FR2567753A1 - PLANT OIL ADDITION PRODUCTS FOR USE AS EMOLLIENTS IN SKIN AND HAIR CARE PRODUCTS - Google Patents

Abstract

THE INVENTION DESCRIBES CERTAIN VEGETABLE OIL LIPID ADDITION PRODUCTS, USED EITHER ALONE, OR IN COMBINATION WITH VEGETABLE OILS AND OR MODIFIED VEGETABLE OILS, THESE ADDITION PRODUCTS HAVING PERSISTENT SOFTENING EFFECTS WHEN THEY ARE INCORPORATED IN PREPARATIONS FOR SKIN AND HAIR CARE. THE EMOLLIENTS OF THE INVENTION CONTAIN BOTH THE WATER SOLUBLE AND WATER INSOLUBLE SALTS OF THE VEGETABLE OIL ADDITION PRODUCTS. THE ADDITIONAL PRODUCTS OF THE INVENTION ARE THOSE PREPARED FROM VEGETABLE OILS CONTAINING NON-CONJUGATE POLYINSATURE FATTY ACID ESTERS, WHICH ARE CONJUGATE AND THEN MODIFIED BY ADDITION ACCORDING TO THE REACTION OF DIELS-ALDER WITH ACRYLIC ACID, D 'FUMARIC ACID OR MALEIC ANHYDRIDE.

Description

Additives of vegetable oils used as emollients in

skin care products and

the hair.

  The present invention relates to the use of pro-

  additives of vegetable oils, either alone or

  in combination with vegetable oils and / or oils

  modified plants as additives in soils for the skin and hair. More particularly, this invention relates to the use of both water-soluble and water-insoluble salts of vegetable oil adducts, in combination or not with vegetable oils or oils. modified vegetable products, as emollients in skin and hair care products. Specifically, this invention relates to the use of

  Additives prepared from vegetable oils

  tales containing esters of unconjugated polyunsaturated fatty acids, which are conjugated and then modified, by Diels-Alder reaction, with acrylic acid, fumaric acid or maleic anhydride, as emollients in care products for -the

skin and hair.

  The skin is made up of several layers of cellu-

  which cover and protect the fibrous proteins

  its keratin and collagen which form the sque-

  of its structure. Anionic surfactants

  outermost of these layers, known as the stratum corneum, by delipidization to

  destroy its entirety. This destruction of the topo-

  1 (<surface area of the skin leads to a rough touch

  poor and can possibly allow the surfactant

  to react with keratin creating irritation.

  Organic solvents are a main cause of the defatting of the stratum corneum. In addition, solvents or mixtures of solvents soluble both in lipids and in water lead to more complete defatting, sometimes removing

  up to 10 to 20% of skin lipids during an

  prolonged mersion. Specific long chains of

  organic products less soluble in water are also

  slightly harmful. Hydrocarbons having the chain lengths found in kerosene (boiling range from 272 to 333 C) react with lipids to cause abnormal thickening of the stratum corneum. Of course, kerosene is a component commonly used in dry hand cleaning products. Surfactants with medium length chains, such as sodium lauryl sulfate and α-olefin sulfonates, commonly used in dishwashing detergents, are harmful to the skin, even in very dilute solutions. It is believed that the activity of this class of products is due to a strong bond of the functional group of the surfactant with

  protein molecules in kera filaments

  tine, reversibly denaturing them in a confi-

  helical guration a in configuration B by a unwinding

  filaments which dilate the tissues. As soon as

  this has happened, the barrier function is not likely

  not fully recovered, even after removing all of the surfactant, due to the composition

  and the complex nature of the stratum corneum.

  Cosmetic creams, which use mineral oils

  0 rales, also contain vegetable oils to partially replace the lipids from the skin surface which have been removed by the action of solvent

mineral oil.

