JPH03163043A - Polyglycerol compound and cosmetic containing the same - Google Patents

Abstract

NEW MATERIAL:The polyglycerol compound of formula (R is 7-35C straight or branched-chain saturated or unsaturated fatty acid residue; X is CH2CH2CH2O and/or CH2CH2CH2CH2O; Y is glyceryl; m is 1-60; n is 3-60). EXAMPLE:Polyglycerol(6)polyoxytrimethylene(4)2-heptylundecanoic acid ester. USE:A nonionic surfactant free from elution of formaldehyde even under a severe temperature condition, having high safety, quickly defoamable in a solubilized system, usable as an additive for cosmetics without lowering the effect of antiseptic and useful as an emulsifier or solubilizer of cosmetics. PREPARATION:The compound of formula can be produced by polymerizing glycidol with a polymethylene oxide in the presence of a compound of formula RCOOH as a Lewis acid catalyst.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to an ester type polyglycerol compound used as a nonionic surfactant suitable as an emulsifier or solubilizer, and a hydrophilic cosmetic containing the same.

[Conventional technology]

Conventionally, nonionic surfactants frequently used as emulsifiers include glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxy Ethylene hydrogenated castor oil derivatives are known. These emulsifiers are divided into hydrophobic surfactants containing long polyoxyethylene chains or short hydrophobic surfactants and hydrophilic surfactants containing long polyoxyethylene chains, and these are mixed appropriately to obtain the desired HLB value. When the HLB value is set to 10 to 15, an oil-in-water (0/W) type emulsion is created, and when the HLB value is set to 4-6, a water-in-oil (W/W) type emulsion is created.
0) type emulsion is obtained. In addition, nonionic surfactants that have traditionally been widely used as solubilizers include polyoxyethylene octylphenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene monolaurate, and polyoxyethylene Monoolet, hydrogenated castor oil polyoxyethylene adduct, polyoxybrobylene polyoxyethylene cetyl ether,
Polyoxyethylene, 2-hexyldecyl ether, and the like are known. All of these solubilizers dissolve into micelles in water, and then add H to solubilize oils, fragrances, oil-soluble ingredients, etc.
It is adjusted to be relatively hydrophilic with an LB value of 12 or more. [Problem to be Solved by the Invention J] However, the emulsifiers and solubilizers made of nonionic surfactants, which have been widely used in the past, all utilize polyoxyethylene chains to adjust the HLB value. . This is because the ethylene oxide chain length can be easily controlled and the HLB value can be delicately adjusted. Therefore, there are drawbacks such as dioxane being generated during the agitation process, ethylene oxide chains being oxidized over time, formaldehyde being eluted, and the hydrogen ion concentration (pEI) gradually shifting to the acidic side. Although these drawbacks are compensated for by adding agents and buffers, the use of antioxidants is not preferred from the standpoint of safety. In addition, the conventional solubilizers generally have a long defoaming time when used, and when used in cosmetics, bubbles remain in the filling container or on the surface of the skin to which they are applied, resulting in visual and tactile problems. Undesirable. Furthermore, when the conventional nonionic surfactant is used as an emulsifier or solubilizer in cosmetics, the ethylene oxide chain of the nonionic surfactant contains parabens such as methylparaben, which is used as a preservative in cosmetics. There is a problem that the antiseptic effect cannot be fully exerted due to adsorption of the antiseptic. The present invention has been made in view of the above circumstances, and is safe without elution of formaldehyde even under severe temperature conditions, and has a short defoaming time in a solution-forming system.
Another object of the present invention is to provide a polyglycerol compound that does not reduce the effect of a preservative when added to a cosmetic, and a cosmetic containing the same. [Means for Solving the Problems] In order to solve the above problems, the polyglycerol compound of the present invention has the general formula RCOO(X)m {Y+n H (wherein R is a linear or branched chain having 7 to 35 carbon atoms). saturated or unsaturated fatty acid residue group in the chain, X is CH, CH2CH20 or a mixture of one or both of CH2CH, CH2CH, O, Y is a glyceryl group, m=1-60, n=
