SE469414B - SKIN AND HAIR HAIR PRODUCTS CONTAINING SUCH AS EMERGENCY AGENTS ADDED FROM SOYBEAN OIL. - Google Patents

Description

469 414 10 15 20 25 30 35 point range 272 ° C to 333 ° C) interact with the lipids so that thickening of the stratum corneum is formed. Kerosene is a common component used in anhydrous hand cleaners.

Medium chain surfactants such as sodium lauryl sulfate and CX olefin sulfonates commonly used in dishwashing detergents are harmful to the skin even in very dilute solutions. The activity of this class of substances is considered to be due to a strong binding of the surfactant functional group of the protein molecules in keratin the fibers and causes them to be reversibly denatured from Ö (spiral to / 2 configuration by a rollout of the fibers thereby stretching the tissue. Once this once has occurred probably does not appear complete recovery of the blocking function even after everything surfactant has been removed because the stratum corneum has a complex composition and nature.

Cosmetic creams that use mineral oil include also vegetable oils for the partial replacement of surface lipids removed due to solvent inversion can in mineral oil.

A correct water gradient over the stratum corneum is important for the function. Most of this water, as sometimes considered the softener of the stratum corneum, comes from inside of the body. If the humidity is too low, as in a cold climate, insufficient water remains in the outer layers of the stratum corneum in order to on a real way soften the tissue and the skin begins to flake and itch.

Skin permeability is also slightly reduced when present insufficient water over the stratum corneum. On the other the side causes too much water on the outside of the skin to the stratum corneum absorbs 3 to 5 times its own weight of bound water. This causes the skin to swell and wrinkle and results in an approximately two to threefold increase of the permeability to water and other polar molecules over the permeability at optimal hydration. lO 15 20 25 30 35 3 469 414 Hair contains many of the ingredients found in the tum corneum. The outermost region of the cells forms a relatively thick chemically resistant protective layer which surrounds the hair fiber called the dermis. The surface of the the dermis is covered with a thin layer called the epidermis as is considered to consist of lipids and protein. The dermis encloses the cortex cells that make up the bulk of the fibrous mass.

Keratin formation takes place in the cortex to build in stability in the hair structure.

There is thus a need for substances to be assisted tera stratum corneum and the scalp skin in maintaining barrier and water retention functions at optimal performance despite the harmful effects that the skin can exposed to washing, work and recreation.

In the discussion of cosmetic creams and lotions in Encyclo- pedia of Chemical Technology, third edition, volume 7 is given a classic example of a cream composition that includes ll, 8 - l2, l% valrav. It is also stated that compositions that use mineral oil instead for as previously almond oil must include vegetable oil for partial replacement of skin surface lipids removed through the solvent effect of the mineral oil.

Cosmetic lotion compositions are almost identical with the creams except that an oil-in-water softener lotions usually contain more water than the equivalent cream. These lotions are preferred for use during the day because they produce a thinner or less oily softening film. Cosmetic lotion compositions in Encyclopedia of chemical technology includes l - 1.5% anhydrous lanolin as the primary emollient.

Unfortunately, the emollient additives do not work currently used in creams and lotions the desired 469 434 10 15 20 25 30 35 lasting skin softening effect. Therefore exists there is a special need for emollient additives that keeps the skin softening for a longer period of time than that the currently available emollients do.

Hair products also benefit from the addition of softeners.

The barrier and water retention functions of the hair leather the skin can be assisted in the same way as the stratum corneum in the skin, especially in shampoos and conditioners. Lanolin and its derivatives are included in shampoo compositions such as conditioners to provide easy combing, investigation, volume, gloss, manageability, repair of broken tops, and prevention of static electricity.

The beneficial effects of softening for both skin and hair is perhaps most appreciated in dandruff shampoo. Dandruff is a product of hyperkeratin formation. The speed of ke- rate formation increases until the flaking becomes more visible. Dandruff shampoo contains ingredients that are effective controls dandruff by allowing a normal turnover rate of epidermal cells. An emollient for skin and hair should reduce the rate of keratin formation in the stratum corneum of the scalp and at the same time be partly for the leather skin of the hair.

An object of the present invention is therefore that provide additives for skin and hair preparations. An external more objective is to provide softening additives for skin and hair preparations, which additives give a softening effect for the stratum corneum of the skin or the dermis of the hair. Yet an object of the present invention is to achieve additives for skin and hair preparations, which additives give one more lasting softening effect than known softeners do.

The above-mentioned object is achieved in the discovery that certain tabular oil lipid adducts, either alone or in combination with vegetable oils and / or modified vegetable oils, provides a lasting softening effect l0 l5 20 25 30 35 469 414 when added to skin and hair care preparations. The softeners according to the present invention includes both soluble and water-insoluble salts of vegetable oils adducts. The preferred vegetable oil adducts according to the present invention, the adducts are prepared from non-conjugated polyunsaturated fatty acid esters from soybean oil which is conjugated and elaidinated and then is defined via Diels-Alder addition with acrylic acid, fumaric acid or maleic anhydride.

