted from sheep's wool, is commonly used by the cosmetic and pharmaceutical industries for its emollient, moisturizing, emulsifying properties and its water absorption capacity.

Despite all these properties, the animal origin of lanolin less and less satisfies the consumer, made worried by the disease called "scrapie of the sheep". Allergic reactions from pesticide residues, its strong odor, its variable composition, its irregular supply etc. are additional factors which push scientists to look for lanolin substitutes.

There have been many attempts to replace lanolin with oleochemicals.

However, the substitutes proposed so far do not provide complete satisfaction by their properties, the complexity of their composition, certain high physicochemical characteristics such as the acid number, and / or their manufacturing cost.

The Applicant has filed a patent application FR N ° 01 08905 concerning an original and economical process for obtaining a lanolin substitute and derivatives (lanolin alcohol ...), capable of absorbing up to at least twice its weight in water or aqueous solution or aqueous suspension. As described in this aforementioned patent, the substitute for lanolin and derivatives (lanolin alcohol, etc.) forms real emulsions, stable over time with a water retention power greater than that of lanolin and it also has the properties emollient, moisturizing and occlusive known to lanolin, without having the disadvantages. The Applicant proposes in this present invention to further improve the organoleptic and physicochemical characteristics of the lanolin substitute and derivatives (lanolin alcohol, etc.) described in said aforementioned patent: the new lanolin substitutes and derivatives (alcohol lanolin ...) retain the properties of the previous one (water absorption, hydration, emollience ...) but they also meet other criteria very important for the industry such as touch, color, index d 'iodine and the melting point.

The objective of such an invention is to obtain lanolin substitutes and derivatives (lanolin alcohol, etc.) which bring complete satisfaction whatever the application concerned, which is impossible to date.

Prior art:

The Applicant has filed an aforementioned patent application not yet published to date and concerning a process for obtaining a lanolin substitute and derivatives (lanolin alcohol ...). In said patent is described the prior art relating to lanolin. This prior art also applies to the preparation of this new substitute for lanolin and derivatives (lanolin alcohol, etc.) envisaged here.

For the convenience of those skilled in the art, an extract is given below. Those skilled in the art may usefully refer to the aforementioned patent application for the details.

Lanolin

• Composition and specifications of lanolin:

Lanolin is a solid, amber-yellow wax with a characteristic odor. It is insoluble in water but soluble in hot ethanol, ether and chloroform.

It is a mixture of sterols and long chain fatty alcohols. This mixture sometimes contains other substances (nickel, chromium, copper ...) in the form of traces. Lanolin is made up of carbon chains that can range from C14 to C30. Its composition is complex: Free acids; Esters of triterpene alcohols and sterols; Esters of aliphatic alcohols; sterol monohydroxyesters, alcohols aliphatic and triterpenic; Free aliphatic alcohols; Triterpenic alcohols and free sterols; Di and polyhydroxy esters and free diols; Oxidation derivatives; hydrocarbons

The following table gathers the physico-chemical characteristics of this product:

Table 1: Specifications of the lanolin

Obtaining lanolin

Lanolin is extracted from sheep's ointment, a sebaceous material secreted by the sweat glands of the animal. The. grease represents 15 to 75% of the weight of the wool fibers.

• Functions and applications of lanolin:

- cosmetic and dermatological functions and applications

Lanolin is widely used in cosmetics and dermatology for its emollient, hydrating, emulsifying, occlusive properties. It softens the skin, protects it and prevents its dehydration. Lanolin also has the power to absorb up to 4 times its weight in water. In addition, it is not very sensitive to oxidation. The extremely numerous lanolin derivatives obtained by physical or chemical transformation, having better odor, color and touch characteristics, are preferably used.

Due to its remarkable properties, lanolin and its derivatives are used in the composition of many preparations such as: bubble baths, lipsticks, creams, shaving creams, after shave lotions, powders, soaps, shampoos.

- industrial functions and applications

Lanolin is also used in the industrial sector with various applications: waxes, printing inks, anti-rust and anti-corrosion protective films deposited on certain metals, leather and fur industry for waterproofing, paints ...

Reasons to substitute lanolin

Despite all its properties, lanolin is increasingly criticized for the following reasons:

- its animal origin.

- its possible impurities (example: pesticides) and the allergic reactions which result from it

- its strong odor which must be masked by the use of perfuming agents, sometimes poorly tolerated in people with sensitive skin

- its variable composition due to the diversity of sheep species, their ages ...

For all of its reasons, many scientists are looking to substitute lanolin.

Lanolin substitution alternatives

Up to now, the proposed substitutes have not been entirely satisfactory: they are emollients and moisturizers, but they do not have the power to absorb water. In addition, the complexity of their composition, certain high physicochemical characteristics such as the acid number, and / or their manufacturing cost needs to be optimized.