3 to 60 are shown respectively. ) The cosmetic of the present invention is characterized by containing at least one type of polyglycerol compound represented by the above general formula. The polyglycerol compound of the present invention represented by the above general formula contains linear or branched higher saturated/unsaturated fatty acids having 8 to 36 carbon atoms, polymethylene oxide, and glycidol in a random amount ranging from 4 to 120 moles in total. It is an addition-polymerized compound, and the composition ratio of the parent wood group moiety is glycerin:oxypolymethylene=95:5 to 1:3. Further, in the general formula, m is 1-60 and n is 3-60, and preferably m is 1-30 and n is 3-30. . When m and n each exceed fL60 and when the value of m/n is 3 or more, the surfactant ability is significantly reduced and the desired emulsifying or solubilizing effect cannot be exerted. In addition, when R in the above general formula is a linear fatty acid residue, it has preferable properties as an emulsifier, and when it is a branched fatty acid residue, it has preferable properties as a solubilizer. In the polyglycerol compound of the present invention, linear
Examples of branched higher saturated or unsaturated fatty acids include lauric acid, mystilic acid, valmitic acid, stearic acid, oleic acid, behenic acid, cerotic acid, melisic acid,
2-ethylhexanoic acid, 2-hexyldecanoic acid, 2-heptylundecanoic acid, 2-octyldodecanoic acid, 5,
7. 7-}limethyl-2-(1', 3', 3
'-Trimethylbutyl> A higher fatty acid having 8 to 36 carbon atoms such as octanoic acid or neodecanoic acid obtained by a reaction between an olefin and carbon monoxide is used. Further, as the polymethylene oxide, trimethylene oxide, tetrahydrofuran, etc. are used. Specific examples of the polyglycerol compounds of the present invention include polyglycerol (6) polyoxytrimethylene (4) 2-heptylundecanoate, polyglycerol (10) polyoxytrimethylene (8) stearate, Polyglycerol (30) Polyoxytrimethylene (8) Stearate ester, Polyglycerol (30) Polyoxytrimethylene (20) Oleate ester, Polyglycerol (14) Polyoxytrimethylene (16) 2-year-old ctyldodecanoate ester , polyglycerol (5) polyoxytetramethylene (6)
Valmitic acid ester, polyglycerol (3) polyoxytetramethylene (3) stearic acid ester, polyglycerol (6) polyoxytetramethylene (4) stearic acid ester, polyglycerol (12) polyoxytetramethylene (10) stearic acid Ester, polyglycerol (20) polyoxytetramethylene (1
0) 2-hexyldecanoic acid ester, polyglycerol (8) polyoxytetramethylene (8) eicosenoic acid ester, and the like. In order to produce the polyglycerol compound of the present invention, it is best to use the combined method using a Lewis acid catalyst. Alternatively, a mixture of glycidol and polymethylene oxide is gradually added to polymerize without using a solvent, for example, using a Lewis acid such as aluminum chloride, zinc chloride, zinc perchlorate, or boron trifluoride ether complex as a catalyst. After the polymerization reaction is completed, the catalyst is decatalyzed with one or more alkalis such as sodium bicarbonate, sodium carbonate, potassium carbonate, basic alumina, etc., and the solvent and unreacted substances are distilled off under reduced pressure to form a viscous product. The polyglycerol compound of the invention can be obtained in the form of an oil or a semi-solid. Also,
Alternatively, a mixture of GJ Sidol and polymethylene oxide is combined in glycerin or a diol corresponding to the polymethylene oxide using the Lewis acid as a catalyst, and after decatalyzing in the same manner as above, a conventional It can also be obtained by esterification. In addition, when the polymethylene oxide is tetramethylene oxide, only glycidol may be added dropwise using tetrahydrofuran as a solvent. Furthermore, to increase the content of polymethylene oxide, the amount of polymethylene oxide may be increased, and to decrease the content, it is sufficient to reduce the amount of polymethylene oxide. Next, a production example of the polyglycerol compound of the present invention will be shown.

[Production Example 11] [Polyglycerol (6) Polyoxytrimethylene (4) 2-heptylundecanoic acid ester] 2. Add 1 g of boron trifluoride ether complex to 28.4 g of heptyl undecanoic acid and IQO ml of dichloromethane,
A mixture of 45 g of glycidol and 24 g of trimethylene oxide was added dropwise over 4 hours in a nitrogen stream while heating and stirring under reflux. After finishing the dropwise addition, leave it for 2 hours to complete the reaction.
Add 30 g of potassium carbonate and perform alkali treatment under these conditions for 4 hours. Insoluble materials are filtered off, and unreacted glycidol and solvent are distilled off under reduced pressure to obtain a colorless oily compound. The yield in this production example was 93g, and the elemental analysis was C, 8E.
[,,O! , the theoretical value: carbon 60.00%, hydrogen io. oo%, actual value: carbon 60.21%, hydrogen 10.
It was 21%.

