Patent Application
20110091946
The aim of the present invention is to obtain fatty esters from fatty acids derived from vegetable oils and butters, through an enzymatic process, so that said esters can act as emollients, emulsifiers and co-emulsifiers with differentiated performance, having high spreadability and slidability compared to the prior-art products.
More specifically, the present invention relates to an enzymatic process for obtaining a fatty ester, comprising:
a) obtaining a fatty acid through the enzymatic hydrolysis (saponification) of vegetable oils and butters selected from cupuaçu (Theobroma grandiflorum) butter, sapucainha (Carpotroche Brasiliensis) butter, ucuúba (Virola sebifera) butter, murumuru (Astrocaryum murumuru) butter, palm olein, patau ucuá (Oenocarpus bataua) oil, tucumä (Astrocaryum aculeatum) oil, inajá (Maximiliana Maripa) oil, passion fruit oil, pequi (Caryocar brasiliense) oil and nasturtium oil;
b) reacting the fatty acid with a fatty alcohol selected from capric alcohol, caprylic alcohol, isoamylic alcohol, lauric alcohol, myristic alcohol, lorol (70:30 mixture of lauric alcohol and myristic alcohol), cetyl alcohol, steparyl alcohol, cetostearyl alcohol (70:30 mixture of cetyl alcohol and stearyl alcohol), sorbitol, sorbitan, glycerin, polyglycerin, other polyols and mixture thereof, in the presence of an enzyme, in at least one reactor, at a temperature of from 40 to 80° C.;
c) stirring the reaction solution;
d) removing moisture from the reaction medium;
e) vacuum filtering said solution to obtain the fatty ester.
The fatty esters obtained through the process of the present invention can be used in the preparation of cosmetic compositions.
Document U.S. Pat. No. 6,933,139 B2 discloses a method for the enzymatic splitting of fatty acids and glycerol obtained from oils and fats by using lipases being added to a mixture containing an oil or fat and water. The splitting reaction is performed only up to a splitting degree at which slowing-down of the splitting reaction is still below a preset value using discontinuously operated loop reactors. The fatty acids to be obtained are separated from the reaction mixture that is only partially split, by first separating an aqueous glycerol-containing phase from a partially split organic phase containing split fatty acids, in a self-cleaning centrifugal separator. Afterwards, the fatty acids are separated from the partially split organic phase and the residue of the organic phase freed from the free fatty acids is fed back into the splitting process.
Therefore, said document discloses neither the step of removing the humidity of the reaction medium, in particular by means of an inline flash tank, to distill the water generated during the esterification process nor the use of an enzymatic recirculation reactor. Additionally, the document does not disclose the use of immobilized enzymes either, and the lipases used in the document and in the present invention are different, since they have different specificities. Finally, the starting material of the present invention is different from the starting triglycerides of said document.
Document U.S. Pat. No. 5,219,733 discloses a process for reacting a component selected from the group consisting of sterols and branched aliphatic primary or secondary alcohols having 14 to 32 carbon atoms, and a component selected from the group consisting of fatty acids and fatty acid esters in contact with an enzyme selected from the group consisting of lipase and cholesterol esterase or with the selected enzyme in an immobilized form, in a system selected from the group consisting of an aqueous medium and water-containing organic solvent to prepare a fatty acid ester of the initial component.
Said document does not disclose the use of oils such as the cupuaçu butter and the sapucainha butter. Additionally, said document does not disclose the use of lipases derived from the microorganisms Candida Antarctica, Rhizomucor miehei and Thermomyces lanuginosus either. Therefore, the enzymes used in the present invention are not anticipated by the document above. Finally, the document does not disclose the use of a completely organic reaction medium, but rather of an aqueous medium containing an organic solvent to solubilize one of the phases.
Document US 2005/0014237 A1 discloses a method to improve the productivity in an enzymatic method for making esterified, transesterified or interesterified products. Specifically, it discloses a method that can improve the productivity of enzymatic transesterification or esterification by deodorization alone, or by deodorization and purification of the initial substrate to extend the useful life of the enzymes.
