CA1230558A - Vegetable oil adducts as emollients in skin and hair care products - Google Patents
Vegetable oil adducts as emollients in skin and hair care productsInfo
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- CA1230558A CA1230558A CA000480002A CA480002A CA1230558A CA 1230558 A CA1230558 A CA 1230558A CA 000480002 A CA000480002 A CA 000480002A CA 480002 A CA480002 A CA 480002A CA 1230558 A CA1230558 A CA 1230558A
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- vegetable oil
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
- A61K8/922—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
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Abstract
VEGETABLE OIL ADDUCTS AS EMOLLIENTS IN
SKIN AND HAIR CARE PRODUCTS
Abstract of the Invention Certain vegetable oil lipid adducts, either alone or in combination with vegetable oils and/or modified vegetable oils, are disclosed which provide persistent softening effects upon incorporation in skin and hair care preparations. The emollients of the invention include both the water-soluble and water-insoluble salts of the vegetable oil adducts. The certain vegetable oil adducts of the invention are the adducts prepared from vegetable oils containing nonconjugated polyunsaturated fatty acid esters which are conjugated and then modified via Diels-Alder addition with acrylic acid, fumaric acid, or maleic anhydride.
SKIN AND HAIR CARE PRODUCTS
Abstract of the Invention Certain vegetable oil lipid adducts, either alone or in combination with vegetable oils and/or modified vegetable oils, are disclosed which provide persistent softening effects upon incorporation in skin and hair care preparations. The emollients of the invention include both the water-soluble and water-insoluble salts of the vegetable oil adducts. The certain vegetable oil adducts of the invention are the adducts prepared from vegetable oils containing nonconjugated polyunsaturated fatty acid esters which are conjugated and then modified via Diels-Alder addition with acrylic acid, fumaric acid, or maleic anhydride.
Description
~230~
This invention relates to the use of vegetable oil adc1ucts, either alone or in combination with vegetable oils and/or modified vegetable oils as additives in skin and hair care products. More particularly, tlliS invention relates to the use of both water-soluble and wa-ter-insoluble salts of vegetablc oil adducts with or without vegetable oils or modiEied vegetable oils as emollients in skin and hair care products. Specifically, this invention relates to the use of adducts prepared from vegetable oils containing nonconjugated polyunsaturated fatty acid esters which are conjugated and then modified via Diels-~lder addition with acrylic acid, fumaric acid or maleic anhydrlde as emollients in skin and hair care products.
Skin is made up of several layers of cells which coat and protect the keratin and collegen fibrous proteins that form the skeleton of its structure. ~nionic surfactants typically penetrate the outermost of these layers, known as the stratum corneum membrane, by delipidization to destroy its integrity. This destruc-tion of the skin surface topo-graphy leads to a rough feel and may eventually permi t thesurfactant to interact with the keratin, crea-ting irritation.
Organic solvents are a major cause of delipidiza-tion of the stratum corneum. Also, solvents or solvent mixtures whicll are both lipid and water soluble are most effective in delipid:izatioll ~ somet:imes removinc3 LIS IllUCh as 10% to ~0% oE
i ~3(~5~8 Case Docket No. C~R 84-10 lipids from the skin upon long soaking. Specific chain length ! ranges of less water soluble organics are also deleterious.
` Hydrocarbons of the chain lengths present in kerosene ~bolling range 272C to 333C) interact with the lipids to yroduce abnormal thickening of the stratum corneum. Kerosene, of course, ~jis a common component utilized in waterless hand cleaners.
Medium chain length surfactants such as sodium lauryl sulfate and ~-olefin sulfonates commonly used in dish washing detergents are deleterious to the skin even in very dilute solutions. The activity of this class of substances is thought to be due to a Istrong binding of the surfactant functional group with protein ¦jmolecules in the keratin filaments causing them to be reversibly ¦jdenatured from the a-helix to the ~-configuration through an ¦luncoiling of the filaments which expands the tissue. Once this has occurred, complete recovery of the barrier function probably does not occur even ater all of the surfactant is removed because of the complex composition and nature of the stratum corneum.
jl Cosmetic creams which employ mineral oil also include ~vegetable oils for partial replacement of skin surface lipids ! removed due to the solvent action of the mineral oil.
~¦ The proper water gradient across the stratum corneum is important to its functionality. Most of this water, which is sometimes considered to be the stratum corneum's plasticizer, ;comes from inside the body. If the humidity is too low, such as in a cold climate, insufficient water remains in the outer layers of the stratum corneum to properly plastici~e the tissue; and the skin begins to scale and becomes itchy. Skin permeability is also decreased somewhat when there is inadequate water across the stratum corneum. On the other hand, too much water on the outside of the skin causes the stratum corneum to ultimately sorb
This invention relates to the use of vegetable oil adc1ucts, either alone or in combination with vegetable oils and/or modified vegetable oils as additives in skin and hair care products. More particularly, tlliS invention relates to the use of both water-soluble and wa-ter-insoluble salts of vegetablc oil adducts with or without vegetable oils or modiEied vegetable oils as emollients in skin and hair care products. Specifically, this invention relates to the use of adducts prepared from vegetable oils containing nonconjugated polyunsaturated fatty acid esters which are conjugated and then modified via Diels-~lder addition with acrylic acid, fumaric acid or maleic anhydrlde as emollients in skin and hair care products.
Skin is made up of several layers of cells which coat and protect the keratin and collegen fibrous proteins that form the skeleton of its structure. ~nionic surfactants typically penetrate the outermost of these layers, known as the stratum corneum membrane, by delipidization to destroy its integrity. This destruc-tion of the skin surface topo-graphy leads to a rough feel and may eventually permi t thesurfactant to interact with the keratin, crea-ting irritation.
Organic solvents are a major cause of delipidiza-tion of the stratum corneum. Also, solvents or solvent mixtures whicll are both lipid and water soluble are most effective in delipid:izatioll ~ somet:imes removinc3 LIS IllUCh as 10% to ~0% oE
i ~3(~5~8 Case Docket No. C~R 84-10 lipids from the skin upon long soaking. Specific chain length ! ranges of less water soluble organics are also deleterious.
` Hydrocarbons of the chain lengths present in kerosene ~bolling range 272C to 333C) interact with the lipids to yroduce abnormal thickening of the stratum corneum. Kerosene, of course, ~jis a common component utilized in waterless hand cleaners.
