CA2087488A1 - Oil soluble polysaccharides - Google Patents
Oil soluble polysaccharidesInfo
- Publication number
- CA2087488A1 CA2087488A1 CA002087488A CA2087488A CA2087488A1 CA 2087488 A1 CA2087488 A1 CA 2087488A1 CA 002087488 A CA002087488 A CA 002087488A CA 2087488 A CA2087488 A CA 2087488A CA 2087488 A1 CA2087488 A1 CA 2087488A1
- Authority
- CA
- Canada
- Prior art keywords
- palmitate
- ester
- polysaccharide
- stearate
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
ABSTRACT OF THE DISCLOSURE
OIL SOLUBLE POLYSACCHARIDES
Palmitate and stearate esters of polysaccharides such as cellulose ethers and guars are soluble in mineral oil and fatty ester solvents making them useful for cosmetic and oil lubricant applications. A preferred process involve mixing a polysaccharide in an organic solvent and esterifying with an acid chloride in the presence of a catalyst such as triethylamine.
OIL SOLUBLE POLYSACCHARIDES
Palmitate and stearate esters of polysaccharides such as cellulose ethers and guars are soluble in mineral oil and fatty ester solvents making them useful for cosmetic and oil lubricant applications. A preferred process involve mixing a polysaccharide in an organic solvent and esterifying with an acid chloride in the presence of a catalyst such as triethylamine.
Description
MAJEWICZ~MESHRE~I 1 ~ 3 ,~ AQA
OI~ SOLUBLE POLYSACCHARID~S
Field of ~h~ Iav~
This invention relates to polymers which are soluble in and thick~n organic solvents such as mineral oil and fatty esters. In particular the invention relates to palmitate and stearate esters of polysaccharides.
~ackg~oun~Lof th~ In~n~iQn:
Esterification of polysaccharides was known prior to the present invention U.5. Patents 2,055,892 and 2,055,893 which disclose a process for manufacturing hydro~yalkyl derivatives of cellulose and other carbohydrate materials.
U.S. Patent 2,816,887 discloses the acid catalyzed, fatty acid acylation of cellulose and cellulose ethers to produce hydro~yethyl cellulose acetate and hydro~yethyl cellulose propionate. U.S. 3,435,027 discloses a process of preparing water soluble ether esters of cellulose by acylating a water soluble cellulose ether. It also discloses a water-based mi~ture of hydro~yethylcellulose and stearic acid. German Offenle~ungsshri t DE 31 26 593 Al "Lubricants and New Cellulose Ether Esters~ diicloses stearic and palmitic acid esters of hydro~yethylcellulose and methylcellulose as lubricant viscosifiers. U.S. Patent 4,963,492 discloses a transesteriication process. U.S. 3,629,277 discloses phthalic acid esters of hydroxypropylcellulose and other cellulose ether~. U.S. Patent 3,824,085 discloses the acetate and laurate esters of hydro~ypropylcellulose and hydroxypropyl star~h. U.S. Patent 3,870,701 discloses the acetate ester of benzyl hydro~ypropylcellulose and its use as a gelling agent for organic solvents. U.S. Patent 3,940,389 discloses the acetat~ ester of methyl hydro~ypropylcellulose . , ,. ~ ~, . .
: , ' , . ~ , " .~ , : ' ' . ' -' ' ~ . - ,' ', ' ', . '.~ ' ' ':
:, and its use as a gelling agent for orqaniC solvents~ U. S.
Patent 4,226,981 discloses a mi~ed ester useful as an enteric coating for drugs prepared by esterification of a cellulose ether with a mi~ture of succinic anhydride and an anhydride of an aliphatic monocarboxylic acid.
Yet in spite of what was known, it remained for the present discovery to provide oil soluble polysaccharides useful as thickeners for cosmetic and toiletry applications.
Sum~rr o~ t~ In~e~tiQ~:
It is an object of the invention to provide palmitate and stearat~ esters of polysaccharides in particular cellulose ethers.
.
Stearate and palmitate esters of hydro~ypropylcellulose are preferred where the hydro~ypropylcellulose has a molecular weight above 50,000 and tha exten~ of ester substitution is sufficient to impart solubility in mineral oil and~or fatty acids.
It is a further object of the invention to provide a method for producing p~lysaccharide palmitats and stearate esters comprising the steps:
(l) mising a polysaccharide in an organic solvent;
OI~ SOLUBLE POLYSACCHARID~S
Field of ~h~ Iav~
This invention relates to polymers which are soluble in and thick~n organic solvents such as mineral oil and fatty esters. In particular the invention relates to palmitate and stearate esters of polysaccharides.
~ackg~oun~Lof th~ In~n~iQn:
Esterification of polysaccharides was known prior to the present invention U.5. Patents 2,055,892 and 2,055,893 which disclose a process for manufacturing hydro~yalkyl derivatives of cellulose and other carbohydrate materials.
U.S. Patent 2,816,887 discloses the acid catalyzed, fatty acid acylation of cellulose and cellulose ethers to produce hydro~yethyl cellulose acetate and hydro~yethyl cellulose propionate. U.S. 3,435,027 discloses a process of preparing water soluble ether esters of cellulose by acylating a water soluble cellulose ether. It also discloses a water-based mi~ture of hydro~yethylcellulose and stearic acid. German Offenle~ungsshri t DE 31 26 593 Al "Lubricants and New Cellulose Ether Esters~ diicloses stearic and palmitic acid esters of hydro~yethylcellulose and methylcellulose as lubricant viscosifiers. U.S. Patent 4,963,492 discloses a transesteriication process. U.S. 3,629,277 discloses phthalic acid esters of hydroxypropylcellulose and other cellulose ether~. U.S. Patent 3,824,085 discloses the acetate and laurate esters of hydro~ypropylcellulose and hydroxypropyl star~h. U.S. Patent 3,870,701 discloses the acetate ester of benzyl hydro~ypropylcellulose and its use as a gelling agent for organic solvents. U.S. Patent 3,940,389 discloses the acetat~ ester of methyl hydro~ypropylcellulose . , ,. ~ ~, . .
: , ' , . ~ , " .~ , : ' ' . ' -' ' ~ . - ,' ', ' ', . '.~ ' ' ':
:, and its use as a gelling agent for orqaniC solvents~ U. S.