The document describes a method that is different from that of the present invention and does not disclose the use of fatty acids selected from capric alcohol, caprylic alcohol, isoamylic alcohol, lauric alcohol, myristic alcohol, lorol (70:30 mixture of lauric alcohol and myristic alcohol), cetyl alcohol, stearyl alcohol, cetostearyl alcohol (70:30 mixture of cetyl alcohol and stearyl alcohol), sorbitol, sorbitan, glycerin, polyglycerin, other polyols and mixture thereof.
The objective of the present invention is to obtain fatty esters from fatty acids derived from vegetable oils and butters, through an enzymatic process, so that said esters can act as emollients, emulsifiers and co-emulsifiers with differentiated performance, having high spreadability and slidability compared to standard formulae.
The fatty esters obtained through the process of the present invention can be used in the preparation of cosmetic compositions.
The present invention relates to an enzymatic process for obtaining a fatty ester, comprising:
a) obtaining a fatty acid through the enzymatic hydrolysis (saponification) of vegetable oils and butters selected from cupuaçu butter, sapucainha butter, ucuúba butter, murumuru butter, palm olein, patauá oil, tucumä oil, inajá oil, passion fruit oil, pequi oil and nasturtium oil;
b) reacting the fatty acid with a fatty alcohol selected from capric alcohol, caprylic alcohol, isoamylic alcohol, lauric alcohol, myristic alcohol, lorol (70:30 mixture of lauric alcohol and myristic alcohol), cetyl alcohol, stearyl alcohol, cetostearyl alcohol (70:30 mixture of cetyl alcohol and stearyl alcohol), sorbitol, sorbitan, glycerin, polyglycerin, other polyols and mixture thereof, in the presence of an enzyme, in at least one reactor, at a temperature of from 40 to 80° C.;
c) stirring the reaction solution;
d) removing moisture from the reaction medium;
e) vacuum filtering said solution to obtain the fatty ester.
The present invention relates to an enzymatic process for obtaining a fatty ester, comprising a step of melting the fatty acid. Then the fatty acid is reacted with a fatty alcohol, in the presence of an enzyme, in at least one reactor, at a temperature of from 40 to 80° C. The reaction solution is stirred and the humidity is removed from the reaction medium. Finally, said solution is vacuum filtered to obtain the fatty ester.
The fatty acids used as raw-material for the process of the present invention are fatty acids obtained through a process of enzymatic hydrolysis (saponification) of butters and oils selected from cupuaçu butter, sapucainha butter, ucuúba butter, murumuru butter, palm olein, patauá oil, tucumä{umlaut over ( )} oil, inajá oil, passion fruit oil, pequi oil and nasturtium oil. Preferably, they are selected from cupuaçu butter, sapucainha butter and palm olein.
The saponification process of the butter or oil can be carried out by adding a base at a temperature of from 80 to 90° C. Preferably, the base used is KOH or NaOH.
After this step, H2SO4 is added, which results in the obtainment of said fatty acids, which may be washed until they reach a neutral pH. The enzymatic hydrolysis process of the butter or oil can be carried out by using 1.5% of the enzyme blend relative to the butter or oil, in three additions of 0.5% and with the addition of the same amount of water by weight, corresponding to the amount of butter used. The additions were made every 12 hours, totaling over 48 hours.
The fatty acids obtained through the process described above are then used as raw-material in the enzymatic esterification process of the present invention.
The enzymatic esterification is carried out by reacting said fatty acids obtained from the vegetable oils and butters with fatty alcohols.
Said fatty alcohol can be selected from capric alcohol, caprylic alcohol, isoamylic alcohol, lauric alcohol, myristic alcohol, lorol (70:30 mixture of lauric alcohol and myristic alcohol), cetyl alcohol, stearyl alcohol, cetostearyl alcohol (70:30 mixture of cetyl alcohol and stearyl alcohol), sorbitol, sorbitan, glycerin, polyglycerin, other polyols and mixture thereof. Preferably, lorol, mystiric alcohol, cetostearyl alcohol or sorbitan are used.