Medium chain length surfactants such as sodium lauryl sulfate and ~-olefin sulfonates commonly used in dish washing detergents are deleterious to the skin even in very dilute solutions. The activity of this class of substances is thought to be due to a Istrong binding of the surfactant functional group with protein ¦jmolecules in the keratin filaments causing them to be reversibly ¦jdenatured from the a-helix to the ~-configuration through an ¦luncoiling of the filaments which expands the tissue. Once this has occurred, complete recovery of the barrier function probably does not occur even ater all of the surfactant is removed because of the complex composition and nature of the stratum corneum.
jl Cosmetic creams which employ mineral oil also include ~vegetable oils for partial replacement of skin surface lipids ! removed due to the solvent action of the mineral oil.
~¦ The proper water gradient across the stratum corneum is important to its functionality. Most of this water, which is sometimes considered to be the stratum corneum's plasticizer, ;comes from inside the body. If the humidity is too low, such as in a cold climate, insufficient water remains in the outer layers of the stratum corneum to properly plastici~e the tissue; and the skin begins to scale and becomes itchy. Skin permeability is also decreased somewhat when there is inadequate water across the stratum corneum. On the other hand, too much water on the outside of the skin causes the stratum corneum to ultimately sorb
- 2 -~'~3~58 ;.
! Case Docket No. CIIR 84-10 ~three to five times its own weight of bound water. This swells and puckers the skin and results in an approximately two to three fold increase of the permeability to water and other polar "molecules above the permeability at optimum hydration.
j Hair consists of many of the same constituents as the ¦stratum corneum. The outermost region of cells forms a rather thick chemically resistant protective coating enclosing the hair fiber which is called the cuticle. The surface of the cuticle is Illcovered with a thin layer called the epicuticle which is thought ¦to contain lipids and protein. The cuticle envelopes the cortex ¦¦cells which comprise the major part of the fiber mass.
Keratinization takes place in the cortex to build stability into the hair structure.
Thus, a need exists for substances which will assist the stratum corneum and hair cuticle in maintaining their barrier l,and water retention functions at optimum performance in spite of ¦'~deleterious interactions which the skin may encounter in washing, )work, and recreation.
Ij In the discussion on cosmetic creams and lotions in the ¦:Encyclopedia of Chemical Technolo~y, Third Edition, Volume 7, a llclassic example of a cream formulation is given which includes 1!11 . 8-12.1% spermaceti. It is also noted that modern formulations which employ mineral oil in place of the earlier used almond oil must include vegetable oil for`partial replacement of skin surface lipids removed by the solvent action of the mineral oil.
Cosmetic lotion formulations are almost identical to the creams except an oil-in-water emollient lotion usually contains more water than the corresponding cream. These lotions are preferred for use during the day because they produce a 'lighter or less oily emollient film. Cosmetic lotion
! Case Docket No. CIIR 84-10 ~three to five times its own weight of bound water. This swells and puckers the skin and results in an approximately two to three fold increase of the permeability to water and other polar "molecules above the permeability at optimum hydration.
j Hair consists of many of the same constituents as the ¦stratum corneum. The outermost region of cells forms a rather thick chemically resistant protective coating enclosing the hair fiber which is called the cuticle. The surface of the cuticle is Illcovered with a thin layer called the epicuticle which is thought ¦to contain lipids and protein. The cuticle envelopes the cortex ¦¦cells which comprise the major part of the fiber mass.
Keratinization takes place in the cortex to build stability into the hair structure.
Thus, a need exists for substances which will assist the stratum corneum and hair cuticle in maintaining their barrier l,and water retention functions at optimum performance in spite of ¦'~deleterious interactions which the skin may encounter in washing, )work, and recreation.
Ij In the discussion on cosmetic creams and lotions in the ¦:Encyclopedia of Chemical Technolo~y, Third Edition, Volume 7, a llclassic example of a cream formulation is given which includes 1!11 . 8-12.1% spermaceti. It is also noted that modern formulations which employ mineral oil in place of the earlier used almond oil must include vegetable oil for`partial replacement of skin surface lipids removed by the solvent action of the mineral oil.
Cosmetic lotion formulations are almost identical to the creams except an oil-in-water emollient lotion usually contains more water than the corresponding cream. These lotions are preferred for use during the day because they produce a 'lighter or less oily emollient film. Cosmetic lotion
- 3 - i .
~2~
,~ Case Doclcet No. CIIR 84-10 ~formulations in the Encyclopedia of Chemical Technolo~y include 1-1.5% lanolin anhydrous as the primary emollient.
Unfortunately, emollient additives presently employed ~,in creams and lotions do not provide the persistency desired in ¦Itheir skin softening effects. Therefore, a particular need exists for emollient additives which promote skin softening ~or a ¦ilonger period of time than presently available emollients.
¦! Hair preparations also may benefit from inclusion of emollients. The barrier and water retention functions of the j~hair cuticle may be assisted similarly to the stratum corneum of 'ithe skin, particularly in shampoos and hair straighteners, ¦'ILanolin and its derivatives are included in shampoo,formulations as conditioning agents to impart ease of combing, detangling, !,bodY shine, manageability, split-end mending, and prevention of llstatic build-up.
!~ The beneficial effects of emolliency to both skin and jhair may be most appreciated in dandruff shampoos. Dandruff is ithe product of hyperkeratinization. The rate of keratinization ;increases to the point that the scales become more visible.
~Dandruff shampoos contain ingredients that effectively control dandruff by allowing a normal turnover rate of epidermal cells.
A s~in and hair softening emollient should reduce the rate of keratinization in the scalp stratum corneum and, at the same time, benefit the hair cuticle.
Therefore, an object of the present invention is to provide additives for skin and hair preparations. A further object is to provide skin and hair preparation e~lmollient additives which give a softening effect to the skin stratum corneum or the hair cuticle. A still further object of this invention is to provide skin and hair preparation additives which provide a more persistent softening effect than known emollients.
'1 ;, - 4 -.~30~
It has now been d:iscovered -that certain vegetable oil lipid adduets, either alone or in combination witll vege-table oils and/or modified vegetable oils, provide persistent softenillg effeets upon ineorporation in skin and hair care preparations.
~ ccordingly, one aspeet of the invention provides an improved skin eare formulation including, as an emollient therefor, one or more vegetable oil adducts afEording enhanced persistency of softening, the adducts being prepared from 10 vegetable oils containing nonconjugated polyunsaturated fatty aeid esters whieh are eonjugated and elaidinized and -then modified via Diels-Alder addition with a member of the group eonsisting of aerylie aeid, fumarie aeid and maleic anhydride.