Patent 4,226,981 discloses a mi~ed ester useful as an enteric coating for drugs prepared by esterification of a cellulose ether with a mi~ture of succinic anhydride and an anhydride of an aliphatic monocarboxylic acid.
Yet in spite of what was known, it remained for the present discovery to provide oil soluble polysaccharides useful as thickeners for cosmetic and toiletry applications.
Sum~rr o~ t~ In~e~tiQ~:
It is an object of the invention to provide palmitate and stearat~ esters of polysaccharides in particular cellulose ethers.
.
Stearate and palmitate esters of hydro~ypropylcellulose are preferred where the hydro~ypropylcellulose has a molecular weight above 50,000 and tha exten~ of ester substitution is sufficient to impart solubility in mineral oil and~or fatty acids.
It is a further object of the invention to provide a method for producing p~lysaccharide palmitats and stearate esters comprising the steps:
(l) mising a polysaccharide in an organic solvent;
(2) est~rifying the polysaccharide with a palmitate and/or stearate moiety in the pre~ence of a catalyst; and (3) recovering a palmitate polysaccharide ester, a stearate polysaccha~ide ester or a mi2ed palmitate and stearate polysaccharide ester.
. : ~ : . . .
- - .
Ln a preferred method the catalyst is triethylamine~
the polysaccharide is hydro~ypropylcellulose and the organic solvent is methylene chloride.
Detq~ rie~iQ~ of th~ ~ve~iQ~:
various grades of mineral oil, as well as aliphatic esters such as isopropyl myristate and isopropyl palmitate, and aromatic esters such as alkyl benzoate esters, are widely used in the cosmetic industry. Silicone fluids, jojoba oil and essential oils are also used. Compositions o~ matter which would be suitabla to dissolve in and thicken these oils and esters have been sought after to aid in cosmetic formulations. The discovery provided by the present invention makes possible such an advance in the state of th~
art .
Polysaccharide~ suitable for the practice of the invention are currently available in commercial or developmental quantitie~ from a variety of sources. These polysaccharides can b~ grouped into the categories of (l) cellulose ethers, (2) polygalactomannans and (3~ starches.
Within group ~1) hydro~ypropylcellulose is a preferred cellulose ether, whil~ other suitable cellulose eth~rs include methylcellulose, carboxymethylhydro~ypropylcellulose, hydro~ypropylm~thylcollulose and hydroxypropylhydro~yethylcellulose. Thes~ materials are available from Rqualon Company (a Hercules Incorporated company), Dow Chemical Company and Shin-Etsu Chemical.
Within qroup (2) hydro~ypropylguar i5 a preferred polygalactomman whil~ guar and carbo~ymethylhydro~ypropylguar are also suitable within group (~) hydro2ypropyl starch is a preferred material.
':
'~ '' ' . ~
The preferred polysaccharide is hydroxypropylcellulose of M.S. 3.0-4.5 (available from Aqualon Company under the tradename Klucel 3) .
It was discovered that a polysaccharide substituted with hydro~ypropyl groups gave particularly useful benefits for cosmetic and toiletry applications. In this respect a palmitate ester of hydro~ypropylcellulose having a molar substitution by hydro~ypropyl betweerl 3.0 and 4.5 and a molecular weight above 50,000 was discovered to be the most beneficial for cosmetic and toiletry applications.
Esterification of the polysaccharide in an organic solvent or mi~ture o solvents is accomplished usin~ a moiety such as stearic acid chlorid~ or palmatic acid chloride or an anhydride thereof which can react to orm the palmitate and/or stoarate ester. It is essential for a cellulose ether, polygalactomannan or starch to contain reactive hydro~yl groups in order for esterification to take placa.
This hydro~yl reactivity i9 not inhibited if the polysaccharide is partially modified with oth2r groups.
Thus, the preferred hydro~ypropylcellulose could contain other modifying group~ ~uch as methyl, ethyl, carbo~ymethyl, etc. or even long chain hydrophobic alkyl or arylalkyl groups such as butyl, cetyl or nonylph2nyl.
It ha~ been the e~perience of persons of ordinary s~ill in the art that degr~ of substitution values determined by sa~onification technigu~s lack accuracy and precision for cellulo~ic derivatives. As a result it ha~ been discovered that measurements of the ratio of the carboxyl ester to hydro~yl stretching bands in ths Infra Red (IR) at 30 appro~imately 1734 cm~l and 3470 cm~l is useful in assessing .
.. :
2~
ae degree of esterification. A ratio great:er than 0.5 roughly corr~sponds to degrees of substitution which promote oil solubility. A preferred range for this ratio is from about 0.5 to about 50Ø
Esterification equipment and techniques useful for the practice of the invention are known irom general practice in the art and as described in the refer.ences contained in the Background of the Invention. Triethylamine is a preferred catalyst for esterification of the polysaccharide. It is also preferred that tetrabutylammonium hydrogen sulfate be used as a catalyst for a phase transfer esterification, whereas sodium methoside/sodium borohydride is a preferred catalyst for trans-esterification.
In d~tail the process of the invention involves:
Mi~in~: A solution or slurry su~pen~ion of the polysaccharide is prepared in at least one organic solvent. The solution or slurry suspen~ion typically will contain from 0.05 to 0.15 mole of polysaccharide in from 0.5 to 1.5 mole of organic solvent. Good result have been obtained usinq methylene chloride, pyridine, toluen~ and 1,4-dio~ane and combinations thereof~ An aqueous phase will also be required when a phase transfer reaction is run.
Est&Liicatio~: Once the polysaccharide has been susp~nded in either solution or slurry suspension, est~rification can occur. In the event it is desired to pr~pare a mi~ed ester, the esterification can be done in one step with a mixture of, for instance, stearic acid chloride and palmitic acid chloride or stepwise by first reactin~ with stearic acid chloride followed by palmitic acid chloride. Suitable catalysts include triethylamine, sodium metho~ide/sodium borohydride, tetrabutylammonium hydrogen sulfate, concentrsted sulfuric acid, p toluenesulfonic acid or a cation e~change resin in hydrogen or acid orm, depending on the type of esteriEication reaction being undertaken.
RecQvery: When the esterification reaction has been completed, ~i~ed or single esters can be recovered by conventional steps of neutraliz:ation and washing.