The Applicant has filed the aforementioned patent application which has already considerably improved the properties of lanolin substitutes and derivatives (lanolin alcohol, etc.), in areas where no results had been achieved before.

However, there is still an important and recognized need to find a real substitute for lanolin, that is to say to improve the aforementioned patent.

The Applicant proposes in this present invention to further improve the organoleptic and physico-chemical characteristics of the lanolin substitute and derivatives (lanolin alcohol, etc.) described in said aforementioned patent.

Summary of the invention:

The present invention provides new lanolin substitutes and derivatives (lanolin alcohol, etc.), which not only have the properties of the previous lanolin substitute and derivatives (lanolin alcohol, etc.), described in said aforementioned patent (ability to absorb up to twice its weight in water, formation of stable emulsions, hydration, emollience, occlusiveness) but also other organoleptic and physicochemical characteristics of lanolin such as touch, color, index iodine and melting point.

Their manufacturing process is simple and economical compared to the previous ones, known to those skilled in the art.

Applications:

The Applicant has discovered new lanolin substitutes and derivatives (lanolin alcohol, etc.) for the cosmetic and dermatological market and all the other applications of lanolin, and an original preparation process. Examples of cosmetic applications:

- bubble baths,

- lipsticks, - skincare creams for dry skin,

- shaving creams,

- after shave lotions,

- powders,

- soaps, - shampoos,

- waterproof sunscreen,

- make-up removers,

- bath oils,

- lip balms - ointments

- lip sticks ...

Examples of industrial applications:

- polishes

- printing inks,

- anti-rust and anti-corrosion protective films deposited on certain metals,

- leather and fur industry for waterproofing,

- additives for lubricants,

- the paintings...

This list is not exhaustive. These lanolin substitutes and derivatives (lanolin alcohol, etc.) can be used in all current and future applications of lanolin.

The invention is particularly, but not limited to, heat treatment of saturated and / or unsaturated fatty acids, esters of saturated and / or unsaturated fatty acids, saturated and / or unsaturated hydrocarbons or derivatives saturated and / or unsaturated thereof and of compounds comprising or generating hydroxyl functions, such as glycerol, preferably without catalyst and in an oxygen-free atmosphere.

Description of the invention

The present invention provides new lanolin substitutes and derivatives (lanolin alcohol, etc.).

Their manufacturing process is simple and economical compared to the previous ones. These lanolin substitutes and derivatives (lanolin alcohol, etc.) are obtained by hemisynthesis from a mixture of saturated and / or unsaturated fatty acids, esters of saturated and / or unsaturated fatty acids, hydrocarbons. saturated and / or unsaturated or saturated and / or unsaturated derivatives of the latter and of compounds comprising or generating hydroxyl functions, such as glycerol, preferably without catalyst and in an atmosphere devoid of oxygen.

The invention relates to the properties of these products:

- Surprisingly, they have the power to absorb up to at least 2 times their weight in water. In addition, the emulsions formed are stable over time and after several passages in an oven at 40 ° C. This phenomenon is not observed for lanolin which releases all its water in less than 15 days.

- Added to this water absorption capacity, the products are emollients, moisturizers, emulsifiers and occlusive. They soften the skin, protect it and prevent its dehydration.

- They also have other organoleptic and physicochemical characteristics which are more and more and surprisingly similar to those of lanolin: o melting point o length of the carbon chains o softness, penetration, spreading, shine, color, odor. ..

The particularity of this invention comes from the combination of the reagents used in the reaction medium: - reagents including unsaturations (acids, esters, hydrocarbons and their derivatives)

- reagents containing or generating hydroxyl functions, called 'OH reagents'

- high melting point reagents

- reagents made up of short carbon chains

- reagents made up of long carbon chains

The invention therefore relates to the general process characterized in that the combination of the above reagents is reacted in the reaction medium.

The invention also relates to new industrial products which in themselves have properties which clearly distinguish them from previously known industrial products.

The particularity of these products comes from the fact that in the same product different parameters are gathered: water absorption + emollience + hydration + melting point + odor + color + ... The products according to the invention are therefore clearly distinguished from prior art.

• Reagents including unsaturations: at the origin of water absorption (40 to 89.95%)

Reagents comprising unsaturations (acids, esters, hydrocarbons and their derivatives) make it possible to obtain polymers of unsaturated fatty acids, esters of unsaturated fatty acids, unsaturated hydrocarbons, unsaturated derivatives of these compounds, alone or in mixture. This process is described in patent application FR 98 13770 and PCT patent application WO 00/26265 (PCT / FR99 / 02646) to which a person skilled in the art can refer. However, the emulsions obtained are not stable: the water is released in less than 24 hours.