Another aspeet of the invention provides an improved hair eare preparation including as an emollient therefor one or more vegetable oil adduets, affording enhanced softening of hair euticle, the adducts being pre-pared from vegetable oils eontaining noneonjugated polyunsa-turated fatty acid esters which are conjugated and elaidin-20 ized and then modified via Diels-~lder addition with a member of the group consisting of acrylic aeid, fumaric acid and maleic anhydride.
The emollients of this invention inelude both the water-soluble and water-insoluble salts of the vegetable oil 25 adducts. ~s indieated above, -the vegetable oil aclduets of the invention are adduets prepared Erom vegetable oils eon--taining noneonjugated polyunsaturatecl Eatty aeid esters whLeh :~3~
are conjllgated alld tllen mod-ified via Diels-Alcler a~`ldition with acrylic aci.d, fumaric acid, or maleic anllydri.de.
Tlle vegetabl.e oil adclucts essential to this invention may be made from vegetable oils having polyunsatur-ated fatty acld ester groups in the triglyceride moleculethereby increasing the carboxyl content of the fa-tty acid ester groups. These vegetable oil adducts are made by first conjugating and elaidinizing the nonconjuga-ted portion Or the polyunsaturated fatty acid, mainly linol.e:ic acid, followed by Diels-AI.der addition witll fumaric acid, maleic anhydride or acrylie aeid. It is essential that the eonjugation and elaidinization take place before the acrylie add.ition to produee the aerylie acid adduct in optimum yield. With fumarie aeid or maleie anhydride the aeid or anhydride can be present at the time conjugation and elaidiniza-tion -takes place without adversely affecting the reaction.
These vegetable oil adducts and their preparation are taught in U.S. Patent 2,678,~34 to Grummitt and U.S.
Patent - 5a -~3~ 8 Case Docket No. CIIR 84-10 ` b,196,134 to Ball et al The vegetable oil adducts form , triglyceride acids of the general formula ,j O
CH2 - - C Rl Il O / CH = CH
! CH - O - C - (CH2)y - CH / ( 2)x 3 O CH - CH
. . Il wherein x and y are integers from 3 to 9, x and y together equal 12, each Z can be a carboxylic acid group in which all or part of the carboxyl groups may be in the anhydride form or one Z can be hydrogen and the other Z a carboxylic acid group, and Rl and R2 are saturated/unsaturated hydrocarbon radicals. These triglyceride acids may be converted into their soap forms including the soluble alkali metal soaps and amine soaps, the insoluble alkaline earth and higher valent metal soaps or be incorporated as the free acid to achieve the benefits of this invention.
These benefits include a softening or emolliency of the skin or hair which is retained at maximum activity for a period of up to twenty hours. This activity is not diminished by normal ' cleaning procedures such as washing with soap and water or even cleaning with so called waterless hand cleaners consisting of a cream composed of soap, water, odorless kerosene and a variety of lesser ingredients such as lanolin and sometimes pumice stone to enhance their cosmetic and cleaning properties.
Although the discovered compounds ~roduce good softening and moisturizing of the skin alone, it has been found that these ~enefits can be enhanced by the additiorI of the parent oil to them with the optimum blend being about half vegetable oil ,, I
Case Docket No. CHR 84-10 adduct and half vegetable oil. Still further enhancement results i~ the vegetable oil has been disproportionated to conjugate the double bonds in the linoleic and linolenic acid groups present in the oil. Although any of the adducts mentioned are effective j,emollients, the adduct providing optimum effectiveness is the ¦,fumaric acid Diels-Alder product. A preferred method of achieving the optimized product is to react two moles of vegetable oil with one mole of the dienophile in the presence of catalytic amounts of iodine, the conjugation and elaidinization agent. This simultaneously produces the 50:50 blend of adduct to disproportionated vegetable oil.
From the following examples, it can be seen that the l~adducts of this invention are uniquely advantageous because of the long time period over which they provide softening and emolliency to the skin. In order to remain effective for such long periods, it would appear that they must possess an affinity for or at least optimum compatibility with one or more components of the skin probably present in the stratum corneum. This could be an interaction of the hydrophobic portions of the adduct and free vegetable oil, if it is present, with lipid granules in the, intercellular space or the more hydrophilic lipids which make up the walls of the keratinized cells. If the adduct were capable of entering the cell, its carboxylic acid groups might interact with protein amine groups around the exterior of a-helical disulfide bonded keratin chains. Regardless of how it is retained within the skin, the soybean oil fumaric acid adduct has been demonstrated to possess a very large hydrophilic group area of about 97.5A2 for the free acid and 116.2A2 for the disodium soap. By comparison, the head group of monocarboxylic fat~y acids only occupies 35A2. It would be anticipated that this large a polar region might hydrogen bond considerable amounts of ~58 Case Docket No. CIIR 84-10 ,,water. Thus, it could effectively moisturize the skin with water in the regions where it is located. Although the exact m~chanism 'by~ which these adducts function is unknown, their effectiveness is surprising.
Example 1 In thè one step preparation of an optimized blend of 50X soybean oil fumarir acid adduct and 50% conjugated soybean iloil~ 164 lbs (0.188 lb/moles) of food grade refined soybean oil, lO.6 lbs (0.091 lb/moles) f,umaric acid and 0.66 lb iodine were added to a 30-gallon pressure reaction vessel. The reactor was ¦¦sealed, heated to 250C and held at this temperature for four Ihours while the contents were being stirred. The resulting ¦!product had an acid number of 63.6 and a color of 3~ on the ! iGardner scale.
i, Example 2 !
' The preparation o the soybea~ oil fumaric acid add~lct 'was performed by adding 200 lbs of ~efined soybean oil, 26 lbs of fumaric acid and 0.60 lb of iodine to a 30-gallon pressure ',reactor. The reactor was sealed, heated to 210~C and held at ,that temperature for four hours with stirring. The resulting 'product had an acid number of 114.8 and a color of 5 on the 'Gardner scale.
. i ~
Example_3 This example illustrates the preparation of alkali metal soaps and their efficacy in skin care.
To a 400 ml beaker equipped with a stirrer were added 113.12 grams of water and 13.12 grams of potassium hyclroxide pellets (~6% solids). After heating the solution to 60(`, 100 ., ~
, ~ 8 1230S58 Case Docket No. ClIR 84-10 , ~
~grams of soybean oil fumaric acid adduct from Example 2 was ! slowly added with stirring. After 15 minutes additional stirring at 60C, the mixture was allowed to cool. The viscosity of the ~yellow product was 2,050 centipoise at 50C, and its pH was 8.45.