After cooling the reaction mi~t:ure; organic solvents such as acetone, toluene or methanol containing a small amount of water are added to destroy the e~cess acid chloride and precipitate the ester. Further washing can follow.
~ : Purified e~ters made according to the inv~ntion can be formulated into cosmetics due to their property of being soluble in both mineral oil and light esters such as jojoba oils, isopropyl myristate or isopropyl palmitate and aromatic esters such as benzoic acid alkyl esters.
An oil base cleansing or protective formulation suita~le for incorporating a polysaccharide palmitate comprises:
In~edi~n~ Wt Isopropyl pslmitate 14.9 Lanolin oil 23.9 Light mineral oil 97.2 Dow Corning 345 ~luid 14.0 ~ . .
The following e~amples illustrate the practice o~ the invention~ which has industrial applicability for cosmetics, toiletrieS and oil and gas recovery. E~am~le l represents the best mode envisioned.
E~ample l Five O.1 mole portions of Klucel~
hydro~ypropylcellulose, available from the Aqualon Company as grades EF 80,000 mol. wt. JF (lso~ooo mol. wt.), MF (850,000 mol. wt.) and HF (1,150,000 mol. wt.), were prepared as slurry suspensions in 750 ml methylene chloride and 250 ml triethylamine. A 0.6 mole portion oE either palmitic acid chloride or stearic acid chloride in 150 ml l,4-dio~ane was added to each suspension. With constant stirring, esterification was allowed to proceed or 24 hours at room temperature. As the esterifieation proceeded, the suspension became viscous and hard to stir. All portions reacted equivalently to produce a palmitate or stearate ester of hydro2ypropylcellulose. Purification and recovery were accomplished by pouring the reaction mi~ture with stirring into two liters of 85~ aqueous methanol and filtering the precipitated product which was a gummy solid. The gummy solid was then susp~nded in two lit~r of as~ methaQol and the pH adjusted to 4 with dilut~ hydrochloric acid. The ester was filtered, rewashed with aqucous methanol and dried under vacuum at 50C.
Oil ~ase for Cle~nsing~Protective Skin Product:
W~
Isopropyl Palmitate 14.9 Lanolin Oil 23.9 Light Mineral Oil 4~.2 Dow Corning 345 Fluid 14.0 In general, palmitate esters had bett~r overall solubilitY properties than stearate esters, particularly ~ith respect to solution ~reeze-thaw and heat stability.
Table 1 contain~ comparative ~rookfield viscosity data S (RvT) using Spindle 2 at 20 rpm in both isopropyl palmitate (IPP) available ~rom Stepan, Drakeol mineral oil from Witco and an oil based cosmetic formulation. All measurem~nts in cps ~ mPa.s.
Table 1 Solution of Xl~c~ Es~c~ i~ Co~m~ic Solv~nt~
~olubiLi~y at l~ i~
~lucel~ Oil ~ample Gr~de ste~ Pr~k8Ql-9 ~rakeol-21 ~rakeol-3.,~
cps 1 JF palmitate 10 40 100 220 50 2 MF palmitate 10 85 125 400 155 3 HP palmitate - 200 350 675 135 4 EF stearata 10 90 - - S0 EF palmitate 10 45 - - S5 Tabl~ 2 contain~ comparative data in mineral oil.
.
.
, . , .: . -3 ~ ~,g ~
Table 2 Effect of Hydro~ypropylcellulose Ester Concentration on Viscosity Molecular viscosity in Mineral Oil E3~mpl~ Wei~h~ palmitate ~iQn ~akeQl=~ PÆ~k~n_c~S
1140,000 JF 0.5 35 200 1.0 ~5 Z20 2.l~ 65 345 5.~) 170 ~00 2850,000 MF O.5 60 130 1.0 95 400 2.0 235 835 5.0 1510 4840 31,150,000 HF 0.5 105 355 1.0 180 675 2.0 780 1790 5.0 4810 1870 Weight Average molecular weight wa3 estimated by size e~clusion chromatography.
As shown, not only are the hydroxypropylcellulose stearates and palmitat~s soluble in the esters, oils and lubricants us~ful in cosmetic formulation~; but they are also quite ~fficient thickenQrs.
Laboratory ~amples o~ a hand cream were prepare~
incorporatinq hydro~ypropylcellulose palmitate. Satisfactory thickening wa~ obtained with a 2% by weight addition.
Compared to a formulation for hand cream without thickener with a viscosity of 100, the ~% hydroxypropylcellulose palmitate addition gav~ a viscosity of 135. ~oth control and e~perimental hand creams were clear and stable and able to survive 3 freeze~thaw cycle.
_g_ ,:
'- ~, .' ;
.
, . ~ , -$ ~
E~ample Z
Example 1 is repeated e~cept that the polysaccharide used for esterification is either hydro~yethylcellulose, hydro2ypropylguar or hydro~ypropyl starch. In all case~ a stearate or palmitate ester of the polysaccharide is produced The products were swellable but insoluble in mineral oil.
E~ample 3 Hydro~ypropylcellulose esters of acetic, octanoic and lauric acids were prepared by technilqueA d~scribed in the Background of the Invention. Hydro~1ypropylcellulose stearate and palmitate were prepared as in Esample 1. Table 3 contains comparable solubility data for isopropyl myristate (IPM) from Aldrich and light carnation mineral oil from Witco.
Table 3 IPM Mineral Oil _ Ester Sol~kility ~Qlu~lity Hydro~ypropylcellulose acetate Insoluble Swellable Hydro2ypropylcellulose octanoate Swellable Swellable Hydro~ypropylcellulose laurate Very Swsllabla Swellable Hydro~ypropylcellulose palmitate Soluble Soluble Hydrosypropylcellulose stearate Soluble Soluble As shown, only the novel ester~ of the invention are soluble in both IPM and mineral oil, wherea~ the prior art esters are swellable at be~t. This illustrates that the esters of the invention are suitable for us~ in cosmetic formulation wherea~ th~ est@rs of the prior art are not.
Esample 4 A sample of Klucel~ JF hydro~ypropylcellulose available from Aqualon was heated with slight e~cess palmitic acid in , - . . ::
2 ~ "; ~
~oluene in the presence of p-toluenesulfonic acid and azeotroPiCallY distilled to produce a colored polymer ~hich was insoluble in Drakeol mineral oil.