[Manufacturing example 2]

[Polyglycerol (10) Polyoxytrimethylene (8) Stearate] 1 g of boron trifluoride ether complex was added to 9 g of glycerin and 120 ml of dichloromethane, the temperature was raised to 40'C, and 74 g of glycidol and trifluoride were heated under reflux and stirring in a nitrogen stream. A mixture with 47 g of methylene oxide is added dropwise over 4 hours. After the dropwise addition was completed, the reaction was allowed to stand for 1 hour, and then carbonic acid was added. Add 20 g of sodium chloride, and perform alkali treatment under these conditions for 4 hours. Insoluble matter was filtered out, unreacted glycidol and the solvent were distilled off under reduced pressure, and 28 g of stearic acid was added to the mixture, and the mixture was reacted at 230°C for 4 hours in a nitrogen stream. A compound is obtained. The yield in this production example is 114 g, elemental analysis: C7■H, 403. Theoretical value: carbon 58.
06%, hydrogen 9.68%, actual value: carbon 58.01%,
The hydrogen content was 9.72%.

[Manufacturing example 3]

[Polyglycerol (5) polyoxytetramethylene (6-vanoremitic acid ester)] 1 g of boron trifluoride ether complex was added to 25.6 g of valmitic acid and 100 ml of dichloromethane, and 37.0 g of glycidol was added in a nitrogen stream under heating and reflux stirring. A mixture with 150 ml of tetrahydrofuran is added dropwise over 4 hours. After completion of the dropwise addition, the mixture is allowed to stand for 2 hours to complete the reaction, and then 30 g of potassium carbonate is added and treated with alkali under these conditions for 4 hours. Insoluble matter is filtered out. Unreacted glycidol and solvent are distilled off under reduced pressure to obtain a colorless oily compound.The yield in this production example was 83g, and elemental analysis showed 055'H1.0.
18, theoretical value: carbon, 62.38%, hydrogen 10.
40%, actual value: carbon 62. 29%, hydrogen 10.32
%Met. The polyglycerol compound of the present invention can be used alone as a hydrophilic nonionic surfactant or as a nonionic surfactant such as sorbitan monostearate, glyceryl monostearate, etc., which do not have an ethylene oxide chain and have an HLB value of 7 or less. It can be effectively used as an emulsifier when mixed with an activator. Furthermore, polyglycerol poly(oxyborimethylene) branched fatty acid ester is micelle-dissolved in water and can be effectively used as a solubilizer for oils, fragrances, oil-soluble ingredients, and the like. Next, regarding the polyglycerol compound of the present invention,
The measurement results regarding the elution of formaldehyde over time are shown in FIGS. 1 and 2. The elution of formaldehyde from the emulsifier shown in FIG. Bl [emulsifier consisting of a known hydrophilic nonionic surfactant (polyoxyethylene (2o) sorbitan monooleate) 1%
Formaldehyde when Sample C1 [1% aqueous solution of emulsifier (polyoxyethylene (2o) solpitan monostearate) made of a known hydrophilic nonionic surfactant] was left at 40°C for one month. The measurements of formaldehyde elution from the solubilizing agent shown in FIG. ) Polyoxytrimethylene (16) 2-octyldodecanoic acid ester) 1% aqueous solution] and Sample B, [Solubilizing agent consisting of a known hydrophilic nonionic surfactant (Polyoxytrimethylene (4)
0) [Castor oil derivative] A 1% aqueous solution was prepared in the same manner as for the emulsifier. . 1 and 2 demonstrate that the product of the present invention hardly elutes harmful formaldehyde even under severe conditions of 40°C. Next, the characteristics when the polyglycerol compound of the present invention is blended into cosmetics as an emulsifier or solubilizer will be explained. (Stability) Conventionally known emulsifiers such as polyoxyethylene (1o) stearyl ether have high crystallinity and a melting point of 40°C.
There is a sudden change in hardness in the vicinity, and emulsions tend to solidify at low temperatures and flow at high temperatures. Furthermore, conventional polyoxyethylene sorbitan monostearate has a low melting point and a hardness sufficient for use as a cosmetic cream. On the other hand, the emulsifier made of the polyglycerol compound of the present invention has low crystallinity because it is amorphous semi-solid, and when a semi-solid emulsion such as a cosmetic cream is made, it has low stability against temperature and oxidation. It is an emulsifier that has properties ideal for cosmetics, such as high hardness and extremely small hardness change rate from low to high temperatures. On the other hand, many of the solubilizers made of conventionally known nonionic surfactants have a core alkyl group with a relatively short chain length or have a double bond. This is due to the Kraft point of the solubilizer, and in the case of long-chain alkyl groups, burl-shaped crystals will precipitate, leading to instability of the product. However, in the present invention, it has a low melting point, does not cause crystal precipitation, and can be solubilized even by using a fatty acid with a long alkyl group, thereby providing a cosmetic with better safety and oxidation stability. can do. (Preservative effect) Generally, preservatives such as parabens are added to cosmetics to prevent secondary contamination, but when parabens are added to an emulsifying system, they adsorb to the ethylene oxide chains of the emulsifier. It is widely known that the antiseptic effect cannot be fully exhibited. On the other hand, the emulsifier made of the polyglycerol compound of the present invention does not have an ethylene oxide chain, so the preservative effect does not decrease. Emulsifier consisting of glycerol compound (polygnocerol (1