• Reagents containing or generating hydroxyl functions, called 'OH reactants': (0.05 to 60%) A sufficient quantity of "OH-reactants", that is to say comprising or generating hydroxyl groups, is added to the reaction medium.

It has been surprisingly observed that the products obtained have emollient, hydrating and occlusive properties, but also absorb up to at least twice their weight in water. In addition, the emulsions formed are now stable over time and after several passages in an oven at 40 ° C. This phenomenon is not observed for lanolin which releases all its water in less than 15 days. These products have a higher water retention capacity than lanolin.

It should be noted that the addition of OH-reactants comprising or generating hydroxyl groups also makes it possible to reduce the acidity of the products formed by esterification and / or amidification, thus limiting the risks of thermal degradation and the hydrolysis reactions. The products formed are thus much more stable.

Similarly, the addition of OH-reactants in a given initial mixture of saturated and / or unsaturated fatty acids, esters of saturated and / or unsaturated fatty acids, saturated and / or unsaturated hydrocarbons, saturated derivatives and / or unsaturated thereof, changes the viscosity of the final product.

The preferred compounds are fatty acids or esters of fatty acids containing at least one OH on their chain or alcohols such as glycerol, sterol.

• Reagents with a high melting point: (10 to 60%)

Reagents with a high melting point (example: waxes, hydrogenated and / or saturated products, etc.) increase the melting point of the product formed and give it a pasty to semi-solid or even solid appearance, comparable to that of lanolin.

These reagents often have low iodine numbers. They thus reduce the iodine index of the product and thus approach that of lanolin. In the same way, this gives it better stability over time. Indeed, the risk of oxidation by unsaturations, which are few in the product, is limited. This addition of reagents, used initially to increase the melting point, therefore surprisingly provides several surprising properties. Preferably, fatty acids or esters of fatty acids, in particular hydroxystearic acid or an ester of this acid, will be used.

These reagents not only increase the melting point but also decrease the iodine index of the final product, thereby improving its oxidation stability.

The melting points are adjusted between 36 and 40 ° C corresponding to that of lanolin or around 50 ° C to compare with lanolin alcohol

• Reagents with short and long carbon chains: composition of lanolin

Lanolin is a wax, consisting of sterols and fatty alcohols with short and long carbon chains ranging from C14 to C30.

To get closer to the structure of lanolin, it is advisable to add to the reaction mixture reagents with short and long carbon chains.

The choice of these different reagents also plays on other parameters such as color and touch.

The nature of the reagents and the proportions of the latter in the reaction mixture influence the nature of the product obtained and its characteristics. Those skilled in the art will be able to adapt the reagents to the intended applications, if necessary using a few routine tests. It is possible to specify that for the short carbon chains (0.05% to 10%), one favors fatty acids which refine the touch and one prefers lauric acid or an ester of this acid, giving a very soft touch.

For long carbon chains (90 to 99.5%), the substantivity and the durability of the final product are increased when the length of the chains is increased.

The manufacture of these new lanolin substitutes and derivatives (lanolin alcohol ...)

The invention relates to the general process for obtaining new lanolin substitutes and derivatives (lanolin alcohol, etc.), characterized in that the combination of reagents below is reacted in the reaction medium:

reagents including unsaturations (acids, esters, hydrocarbons and their derivatives) reagents containing or generating hydroxyl functions, called 'reagents

OH 'high melting reagents reactants consisting of short carbon chains reactants consisting of long carbon chains

According to a particular embodiment, the reaction is carried out with a heat treatment.

The heat treatment is carried out by subjecting the reagents to conventional or dielectric heating as described in patent applications FR 98 13770 and PCT WO 00/26265 (PCT / FR99 / 02646) filed by the Applicant and relating to an original dielectric heating process .

Lanolin substitutes and derivatives (lanolin alcohol, etc.) are obtained by heat treatment of saturated and / or unsaturated fatty acids, esters of saturated and / or unsaturated fatty acids, saturated and / or unsaturated hydrocarbons , saturated and / or unsaturated derivatives thereof, or a mixture of these compounds in variable proportion, with one or more OH-reactants comprising or generating hydroxyl functions, preferably without catalyst and in an oxygen-free atmosphere .

• Classic heat treatment:

The conventional heat treatment is carried out between 100 and 400 ° C and better still between 230 and 350 ° C, with permanent stirring and preferably without catalyst and under an inert atmosphere. The reaction temperature depends on the boiling and / or degradation temperatures of the constituents of the mixture.

The total reaction time depends on the reagent (s) used and the viscosity which it is desired to obtain. It is preferably between 3 hours and 24 hours, preferably between 3 hours and 10 hours.