To a 150 ml beaker containing 50 grams of the above 50%
¦Isolids potassium soap of the soybean oil fumaric acid adduct, 25 ;Igrams of soybean oil was slowly added while good agitation was imaintained. The resulting sy~tem had a viscosity of 7,100 ¦¦centipoise and a pH of 8.3.
i` Application to the skin produced a smooth soft feel without slipperlness or other undesirabl~ properties. While rubbing the skin to adsorb the last of the product, the skin developed a slightly sticky feel for an instant until all of the product had disappeared from sight. The normal routine of work, Irecreation and rest was carried out for the next 20 hours which ¦included considerable exposure to water using both hand soap and lliquid dishwashing detergent. At the end of the 20 hours, the '"skin still possessed the smooth softness which the product had 'loriginally imparted.
l .
¦~ Example 4 The sodium soap of the soybean oil fumaric acid adduct ,was prepared by heatin& 108 grams of water ln which was dissolved 8.4 grams of sodium hydroxide pellets ~97.6% solids) to 60C and adding 100 grams of soybean oil fumaric acid adduct from Example 2. After stirring 15 minutes at 60C, the soap was allowed to cool. It had a pll of 8.6 and viscosity of 2,160 centipoise at 45C.
In a 250 ml beaker, 40 grams of soybean oil was slowly added to 80 grams of the above sodium soap. This gave a system with viscosity of 3,200 centipoise and pII 8.7. There was no , _ g _ , :123~)~5~3 Case Docket No. C~IR 84-10 qticky feel at any stage during the rubbing of this product into the skin. It exhibited similar long lasting skin softening to `~the potassium soap.
, ' il Example 5 il To illustrate the preparation of a monovalent amine jlsalt, an anhydrous triethanol amine soap was prepared by mixing 13.9 grams of triethanol amlne into 100 grams of soybean oil ~fumaric acid adduct from Example 2 to give a clear viscous gel.
This soap showed skin softening properties similar to the alkali jmetal soaps. It was compounded into soft soap formulations where ¦lit assisted in pearlescent and improved rinsing from the skin without detracting from the lathering properties of the soft llsoap .
Example 6 This example illustrates the utility of soaps of `multivalent metal ions and soybean oil fumaric acid adduct in iskin care.
~¦ In a 500 ml beaker, 9.29 grams of sodium hydroxide jpellets (97.6% solids) were dissolved in 121 ml of water. One Hundred (100~ grams of soybean oil fumaric acid adduct from Example 2 was then added. After stirring 20 minutes to produce a -viscous homogeneous soap, a solution consisting of 24.85 grams of magnesium sulfate heptahydrate dissolved in 71 ml of water was added over a period of 15 minutes. After about 2/3 of the magnesium sulfate solution had been added, the viscous homogeneous soap~separated into a two phase system. After `stirring for one hour and allowing the system to settle for another hour, the aqueous phase was pourcd off; and the viscous gel was washed twice with 131 ml portions of distilled water to - 10 - `
`' ~230~
`! Case Docket No. C~IR 84-lO
.remove any remaining sodium sulfate. Each batch of wash water ~was stirred with the organic phase for an hour; then the system was allowed to settle for another hour before removing from the ~organic phase. Handling of this magnesium soap of soybean oil . ~')fumaric acid adduct produced a smooth soft feel to the hands which remained for days after application.
Example 7 ! This example illustrates the ability of soybean oil fumaric acid adduct and conjugated soybean oil to provide skin softness and overcome the deleterious effects of kerosene on the skin.
A viscous but pourable soap of the soybean oil fumaric acid adduct-conjugated soybean oil blend in Example l was prepared by slowly adding 50 grams of the adduct to a solution of 56.56 grams of potassium hydroxide pellets (86% solids) dissolved in 56.56 grams of water. The turbid solution had a pH of about ~8.5. .
~¦ To 17 grams of the above soap in a 35 ml screw cap bottle was added kerosene in 3 ml increments until the bottle was full. After each incremental addition of kerosene, the system was stirred with a magnetic stirrer for 45 minutes. The final ~solution was low in viscosity and clear. This blend was found to i,clean hidden dirt from the fingerprint pattern and other crevices iof the hands as evidenced by black colored deposit on a dry paper 'towel used to wipe it off and the visually improved cleanliness '!
of the skin. Further, its viscosity was sufficiently low for it to be easily worked under the fingernails to remove grease and grime, a particularly difficult task for mechanics.
In contrast to commercially available waterless hand cleaners typically composed of about 40Z kerosene, 40Z water and li , ~3~S58 Case Docket ~o. CIIR ~4-l0 20Z oleic acid type soap, the formulation of this example provided skin s~ftening similar to tha~ o hand creams which lasted for several hours. There was also no tendency for this 'formulation to produce painful cracks deep into the stratum ~icorneum in the fingerprint areas of the hands which is the common j~fault of the commercial waterless hand cleaners.
l Example 8 ¦¦ The product of Example 1 (designated as PC~-178) was idirectly compared to anhydrous lanolin and the refined, less !¦viscous lanolin oil for emollient properties in a typical hand ¦llotion formulation at a level of 5%. The evaluation procedure ~employed was that developed by Goldemberg and De la Rosa ¦ described in their article "Correlation of Skin Feel of !IEmollients to Their Chemical Structure," J. Soc. Cosmet. Chem.
¦¦22 635-654 (1971). The emulsions in each case were evaluated as unmarked samples by the same panel of laboratory workers for `~comparisons of initial feeL on the skin, behavior during rub-in, and final feel after the emulsion had been absorbed into the ilskin. Initial Slip was rated on a scale from 1 to 5 ~slight to much slip). End Feel was rated for smoothness, oiliness, ¦,friction and moistness. Each of these four qualities was rated ! on a scale of 1 to 5, with 5 representing the most desirable feel. A numerical value for End Feel was obtained by adding together the scores for each quality rated. Possible values for End Feel thus ranged from 4 to 20. The results are presen~ed in the table presented below j, - 12 -;!
~3~58 i Case Docket No. C~IR 84-10 il "APPLICATION" PROPERTIES OF LOTION
i ~i End Feel ~1 .
i~ Emollient Initial Slip Smoothness Oiliness Friction Moistness I
Anhydrous Lanolin 4 3 3 1 3 . 3 3 3 1 3 i 5 4 4 5 4 16 17 13 ~'~~ 18 il Total - 61 i _ Average Average Score 3 2 Score 12.2 I
I
Lanolin Oil 3 3 2 1 2 .