The main vegetable oil adducts according to The present invention can be accomplished from vegetable oils with polyunsaturated fatty acid ester groups in triglyceride the carboxyl content wherein the carboxyl content of the fatty acid ester groups are increased. These vegetable oil adducts provide by the non-conjugated part of the plural unsaturated fatty acid, essentially linoleic acid is first conjugated and elaidinized, followed by Diels-Alder addition with fumar acid, maleic anhydride or acrylic acid. It is essential conjugation and elaidination take place before the acrylic the addition to produce the acrylic acid adduct at opti- painted yield. With fumaric acid or maleic anhydride can the acid or anhydride may be present at the time of judging and elaidination without adversely affecting the reaction.

By elaidination is meant the transfer of a cis-transfer of a fatty acid sisomer to its trans-trans isomer.

These vegetable oil adducts and their production described in U.S. Patent 2678934 and U.S. Patent 4196134.

The vegetable oil adducts form triglyceride acids with the general formula 10 15 20 25 30 35 0 CH2 ~ .O - C.- Rl I '_Q “CH = CH gg I- Q -.ç _ (c32) Y _ cH \\ CH - (CH2) x - CH3 I CH - CH O 1 s CH O - E - R Zl Z 2 2 where x and y are integers from 3 to 9, x and y together is equal to 12, each Z may be a carboxylic acid group in which all or part of the carboxyl groups may be in the anhydride form or one Z may be hydrogen and the other Z is a carboxylic acid group and R1 and R2 are saturated / unsaturated hydrocarbon radicals. These triglyceride acids can be converted in their soap forms comprising soluble alkali metal soaps and amine soaps, insoluble alkaline earth metal soaps and soaps with metal and higher valence or they may as the free acid to achieve the benefits of the present invention.

These benefits include a softening or softening of the skin or hair held at maximum activity during a period of up to 20 hours. This activity is reduced not in normal washing procedures such as washing with soap and water or t.o.m. washing with so-called vat- free hand cleanser consisting of a cream compound soap, water, odorless kerosene and a variety of components such as lanolin and sometimes pumice to increase the cosmetic and cleansing properties.

Although the detected components alone produce good softening and moisture retention of the skin has been found to these benefits can be increased by adding the original oil the optimal mixture being about half of the vegetative bilical oil adduct and half vegetable oil. Outside- further improvement is obtained on the vegetable oil 10 l5 20 25 30 35 469 414 has been disproportionated to conjugate double-bonded in the linoleic acid and the linolenic acid groups present and oil. Although all the adducts mentioned are effective softer is the adduct which achieves optimal efficiency The Diels-Alder product with fumaric acid. A preferred method to achieve the optimal product is to react two moles of vegetable oil with one mole of dienophile in the presence of catalytic amount of iodine, the conjugating agent and that elaidic acid-forming agent. This produces simultaneously The 50:50 mixture of adduct to disproportionate vegetable tabilisk oil.

The following examples show that the adducts The present invention has unique advantages because they provide softening and softening to the skin for a long time period. To preserve efficiency for so long times they should have an affinity for or at least optimal compatibility with one or more components of the skin of the stratum corneum. This can be a collaboration with the hydrophobic parts of the adduct and free vegetable oil if such is present with the lipid particles in the intermediate lying cellular space or with the more hydrophilic ones the lipids that make up the walls of the keratinized cells lerna. If the adduct was capable of penetrating the cell perhaps its carboxylic acid groups would interact with the teinamine groups around the exterior of disulfide-bonded; ralkeratin chains. Regardless of how it is retained skin, the soybean oil-fumaric acid adduct has shown a myc- large hydrophilic group area of about 97.5 A2 for it free acid and ll6.2 Å2 for disodium soap. As a comparison occupies the major group of monocarboxylic fatty acids only 35 A2. It is believed that this large polar region may be hydrogenated. bind significant amounts of water. It would thus be effective be able to moisturize the skin with water in the regions where it is located. Although the exact mechanism by which these adducts work is unknown, their effectiveness is disturbing. 10 l5 20 25 30 35 Example 1 In the one-step production of an optimized mixture of 50% soybean oil fumaric acid adduct and 50% conjugated soybean bean oil was added 74.4 kg (0.085 kg / mol) of refined soybean oil. bean oil of nutrient grade, 4.8 kg (0.041 kg / mol) marsic acid and 0.3 kg of iodine to a pressure reaction vessel on 136 liters. The reactor was closed and heated to 25,000 and kept at this temperature for four hours while contains stirred. The resulting product had one acid number of 63.6 and a color of 3+ on the Gardner scale.