E~ample 5 A sample of Klucel~ MF hydro~ypropylcellulose was suspended in water/sodium hydroxide containing tetrabutylammonium hydrogen sulfate as a phase transfer catalyst. Palmitoyl chloride in methylene chloride was added and the suspension was stirred for s~everal hours at room temperature. The reaction mi~ture Wi3S diluted with methanol and the reaction product was filtered, wa~hed and dried. A
white powder was obtained which was insoluble in mineral oils.
E2ample 6 Hydro~ypropylcellulose palmitate was prepar~d according to th~ following transesterification reaction:
RCOOMe ~ R'OH ~ ---> RCOOR' + Me OH
Methyl palmitate HP~ ~PC palmitate Methyl palmitate was reacted with hydro3ypropylcellulose at 100C for 7 hours in toluene using sodium methoxide/sodium ZO borohydride as a catalyst. The product obtained was soluble in mineral oil.
E~ample 7 Hydro2ypropyl~ellulose (0.12 moles) was placed in a three-nec~ round bottom flask equipped with a stirrer, Dean Stark trap, thermometer, condenser, and a nitrogen inlet; 0.1 moles fatty acid, 250 ml toluene and 0.005 mole para-toluenesulfonic acid were added. The reaction mixture S~
as reflu~ed under nitrogen atmo~phere and water azeotroPically removed at 110C for 7 hours. The residue after decantation of solvent was pulverized in methanol, filtered and dried. The ester was insoluble in mineral oil.
E~ample 8 E~ample 7 was repeated e~cept that a fatty acid methyl ester was substituted for the fatty acid. Sirnilar results were obtained. This illustrates the use o~ an acid catalysed transesterification reaction.
E~ample 9 Klucel~ hydro~ypropylcellulose (0.1 mole) as used in E~ample 1 was placed in a three neck round bottom flask equipped with a mechanical stirrer, addition funnel, thermometer and condenser. Pyridine (O.42 moles) was added.
Sufficient 1,4-dio~ane was then added to give a total liquid to solid ratio of 16 to 1 after the addition of the acid chloride. The hydrosypropylcellulose suspension was stirred and 0.36 moles of acid chloride diluted with an equal weight of 1,4-dio~ane was added over a period of 15 minutes. The reaction misture was raised to 100C and held there with continuous stirrinq for ~-8 hours. After cooling, the reaction mi3ture wa~ diluted with methanol containing a small amount of water to d~stroy e~ces~ acid chloride. The ester was recovered and purified by dissolving in methylene chloride, reprecipitated with methanol, washed with methanol and dried.
Hydro3ypropylcsllulos~ stearates and palmitates were produced with avera~e molecular weights of from 80,000 to 350,000.
- ' - ;' ~ : .
.
~ ?~
E~ample lO
A sample of hydro~ypropylcellulose palmitate, prepared from Klucel~ MF hydro~ypropylcellulose as in E~ample l, wa~
tested for solubility in and viscosification of various C-5 to C-lO fatty acid esters of mono-, di- and poly-pentaerythritols. Hydro~ypropylcellulos~ palmitate dissolved in and viscosified Hercolube~ 202 and Hercolube~ J
pentaerythritols available from Aqualon. The viscosity of Hercolube~ 202 increased from 188 to 300 mPa.s and the viscosity of Hercolube~ J increased from 40 to 140 mPa.~ using a l~ by weight concentration of the ester.
In a similar manner various hydro~ypropylcellulose palmitates from E~ample l were found to be soluble in and thickened jojoba oil. Jojoba oil is an expensiv~ oil used in cosmetic formulations such as shampoo and skin care products.
Conc~ntration3 of l to 3% provided viscou~ solution which were thermally stable.
This egample further illustrates the thickening and/or viscosification utility of the ester of the invention.
Example ll E~ample l was repeated e~cept that carbo~ym~thylhydro3ypropylcellulose with a carbo~ymethyl substitution of 0.0~ - O.l~ was ~ub3tituted for hydro~ypropylcellulo 9. Similar solubilitie3 were obtained.
Example 12 E~ample l i3 r~peated e~cept that hydro~yethylhydro~ypropylcellulose, carbosymethylcellulose, m~thylhydroxypropylcellulose, methylcellulose, carbo~ymethylguar, and guar are substituted for ~i~ i 7~ ~
dro~yproPylcellulose- Esters of stearic ac:id and palmitic acid are formed in all cases.
E~ample 13 Several Klucel~ HPC palmitates (of Molecular Weight ~ 1.15 MM) were prepared in a similar procedure as in E~ample 1 e~cept the molar ratio of palmitic acid chloride to HPC was varied ~rom 2 to 10. The esterificat:ion was allowed to proceed 72 hours at room temperature. The estsnt of ester substitution was conveniently determirled by infrared spectroscopy.
Listed below are the calculated ratios of the ester band at 1734 cm to the -OH band at 3470 cm.
~oles HPC/Palmitoyl ~hlorid~ Ra~iQL5~o ~ Lcm)~-O~ (347Q cmL
HPC (control) 0.04 1:2 0.~3 1:3 1.64 1:4 3.35 1:4 3.50 1:6 11.15 ZO 1:8 18.50 1:10 50.50 Tables 4 and 5 contain comparative 3rookfield (LVT) viscosity data using spindle 2 at 30 rpm in various solvents.
All measurements are in cps ~ mPa.s.
-c~ ~
Table Mol~L_~atio b Solukility at 1~ ~
Product L~a Fi~QL~n ~N Pr~kQO L ~lc --~b~---- d 51:3 14 27~ 80 44 49 1:4 320 150 100 - -1:5 76 245 105 610 1000 1:6 12 23 80 - -1:8 37 20 165 lol:lo 26 37 300 100 48 (a) IPP igopropyl palmitate availa:ble from Stepan (b) Finsolv~ TN a C12-15 alkyl benzoate from Finte~ Company (c) Drakeol-21 mineral oil available from Witco (d) Hercolube~ A is a pentaerythritol estar available from Aqualon Company lS Though the Klucel~ HPC palmitates are not soluble in pure silicone fluid~, such a~ Dow Corning'3 556 (phsnyltrimethicone) or 345 (cyclomethicone), they are soluble in and thicken Finsolv ~N silicone solvent mi~tures as shown in Table 5.