~2~
,~ Case Doclcet No. CIIR 84-10 ~formulations in the Encyclopedia of Chemical Technolo~y include 1-1.5% lanolin anhydrous as the primary emollient.
Unfortunately, emollient additives presently employed ~,in creams and lotions do not provide the persistency desired in ¦Itheir skin softening effects. Therefore, a particular need exists for emollient additives which promote skin softening ~or a ¦ilonger period of time than presently available emollients.
¦! Hair preparations also may benefit from inclusion of emollients. The barrier and water retention functions of the j~hair cuticle may be assisted similarly to the stratum corneum of 'ithe skin, particularly in shampoos and hair straighteners, ¦'ILanolin and its derivatives are included in shampoo,formulations as conditioning agents to impart ease of combing, detangling, !,bodY shine, manageability, split-end mending, and prevention of llstatic build-up.
!~ The beneficial effects of emolliency to both skin and jhair may be most appreciated in dandruff shampoos. Dandruff is ithe product of hyperkeratinization. The rate of keratinization ;increases to the point that the scales become more visible.
~Dandruff shampoos contain ingredients that effectively control dandruff by allowing a normal turnover rate of epidermal cells.
A s~in and hair softening emollient should reduce the rate of keratinization in the scalp stratum corneum and, at the same time, benefit the hair cuticle.
Therefore, an object of the present invention is to provide additives for skin and hair preparations. A further object is to provide skin and hair preparation e~lmollient additives which give a softening effect to the skin stratum corneum or the hair cuticle. A still further object of this invention is to provide skin and hair preparation additives which provide a more persistent softening effect than known emollients.
'1 ;, - 4 -.~30~
It has now been d:iscovered -that certain vegetable oil lipid adduets, either alone or in combination witll vege-table oils and/or modified vegetable oils, provide persistent softenillg effeets upon ineorporation in skin and hair care preparations.
~ ccordingly, one aspeet of the invention provides an improved skin eare formulation including, as an emollient therefor, one or more vegetable oil adducts afEording enhanced persistency of softening, the adducts being prepared from 10 vegetable oils containing nonconjugated polyunsaturated fatty aeid esters whieh are eonjugated and elaidinized and -then modified via Diels-Alder addition with a member of the group eonsisting of aerylie aeid, fumarie aeid and maleic anhydride.
Another aspeet of the invention provides an improved hair eare preparation including as an emollient therefor one or more vegetable oil adduets, affording enhanced softening of hair euticle, the adducts being pre-pared from vegetable oils eontaining noneonjugated polyunsa-turated fatty acid esters which are conjugated and elaidin-20 ized and then modified via Diels-~lder addition with a member of the group consisting of acrylic aeid, fumaric acid and maleic anhydride.
The emollients of this invention inelude both the water-soluble and water-insoluble salts of the vegetable oil 25 adducts. ~s indieated above, -the vegetable oil aclduets of the invention are adduets prepared Erom vegetable oils eon--taining noneonjugated polyunsaturatecl Eatty aeid esters whLeh :~3~
are conjllgated alld tllen mod-ified via Diels-Alcler a~`ldition with acrylic aci.d, fumaric acid, or maleic anllydri.de.
Tlle vegetabl.e oil adclucts essential to this invention may be made from vegetable oils having polyunsatur-ated fatty acld ester groups in the triglyceride moleculethereby increasing the carboxyl content of the fa-tty acid ester groups. These vegetable oil adducts are made by first conjugating and elaidinizing the nonconjuga-ted portion Or the polyunsaturated fatty acid, mainly linol.e:ic acid, followed by Diels-AI.der addition witll fumaric acid, maleic anhydride or acrylie aeid. It is essential that the eonjugation and elaidinization take place before the acrylie add.ition to produee the aerylie acid adduct in optimum yield. With fumarie aeid or maleie anhydride the aeid or anhydride can be present at the time conjugation and elaidiniza-tion -takes place without adversely affecting the reaction.
These vegetable oil adducts and their preparation are taught in U.S. Patent 2,678,~34 to Grummitt and U.S.
Patent - 5a -~3~ 8 Case Docket No. CIIR 84-10 ` b,196,134 to Ball et al The vegetable oil adducts form , triglyceride acids of the general formula ,j O
CH2 - - C Rl Il O / CH = CH
! CH - O - C - (CH2)y - CH / ( 2)x 3 O CH - CH
. . Il wherein x and y are integers from 3 to 9, x and y together equal 12, each Z can be a carboxylic acid group in which all or part of the carboxyl groups may be in the anhydride form or one Z can be hydrogen and the other Z a carboxylic acid group, and Rl and R2 are saturated/unsaturated hydrocarbon radicals. These triglyceride acids may be converted into their soap forms including the soluble alkali metal soaps and amine soaps, the insoluble alkaline earth and higher valent metal soaps or be incorporated as the free acid to achieve the benefits of this invention.
These benefits include a softening or emolliency of the skin or hair which is retained at maximum activity for a period of up to twenty hours. This activity is not diminished by normal ' cleaning procedures such as washing with soap and water or even cleaning with so called waterless hand cleaners consisting of a cream composed of soap, water, odorless kerosene and a variety of lesser ingredients such as lanolin and sometimes pumice stone to enhance their cosmetic and cleaning properties.
Although the discovered compounds ~roduce good softening and moisturizing of the skin alone, it has been found that these ~enefits can be enhanced by the additiorI of the parent oil to them with the optimum blend being about half vegetable oil ,, I
Case Docket No. CHR 84-10 adduct and half vegetable oil. Still further enhancement results i~ the vegetable oil has been disproportionated to conjugate the double bonds in the linoleic and linolenic acid groups present in the oil. Although any of the adducts mentioned are effective j,emollients, the adduct providing optimum effectiveness is the ¦,fumaric acid Diels-Alder product. A preferred method of achieving the optimized product is to react two moles of vegetable oil with one mole of the dienophile in the presence of catalytic amounts of iodine, the conjugation and elaidinization agent. This simultaneously produces the 50:50 blend of adduct to disproportionated vegetable oil.