2) Emollient cream (0/W) shown in Example 1 below, produced using polyoxytetramethylene (10) stearate and polyglycerol (3) polyoxytetramethylene (3) stearate> 5% by weight. emulsions) and traditional emulsifiers (sorbitan monostearate and polyoxyethylene (
20) Sorbitan monomonostearate) 51
The results are shown below, in which 0.3% by weight of a preservative (paraben (a mixture of methylparaben and butylparaben)) was added to the emollient cream, which is a control product using % by weight, and the preservative power was tested. Preservative power is the number of colonies of several types of mold and bacteria in one week, and 1 is 0, shi is 1 to 4, + is 5 to less than 200, Tsukuda is 200 to less than 1000, and masu is 1000. ~10' showing unskinned skin. (Left below) Table 1 According to Table 1, the product using the emulsifier made of the polyglycerol compound of the present invention is superior to the product using the conventionally used polyoxyethylene sorbitan emulsifier. It is found that it has antiseptic properties. Furthermore, it has been reported that when parabens are adsorbed to surfactants, the fluorescence intensity increases (34th Colloid Symposium). Therefore, we added an emulsifier (polyglycerol (20) polyoxytetramethylene (10) 2-hexyl decanoate ester) consisting of the same amount of the polyglycerol compound of the present invention to a 4 ppm methylparaben aqueous solution and a commercially available emulsifier "Nikkor HCO50J (trade name, When the fluorescence intensity of the polyethylene oxide surfactant (manufactured by Nikko Chemicals Co., Ltd.) was measured using a fluorometer (model RF510, manufactured by Shimadzu Corporation), the fluorescence intensity of the emulsifier made of the polyglycerol compound in the present invention was It was further demonstrated that the same effect can be obtained with less preservatives. (Disappearance of foam) Generally, solubilized lotion foams and does not disappear easily, but the foam is visually and tactilely smaller. Therefore, the foam disappearance rate at 20''C when the fragrance was solubilized for the present invention and the comparative example was measured, and the results are shown in FIG. Sample A3 is a solubilizer (polyglycerol (
14) Lotion solubilized with polyoxytrimethylene (16) 2-octyldodecanoate), Comparative Example B3
is a lotion solubilized with a town solubilizing agent (polyoxyethylene (30) 2-hexyldecanoic acid is an ester), Comparative Example C,
is a lotion that has been solubilized with a solubilizer (polyoxyethylene (20) oleyl ether), and Comparative Example D is a lotion that has been solubilized with a solubilizer (polyoxyethylene (50) hydrogenated castor oil). 10 ml of each was placed in a 30 ml test tube and vigorously shaken up and down 50 times, and the volume of the foam formed was measured over time to determine the remaining amount of foam. According to FIG. 3, among the comparative examples using conventional solubilizers, the hydrogenated castor oil ethylene oxide adduct has a faster foam disappearance rate, but when using the solubilizer consisting of the polyglycerol compound of the present invention, the foam disappears faster. It turns out that it is even better if there is. (Skin Irritation) It is well known that the solubility of a surfactant is greatly influenced by the HLB value, and the optimum HLB value is said to be 12-15. Furthermore, products used on human skin, such as cosmetics, must be extremely safe, and it is said that increasing the molecular weight is effective for this purpose. In order to increase the molecular weight with a nonionic surfactant, the number of moles of parent wood groups added may be increased, but if it is increased too much, the range of the optimal HLB value for solubilization will be exceeded. On the other hand, the polyglycerol compound of the present invention has a group such as tetramethylene oxide that makes the HLB value lipophilic, so it is possible to increase the molecular weight while maintaining the same HLB value. It is possible. Next, Table 2 shows the results of a transdermal primary irritation test for the polyglycerol compound of the present invention and a comparative example. In the table, sample A simple emulsion consisting of liquid paraffin and water each containing 20% by weight of polyoxyethylene (20) sorbitan monostearate, 0.1 ml of which was applied to the skin of Angora rabbits three times at 24 hour intervals, and 4 days later. The transdermal stimulation was measured. Rating is O(
Divided into 20 levels from no stimulation to 3.0 (strong stimulation), 20
The samples were measured and the average value was expressed. (Margin below) Table 2 According to Table 2, the polyglycerol compound of the present invention causes skin irritation to the same level or less than sorbitan fatty acid ester, which has been said to be extremely safe, and is extremely safe. Proven to be safe. As mentioned above, the polyglycerol compound of the present invention is extremely excellent in stability and safety, and in the case of cosmetics, it is blended according to various dosage forms.For example, in lotion, it is used as a Tir solubilizer of 0.1-1011 %, and in cosmetic creams, it is blended as an emulsifier in an optimum range of 0.5 to 60% by weight. [Example] Next, examples of cosmetics that are one of the present invention will be listed. The numerical value of each weight indicates weight %.