Tabl~ 5 Solubility in Fin~olv~ TN and DC 345 Mi2ture~ at 1~ Concentration Molar Ratio P~s~stFin~slv~ T~ pC 34~ v~o~i~Y
1:3.5 99.0 30.0 90 slight hazy 1:5 99.0 30.0 60 clear 1:3.5 49.5 49.5 17 2 phases 1:5 49.5 49.5 130 clear 1:5 24.75 74.25 56 slight hazy :, -$
As shown, not only are the hydro~yproPY~LCellulose palmitateS soluble in the esters, and oils u5eful in cosmetic formulationS but also are quite efficient thickeners, This e~ample illustrates the importance of the extent of ester substitution on solubility and thickening properties in different solvents.
- '- ~ . .
-.
, . ~.
. : ~ : . . .
- - .
Ln a preferred method the catalyst is triethylamine~
the polysaccharide is hydro~ypropylcellulose and the organic solvent is methylene chloride.
Detq~ rie~iQ~ of th~ ~ve~iQ~:
various grades of mineral oil, as well as aliphatic esters such as isopropyl myristate and isopropyl palmitate, and aromatic esters such as alkyl benzoate esters, are widely used in the cosmetic industry. Silicone fluids, jojoba oil and essential oils are also used. Compositions o~ matter which would be suitabla to dissolve in and thicken these oils and esters have been sought after to aid in cosmetic formulations. The discovery provided by the present invention makes possible such an advance in the state of th~
art .
Polysaccharide~ suitable for the practice of the invention are currently available in commercial or developmental quantitie~ from a variety of sources. These polysaccharides can b~ grouped into the categories of (l) cellulose ethers, (2) polygalactomannans and (3~ starches.
Within group ~1) hydro~ypropylcellulose is a preferred cellulose ether, whil~ other suitable cellulose eth~rs include methylcellulose, carboxymethylhydro~ypropylcellulose, hydro~ypropylm~thylcollulose and hydroxypropylhydro~yethylcellulose. Thes~ materials are available from Rqualon Company (a Hercules Incorporated company), Dow Chemical Company and Shin-Etsu Chemical.
Within qroup (2) hydro~ypropylguar i5 a preferred polygalactomman whil~ guar and carbo~ymethylhydro~ypropylguar are also suitable within group (~) hydro2ypropyl starch is a preferred material.
':
'~ '' ' . ~
The preferred polysaccharide is hydroxypropylcellulose of M.S. 3.0-4.5 (available from Aqualon Company under the tradename Klucel 3) .
It was discovered that a polysaccharide substituted with hydro~ypropyl groups gave particularly useful benefits for cosmetic and toiletry applications. In this respect a palmitate ester of hydro~ypropylcellulose having a molar substitution by hydro~ypropyl betweerl 3.0 and 4.5 and a molecular weight above 50,000 was discovered to be the most beneficial for cosmetic and toiletry applications.
Esterification of the polysaccharide in an organic solvent or mi~ture o solvents is accomplished usin~ a moiety such as stearic acid chlorid~ or palmatic acid chloride or an anhydride thereof which can react to orm the palmitate and/or stoarate ester. It is essential for a cellulose ether, polygalactomannan or starch to contain reactive hydro~yl groups in order for esterification to take placa.
This hydro~yl reactivity i9 not inhibited if the polysaccharide is partially modified with oth2r groups.
Thus, the preferred hydro~ypropylcellulose could contain other modifying group~ ~uch as methyl, ethyl, carbo~ymethyl, etc. or even long chain hydrophobic alkyl or arylalkyl groups such as butyl, cetyl or nonylph2nyl.
It ha~ been the e~perience of persons of ordinary s~ill in the art that degr~ of substitution values determined by sa~onification technigu~s lack accuracy and precision for cellulo~ic derivatives. As a result it ha~ been discovered that measurements of the ratio of the carboxyl ester to hydro~yl stretching bands in ths Infra Red (IR) at 30 appro~imately 1734 cm~l and 3470 cm~l is useful in assessing .
.. :
2~
ae degree of esterification. A ratio great:er than 0.5 roughly corr~sponds to degrees of substitution which promote oil solubility. A preferred range for this ratio is from about 0.5 to about 50Ø
Esterification equipment and techniques useful for the practice of the invention are known irom general practice in the art and as described in the refer.ences contained in the Background of the Invention. Triethylamine is a preferred catalyst for esterification of the polysaccharide. It is also preferred that tetrabutylammonium hydrogen sulfate be used as a catalyst for a phase transfer esterification, whereas sodium methoside/sodium borohydride is a preferred catalyst for trans-esterification.
In d~tail the process of the invention involves:
Mi~in~: A solution or slurry su~pen~ion of the polysaccharide is prepared in at least one organic solvent. The solution or slurry suspen~ion typically will contain from 0.05 to 0.15 mole of polysaccharide in from 0.5 to 1.5 mole of organic solvent. Good result have been obtained usinq methylene chloride, pyridine, toluen~ and 1,4-dio~ane and combinations thereof~ An aqueous phase will also be required when a phase transfer reaction is run.
Est&Liicatio~: Once the polysaccharide has been susp~nded in either solution or slurry suspension, est~rification can occur. In the event it is desired to pr~pare a mi~ed ester, the esterification can be done in one step with a mixture of, for instance, stearic acid chloride and palmitic acid chloride or stepwise by first reactin~ with stearic acid chloride followed by palmitic acid chloride. Suitable catalysts include triethylamine, sodium metho~ide/sodium borohydride, tetrabutylammonium hydrogen sulfate, concentrsted sulfuric acid, p toluenesulfonic acid or a cation e~change resin in hydrogen or acid orm, depending on the type of esteriEication reaction being undertaken.
RecQvery: When the esterification reaction has been completed, ~i~ed or single esters can be recovered by conventional steps of neutraliz:ation and washing.
After cooling the reaction mi~t:ure; organic solvents such as acetone, toluene or methanol containing a small amount of water are added to destroy the e~cess acid chloride and precipitate the ester. Further washing can follow.