From the following examples, it can be seen that the l~adducts of this invention are uniquely advantageous because of the long time period over which they provide softening and emolliency to the skin. In order to remain effective for such long periods, it would appear that they must possess an affinity for or at least optimum compatibility with one or more components of the skin probably present in the stratum corneum. This could be an interaction of the hydrophobic portions of the adduct and free vegetable oil, if it is present, with lipid granules in the, intercellular space or the more hydrophilic lipids which make up the walls of the keratinized cells. If the adduct were capable of entering the cell, its carboxylic acid groups might interact with protein amine groups around the exterior of a-helical disulfide bonded keratin chains. Regardless of how it is retained within the skin, the soybean oil fumaric acid adduct has been demonstrated to possess a very large hydrophilic group area of about 97.5A2 for the free acid and 116.2A2 for the disodium soap. By comparison, the head group of monocarboxylic fat~y acids only occupies 35A2. It would be anticipated that this large a polar region might hydrogen bond considerable amounts of ~58 Case Docket No. CIIR 84-10 ,,water. Thus, it could effectively moisturize the skin with water in the regions where it is located. Although the exact m~chanism 'by~ which these adducts function is unknown, their effectiveness is surprising.
Example 1 In thè one step preparation of an optimized blend of 50X soybean oil fumarir acid adduct and 50% conjugated soybean iloil~ 164 lbs (0.188 lb/moles) of food grade refined soybean oil, lO.6 lbs (0.091 lb/moles) f,umaric acid and 0.66 lb iodine were added to a 30-gallon pressure reaction vessel. The reactor was ¦¦sealed, heated to 250C and held at this temperature for four Ihours while the contents were being stirred. The resulting ¦!product had an acid number of 63.6 and a color of 3~ on the ! iGardner scale.
i, Example 2 !
' The preparation o the soybea~ oil fumaric acid add~lct 'was performed by adding 200 lbs of ~efined soybean oil, 26 lbs of fumaric acid and 0.60 lb of iodine to a 30-gallon pressure ',reactor. The reactor was sealed, heated to 210~C and held at ,that temperature for four hours with stirring. The resulting 'product had an acid number of 114.8 and a color of 5 on the 'Gardner scale.
. i ~
Example_3 This example illustrates the preparation of alkali metal soaps and their efficacy in skin care.
To a 400 ml beaker equipped with a stirrer were added 113.12 grams of water and 13.12 grams of potassium hyclroxide pellets (~6% solids). After heating the solution to 60(`, 100 ., ~
, ~ 8 1230S58 Case Docket No. ClIR 84-10 , ~
~grams of soybean oil fumaric acid adduct from Example 2 was ! slowly added with stirring. After 15 minutes additional stirring at 60C, the mixture was allowed to cool. The viscosity of the ~yellow product was 2,050 centipoise at 50C, and its pH was 8.45.
To a 150 ml beaker containing 50 grams of the above 50%
¦Isolids potassium soap of the soybean oil fumaric acid adduct, 25 ;Igrams of soybean oil was slowly added while good agitation was imaintained. The resulting sy~tem had a viscosity of 7,100 ¦¦centipoise and a pH of 8.3.
i` Application to the skin produced a smooth soft feel without slipperlness or other undesirabl~ properties. While rubbing the skin to adsorb the last of the product, the skin developed a slightly sticky feel for an instant until all of the product had disappeared from sight. The normal routine of work, Irecreation and rest was carried out for the next 20 hours which ¦included considerable exposure to water using both hand soap and lliquid dishwashing detergent. At the end of the 20 hours, the '"skin still possessed the smooth softness which the product had 'loriginally imparted.
l .
¦~ Example 4 The sodium soap of the soybean oil fumaric acid adduct ,was prepared by heatin& 108 grams of water ln which was dissolved 8.4 grams of sodium hydroxide pellets ~97.6% solids) to 60C and adding 100 grams of soybean oil fumaric acid adduct from Example 2. After stirring 15 minutes at 60C, the soap was allowed to cool. It had a pll of 8.6 and viscosity of 2,160 centipoise at 45C.
In a 250 ml beaker, 40 grams of soybean oil was slowly added to 80 grams of the above sodium soap. This gave a system with viscosity of 3,200 centipoise and pII 8.7. There was no , _ g _ , :123~)~5~3 Case Docket No. C~IR 84-10 qticky feel at any stage during the rubbing of this product into the skin. It exhibited similar long lasting skin softening to `~the potassium soap.
, ' il Example 5 il To illustrate the preparation of a monovalent amine jlsalt, an anhydrous triethanol amine soap was prepared by mixing 13.9 grams of triethanol amlne into 100 grams of soybean oil ~fumaric acid adduct from Example 2 to give a clear viscous gel.
This soap showed skin softening properties similar to the alkali jmetal soaps. It was compounded into soft soap formulations where ¦lit assisted in pearlescent and improved rinsing from the skin without detracting from the lathering properties of the soft llsoap .
Example 6 This example illustrates the utility of soaps of `multivalent metal ions and soybean oil fumaric acid adduct in iskin care.
~¦ In a 500 ml beaker, 9.29 grams of sodium hydroxide jpellets (97.6% solids) were dissolved in 121 ml of water. One Hundred (100~ grams of soybean oil fumaric acid adduct from Example 2 was then added. After stirring 20 minutes to produce a -viscous homogeneous soap, a solution consisting of 24.85 grams of magnesium sulfate heptahydrate dissolved in 71 ml of water was added over a period of 15 minutes. After about 2/3 of the magnesium sulfate solution had been added, the viscous homogeneous soap~separated into a two phase system. After `stirring for one hour and allowing the system to settle for another hour, the aqueous phase was pourcd off; and the viscous gel was washed twice with 131 ml portions of distilled water to - 10 - `
`' ~230~
`! Case Docket No. C~IR 84-lO
.remove any remaining sodium sulfate. Each batch of wash water ~was stirred with the organic phase for an hour; then the system was allowed to settle for another hour before removing from the ~organic phase. Handling of this magnesium soap of soybean oil . ~')fumaric acid adduct produced a smooth soft feel to the hands which remained for days after application.
Example 7 ! This example illustrates the ability of soybean oil fumaric acid adduct and conjugated soybean oil to provide skin softness and overcome the deleterious effects of kerosene on the skin.
A viscous but pourable soap of the soybean oil fumaric acid adduct-conjugated soybean oil blend in Example l was prepared by slowly adding 50 grams of the adduct to a solution of 56.56 grams of potassium hydroxide pellets (86% solids) dissolved in 56.56 grams of water. The turbid solution had a pH of about ~8.5. .