Example 2 The preparation of the soybean oil-fumaric acid adduct was carried out by adding 90.7 kg of refined soybean oil, 11.8 kg of fumaric acid and 0.27 kg of iodine to a pressure reactor of 136 liters. The reactor was closed, heated to 210 ° C and kept at this temperature for four hours during stirring. The resulting product had an acid number at 114, 8and a color of 5 on the Gardner scale.

Example 3 This example illustrates the preparation of alkali metal soaps and their effectiveness in skin care.

To a 400 ml beaker equipped with a stirrer was added 113.12 g of water and 13.12 g of potassium hydroxide pellets (86% solid). After heating the solution to 6000 slowly added with stirring 100 g of soybean oil-fu Marchic acid adduct from Example 2. After a further 15 minutes further stirring at 60 ° C, the mixture was allowed to cool. Way- the cosity of the yellow product was 2,050 cP at 50 ° C and its pH was 8.45. (x 10 15 20 25 30 35 9 469 414 To a 150 ml beaker containing 50 g of the above potassium soap of the soybean oil-fumaric acid adduct with 50% solids substance was added slowly while stirring well 25 g of soybean oil were maintained. The system obtained had a viscosity of 7.150 cP and a pH of 8.3.

Application to the skin gives a smooth and soft feeling without slipperiness or other undesirable properties. While the skin is rubbed to absorb the last of the product the skin develops a slightly sticky feeling for a moment until all of the product has disappeared from view.

The normal routine of work, recreation and rest is were carried out for the following 20 hours which included significantly exposed to water using both hand soap and liquid detergent. At the end of the 20 hours The skin still showed the suppleness and softness which the product had originally added.

Example 4 The sodium soap of the soybean oil-fumaric acid adduct is prepared was obtained by heating 108 g of water in which dissolved 8.4 g of sodium hydroxide pellet (97.7% solids) to 60 ° C and adding 100 g of soybean oil-fumaric acid raaddukt from example 2. After stirring for 15 minutes at 60 ° C the soap was allowed to cool. It had a pH of 8.6 and a viscosity of 2.160 cP at 45 ° C.

To a 250 ml beaker was slowly added 40 g of soybean oil to 20 g of the above-mentioned sodium soap. This provided a system with a viscosity of 3,200 cP and a pH of 8.7. There was no one stickiness during any step when ingested product in the skin. It showed similar long-lasting skin softening like the potassium soap. 10 469 414 Example 5 To illustrate the preparation of a monovalent amine salt, an anhydrous triethanolamine soap was prepared by To mix 13.9 g of triethanolamine in 100 g of soybean oil martic acid adduct from Example 2 to give a clear viscous gel. This soap showed skin softening properties similar the alkali metal soaps. It was involved in soft soap manners where it assisted in mother-of-pearl imagery And improved rinsing from the skin without reduction of the foaming properties of the soft soap.

Example 6 This example illustrates the use of soaps from polyvalent metal ions and soybean oil-fumaric acid adduct in skin care.

In a 500 ml beaker was dissolved 9.29 g of sodium hydroxide pellets (97.6% solids) in 121 ml of water. 100 g soybean oil fumaric acid adduct from Example 2 was then added. After stirring for 20 minutes to give a viscous homogeneous soap was added over a period of 15 minutes a solution consisting of 24.85 g of magnesium sulphate heptahydrate Dissolved in 71 ml of water. After about 2/3 of the magnesium the sulfate solution had been added separated the viscous homogeneous soap in two phase systems. After stirring during one hour and rest for another 1 hour, the water was poured ten phase of; and the viscous gel was washed twice With 131 ml portions of distilled water to remove remove residual sodium sulfate. Each addition of water was stirred with the organic phase for one hour; the system was then allowed to rest for another hour before removal from the organic phase. The handling Of this magnesium soap of soybean oil-fumaric acid adduct gave a smooth and soft feeling to the hands, what a feeling persisted for days after application. 10 15 20 25 30 35 ll 469 414 Example 7 This example illustrates the ability of soybean oil fumarate acid adduct and conjugated soybean oil to provide skin softness and overcome harmful effects of kerosene on the skin.

A viscous but pourable soap of the mixture of soybean oil yes-fumaric acid adduct and conjugated soybean oil in examples 1 was prepared by slow addition of 50 g of the adduct to a solution containing 56.56 g of potassium hydroxide pellets (86% solids) dissolved in 56.56 g of water. The turbida the solution had a pH of about 8.5.