  The gradient of the water content across the stratum corneum is important for its functionality. Most of this water, which is sometimes thought of as the plasticizer of the stratum corneum, comes from inside the body. If the humidity is too low, for example in a cold climate, the amount of water remaining in the outer layers of the stratum corneum is insufficient to laminate properly

  tissues; and the skin begins to flake and

  eat. The permeability of the skin also decreases somewhat when the water content through the stratum corneum is unsuitable. On the other hand, too much water on the outside of the skin leads

  the stratum corneum to absorb three to five times its pro-

  pre weight of bound water. As a result, the skin swells and wrinkles, and as a result, the permeability to water and other polar molecules is about two to three times greater than the permeability for optimal hydration. Hair contains most of the constituents of the stratum corneum. The outermost region of the cells forms a relatively thick, chemically resistant protective coating surrounding the

  hair fibers, a coating called the cuticle. The over-

  face of the cuticle is coated with a thin layer called the epicuticle, which contains lipids and

  proteins. The cuticle envelops the cells of the cor-

  tex, which constitutes the largest part of the fibrous mass. Keratinization takes place in the cortex to

  stabilize the hair structure.

  There is therefore a need for substances which help

  the stratum corneum and the cuticle of the hair to maintain at the optimum their barrier and water retention functions in spite of harmful interactions

  with the skin in washes, work and hobbies.

  An article by Encyclopedia of Chemical Technology (Ency-

  Clopedia of Chemical Technology), third edi-

  tion, volume 7, on cosmetic creams and lo-

  tions gives a classic example of a formula

  of cream which contains 11.8-12.1% whale white.

  It should also be noted that modern formulas, which use mineral oil instead of almond oil previously used, must contain a vegetable oil for the partial replacement of lipids on the surface of the skin removed by the action of solvent

mineral oil.

  Cosmetic lotion formulas are almost ideal

  creams, except that the oil-in-water emollient lotion usually contains more water than the corresponding cream. These lotions are preferred for daytime use, since they produce a

  lighter or less oily emollient film. The formu-

  cosmetic lotions in Encyclopedia of Tech-

  nical Technology contain 1 to 1.5% lanolin anhy-

dre as the main emollient.

  Unfortunately, the emollient additives currently used in creams and lotions have skin softening effects that do not last as long.

  as long as desired. There is therefore a need per-

  especially for emollient additives that provide softening of the skin for longer than in

the case of current emollients.

  Hair preparations can also benefit

  cier of the inclusion of emollients. We can similarly help the barrier and water retention functions of the hair cuticle as in the case of the stratum corneum of the skin, in particular in shampoos and products for straightening the hair. The formulas

  of shampoos contain lanolin and its derivatives

  used as conditioning agents to facilitate

  combing, detangling, improving four-point

  plump, to give body, shine and support

  crashes and to prevent the build up of static electricity. The beneficial effects of emollients on both the skin and the hair can be best appreciated in anti-dandruff shampoos. Dandruff is the product of hyper-keratinization. Degree

  of keratinization increases to the point that the scales

  them become more visible. Anti shampoos

  dandruff contain ingredients that control

  actually slows dandruff formation

  putting a normal rate of renewal of the cells of the epidermis. A softening emollient for the skin and hair should reduce the degree of keratinization in the horny layer of the scalp and at the same time

  benefit the hair cuticle.

  It is therefore an object of the present invention to provide additives for preparations for skin and hair care. Another object is to provide emollient additives for preparations for skin and hair care, which have a softening effect on the stratum corneum or on the hair cuticle. Another purpose of this

  invention is to provide additives for prepa-

  rations for skin and hair care whose softening effect lasts longer than that

known emollients.

  The aforementioned aims are achieved by the fact that certain lipid addition products of vegetable oils,

  used either alone or in combination with oils

  modified vegetables and / or vegetable oils,

  provide persistent softening effects when

  that they are incorporated into preparations for skin and hair care. The emollients of this invention contain both the soluble and the insoluble salts of these adducts

  vegetable oils. These addition products according to the

  vention are those prepared from vegetable oils containing esters of non-conjugated polyunsaturated fatty acids, which are conjugated and then modified, by Diels-Alder reaction, with acrylic acid,

  fumaric acid or maleic anhydride.