~ : Purified e~ters made according to the inv~ntion can be formulated into cosmetics due to their property of being soluble in both mineral oil and light esters such as jojoba oils, isopropyl myristate or isopropyl palmitate and aromatic esters such as benzoic acid alkyl esters.
An oil base cleansing or protective formulation suita~le for incorporating a polysaccharide palmitate comprises:
In~edi~n~ Wt Isopropyl pslmitate 14.9 Lanolin oil 23.9 Light mineral oil 97.2 Dow Corning 345 ~luid 14.0 ~ . .
The following e~amples illustrate the practice o~ the invention~ which has industrial applicability for cosmetics, toiletrieS and oil and gas recovery. E~am~le l represents the best mode envisioned.
E~ample l Five O.1 mole portions of Klucel~
hydro~ypropylcellulose, available from the Aqualon Company as grades EF 80,000 mol. wt. JF (lso~ooo mol. wt.), MF (850,000 mol. wt.) and HF (1,150,000 mol. wt.), were prepared as slurry suspensions in 750 ml methylene chloride and 250 ml triethylamine. A 0.6 mole portion oE either palmitic acid chloride or stearic acid chloride in 150 ml l,4-dio~ane was added to each suspension. With constant stirring, esterification was allowed to proceed or 24 hours at room temperature. As the esterifieation proceeded, the suspension became viscous and hard to stir. All portions reacted equivalently to produce a palmitate or stearate ester of hydro2ypropylcellulose. Purification and recovery were accomplished by pouring the reaction mi~ture with stirring into two liters of 85~ aqueous methanol and filtering the precipitated product which was a gummy solid. The gummy solid was then susp~nded in two lit~r of as~ methaQol and the pH adjusted to 4 with dilut~ hydrochloric acid. The ester was filtered, rewashed with aqucous methanol and dried under vacuum at 50C.
Oil ~ase for Cle~nsing~Protective Skin Product:
W~
Isopropyl Palmitate 14.9 Lanolin Oil 23.9 Light Mineral Oil 4~.2 Dow Corning 345 Fluid 14.0 In general, palmitate esters had bett~r overall solubilitY properties than stearate esters, particularly ~ith respect to solution ~reeze-thaw and heat stability.
Table 1 contain~ comparative ~rookfield viscosity data S (RvT) using Spindle 2 at 20 rpm in both isopropyl palmitate (IPP) available ~rom Stepan, Drakeol mineral oil from Witco and an oil based cosmetic formulation. All measurem~nts in cps ~ mPa.s.
Table 1 Solution of Xl~c~ Es~c~ i~ Co~m~ic Solv~nt~
~olubiLi~y at l~ i~
~lucel~ Oil ~ample Gr~de ste~ Pr~k8Ql-9 ~rakeol-21 ~rakeol-3.,~
cps 1 JF palmitate 10 40 100 220 50 2 MF palmitate 10 85 125 400 155 3 HP palmitate - 200 350 675 135 4 EF stearata 10 90 - - S0 EF palmitate 10 45 - - S5 Tabl~ 2 contain~ comparative data in mineral oil.
.
.
, . , .: . -3 ~ ~,g ~
Table 2 Effect of Hydro~ypropylcellulose Ester Concentration on Viscosity Molecular viscosity in Mineral Oil E3~mpl~ Wei~h~ palmitate ~iQn ~akeQl=~ PÆ~k~n_c~S
1140,000 JF 0.5 35 200 1.0 ~5 Z20 2.l~ 65 345 5.~) 170 ~00 2850,000 MF O.5 60 130 1.0 95 400 2.0 235 835 5.0 1510 4840 31,150,000 HF 0.5 105 355 1.0 180 675 2.0 780 1790 5.0 4810 1870 Weight Average molecular weight wa3 estimated by size e~clusion chromatography.
As shown, not only are the hydroxypropylcellulose stearates and palmitat~s soluble in the esters, oils and lubricants us~ful in cosmetic formulation~; but they are also quite ~fficient thickenQrs.
Laboratory ~amples o~ a hand cream were prepare~
incorporatinq hydro~ypropylcellulose palmitate. Satisfactory thickening wa~ obtained with a 2% by weight addition.
Compared to a formulation for hand cream without thickener with a viscosity of 100, the ~% hydroxypropylcellulose palmitate addition gav~ a viscosity of 135. ~oth control and e~perimental hand creams were clear and stable and able to survive 3 freeze~thaw cycle.
_g_ ,:
'- ~, .' ;
.
, . ~ , -$ ~
E~ample Z
Example 1 is repeated e~cept that the polysaccharide used for esterification is either hydro~yethylcellulose, hydro2ypropylguar or hydro~ypropyl starch. In all case~ a stearate or palmitate ester of the polysaccharide is produced The products were swellable but insoluble in mineral oil.
E~ample 3 Hydro~ypropylcellulose esters of acetic, octanoic and lauric acids were prepared by technilqueA d~scribed in the Background of the Invention. Hydro~1ypropylcellulose stearate and palmitate were prepared as in Esample 1. Table 3 contains comparable solubility data for isopropyl myristate (IPM) from Aldrich and light carnation mineral oil from Witco.
Table 3 IPM Mineral Oil _ Ester Sol~kility ~Qlu~lity Hydro~ypropylcellulose acetate Insoluble Swellable Hydro2ypropylcellulose octanoate Swellable Swellable Hydro~ypropylcellulose laurate Very Swsllabla Swellable Hydro~ypropylcellulose palmitate Soluble Soluble Hydrosypropylcellulose stearate Soluble Soluble As shown, only the novel ester~ of the invention are soluble in both IPM and mineral oil, wherea~ the prior art esters are swellable at be~t. This illustrates that the esters of the invention are suitable for us~ in cosmetic formulation wherea~ th~ est@rs of the prior art are not.
Esample 4 A sample of Klucel~ JF hydro~ypropylcellulose available from Aqualon was heated with slight e~cess palmitic acid in , - . . ::
2 ~ "; ~
~oluene in the presence of p-toluenesulfonic acid and azeotroPiCallY distilled to produce a colored polymer ~hich was insoluble in Drakeol mineral oil.