The reaction between the fatty acid and the fatty alcohol in the presence of an enzyme is carried out in at least one enzymatic reactor. Said at least one enzymatic reactor is preferably a fixed bed enzymatic reactor. Preferably, the enzyme to be used is selected from lipases, particularly the Novozymes® 435 (lipase B), Lipozyme® RM 1M and Lipozyme® TL IM lipases, derived from the microorganisms Candida antarctica, Rhizo-mucor miehei and Thermomyces lanuginosus, respectively. The aforementioned lipases are commercialized by Novozymes. Preferably, the lipase used is Novozymes® 435. In accordance with one embodiment of the invention the enzyme used is a blend consisting of CALB and Lypozyme TL 100 L at the ratio of 1:9 or 9:1 added at a temperature of from 50 to 60° C., followed the addition of water.
Preferably, the enzyme selected is immobilized. The lipases Novozymes® 435 (lipase B) and Lipozyme® RM IM are thermoresistant enzymes, and the support used is of polymeric origin. In the case of the lipase Lipozyme® TL 1M, the support used is silica.
The reactor used in the process of the present invention is selected from a single reactor, two reactors in series or four reactors in series. The process can be a batch, semi-continuous or continuous process.
Particularly, the process of the present invention is carried out in stoichiometric/molar scale, the preferred fatty acid to enzyme ratio being 1:1.1 in moles. Preferably, the enzyme represents about 2 to 10% by weight of the total weight of the fatty acid.
In case a single reactor is used, for example, for use in a batch process, said reactor can be a multipurpose stirred reactor, preferably a glass-lined reactor (
When a single reactor is used, the fatty acid is previously molten. The reactor should be lined and the circulating liquid can be water or thermal oil. The reactor is heated to a temperature of from 55 to 75° C., preferably from 60 to 70° C. When the temperature of the lining reaches about 50° C., the molten fatty acid and the alcohol are added, followed by the addition of the enzyme. The reaction medium is then stirred at about from 276 to 300 rpm, preferably at 276 rpm. Finally, the product obtained is vacuum filtered through a filter with porosity between 0.01 and 0.1 mm, which filter can be made of stainless steel or any other type of mesh.
In case two or more reactors in series are used, preferably four reactors in series, they can have an internal “basket” containing said enzyme. The use of reactors in series is particularly useful in the semi-continuous and continuous processes.
Additionally, a stirred, and optionally heated, feed tank can be connected to the system to homogenize the substrates (fatty acid and fatty alcohol). The substrates circulate through the reactors, through a loop, and may return or not to the feed tank, according to the esterification result. The substrate must circulate for a period of about 5 hours for the product to be obtained, making the process semi-continuous.
After it has passed through the last reactor, a flash tank is optionally connected. The purpose of the flash tank is to remove the excess humidity generated in the esterification process, thus shifting the reaction equilibrium towards the formation of the fatty ester.
When two or more reactors, preferably four reactors in series, are used, the fatty acid and/or the fatty alcohol can be previously molten. The two reagents are then weighed and transferred to the feed tank and mixed. The bath is then heated to about 70° C. and the recirculation is activated. At the end of the process, the product is vacuum discharged.
Typically, the reaction time is of 5 to 72 hours and the reaction is carried out at atmospheric pressure. However, the presence of vacuum in the system significantly decreases the reaction time, in addition to preventing the oxidation of the unsaturated fatty chains, such as the oleic, linoleic and linoleis acids. Additionally, the presence of vacuum increases the contact surface between the reagents, favoring the formation of the product.
Both in the case where only one reactor is used and in the case where two or more reactors in series are used, the process can be followed and controlled through the acidity index.
The process can be controlled through the acidity index (mgKOH/g), by the AOCS method, in which the product is titrated with a titrated solution of 0.1N aqueous KOH. The results of the acidity indexes are shown in Table 1.
The esterification conversion through the process described above provides a esterification conversion of 95 to 100% and a process yield of 85 to 98%.