  The vegetable oil adducts essential in this invention can be prepared from vegetable oils having groups of polyunsaturated fatty acid esters in the triglyceride molecule, which increases the carboxyl content of the groups

  fatty acid esters. These oil additives

  the plants are prepared by conjugating and elaydi-

  first of all the unconjugated portion of the polyunsaturated fatty acid, mainly linoleic acid, this reaction being followed by a Diels-Alder reaction

  with fumaric acid, maleic anhydride or acid

  of acrylic. It is essential that the conjugation and

  elaidinisation is carried out before addition of the acid

  of acrylic to produce with optimal yield the

  acrylic acid adduct. With fu- acid

  marique or maleic anhydride, acid or anhydride may be present at the time of conjugation and

  elaidinisation without harming the reaction.

  These vegetable oil adducts and their preparation are described in US Patents 2,678,934 and 4,196,134. Vegetable oil addition products

  form triglyceride acids of the formula ge-

neral O Il

CH - O - C - R1

I!

O / CH - CH

CH CH C CH - O -C - (CH2) yCH (2) x 3

O | 2 CH - CH-C

I.I i

CH2-O C - R2-O

2 C -R2 Z Z

  in which x and y are integers from 3 to 9, the sum of x and y is equal to 12, each group Z may be a carboxylic acid group in which all or part of the carboxyl groups may be in the form of anhydride, or one of the Z can be

  hydrogen and the other Z a carboxy-

  lique, and R1 and R2 are saturated or unsaturated hydrocarbon radicals. These triglyceride acids can be transformed into their soap form, including

  alkali metal soaps and amine soaps

  blends, soils of alkaline earths and metals of higher insoluble value, or be incorporated in the form of free acids to obtain the benefits of

  this invention. These benefits include a softening-

  or an emollience of the skin or hair, which

  is kept at its maximum value for a period of time

  before reaching 8 p.m. This activity is not dimi-

  clouded by normal cleaning processes such as washing with soap and water, or even cleaning with dry hand cleaning products consisting of

  a cream containing soap, water, kerosene ino-

  gold and a variety of lesser ingredients such as lanolin and sometimes pumice to improve

  their cosmetic and cleaning properties.

  Although the compounds discovered provide good softening

  cisse and good hydration - of the skin during-

  that they are used alone, we found that their pro-

  properties could be improved by adding mother oil, the optimal mixture being approximately 50% vegetable oil and 50% of additives of this

  vegetable oil. Even better results are obtained.

  res if the vegetable oil has been disassembled. - for

  Judge the double bonds in the groups of linoleic and linolenic acids present in the oil. Although all of the additives mentioned are effective emollients, maximum effectiveness is obtained

  by the product of the Diele-Alder reaction with fumed acid

  risk. A preferred process for preparing the opti-

  bet is to react two moles of vegetable oil

  with one mole of the dienophile product in the presence of quan-

2S67753

  catalytic iodine, serving as a conjunctive agent

  gaison and elaidinisation. The mixture is obtained simultaneously in equal parts of the adduct and

disproportionated vegetable oil.

  We can see from the following examples that the pro-

  additives of this invention are advantageous

  due to the long period during which they

  curent softening and emollience to the skin. In order to remain effective for such long periods, it appears that they must have an affinity or all

  at least optimal compatibility, with one or more

  several components of the skin probably present in the stratum corneum. It can be an interaction of the hydrophobic portions of the adduct and of the free vegetable oil, if there are any, with grains of lipids in the intercellular space or with the more hydrophilic lipids which constitute the walls of the cells. keratinized. If the adduct could penetrate

  in the cell, its carboxylic acid groups can-

  could react with amino groups of proteins around the outside of the keratin chains with bisulfide bridges in the form of a helix a. Whether he is or

  not retained inside the skin, the product of

  addition of fumaric acid and soybean oil

  have a very large area of hydrophilic groups

  , approximately 97.5 A2 for free acid and 116.2 A2 for disodium soap. By comparison, the leading group of monocarboxylic fatty acids occupies only 2 35 A. It is assumed that this large polar region can form

  hydrogen bonds with considerable amounts of water.

  It can thus hydrate the skin in regions where

  it is located. Although the exact mechanism of operation

  of these adducts is unknown, their

efficiency is surprising.