E~ample 5 A sample of Klucel~ MF hydro~ypropylcellulose was suspended in water/sodium hydroxide containing tetrabutylammonium hydrogen sulfate as a phase transfer catalyst. Palmitoyl chloride in methylene chloride was added and the suspension was stirred for s~everal hours at room temperature. The reaction mi~ture Wi3S diluted with methanol and the reaction product was filtered, wa~hed and dried. A
white powder was obtained which was insoluble in mineral oils.
E2ample 6 Hydro~ypropylcellulose palmitate was prepar~d according to th~ following transesterification reaction:
RCOOMe ~ R'OH ~ ---> RCOOR' + Me OH
Methyl palmitate HP~ ~PC palmitate Methyl palmitate was reacted with hydro3ypropylcellulose at 100C for 7 hours in toluene using sodium methoxide/sodium ZO borohydride as a catalyst. The product obtained was soluble in mineral oil.
E~ample 7 Hydro2ypropyl~ellulose (0.12 moles) was placed in a three-nec~ round bottom flask equipped with a stirrer, Dean Stark trap, thermometer, condenser, and a nitrogen inlet; 0.1 moles fatty acid, 250 ml toluene and 0.005 mole para-toluenesulfonic acid were added. The reaction mixture S~
as reflu~ed under nitrogen atmo~phere and water azeotroPically removed at 110C for 7 hours. The residue after decantation of solvent was pulverized in methanol, filtered and dried. The ester was insoluble in mineral oil.
E~ample 8 E~ample 7 was repeated e~cept that a fatty acid methyl ester was substituted for the fatty acid. Sirnilar results were obtained. This illustrates the use o~ an acid catalysed transesterification reaction.
E~ample 9 Klucel~ hydro~ypropylcellulose (0.1 mole) as used in E~ample 1 was placed in a three neck round bottom flask equipped with a mechanical stirrer, addition funnel, thermometer and condenser. Pyridine (O.42 moles) was added.
Sufficient 1,4-dio~ane was then added to give a total liquid to solid ratio of 16 to 1 after the addition of the acid chloride. The hydrosypropylcellulose suspension was stirred and 0.36 moles of acid chloride diluted with an equal weight of 1,4-dio~ane was added over a period of 15 minutes. The reaction misture was raised to 100C and held there with continuous stirrinq for ~-8 hours. After cooling, the reaction mi3ture wa~ diluted with methanol containing a small amount of water to d~stroy e~ces~ acid chloride. The ester was recovered and purified by dissolving in methylene chloride, reprecipitated with methanol, washed with methanol and dried.
Hydro3ypropylcsllulos~ stearates and palmitates were produced with avera~e molecular weights of from 80,000 to 350,000.
- ' - ;' ~ : .
.
~ ?~
E~ample lO
A sample of hydro~ypropylcellulose palmitate, prepared from Klucel~ MF hydro~ypropylcellulose as in E~ample l, wa~
tested for solubility in and viscosification of various C-5 to C-lO fatty acid esters of mono-, di- and poly-pentaerythritols. Hydro~ypropylcellulos~ palmitate dissolved in and viscosified Hercolube~ 202 and Hercolube~ J
pentaerythritols available from Aqualon. The viscosity of Hercolube~ 202 increased from 188 to 300 mPa.s and the viscosity of Hercolube~ J increased from 40 to 140 mPa.~ using a l~ by weight concentration of the ester.
In a similar manner various hydro~ypropylcellulose palmitates from E~ample l were found to be soluble in and thickened jojoba oil. Jojoba oil is an expensiv~ oil used in cosmetic formulations such as shampoo and skin care products.
Conc~ntration3 of l to 3% provided viscou~ solution which were thermally stable.
This egample further illustrates the thickening and/or viscosification utility of the ester of the invention.
Example ll E~ample l was repeated e~cept that carbo~ym~thylhydro3ypropylcellulose with a carbo~ymethyl substitution of 0.0~ - O.l~ was ~ub3tituted for hydro~ypropylcellulo 9. Similar solubilitie3 were obtained.
Example 12 E~ample l i3 r~peated e~cept that hydro~yethylhydro~ypropylcellulose, carbosymethylcellulose, m~thylhydroxypropylcellulose, methylcellulose, carbo~ymethylguar, and guar are substituted for ~i~ i 7~ ~
dro~yproPylcellulose- Esters of stearic ac:id and palmitic acid are formed in all cases.
E~ample 13 Several Klucel~ HPC palmitates (of Molecular Weight ~ 1.15 MM) were prepared in a similar procedure as in E~ample 1 e~cept the molar ratio of palmitic acid chloride to HPC was varied ~rom 2 to 10. The esterificat:ion was allowed to proceed 72 hours at room temperature. The estsnt of ester substitution was conveniently determirled by infrared spectroscopy.
Listed below are the calculated ratios of the ester band at 1734 cm to the -OH band at 3470 cm.
~oles HPC/Palmitoyl ~hlorid~ Ra~iQL5~o ~ Lcm)~-O~ (347Q cmL
HPC (control) 0.04 1:2 0.~3 1:3 1.64 1:4 3.35 1:4 3.50 1:6 11.15 ZO 1:8 18.50 1:10 50.50 Tables 4 and 5 contain comparative 3rookfield (LVT) viscosity data using spindle 2 at 30 rpm in various solvents.
All measurements are in cps ~ mPa.s.
-c~ ~
Table Mol~L_~atio b Solukility at 1~ ~
Product L~a Fi~QL~n ~N Pr~kQO L ~lc --~b~---- d 51:3 14 27~ 80 44 49 1:4 320 150 100 - -1:5 76 245 105 610 1000 1:6 12 23 80 - -1:8 37 20 165 lol:lo 26 37 300 100 48 (a) IPP igopropyl palmitate availa:ble from Stepan (b) Finsolv~ TN a C12-15 alkyl benzoate from Finte~ Company (c) Drakeol-21 mineral oil available from Witco (d) Hercolube~ A is a pentaerythritol estar available from Aqualon Company lS Though the Klucel~ HPC palmitates are not soluble in pure silicone fluid~, such a~ Dow Corning'3 556 (phsnyltrimethicone) or 345 (cyclomethicone), they are soluble in and thicken Finsolv ~N silicone solvent mi~tures as shown in Table 5.