Dielectric heating treatment For reasons of time and energy savings, combined with a lower investment cost, use will preferably be made of dielectric heating, that is to say heating under microwave or high frequency frequencies, as described in the patents. cited above FR 98 13770 and PCT WO 00/26265 (PCT / FR99 / 02646). A person skilled in the art can also refer to the patent application filed by the Applicant and concerning an improved apparatus for the implementation of dielectric heating. The essential details of the process will nevertheless be described below.

The benefits of dielectric heating are:

1- to significantly reduce reaction times;

2- to carry out the reaction in a single step;

3- not to use solvent

4- to save energy (because times are significantly shorter); 5- to avoid “burn-up” and unwanted sub-reactions.

It is preferable to operate without a catalyst, and it is quite surprising to find that one obtains, without a catalyst, an esterification of the free fatty acids with a reactive product such as glycerol.

It is also very surprising to note that no parasitic or concurrent reactions develop, as was on the contrary predictable, which may have blocked research in this direction, and that a good yield is therefore obtained.

The reactions involved are as follows:

- The polymerization of unsaturated fatty acids, esters of unsaturated fatty acids, unsaturated hydrocarbons, unsaturated derivatives of these compounds, alone or as a mixture. This process is described in patent application FR 98 13770 and PCT patent application WO 00/26265 (PCT / FR99 / 02646) to which a person skilled in the art can refer.

- transesterification between the reagents comprising or generating hydroxyl functions, called 'OH reagents' and the esters of saturated and / or unsaturated fatty acids esterification between reagents containing or generating hydroxyl functions, called 'OH reagents' and saturated and / or unsaturated fatty acids

The microwave frequencies MO are between approximately 300 MHz and approximately 30 GHz, preferably at 915 MHz (authorized frequency with a tolerance of 1.4%) or 2.45 GHz (authorized frequency with a tolerance of 2%).

The high HF frequencies are between approximately 3 MHz and approximately 300 MHz, preferably at 13.56 MHz (authorized frequency with a tolerance of 0.05%) or at 27.12 MHz (authorized frequency with a tolerance of 0.6%).

The reaction temperatures are between 100 and 400 ° C and better still between 200 and 350 ° C, with permanent stirring and preferably without catalyst and under an inert atmosphere. The reaction temperature depends on the boiling and / or degradation temperatures of the constituents of the mixture.

The total reaction time depends on the reagent (s) used and the viscosity which it is desired to obtain. It is preferably between 15 minutes and 15 hours, preferably between 15 minutes and 2 hours.

The amount of reagents added to the reaction medium depends on the nature of the reagents used and on the expected characteristics: water absorption level, expected viscosity, melting point, iodine index, etc.

The reagents can be introduced into the reaction medium at the start, during or at the end of the reaction. Adding products at the end of the reaction is generally not economically advantageous since the reaction times are increased. However, it can be used in certain cases. The products obtained by this process can undergo additional treatments such as hydrogenation, discoloration, deodorization or other functionalizations if these treatments provide additional properties such as odor, color, etc. Reagents

The reagents mentioned below as well as their derivatives, can undergo a preliminary treatment aiming to make them more reactive or on the contrary less reactive as for example example hydrogenation, hydroxylation, epoxidation, phosphitation, sulfonation.

The invention relates both to the use of an isolated reagent and to a reaction mixture comprising two or more components. These reaction mixtures can comprise equivalent proportions of each component or certain components can be in the majority.

vegetable oils

As oils of vegetable origin, there may be mentioned, inter alia, rapeseed oil, sunflower oil, peanut oil, olive oil, walnut oil, l corn oil, soybean oil, linseed oil, safflower oil, apricot kernel oil, sweet almond oil, hemp oil, grape seed oil, coconut oil, palm oil, cottonseed oil, babassu oil, jojoba oil, sesame oil, argan oil, thistle oil marie, pumpkin seed oil, raspberry oil, Karanja oil, Neem oil, flaxseed oil, Brazil nut oil, castor oil, castor oil dehydrated, hazelnut oil, wheat germ oil, borage oil, evening primrose oil, Tung oil, tall oil or "tall oil".

• oils and fats of animal origin

Although oils and fats of animal origin are not preferably used, there may be mentioned, among others, sperm whale oil, dolphin oil, whale oil, seal oil, oil sardines, herring oil, shark oil, cod liver oil, beef foot oil, pork and horse fat.

hydrocarbons

As unsaturated hydrocarbons, there may be mentioned, alone or as a mixture, and by way of nonlimiting examples, an alkene, for example one or more terpene hydrocarbons, that is to say one or more polymers of isoprene, or one or more polymers of isobutene, styrene, ethylene, butadiene, isoprene, propene, or one or more copolymers of these alkenes.