To 17 g of the above soap in a 35 ml thread bottle, kerosene was added in 3 mlzs additives until then the bottle was full. After each addition of kerosene was stirred the system with a magnetic stirrer for 45 min. The final the solution had a low viscosity and was ready. This mixture was found to remove hidden dirt from the fingerprint pattern and other cavities of the hands as was evident of the black deposit on a dry paper towel used to wipe and visually improve the purity of the skin the. Furthermore, its viscosity was low enough to can be easily used under the fingernails to remove grease and dirt, which is particularly troublesome for niker.

In contrast to commercially available anhydrous cleaners usually composed of about 40% kerosene, 40% water and 20% oleic acid type soap gave the composition according to this example a skin emollient similar to the one for hand creams that lasted for several hours. There was nor any tendency for this composition to give painful depths of crack in the stratum corneum in the finger the pressure range of the hands, which is the common mistake at commercial anhydrous hand cleaners. 469 l0 l5 20 25 30 35 A 14 12 Example 8 The product of Example 1 (designated as PCW-178) was directly with anhydrous lanolin and the refined less viscous lanolin oil with respect to emollient properties of a typical hand lotion composition at a level of 5%. The evaluation procedure used was that developed by Goldemberg and De la Rosa described "Correlation of Skin Feel of Emollients to their Chemical Structure, "J. Soc. Cosmet. Chem., 22: 635- in their article 654 (l97l). In all cases, the emulsions were evaluated such as unlabeled samples of the same panel of laboratory workers for comparisons of original sensation on the skin, behavior during lubrication and final feeling after the emulsion had been absorbed into the skin. Original slipperiness was recorded on a scale from 1 to 5 (some to extensive slipperiness).

Final feeling was registered for agility, oiliness, friction and humidity. Each of these four characteristics was recorded on a scale of 1 to 5 with 5 as the most desired feeling. A numerical value for final feeling obtained by adding together the points for each registered property. Possible values for final feeling low thus between 4 and 20. The results are presented in table on p. 13.

Although originality was not recorded as the emollient according to the present was noted invention as superior to the two commercial with regard to final feeling.

Although the invention has been described and illustrated with reference to various specific materials, manufacturing methods and examples it will be apparent that the invention is not limited to these special materials, combined nations of materials and methods of production. Numerous va- variations on such details can be applied which should be obvious to those skilled in the art. 13 469 414 "APPLICATION PROPERTIES" AT LOTION Final feeling Softer Original Flexibility Oily Friction Moisture halhet Anhydrous Lanolin 4 3 3 l 3 1 2 l 2 3 3 5 4 4 5 3 3 3 l 3 _â i i __5 i 16 l7 13 13 18 Total -61 Medium- Medium- value 3.2 value 12.2 Lanolin oil 3 3 2 l 2 2 3 l 3 3 5 5 4 3 5 3 3 4 2 2 __5. _51 i _5 i 8 19 l5 14 6 -64 Medium- Medium- value 3.6 value 12.8 PCW-178 Product en- ligt ex. 1 2 3 3 4 4 2 3 l 3 4 l 5 5 5 5 4 4 4 2 3 i i _â i i 3 9 8 18 0 -75 Medium- Medium- value 2.6 value 15.0

Claims (1)

469 4% l0 15 20 25 30 35 14 CLAIMS ll An improved skin and hair care preparation with increased duration of skin and hair softening, characterized in that the preparation as a plasticizer contains adducts prepared from non-conjugated polyunsaturated fatty acid esters and soybean oil and soybean oil then modified via Diels-Alder addition with a compound from the group consisting of acrylic acid, fumaric acid or maleic anhydride and having the general formula: S? cH-ocR 12 l CH '° ”C ° (CH) .- cH c- (cH) -cH i 21 \ 5¿H_CHÄ zx 3 1 I zz where x and y are integers from 3 to 9, x and y to together is equal to 12, at least one Z is a carboxylic acid group and any remaining Z is hydrogen and R 1 and R 2 are saturated / unsaturated hydrocarbon radicals. An improved skin and hair care composition according to claim 1, characterized by a compound from the group consisting of soybean oil, modified soybean oil or a mixture thereof. It also contains an improved skin and hair care composition according to claim 2, characterized in that the modified soybean oil is prepared by disproportionating the oil to conjugate the double bonds in the linoleic and linolenic acid groups. and oil. An improved skin and hair care composition according to claim 1, characterized in that the Diels-Alders modification reaction is carried out by reacting the conjugated and elaidinated fatty acids, derived from soybean oil, with fumaric acid. An improved skin and hair care composition according to claim 1, characterized in that each Z is a carboxylic acid group where all or part of the carboxylic acid groups may be in anhydride form. An improved skin and hair care composition according to claim 1, characterized in that the adducts are later reacted with compounds selected from the group consisting of potassium hydroxide, sodium hydroxide, triethanolamine, magnesium sulphate heptahydrate.