~¦ To 17 grams of the above soap in a 35 ml screw cap bottle was added kerosene in 3 ml increments until the bottle was full. After each incremental addition of kerosene, the system was stirred with a magnetic stirrer for 45 minutes. The final ~solution was low in viscosity and clear. This blend was found to i,clean hidden dirt from the fingerprint pattern and other crevices iof the hands as evidenced by black colored deposit on a dry paper 'towel used to wipe it off and the visually improved cleanliness '!
of the skin. Further, its viscosity was sufficiently low for it to be easily worked under the fingernails to remove grease and grime, a particularly difficult task for mechanics.
In contrast to commercially available waterless hand cleaners typically composed of about 40Z kerosene, 40Z water and li , ~3~S58 Case Docket ~o. CIIR ~4-l0 20Z oleic acid type soap, the formulation of this example provided skin s~ftening similar to tha~ o hand creams which lasted for several hours. There was also no tendency for this 'formulation to produce painful cracks deep into the stratum ~icorneum in the fingerprint areas of the hands which is the common j~fault of the commercial waterless hand cleaners.
l Example 8 ¦¦ The product of Example 1 (designated as PC~-178) was idirectly compared to anhydrous lanolin and the refined, less !¦viscous lanolin oil for emollient properties in a typical hand ¦llotion formulation at a level of 5%. The evaluation procedure ~employed was that developed by Goldemberg and De la Rosa ¦ described in their article "Correlation of Skin Feel of !IEmollients to Their Chemical Structure," J. Soc. Cosmet. Chem.
¦¦22 635-654 (1971). The emulsions in each case were evaluated as unmarked samples by the same panel of laboratory workers for `~comparisons of initial feeL on the skin, behavior during rub-in, and final feel after the emulsion had been absorbed into the ilskin. Initial Slip was rated on a scale from 1 to 5 ~slight to much slip). End Feel was rated for smoothness, oiliness, ¦,friction and moistness. Each of these four qualities was rated ! on a scale of 1 to 5, with 5 representing the most desirable feel. A numerical value for End Feel was obtained by adding together the scores for each quality rated. Possible values for End Feel thus ranged from 4 to 20. The results are presen~ed in the table presented below j, - 12 -;!
~3~58 i Case Docket No. C~IR 84-10 il "APPLICATION" PROPERTIES OF LOTION
i ~i End Feel ~1 .
i~ Emollient Initial Slip Smoothness Oiliness Friction Moistness I
Anhydrous Lanolin 4 3 3 1 3 . 3 3 3 1 3 i 5 4 4 5 4 16 17 13 ~'~~ 18 il Total - 61 i _ Average Average Score 3 2 Score 12.2 I
I
Lanolin Oil 3 3 2 1 2 .
4 3 5 18 19 ~ 14 ~'~
Total - 64 Average Average ~~ Score 3.6 Score 12.8 i' PCW-178 2 3 3 4 4 !1 4 4 4 2 3 'i 4 4 5 4 4 'il 13 19 -18 18 20 i Total - 75 !i I
, Average Average '! Score 2.6 Score 15.0 _ .
Although the Initial Slip was not rated as favorably, the emollient of the invention was rated superior to both .commercial emollients in End Feel.
.j i 1 1230558 Case Docket No. Cllr~ ~4-10 While the invention has been described and illustrated herein by references to various specific materials, procedures ','and examples, it is understood that the invention is not "restricted to the particular materials, combinations of 'Imaterials, and procedures selected for that purpose. Numerous ,,variations of such details can be employed, as will be appreciated by those skille in the art.
!. ~
., .
Total - 64 Average Average ~~ Score 3.6 Score 12.8 i' PCW-178 2 3 3 4 4 !1 4 4 4 2 3 'i 4 4 5 4 4 'il 13 19 -18 18 20 i Total - 75 !i I
, Average Average '! Score 2.6 Score 15.0 _ .
Although the Initial Slip was not rated as favorably, the emollient of the invention was rated superior to both .commercial emollients in End Feel.
.j i 1 1230558 Case Docket No. Cllr~ ~4-10 While the invention has been described and illustrated herein by references to various specific materials, procedures ','and examples, it is understood that the invention is not "restricted to the particular materials, combinations of 'Imaterials, and procedures selected for that purpose. Numerous ,,variations of such details can be employed, as will be appreciated by those skille in the art.
!. ~
., .
Claims (16)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An improved skin care formulation including, as an emollient therefor, one or more vegetable oil adducts affording enhanced persistency of softening, the adducts being prepared from vegetable oils containing nonconjugated polyunsaturated fatty acid esters which are conjugated and elaidinized and then modified via Diels-Alder addition with a member of the group consisting of acrylic acid, fumaric acid and maleic anhydride.
2. The skin care formulation of claim 1 wherein the vegetable oil is soybean oil.
3. The skin care formulation of claim 1 which also includes as an emollient a member of the group consisting of vegetable oil, modified vegetable oil and mixtures thereof.
4. The skin care formulation of claim 3 wherein the modified vegetable oil is produced by disproportionation thereof to conjugate the double bonds in linoleic and lino-lenic acid groups present in the oil.
5. The skin care formulation of claim 1, 2 or 3, wherein the Diels-Alder modification reaction occurs by reacting the vegetable oil with fumaric acid.
6. The skin care formulation of claim 1 wherein the vegetable oil adduct has the general formula wherein x and y are integers from 3 to 9, x and y together equal 12, at least one Z is a carboxylic acid group, and any remaining Z is hydrogen, and R1 and R2 are saturated or un-saturated hydrocarbon radicals.
7. The skin care formulation of claim 6 wherein each Z is a carboxylic acid group in which all or part of the carboxyl groups may be in the anhydride form.
8. The skin care formulation of claim 1, 2 or 3, wherein the vegetable oil adducts are subsequently converted into their soap forms selected from the group consisting of the soluble alkali metal and amine soaps and the insoluble alkaline earth and higher valent metal soaps.
9. An improved hair care preparation including as an emollient therefor one or more vegetable oil adducts, affording enhanced softening of hair cuticle, the adducts being prepared from vegetable oils containing nonconjugated polyunsaturated fatty acid esters which are conjugated and elaidinized and then modified via Diels-Alder addition with a member of the group consisting of acrylic acid, fumaric acid and maleic anhydride.
10. The hair care preparation of claim 9 wherein the vegetable oil is soybean oil.
11. The hair care preparation of claim 9 which also includes as an emollient a member of the group consis-ting of vegetable oil, modified vegetable oil and mixtures thereof.
12. The hair care preparation of claim 10 wherein the modified vegetable oil is produced by disproportionation thereof to conjugate the double bonds in linoleic and lino-lenic acid groups present in the oil.
13. The hair care preparation of claim 9, 10 or 11, wherein the Diels-Alder modification reaction occurs by reacting the vegetable oil with fumaric acid.