[Example 1] Component B heated to 70°C is added to emollient cream A heated to 70°C with stirring, and after the reaction, it is uniformly emulsified with a homomixer and heated to 30°C with a heat exchanger. Cool and obtain the product.

[Example 2] Emollient lotion precept C 1
0% triethanolamine aqueous solution 10. Add component B heated to 70°C to component A heated to 70°C with stirring, and after the reaction, uniformly emulsify with a homomixer. Next, add component C slowly while stirring to effect neutralization, and cool to 30''C using a heat exchanger to obtain a product.

[Example 3] Cream foundation and colored pigment
Appropriate precepts D fragrance
Heat ``Kibun B'' to 80 degrees Celsius, and add ``C'' which has been mixed with a pigment and disperse it. A certain amount of A dissolved in go'c is gradually added to this while stirring to emulsify. Next, cool while stirring and add component D. 】Cool to 30°C to obtain a product.

[Example 4] Lotion polyglycerol (14) Polyoxytrimethylene (16) -2-octyldodecanoic acid ester Fragrance 1.3-Butylene glycol Sorbitol Ethanol Distilled water Methyl paraben Polyglycerol (14) Polyoxytrimethylene (1
6) -2-octyldodecanoic acid ester, fragrance, 1,3
- Dissolve butylene glycol and methylparaben uniformly, and add distilled water to the solution while stirring at room temperature. Further, nlubitol and ethanol are added and dissolved to obtain a product. This lotion was stable for 3 months at 5-40'C.

[Example 5] Solubilization of jojoba oil Polyglycerol (8) Polyoxytetramethylene (8) Eicosenoic acid ester Jojoba oil fragrance 1.3-Butylene glycol Distilled water Ethanol Preservative Polyglycerol (8) Polyoxytetramethylene (8)
) Eicosenoic acid ester, hopopa oil, fragrance, 1,3-butylene glycol and preservative are uniformly dissolved, distilled water is added with stirring at room temperature, and ethanol is further added. This product was stable for 3 months at 5 to 40"C. [Effects of the Invention] The polyglycerol compound and cosmetics of the present invention having the above-mentioned precautions do not contain formaldehyde even under severe temperature conditions. It is safe because it does not elute, and it also has the effect of short defoaming time in the solubilization system.
In particular, nonionic surfactants made of polyglycerol compounds can be used not only in cosmetics as in the present invention, but also in many other applications such as detergents, soaps, and pharmaceuticals.

[Brief explanation of the drawing]

Figures 1 and 2 are graphs showing changes in formaldehyde elution over time for the emulsifier and solubilizer made of the polyglycerol compound of the present invention, together with known emulsifiers and solubilizers; The figure is a graph showing the measured values of the foam disappearance rate when perfumes of the present invention and comparative examples were dissolved.

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R is a linear or branched saturated or unsaturated fatty acid residue having 7 to 36 carbon atoms, and
H_2CH_2CH_2O or a mixture of both, Y represents a glyceryl group, m=1 to 60, and n=3 to 60, respectively. ) A polyglycerol compound represented by 2. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R is a linear or branched saturated or unsaturated fatty acid residue with 7 to 35 carbon atoms, and X is CH_2CH_2CH_2
O or CH_2CH_2CH_2CH_2O or a mixture of both, Y is a glyceryl group, m = 1
~60 and n=3 to 60, respectively. ) A cosmetic comprising at least one polyglycerol compound represented by the following.