The examples below are preferred and illustrative embodiments of the esterification process of the present invention and should not be interpreted as limitations thereof. In this sense, it is to be understood that the scope of the present invention embraces other possible variations, being limited solely by the appended claims, including the possible equivalents therein.
Multifunctional Gas-lined Reactor (batch process)
Raw materials
1) The fatty acid was previously melted.
2) The bath was activated at 60° C.
3) When the bath temperature reached 50° C., fatty acid and lorol CD were added.
4) The temperature was increased to 60° C.
5) The enzyme was added to the reactor.
6) The stirrer was turned on at 276 rpm.
7) After the specification was met, the product was discharged by vacuum filtration.
Multifunctional Gas-lined Reactor (batch process)
Raw materials
1) The fatty acid was previously melted.
2) The bath was activated at 60° C.
3) When the bath temperature reached 50° C., fatty acid and lorol CD were added.
4) The temperature was increased to 60° C.
5) The enzyme was added to the reactor.
6) The stirrer was turned on at 276 rpm.
7) After the specification was met, the product was discharged by vacuum filtration.
Multifunctional Gas-lined Reactor (batch process)
Raw materials
1) The fatty acid was previously melted.
2) The bath was activated at 70° C.
3) When the bath temperature reached 50° C., fatty acid and 1290.0 g of Sorbitol 70% were added.
4) The enzyme was added to the reactor.
5) The stirrer was turned on at 300 rpm.
6) On the 2nd day, 1110.0 g of Sorbitol 30% was added.
7) The product was discharged by vacuum filtration.
Stainless Steel Reactors in series (semi-continuous process)
Bath temperature=70° C.
Raw materials
1) The sapucainha fatty acid was previously melted in the feed tank.
2) The reactor was heated for the product to reach 70° C.
3) Recirculation was turned on.
4) After 12 hours, the product was vacuum discharged.
Stainless Steel Reactors in series (semi-continuous process)
Bath temperature=702C
Raw materials
1. The cupuaçu fatty acid and myristol was previously melted.
2. The two reagents are then weighed and transferred to the feed tank and mixed.
3. The bath was heated for the product to reach 70° C.
4. Recirculation was turned on.
5. After 12 hours, the product was vacuum discharged.
Stainless Steel Reactors in series (semi-continuous process)
Bath temperature=70° C.
Raw materials
1) The palm olein fatty acid and the cetostearyl alcohol were previously melted.
2) The two reagents are then weighed and transferred to the feed tank and mixed.
3) The bath was heated for the product to reach 70° C.
4) Recirculation was turned on.
5) After 12 hours, the product was vacuum discharged.
The esters obtained from the process of the present invention were tested in terms of safety, efficacy and use as sun filter solubilizers. Furthermore, a sensorial analysis was performed of the esters obtained from the process of the present invention. This data is indicated below.
The safety of the esters obtained from the process of the present invention was tested according to conventional methods for assessing cytotoxicity, PC5 and complete irritation. The results obtained are indicated in Table 2.
Esters obtained from the process of the present invention were assessed as emulsifiers in galenic forms. By assessing the stability of the formulations in comparison with emulsifiers commonly available in the market, it was possible to approve the performance of the esters as emulsifiers.
Thus, from a known base O/W formula as described in Table 3, 13 formulations were prepared, as indicated in Table 4, wherein the cetearyl olivate/sorbitan olivate (Oliven 1000) of said base formula was substituted with sorbitan olivate (Oliven 900) and fatty esters and sorbitol esters obtained from fatty acids of cupuaçu, sapucainha and palm olein.
The stability of formulations 1 to 13 was analyzed at 5° C., 45° C., 50° C. and dark conditions (room temperature) for 7, 14, 30, 60 and 90 days. The results obtained are indicated in Table 5.