14. The hair care preparation of claim 9, wherein the vegetable oil adduct has the general formula wherein x and y are integers from 3 to 9, x and y together equal 12, at least one z is a carboxylic acid group, and any remaining Z is hydrogen, and R1 and R2 are saturated or unsat-urated hydrocarbon radicals.
15. The hair care preparation of claim 9, 10 or 11, wherein the vegetable oil adducts are susbsequently converted into their soap forms selected from the group consisting of the soluble alkali metal and amine soaps and the insoluble alkaline earth and higher valent metal soaps.
16. The hair care preparation of claim 14 wherein each Z is a carboxylic acid group in which all or part of the carboxyl groups may be in the anhydride form.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US63258984A | 1984-07-19 | 1984-07-19 | |
| US632,589 | 1984-07-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1230558A true CA1230558A (en) | 1987-12-22 |
Family
ID=24536131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000480002A Expired CA1230558A (en) | 1984-07-19 | 1985-04-24 | Vegetable oil adducts as emollients in skin and hair care products |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS61500791A (en) |
| BE (1) | BE902310A (en) |
| CA (1) | CA1230558A (en) |
| DE (2) | DE3590272T (en) |
| FR (1) | FR2567753B1 (en) |
| GB (1) | GB2169201B (en) |
| IT (1) | IT1188161B (en) |
| SE (1) | SE469414B (en) |
| WO (1) | WO1986000800A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2239369A1 (en) | 2009-04-09 | 2010-10-13 | Kemira OYJ | Product for the sizing of paper |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IN184497B (en) * | 1990-10-12 | 2000-08-26 | Procter & Gamble | |
| DE4403570A1 (en) * | 1994-02-05 | 1995-08-10 | Henkel Kgaa | Active ingredient complex for hair treatment products |
| GB2290551B (en) * | 1994-05-11 | 1998-06-10 | Procter & Gamble | Cleansing compositions |
| GB2319177A (en) * | 1996-11-11 | 1998-05-20 | Procter & Gamble | Cosmetic compositions |
| RU2157175C1 (en) * | 2000-03-10 | 2000-10-10 | Болобан Леонид Григорьевич | Natural cream |
| WO2013126916A2 (en) * | 2012-02-25 | 2013-08-29 | Ethox Chemicals, Inc. | Natural oil based gels, applications and methods of preparation |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB312568A (en) * | 1928-10-23 | 1929-05-30 | Yasukazu Shimura | Improvements in the manufacture of hair toilet oil |
| US2188882A (en) * | 1934-12-24 | 1940-01-30 | Edwin T Clocker | Condensation product and method |
| US2396763A (en) * | 1943-12-20 | 1946-03-19 | Harry M Ullmann | Modified oil |
| US2678934A (en) * | 1951-08-09 | 1954-05-18 | Sherwin Williams Co | Method of making glyceride-fumaric acid reaction products |
| US3956161A (en) * | 1974-06-03 | 1976-05-11 | Westvaco Corporation | Cleaning compositions containing C21 dicarboxylic acid |
| IL47655A (en) * | 1974-08-02 | 1978-08-31 | Pennwalt Corp | Aqueous germicidal composition |
| US4150041A (en) * | 1975-01-31 | 1979-04-17 | Agency Of Industrial Science & Technology | Method for manufacture of poly-fatty acids and maleic anhydride-added fatty acids |
| US4196134A (en) * | 1977-01-31 | 1980-04-01 | Westvaco Corporation | Vegetable oil adducts |
| DE2754831C2 (en) * | 1977-12-09 | 1985-02-07 | Basf Ag, 6700 Ludwigshafen | Process for the preparation of strongly alkaline, aqueous solutions of non-ionic surfactants |
| JPS5531037A (en) * | 1978-08-26 | 1980-03-05 | Kanebo Ltd | W/o-type creamy or milky lotion composition |
| DE3032612A1 (en) * | 1980-08-29 | 1982-03-25 | Grillo-Werke Ag, 4100 Duisburg | IF REQUIRED, SULFIED PARTIALESTERS OF MULTI-VALUE ALCOHOLS - METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS SKIN-FRIENDLY, NON-IONOGENIC AND / OR ANION-ACTIVE SURFACE-ACTIVE SUBSTANCES |
| JPS57179109A (en) * | 1981-04-25 | 1982-11-04 | Lion Corp | Hair treating agent |
-
1985
- 1985-04-19 DE DE19853590272 patent/DE3590272T/en active Pending
- 1985-04-19 DE DE3590272A patent/DE3590272C2/en not_active Expired - Lifetime
- 1985-04-19 WO PCT/US1985/000708 patent/WO1986000800A1/en not_active Ceased
- 1985-04-19 JP JP60501918A patent/JPS61500791A/en active Granted
- 1985-04-19 GB GB08529493A patent/GB2169201B/en not_active Expired
- 1985-04-23 IT IT20450/85A patent/IT1188161B/en active
- 1985-04-24 CA CA000480002A patent/CA1230558A/en not_active Expired
- 1985-04-29 BE BE0/214931A patent/BE902310A/en not_active IP Right Cessation
- 1985-04-29 FR FR8506509A patent/FR2567753B1/en not_active Expired - Lifetime
-
1986
- 1986-03-11 SE SE8601115A patent/SE469414B/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2239369A1 (en) | 2009-04-09 | 2010-10-13 | Kemira OYJ | Product for the sizing of paper |
| US8512521B2 (en) | 2009-04-09 | 2013-08-20 | Kemira Oyj | Product for the sizing of paper |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2567753A1 (en) | 1986-01-24 |
| IT8520450A1 (en) | 1986-10-23 |
| SE469414B (en) | 1993-07-05 |
| BE902310A (en) | 1985-08-16 |
| JPH0327523B2 (en) | 1991-04-16 |
| DE3590272T (en) | 1986-07-17 |
| WO1986000800A1 (en) | 1986-02-13 |
| IT8520450A0 (en) | 1985-04-23 |
| JPS61500791A (en) | 1986-04-24 |
| SE8601115D0 (en) | 1986-03-11 |
| GB8529493D0 (en) | 1986-01-08 |
| FR2567753B1 (en) | 1990-12-14 |
| GB2169201B (en) | 1988-07-06 |
| DE3590272C2 (en) | 1994-03-31 |
| SE8601115L (en) | 1986-03-11 |
| GB2169201A (en) | 1986-07-09 |
| IT1188161B (en) | 1988-01-07 |
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