As saturated hydrocarbons, there may be mentioned, inter alia, alkanes, for example ethane, propane. • saturated and / or unsaturated esters

As esters of saturated and / or unsaturated fatty acids, it is possible to use alone or as a mixture and by way of nonlimiting examples, one or more esters obtained by esterification between a monoalcohol and / or polyol and at least one acid saturated and / or unsaturated fat; waxes; butters, phospholipids; spingolipids; glucolipids.

• saturated and / or unsaturated acids

As unsaturated fatty acids, there may be used, alone or as a mixture, and by way of nonlimiting examples, one or more saturated acids such as caprylic acid, lauric acid, myristic acid, acid palmitic, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, one or more monounsaturated fatty acids such as oleic acid, palmitoleic acid, myristic acid, l petroselenic acid, erucic acid; one or more polyunsaturated fatty acids such as for example linoleic acid, alpha and gamma linolenic acids, arachidonic acid; EPA eicosapenten-5c- 8c-11 c-14c-oic acid, DHA dodosahexen-4c-7c-10c-13c-16c-19c-oic acid, one or more acids comprising conjugated dienes or conjugated trienes such as l licanic acid, the isomers of linoleic and linolenic acids; one or more acids comprising one or more hydroxyl groups such as ricinoleic acid.

• OH reagents containing or generating hydroxyl functions

For the present invention, the OH-reactants comprising or generating hydroxyl functions can be chosen from alcohols, amino alcohols, epoxides.

As alcohols, it is possible to use, alone or as a mixture, one or more primary, secondary and / or tertiary mono or polyalcohols. It can be, by way of nonlimiting examples, methanol, ethanol, butanol, glycerol, glycol, sorbitol, mannitol, xylitol, neopentylglycol, pentaerythritol, acid nervonic, cerebronic acid, densipolic acid, lesquerolic acid, vitamins (e.g. tocopheri, ascorbic acid, retinol), sterols (including phytosterols), hemiacetals (e.g. 1-ethoxy - 1-ethanol), polyols, spingolipids, glucolipids, and their analogs. As amino alcohols, monoethanolamine MEA, diethanolamine DEA triethanolamine TEA, 3-amino 1, 2 propanediol, 1-amino 2-propanol, 2- can be used alone or as a mixture and by way of nonlimiting examples. 2'-amino ethoxy ethanol.

As epoxides, there may be used alone or as a mixture and by way of nonlimiting examples, vernolic acid, cooronaric acid, 1,2-epoxy-9-decene, 3-4 epoxy-1-butene , 2-3 epoxy-1-propanol, fatty esters obtained by esterification between 2-3 epoxy-1-propanol and a fatty acid (for example Cardura E10 ^® ).

• catalysts

Among the catalysts or adjuvants, the following are intended to be non-limiting examples of the usual acid catalysts (paratoluenesulfonic acid, sulfuric acid, phosphoric acid, perchloric acid, etc.), the usual basic catalysts (sodium hydroxide, potassium hydroxide, alkali metal alcoholate and of alkaline earth metals, sodium acetate, triethylamines, pyridine derivatives, etc.), acid and / or basic resins such as Amberlite ™, Amberlyst ™, Purolite ™, Dowex ™, Lewatit ™, zeolites and enzymes, carbon blacks and activated carbon fibers.

Concrete but nonlimiting examples of the invention will now be presented.

EXAMPLES

The following examples demonstrate the properties of these new lanolin substitutes and derivatives (lanolin alcohol, etc.).

I- WATER ABSORPTION PROTOCOL

The water absorption capacity tests are carried out cold using a turbine blade Material:

- stainless steel beakers (100-250-500mL)

- VORTEX agitator with deflocculating turbine

- pipettes - spatula

Protocol:

1- weigh the oil in a 500mL stainless steel beaker (m1)

2- weigh the water (m2, here 200%) in a 250mL stainless beaker 3- add the water drop by drop using a pipette

4- once the emulsion has set, quickly add the rest of the water, shaking vigorously

5- wait δminutes after addition for the emulsion to be finished

6- perform stability tests

II- WATER ABSORPTION TESTS CITED IN THE FR FRENCH PATENT APPLICATION (patent application FR No. 0108905)

For the convenience of those skilled in the art, the examples of the aforementioned FR patent application concerning an original and economical process for obtaining a lanolin substitute and derivatives (lanolin alcohol ... ). Those skilled in the art may refer to the aforementioned patent for more details.

• water absorption capacity and stability of the emulsion

Without the addition of OH-reagents, polymers of unsaturated fatty acids, esters of unsaturated fatty acids, unsaturated hydrocarbons or derivatives of these products absorb up to 80% of their weight in water.