Example 1

  In the one-time preparation of an op-

  50% of a fumaric acid adduct to soybean oil and 50% of conjugated soybean oil, 74.5 kg (85 g / mole) of refined soybean oil is added.

  food grade, 4.8 kg (41g / mole) of fumed acid

  and 0.30 kg of iodine in a 113 liter pressure reactor. The reactor is hermetically sealed,

  heated to 250 C and maintained at this temperature for

  for 4 hours, while the contents are stirred continuously

  nence. The resulting product has an acid number of

  63.6 and a color of 3+ on the Gardner scale.

  Example 2 The adduct of fumaric acid is prepared at

  soybean oil by adding 91 kg of refilled soybean oil

  11.8 kg of fumaric acid and 0.27 kg of iodine in a 113 liter pressure reactor. The reactor is hermetically sealed, heated to 210 ° C. and kept at

  this temperature for 4 hours, shaking the con-

  tenuous. The resulting product has an acid number of

  114.8 and a color of 5 on the Gardner scale.

  Example 3 This example illustrates the preparation of metal soaps

  alkalines and their effectiveness for skin care.

  It is added to a 400 ml beaker equipped with a stirrer.

  113.12 g of water and 13.12 g of potassium hydroxide granules (86% solids). After heating the solution to 60 ° C., g of the fumaric acid adduct is added slowly, with stirring.

  soybean oil prepared in Example 2. After 15 minutes

  after stirring at 60 ° C., the mixture is allowed to cool

  mixed. The viscosity of the yellow product is 2050 cen-

  tipoises at 50 C and its pH is 8.45.

  In a 100 ml beaker containing 50 g of soap

  potassium at 50% solids from the acid adduct

  from fumaric to soybean oil, add slowly,

  maintaining good stirring, 25 g of so-

  ja. The resulting system has a viscosity of 7100 centi-

poises, and has a pH of 8.3.

  The application of this product on the skin produces a soft and smooth touch, without slippery or other character.

  unwanted property. By rubbing the skin to absorb

  ber the rest of the product, it develops a light touch

  slightly sticky for a moment, until

  all the product has disappeared from view. The normal process

  sickness at work, leisure and rest takes place during

  during the next twenty hours, during which there is considerable exposure to water using

  both a soap for hand cleaning and a deter-

  nice dishwashing liquid. After these twenty hours, the skin still has the smooth smoothness that the product

initially imparted to the skin.

Example 4

  The sodium soap from the fumaric acid adduct

  that in soybean oil is prepared by heating

  108 g of water, in which 8.4 g of granules have been dissolved

  strips of sodium hydroxide (97.6% solids) at 60 C

  and adding 100 g of the fumed acid adduct

  soybean oil prepared in Example 2. After

  having stirred for 15 minutes at 60 ° C., it is allowed to cool

  say the soap. It has a pH of 8.6 and a viscosity of

2160 centipoises at 45 C.

  40 g are slowly added to a 250 ml beaker

  soybean oil to 80 g of the above sodium soap.

  A system is obtained having a viscosity of 3200 centipedes and a pH of 8.7. There is no sensation

  sticky at no stage when this product is penetrated

  gets in the skin by rubbing. The softening of the skin thus obtained lasts as long as in the case

potassium-based soap.

Example 5

  To illustrate the preparation of the monova-

  slowly, an anhydrous triethanol amine soap is prepared by mixing 13.9 g of triethanol amine in 100 g of the adduct of fumaric acid with soybean oil prepared in Example 2, to obtain a gel

  viscous clear. This soap has softening properties-

  skin similar to alkali metal soaps

  lin. It comes in mild soap formulas in

  which it facilitates the rinsing of the skin without deterioration-

  r the foaming properties of soap.

Example 6

  This example illustrates the usefulness of metallic ion soaps.

  multivalent and acid adduct

  soy oil fumaric for skin care.