Tabl~ 5 Solubility in Fin~olv~ TN and DC 345 Mi2ture~ at 1~ Concentration Molar Ratio P~s~stFin~slv~ T~ pC 34~ v~o~i~Y
1:3.5 99.0 30.0 90 slight hazy 1:5 99.0 30.0 60 clear 1:3.5 49.5 49.5 17 2 phases 1:5 49.5 49.5 130 clear 1:5 24.75 74.25 56 slight hazy :, -$
As shown, not only are the hydro~yproPY~LCellulose palmitateS soluble in the esters, and oils u5eful in cosmetic formulationS but also are quite efficient thickeners, This e~ample illustrates the importance of the extent of ester substitution on solubility and thickening properties in different solvents.
- '- ~ . .
-.
, . ~.
Claims (18)
1. A polysaccharide stearate or palmitate ester wherein the polysaccharide is selected from the group of hydroxypropylcellulose, methylhydroxypropylcellulose, carboxymethylhydroxypropylcellulose, hydroxypropylguar and hydroxypropyl starch.
2. The polysaccharide stearate or palmitate ester of claim 1 which is soluble in at least one of the group of isopropyl palmitate, myristate, mineral oil, jojoba oil, and alkyl benzoate ester solvents.
3. The polysaccharide stearate or palmitate ester of claim 2 where the polysaccharide is hydroxypropylcellulose.
4. The polysaccharide stearate or palmitate ester of claim 2 wherein the molecular weight of the polysaccharide is greater than 50,000.
5. The hydroxypropylcellulose stearate or palmitate ester of claim 4 wherein the ester extent of substitution is definsd by the ratio of the carboxyl ester to hydroxyl stretching bands in IR at 1734 cm-1 and 3470 cm-1 respectively, and is greater than about 0.5.
6. The hydroxypropylcellulose stearate or palmitate of claim 5 with a hydroxypropyl molar substitution of 3 to 4.5.
7. A process of producing a polysaccharide palmitate or stearate ester comprises the steps:
(1) mixing a polysaccharide in an organic solvent;
(2) esterifying the polysaccharide with a palmitate and/or stearate moiety in the presence of a catalyst; and (3) recovering a palmitate polysaccharide ester, a stearate polysaccharide ester or a mixed palmitate and stearate polysaccharide ester.
(1) mixing a polysaccharide in an organic solvent;
(2) esterifying the polysaccharide with a palmitate and/or stearate moiety in the presence of a catalyst; and (3) recovering a palmitate polysaccharide ester, a stearate polysaccharide ester or a mixed palmitate and stearate polysaccharide ester.
8. The process of claim 7 where tha polysaccharide is one or more of hydroxpropylcellulose, methylhydroxypropylcellulose, hydroxypropylguar, hydroxypropyl starch, carboxymethylhydroxypropylcellulose.
9. The process of claim 8 where the moiety is an acid chloride and the catalyst is triethylamine.
10. The process of claim 9 whers the ester is recovered in step (3) using one or more of acetone, methanol or water.
11. The process of claim 7 where the catalyst is a phase transfer catalyst and an aqueous caustic phase is present.
12. The process of claim 11 where the phase transfer catalyst is tetrabutylam~monium hydrogen sulfate.
13. An oil base cleansing or protective skin product containing hydroxypropylcellulose palmitate as a thickener.
14. The product of claim 13 whare the hydroxypropylcellulose palmitate has a degree of hydroxypropyl molar substitution of 3.0 to 4.5.
15. Thc product of claim 13 containing iojoba oil.
16. The product of claim 13 containing mineral oil.
17. The product of claim 13 containing an alkyl benzoate ester.
18. The product of claim 13 containing a cyclomethicone or phenyltrimethicone silicone fluid and an organic oil from the group of mineral oil, jojoba oil, isopropyl palmitate, isopropyl myristate and alkyl benzoate ester.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US82709492A | 1992-01-27 | 1992-01-27 | |
| US827,094 | 1992-01-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2087488A1 true CA2087488A1 (en) | 1993-07-28 |
Family
ID=25248303
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002087488A Abandoned CA2087488A1 (en) | 1992-01-27 | 1993-01-18 | Oil soluble polysaccharides |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH05255401A (en) |
| CA (1) | CA2087488A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010035893A3 (en) * | 2008-09-25 | 2011-01-06 | Kao Corporation | Oil-based cosmetic preparation |
| DE202023107132U1 (en) | 2022-12-01 | 2024-01-23 | Kelp Industries Ltd. | Biodegradable material |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010059408A (en) * | 2008-08-06 | 2010-03-18 | Kao Corp | Cellulose derivative |
| JP5651307B2 (en) * | 2009-08-06 | 2015-01-07 | 花王株式会社 | Oily cosmetics |
| JP5651308B2 (en) * | 2009-08-06 | 2015-01-07 | 花王株式会社 | Oily cosmetics |
| JP5436113B2 (en) * | 2008-09-25 | 2014-03-05 | 花王株式会社 | Oily cosmetics |
| JP5599199B2 (en) * | 2010-02-24 | 2014-10-01 | 花王株式会社 | Oily cosmetics |
| ES2912784T3 (en) * | 2017-03-07 | 2022-05-27 | Kao Corp | Film comprising hydrophobicized cellulose fibers and oil |
-
1993
- 1993-01-18 CA CA002087488A patent/CA2087488A1/en not_active Abandoned
- 1993-01-27 JP JP5011823A patent/JPH05255401A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010035893A3 (en) * | 2008-09-25 | 2011-01-06 | Kao Corporation | Oil-based cosmetic preparation |
| KR20110059834A (en) * | 2008-09-25 | 2011-06-07 | 카오카부시키가이샤 | Oil-based cosmetic preparation |
| CN102159177B (en) * | 2008-09-25 | 2013-05-01 | 花王株式会社 | Oil-based cosmetic preparation |
| US8580284B2 (en) | 2008-09-25 | 2013-11-12 | Kao Corporation | Oil-based cosmetic preparation |
| KR101652536B1 (en) * | 2008-09-25 | 2016-08-30 | 카오카부시키가이샤 | Oil-based cosmetic preparation |
| DE202023107132U1 (en) | 2022-12-01 | 2024-01-23 | Kelp Industries Ltd. | Biodegradable material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05255401A (en) | 1993-10-05 |
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