With the addition of OH-reagents, the products obtained then absorb up to at least twice their weight in water. The emulsions formed by products with a viscosity greater than 1000cP (at 40 ° C) are stable unlike lanolin which releases all of its water in 15 days after passing through an oven at 40 ° C.

The choice of product and its viscosity depends on the desired application and effect. The more viscous the product, the thicker the emulsion obtained. • influence of the percentage of OH reagents

The water absorption capacity increases with the percentage of glycerol. And it should be noted that the viscosity of a given mixture decreases with the percentage of glycerol.

• influence of the nature of the OH reagent

The water absorption capacity depends on the hydroxyl functions of the OH-reactant which can react during the synthesis and those which do not react for reasons of steric hindrance.

III- IMPROVEMENT OF THE ORGANOLEPTIC AND PHYSICOCHEMICAL PROPERTIES OF THE LANOLINE SUBSTITUTE AND DERIVATIVES (LANOLINE ALCOHOL, etc.)

The Applicant proposes in this present invention to further improve the organoleptic and physicochemical characteristics of the lanolin substitute and derivatives (lanolin alcohol, etc.) described in the aforementioned FR patent: the new lanolin substitutes retain the properties of the products subject of this previous patent (water absorption, hydration, emollience ...) but they also meet other criteria such as touch, color, iodine index and melting point.

The nature of the reagents and the proportions of the latter in the reaction mixture influence the nature of the product obtained and its characteristics and the skilled person will be able to adapt the parameters, if necessary using a few routine tests, to optimize the properties of the products obtained.

1- absorption capacity and stability of the emulsion formed

The products which appear in this table are obtained from a heat treatment from a mixture of saturated and / or unsaturated fatty acids, esters of saturated and / or unsaturated fatty acids, saturated hydrocarbons and / or unsaturated or saturated and / or unsaturated derivatives of these and of compounds comprising or generating hydroxyl functions.

Only one compound changes in the mixture. Likewise, in order to obtain the desired viscosity at the end of the synthesis, the percentage of each compound present in the reaction mixture is varied.

Table 2: absorption capacity and stability of the emulsion formed

10

^** The aforementioned patent application concerning an original and economical process for obtaining a lanolin substitute and derivatives (lanolin alcohol, etc.) shows the absorption capacity of the products obtained from a heat treatment of a mixture of unsaturated fatty acids, esters of unsaturated fatty acids, hydrocarbons

15 unsaturated or unsaturated derivatives thereof and compounds having or generating hydroxyl functions.

In this present invention, the Applicant introduces a combination of other compounds into the reaction mixture such as reagents with a high melting point,

20 short and long carbon chain reagents to add additional properties to the finished product. Surprisingly, he observes that:

- the products obtained absorb up to at least twice their weight in water.

- the emulsions formed are stable if the products have a viscosity greater than 1000cP at 40 ° C.

- the emulsions are stable unlike lanolin which releases all of its water in 15 days after passing through an oven at 40 ° C.

Thus, as in said aforementioned FR patent, the Applicant has found a way to introduce new compounds into the reaction mixture without modifying its water absorption capacity. The products are indeed capable of absorbing up to at least twice their weight in water or aqueous solution or aqueous suspension. They form real emulsions, stable over time with a higher water retention capacity than lanolin.

The choice of product and its viscosity depends on the desired application and effect. The more viscous the product, the thicker the emulsion obtained.

2- melting point

As previously, the products which appear in the table below are obtained from a heat treatment of a mixture of saturated and / or unsaturated fatty acids, esters of saturated and / or unsaturated fatty acids, d 'saturated and / or unsaturated hydrocarbons or saturated and / or unsaturated derivatives thereof and of compounds comprising or generating hydroxyl functions.

Only one compound changes in the mixture.

Likewise, to obtain the desired viscosity at the end of the synthesis, the percentage of each compound present in the reaction mixture is varied.

Table 3: melting point

Unlike the aforementioned patent application ^** , the Applicant proposes in this present invention new lanolin substitutes and derivatives (lanolin alcohol ...) with a melting point in accordance with its specifications. Indeed, lanolin has a melting point between 36 and 40 ° C.

3- sensory analyzes

10 The table below brings together the sensory analyzes carried out on a panel of 10 people.

Legend: 1 = little ... 15 5 = lots of ...

Example:

Lanolin smell = 5 = lots of smell

0

table n ° 4: sensory analyzes

From this table follow the following conclusions

advantages of the new substitute compared to lanolin less odor less color more shine 0 more spreading more softness less tackiness more penetration

5 It should be noted that this new substitute for lanolin and derivatives (lanolin alcohol, etc.) has sensory properties close to those of lanolin: the differences in appreciation are small.