  9.29 g of sodium hydroxide granules (97.6% solids) are dissolved in 121 ml of water in a 500 ml beaker. Then added 100 g of the adduct of

  soybean oil fumaric acid prepared in example

  ple 2. After stirring for 20 minutes to produce a viscous homogeneous soap, a solution consisting of 24.85 g of magnesium sulfate heptahydrate dissolved in 71 ml of water is added over a period of 15 minutes. After adding about two-thirds of the magnesium sulphate solution, the homogeneous viscous soap separates into two phases. After having stirred for one hour and leaving the system to deposit for another hour, the aqueous phase is removed; the viscous gel is washed twice with portions of

  131 ml distilled water to remove any residual sul-

  sodium fate. Shake for one hour each batch

  washing water with the organic phase; we leave in-

  then lay down the system for another hour before removing it from the organic phase. The manipulation of

  this magnesian soap from the adduct of the acid fu-

  soybean oil gives the hands a soft, smooth feel that lasts for days after application. EXAMPLE 7 This example illustrates the properties of the mixture of the adduct of fumaric acid with soybean oil and of conjugated soybean oil to give softness to the skin and to eliminate the harmful effects of kerosene on

the skin.

  A viscous but pourable soap is prepared from a mixture of the adduct of fumaric acid with soybean oil and the conjugated soybean oil obtained in Example 1 by slowly adding 50 g. of the product

  addition to a solution of 56.56 g of hydro granules

  potassium xyde (86% solids) dissolved in 56.56 g

  of water. The cloudy solution has a pH of about 8.5.

  17 g of the above soap are added to a ml bottle with a kerosene screw cap in 3 ml increments until the bottle is full. After each

  addition of kerosene, the system is agitated with an

  magnetic detector for 45 minutes. The viscosity of

  the final solution is weak and the solution is clear.

  This mixture cleans the dirt hidden in the footprints.

  your fingerprints and other hand crevices, as evidenced by the black deposit on a dry paper towel used to wipe the mixture and by

  the cleanliness of the skin which is visually improved.

  In addition, the viscosity is low enough that it easily penetrates under the fingernails and

  removes grease and sludge, which is particularly

* hard to obtain for mechanics.

  In contrast to dry hand cleaning products

  commercially available, and composed in a ca

  about 40% kerosene, 40% water and

  20% of an oleic acid soap, the formula of this example

  ple softens the skin as do creams for

  hands and this result lasts for several hours.

  Furthermore, this formula does not tend to produce painful crevices in the stratum corneum in the fingerprint area of the hands, which is the common defect of these dry cleaning products.

hands.

Example 8

  The product of Example 1 is directly compared (re-

  péré PCW-178) with anhydrous lanolin and less viscous refined lanolin oil with respect to the emollient properties of a hand lotion formula, at a concentration of 5%. The procedure

  used is that developed by-Goldem-

  berg and De la Rosa and described in their article "Corre-

  lation of Skin Feel of Emollients to Their Chemical Structure "

  to the skin) J. Soc. Cosmet. Chem. 22: 635-654 (1971).

  The emulsions were evaluated in each case in the form

  anonymous samples from the same labor groups

  tins, which had to compare the sensation on initial touch on the skin, the behavior during massage for penetration, and the final sensation on touch after total absorption of the emulsion in the skin. The initial softness was calibrated on a scale of-1 to (rough to very smooth). The feel to the touch

  nale was calibrated for satin, onc-

  tuosity, sensation of friction and dampness. Cha-

  none of these four qualities was calibrated on a scale of 1 to 5, with 5 representing the most desirable sensation. A numerical value was obtained for the sensation of final touch by adding the scores-for each quality evaluated. The values of the sensation on final touch could thus range from 4'to 20. The

  table below presents the results obtained.

  APPLICATION PROPERTIES

  Sensation to the final touch Emollient Softness Satin Smoothness Sensation to the initial Moisture friction Lanolin 4 3 3 1 3 anhydrous 1 2 1 2 3

3 5 '4 4 5

3 3 3 i 3

4 4 5 4

16 17 15 13 18

  Total - 63 Average 3.2 Average 12.6 Oil 3 3 2 1 2 of 2 3 1 3 - 3 lanolin 5 5 4 3 5

3 3 4 2 2

5 4 5 4

18 19 15 14 16

Total - 64 Average 3.6 Average 12.8

PCW-178 2 3 3 4 4

2 3 1 3 4

1 5 5 5 5

4 4 4 2 3

4 4 5 4 4

13 9 18 18 20

  Total - 75 Average 2.6 Average 15.0 Although the initial softness was not rated as favorably, the emollient of the invention was noted as being superior to the two commercial emollients

  with regard to the final touch sensation.