Analyzing the results, it is concluded that isolated fatty esters can act as emulsifiers without the need of sorbitol esters, as in the case of Oliven 1000 in the base O/W formula used. Oliven 900 is more substituted and therefore more non-polar and has a lower HLB, being more appropriate for W/O formulations. The sorbitol ester produced through the process of the present invention is less substituted, having a higher HLB and, therefore, better performance in O/W formulation, which is reflected in its performance, keeping the emulsion stability for up to 60 days at 45° C. and 50° C. Oliven 900 separated after centrifugation, immediately after the preparation of the formulation.
The stability data (pH and viscosity) of the formulations of cupuaçu fatty ester with myristol (Formula 3) and cupuaçu ester with myristol/cupuaçu ester with sorbitol (Formula 6) is indicated in
The stability of the cupuaçu fatty ester with myristol was assessed at 5° C., 37° C., 45° C., light and dark conditions (room temperature) for 7, 14, 30, 60 and 90 days. Said stability was assessed based on the Acidity Index (AI) and Water Content (%). The results are represented in
The esters obtained from the process of the present invention were also tested as physical and chemical sun filter solubilizing agents in the standard formulation for SPF 30 described in Table 6 below:
In the base formula above, filter solubilizing emollients, such as C12-C15 alkyl benzoate and dicapryl carbonate were substituted with the fatty esters obtained from the process of the present invention, and the film-forming silicones, which promote resistance to the formulation, were substituted with Sapucainha and Ucuúba butters. The prepared formulations are as described in Table 7 below:
The main changes with regard to the standard formula according to Table 6 are indicated in Table 8 below:
The stability of the formulations above was evaluated by electronic microscopy to check the crystallization of the sun filters. The formulations were stable and there was no separation of the emulsion or filter crystallization.
The “in vitro” tests determined that in the formulations in which only the esters (solubilization system) were substituted and the silicones maintained intact, there was no change in the SPF in relation to the standard SPF 30 formulation. In the formulations were the silicones (film-formers) and the esters were substituted simultaneously, there was a reduction in the SPF in relation to the standard SPF 30 formulation.
The “in vitro” test was carried out by comparing the absorbance values of the standard formulations and those in which the sun filter solubilizing emollients were substituted according to Table 7. The result of this test can be seen in
The “in vivo” tests for assessing SPF were carried out according to the most accepted methodologies for assessing the SPF of a protector, which considers biological responses associated with the protection against UVB radiation. The clinical assessments were made according to international protocols (FDA, COLIPA, JCIA, etc). The results relating to SPF and water resistance are indicated in
Tests were carried out with formulas containing with the cupuaçu ester with myristol to assess the performance as skin barrier booster. Four formulations were tested: placebo formula; formula with 1% myristyl cupuçuate; formula with 3% myristyl cupuçuate and formula with 6% myristyl cupuçuate, thus obtaining response curves related with hydration. The skin barrier strengthening potential of the cupuaçu ester with myristol was assessed through the use of cosmetic products after mechanical insult through the tape-stripping removal procedure and subsequent readings of transepidermal water loss (TEWL) in the skin of voluntary individuals during 15 days.
Table 11 shows the formula with 3% myristyl cupuçuate. The other preparations have analogous formulas, in which only the concentration of myristyl cupuçuate is altered.
The results of the abovementioned tests showed that hydration increased statistically as concentration increased, indicating a positive response to the concentration curve and the fatty ester performance as a skin barrier strengthener. The barrier booster test results are shown in
The esters prepared according to the process of the present invention were assessed from basic O/W galenic formulations according to Table 12 below:
Formulas were prepared in which the emulsifiers were substituted according to Table 13 below; in addition, separately a formula was prepared in which all silicones (11.0%) were removed and to which 3% of cupuaçu ester with myristol was added (formula 421.7019.15), totaling 14% of the ester.
The aspects relating to the benefits were classified and analyzed according to the definitions below:
From the definitions above, it was possible to determine a sensorial profile of the formulations prepared. Said profiles are represented in Table 14 below and in
| Number | Date | Country | Kind |
|---|---|---|---|
| 0852949 | Apr 2008 | FR | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/BR09/00113 | 4/30/2009 | WO | 00 | 1/6/2011 |