Only the differences in odor and color are important, but they are a step in the right direction. 0

2- advantages of the new substitute compared to the products manufactured according to the aforementioned patent application

- less smell 5 - less color

- more spreading

- more softness

- less sticky

- more penetration 0

The new substitute has better sensory characteristics than the previous one of the aforementioned patent.

Claims

1 Substitute for lanolin and derivatives (lanolin alcohol, etc.) characterized in that it is obtained by means of a heat treatment of saturated and / or unsaturated fatty acids, of esters of saturated fatty acids and / or unsaturated, saturated and / or unsaturated hydrocarbons or saturated and / or unsaturated derivatives thereof with compounds comprising or generating hydroxyl functions preferably without catalyst and in an atmosphere devoid of oxygen so that it absorbs up to at least twice its weight in water or in aqueous solution or suspension and forms real emulsions stable over time, so that it has sensory and organoleptic properties close to those of lanolin such as l 'spreading, smoothness, shine, streak, penetration and in such a way that it has physico-chemical criteria similar to those of lanolin as the melting point.

2 Products according to claim 1 characterized in that they have, with respect to lanolin,

less odor less color more shine more spread - more softness less tackiness more penetration

with sensory properties close to those of lanolin, the differences in appreciation being therefore small, with differences in smell and color. 3 A process for manufacturing new industrial products according to claim 1 or 2, characterized in that the combination of reagents below is reacted in the reaction medium:

- reagents including unsaturations (acids, esters, hydrocarbons and their derivatives)

- reagents containing or generating hydroxyl functions, called 'OH reagents' - reagents with a high melting point

- reagents made up of short carbon chains

- reagents made up of long carbon chains.

4 Method according to claim 3 characterized in that the reaction is carried out with a heat treatment, preferably without catalyst.

5 Method according to claim 4 characterized in that the heat treatment is carried out by subjecting the reagents to conventional heating.

6 Method according to claim 4 characterized in that the conventional heat treatment is carried out between 100 and 400 ° C and better still between 230 and 350 ° C, with permanent stirring and preferably under an inert atmosphere.

7 Method according to claim 6 characterized in that the total reaction time is preferably between 3 hours and 24 hours, preferably between 3 hours and 10 hours.

8 Method according to claim 4 characterized in that the heat treatment is carried out by subjecting the reagents to dielectric heating.

Method according to claim 8 characterized in that

the microwave frequencies MO are between approximately 300 MHz and approximately 30 GHz, preferably at 915 MHz (authorized frequency with a tolerance of 1.4%) or 2.45 GHz (authorized frequency with a tolerance of 2%); the high HF frequencies are between approximately 3 MHz and approximately 300 MHz, preferably at 13.56 MHz (authorized frequency with a tolerance of 0.05%) or at 27.12 MHz (authorized frequency with a tolerance of 0.6%);

- The reaction temperatures are between 100 and 400 ° C and better still between 200 and 350 ° C, with permanent stirring and preferably without catalyst and under inert atmosphere;

10 Method according to claim 8 or 9 characterized in that the total reaction time is preferably between 15 minutes and 15 hours, preferably between

15 minutes and 2 hours.

11 Method according to claim 8, 9 or 10 characterized in that the reagents can be introduced into the reaction medium at the start, during or at the end of the reaction.

12 Method according to any one of claims 8 to 11 characterized in that the products obtained can undergo additional treatments such as hydrogenation, discoloration, deodorization or other functionalizations.

13 A method according to any one of claims 3 to 12 characterized in that the lanolin substitutes and derivatives (lanolin alcohol ...) are obtained by heat treatment of saturated and / or unsaturated fatty acids, esters of saturated and / or unsaturated fatty acids, saturated and / or unsaturated hydrocarbons, saturated and / or unsaturated derivatives thereof, or a mixture of these compounds in variable proportion, with one or more OH-reactants comprising or generating hydroxyl functions, preferably without catalyst and in an oxygen-free atmosphere.

14 A method according to any one of claims 3 to 13 characterized in that the reagents and their derivatives can undergo a preliminary treatment aimed at making them more reactive or on the contrary less reactive such as for example hydrogenation, hydroxylation, epoxidation, phosphitation, sulfonation.

15 A method according to any one of claims 3 to 14 characterized in that one uses, in the combination of reagents according to claim 3, an isolated reagent or a reaction mixture comprising two or more components in equivalent or majority proportions, that is to say that each component of the reagents is used alone or in mixtures.

16 Method according to any one of claims 3 to 15 characterized in that one uses as one of the reagents according to claim 3:

• oils of vegetable origin

rapeseed oil, sunflower oil, peanut oil, olive oil, walnut oil, corn oil, soybean oil, flaxseed oil, safflower oil, apricot kernel oil, sweet almond oil, hemp oil, grape seed oil, coconut oil, palm oil, seed oil cotton, babassu oil, jojoba oil, sesame oil, argan oil, milk thistle oil, squash seed oil, raspberry oil, Karanja oil , Neem oil, flaxseed oil, Brazil nut oil, castor oil, dehydrated castor oil, hazelnut oil, wheat germ oil, l borage oil, evening primrose oil, Tung oil, tall oil or "tall oil".