  Although the invention has been described with reference to

  to specific products, procedures, and examples

  ques, it is understood that the invention is not there

  limited, and that many variations can be made

  your as will be appreciated by those skilled in the art.

Claims (16)

Claims.   1. Cosmetic formula, characterized in that it   contains, as emollients, pre-   trimmed from vegetable oils containing esters   unconjugated polyunsaturated fatty acids, which are   judged and then modified by addition according to the reaction   Diels-Alder of an element from the group comprising acrylic acid, fumaric acid and anhydride maleic.   2. Cosmetic formula according to claim 1, charac-   terized in that the vegetable oil is soybean oil.   3. Cosmetic formula according to claim 1, ca-   characterized in that it contains as an emollient an element of the group comprising a vegetable oil, a   modified vegetable oil or a mixture of both.   4. Cosmetic formula according to claim 3, ca-   characterized in that the modified vegetable oil is obtained   held in disproportionation - the oil to conjugate the double bonds in the groups of linoleic acids   and linolenic present in oil.   5. Cosmetic formula according to claim 1, characterized in that the modification reaction of   Diels-Alder is carried out by reacting the vegetable oil tale with fumaric acid.   6. Cosmetic formula according to claim 1, characterized in that the addition product of the vegetable oil has the general formula o CH - O - C- R1 j2 iOC C C VS- - CH - O -C- 2 CCH2) CH 2c C CH2 y IyO CH -CH CH I I CH2 - O - C - 2-0-C-R2 Z Z   in which x and Y are integers from 3 to 9, the sum of x and y is 12, at least one group Z is a carboxylic acid group and any remaining Z is hydrogen, and R1 and R2 are hydrocarbon radicals saturated or unsaturated.   7. Cosmetic formula according to claim 6, charac-   terized in that each Z is a carbon acid group   xylic in which all or part of the carbon groups   xyles can be in the form of anhydride.   8. Cosmetic formula according to claim 1,   characterized in that the addition products of the vegetable oil are then transformed into their form of soaps chosen from the group comprising soluble soaps of alkali metals and amines and insoluble soaps   alkaline earths and higher valence metals.   9. Hair preparation, characterized in that it   contains as additives prepa-   res from vegetable oils containing esters   unconjugated polyunsaturated fatty acids, which are   judged and then modified by addition according to the reaction   Diels-Alder tion of an element from the group comprising acrylic acid, fumaric acid or maleic anhydride. 10. Hair preparation according to claim 9, characterized in that the vegetable oil is oil soy.   11. Hair preparation according to claim 9, characterized in that it comprises as an emollient an element of the group comprising a vegetable oil, a   modified vegetable oil and / or a mixture of both.   12. Hair preparation according to claim 10, characterized in that the modified vegetable oil is prepared by dismutant - the oil for conjugating the double bonds in the groups of linoleic acids and   linolenic present in oil.   13. Hair preparation according to claim 9, characterized in that the modification reaction of   Diels-Alder is performed by reacting oil-   the vegetable with fumaric acid.   14: hair preparation according to claim 9, characterized in that the product of addition of vegetable oil to the general formula O o I CH - - C -R 2 1 | I O / CH- CH   CH - O - C - (CH2) - CH CH - (CH2) - CH3 2x 3 I 2y CH - H CH2 - O - C - R2 2 2 Z Z   where x and y are integers from 3 to 9, the sum   me of x and y is 12, at least one Z is a carboxylic acid group and any remaining Z is hydrogen, and R1 and R2 are hydrocarbon radicals saturated or unsaturated.   15. Hair preparation according to claim 9, characterized in that the vegetable oil addition products are then transformed into their form of soaps chosen from the groups comprising soluble soaps of alkali metals and amines and insoluble soaps of alkaline earths and metals at higher valence.   16. Hair preparation according to claim 14, characterized in that each Z is a carboxylic acid group in which all or part of the groups   carboxyls can be in the form of anhydride.