17 Method according to any one of claims 3 to 16 characterized in that one uses as one of the reagents according to claim 3:

• oils and fats of animal origin

sperm whale oil, dolphin oil, whale oil, seal oil, sardine oil, herring oil, shark oil, cod liver oil, beef foot oil, pork and horse fat.

18 A method according to any one of claims 3 to 17 characterized in that one uses as one of the reagents according to claim 3:

hydrocarbons

an alkene, for example one or more terpene hydrocarbons, that is to say one or more polymers of isoprene, or one or more polymers of isobutene, styrene, ethylene, butadiene, isoprene , propene, or one or more copolymers of these alkenes.

saturated hydrocarbons, alkanes, for example ethane, propane. 19 A method according to any one of claims 3 to 18 characterized in that one uses as one of the reagents according to claim 3:

• saturated and / or unsaturated esters

one or more esters obtained by esterification between a monoalcohol and / or polyol and at least one saturated and / or unsaturated fatty acid; waxes; butters, phospholipids; spingolipids; glucolipids.

20 Method according to any one of claims 3 to 19 characterized in that the following are used as one of the reagents according to claim 3:

• saturated and / or unsaturated acids

one or more saturated acids such as caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid , one or more monounsaturated fatty acids such as oleic acid, palmitoleic acid, myristic acid, petroselenic acid, erucic acid; one or more polyunsaturated fatty acids such as for example linoleic acid, alpha and gamma linolenic acids, arachidonic acid; EPA eicosapenten-5c- 8c-11c-14c-oic acid, DHA dodosahexen-4c-7c-10c-13c-16c-19c-oic acid, one or more acids comprising conjugated dienes or conjugated trienes such as licanic acid, the isomers of linoleic and linolenic acids; one or more acids comprising one or more hydroxyl groups such as ricinoleic acid.

21 Method according to any one of claims 3 to 20 characterized in that the following are used as one of the reagents according to claim 3:

• “OH-reactants” (comprising or generating hydroxyl functions)

- chosen from alcohols, amino alcohols, epoxides.

- As alcohols, one or more primary, secondary and / or tertiary mono or polyalcohols: methanol, ethanol, butanol, glycerol, glycol, sorbitol, mannitol, xylitol, neopentylglycol, pentaerythritol, nervonic acid, cerebronic acid, densipolic acid, acid lesquerolic, vitamins (for example tocopherol, ascorbic acid, retinol), sterols (including phytosterols), hemiacetals (for example 1-ethoxy -1-ethanol), polyols, spingolipids, glucolipids.

- As amino alcohols: monoethanolamine MEA, diethanolamine DEA triethanolamine TEA, 3-amino 1, 2 propanediol, 1-amino 2-propanol, 2-2'-amino ethoxy ethanol.

As epoxides: vernolic acid, cooronaric acid, 1,2-epoxy-9-decene, 3-4 epoxy-1 -butene, 2-3 epoxy-1-propanol, fatty esters obtained by esterification between 2-3 epoxy-1-propanol and a fatty acid (eg Cardura E10 ^® ).

22 Process according to any one of Claims 3 to 21, characterized in that the following are used as one of the reagents according to Claim 3:

• catalysts

the usual acid catalysts (paratoluenesulfonic acid, sulfuric acid, phosphoric acid, perchloric acid ...), the usual basic catalysts (sodium hydroxide, potassium hydroxide, alkali metal and alkaline earth metal alcoholate, sodium acetate, triethylamines, pyridine derivatives ...), acid and / or basic resins such as Amberlite ™, Amberlyst ™, Purolite ™, Dowex ™, Lewatit ™, zeolites and enzymes, carbon blacks and activated carbon fibers.

23 Method according to any one of claims 3 to 22 characterized in that it is implemented without solvent.

24 Products obtained by the process according to any one of claims 3 to 23.

25 Applications of the products according to claim 1 or 2 or according to claim 24 in the following fields:

cosmetic applications: - bubble baths,

- lipsticks,

- skincare creams for dry skin, - shaving creams,

- after shave lotions,

- powders,

- soaps,

- shampoos, - waterproof sunscreen,

- make-up removers,

- "bath oils,

- lip balms ^• - ointments - lip sticks

industrial applications:

- polishes - printing inks,

- anti-rust and anti-corrosion protective films deposited on certain metals,

- leather and fur industry for waterproofing,

- additives for lubricants, - paints