JPH0368018B2 - - Google Patents

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. [Prior Art] 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, and polyoxyethylene alkyl. Phenyl ether, polyoxyethylene hydrogenated castor oil derivatives, etc. are known. These emulsifiers can be divided into hydrophobic surfactants that do not contain or have short polyoxyethylene long chains, and hydrophilic surfactants that contain polyoxyethylene long chains, and these can be mixed appropriately to obtain the desired HLB value. The surfactant has been adjusted to have an HLB value of 10 to 15.
When the oil-in-water (O/W) emulsion is
When the HLB value is set to 4 to 6, a water-in-oil (W/O) type emulsion can be obtained. In addition, nonionic surfactants that have conventionally been widely used as solubilizers include polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene monolaurate, polyoxyethylene Ethylene monooleate, hydrogenated castor oil polyoxyethylene adduct, polyoxypropylene, polyoxyethylene cetyl ether,
Polyoxyethylene-2-hexyldecyl ether and the like are known. All of these solubilizers have an HLB value of 12 so that they dissolve into micelles in water and solubilize oils, fragrances, oil-soluble ingredients, etc.
In the above manner, it is adjusted to be relatively hydrophilic. [Problems to be Solved by the Invention] However, the emulsifiers and solubilizers made of nonionic surfactants, which have been commonly used in the past, all utilize polyoxyethylene chains.
Adjusting the HLB value. This is a delicate HLB with easy control of ethylene oxide chain length.
This is because the value can be adjusted. Therefore, dioxane is generated during synthesis, and
Ethylene oxide chains oxidize over time, formaldehyde elutes, and the hydrogen ion concentration (PH) gradually shifts to the acidic side.These drawbacks can be overcome by adding antioxidants and buffers. However, the use of antioxidants is not recommended from a safety standpoint. 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, parabens such as methylparaben, which are used as preservatives in cosmetics, are added to the ethylene oxide chain of the nonionic surfactant. There is a problem that the antiseptic effect cannot be fully exerted due to adsorption of the antiseptic. The present invention has been developed in view of the above circumstances, and is safe because it does not elute formaldehyde even under severe temperature conditions, has a short defoaming time in a solubilized system, and can be added to cosmetics. The object of the present invention is to provide a polyglycerol compound that does not reduce the effect of preservatives and cosmetics 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]-nH (wherein R is a straight carbon number of 7 to 35). a chain or branched saturated or unsaturated fatty acid residue,
CH ₂ CH ₂ CH ₂ O or a mixture of CH ₂ CH ₂ CH ₂ CH ₂ O or both, Y represents a glyceryl group, m = 1 to 60, and n = 3 to 60, 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 its hydrophilic group portion is glycerin:oxypolymethylene=95:5 to 1:3. In addition, m in the general formula is 1 to 60, and n is 3 to 60.
It is preferable that m is 1 to 30 and n is 3 to 30. When m and n each exceed 60 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. Examples of linear/branched higher saturated or unsaturated fatty acids in the polyglycerol compound of the present invention include lauric acid, mystilic acid, palmitic acid, stearic acid, oleic acid, behenic acid, cerotic acid, melisic acid, -Ethylhexanoic acid, 2-hexyldecanoic acid, 2-heptylundecanoic acid, 2-octyldodecanoic acid, 5,7,7
-Higher fatty acids having 8 to 36 carbon atoms such as trimethyl-2-(1',3',3'-trimethylbutyl)octanoic acid and neodecanoic acid obtained by the reaction of olefin and carbon monoxide are used. Ru. Further, as the polymethylene oxide, trimethylene oxide, tetrahydrofuran, etc. are used. To specifically list the polyglycerol compounds of the present invention, polyglycerol (6) polyoxytrimethylene (4) 2-heptylundecanoic acid ester, polyglycerol (10) polyoxytrimethylene
(8) Stearate, polyglycerol (30) Polyoxytrimethylene (8) Stearate, polyglycerol (30) Polyoxytrimethylene (20) Oleate, polyglycerol (14) Polyoxytrimethylene (16) )2-
Octyldodecanoic acid ester, polyglycerol
(5) Polyoxytetramethylene (6) Palmitic acid ester, polyglycerol (3) Polyoxytetramethylene (3) Stearic acid ester, polyglycerol
(6) Polyoxytetramethylene (4) Stearate, polyglycerol (12) Polyoxytetramethylene (10) Stearate, polyglycerol (20) Polyoxytetramethylene (10) 2-hexyldecanoate, 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 a synthesis method using a Lewis acid catalyst. Without any solvent,
For example, a mixture of glycidol and polymethylene oxide is gradually added and polymerized 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, and basic alumina, 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. Alternatively, a mixture of glycidol and polymethylene oxide may be 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, the usual It can also be obtained by esterification. In addition, when 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.

[Manufacturing example 1]

[Polyglycerol (6) polyoxytrimethylene
(4) 2-heptyl undecanoic acid ester] Add 1 g of boron trifluoride ether complex to 28.4 g of 2-heptyl undecanoic acid and 100 ml of dichloromethane, then heat to reflux and stir in a nitrogen stream to create a mixture of 45 g of glycidol and 24 g of trimethylene oxide. is added dropwise over 4 hours. After finishing the dropwise addition, leave it for 2 hours to complete the reaction, then add 30g of potassium carbonate.
Under these conditions, alkali treatment is carried out 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 93 g, and elemental analysis C ₄₈ H ₉₆ O ₁₈ showed theoretical values: 60.00% carbon and 10.00% hydrogen, and actual values: 60.21% carbon and 10.21% hydrogen.

[Manufacturing example 2]

[Polyglycerol (10) polyoxytrimethylene
(8) Stearic acid ester] Add 1 g of boron trifluoride ether complex to 9 g of glycerin and 120 ml of dichloromethane, raise the temperature to 40°C, and dropwise add a mixture of 74 g of glycidol and 47 g of trimethylene oxide in a nitrogen stream over 4 hours while heating and stirring under reflux. do. After the dropwise addition was completed, the mixture was allowed to stand for 1 hour to complete the reaction, and then 20 g of sodium hydrogen carbonate was added, and the mixture was treated with alkali under these conditions for 4 hours. Insoluble materials were filtered out, unreacted glycidol and 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 to remove the resulting water, resulting in a colorless semi-solid compound. get. The yield in this production example was 114g, and elemental analysis: C ₇₂ H ₁₄₄ O ₃₀
Theoretical values: carbon 58.06%, hydrogen 9.68%, actual values: carbon 58.01%, hydrogen 9.72%.

[Manufacturing example 3]

[Polyglycerol (5) polyoxytetramethylene (6) palmitic acid ester] Add 1 g of boron trifluoride ether complex to 25.6 g of palmitic acid and 100 ml of dichloromethane, and add 37.0 g of glycidol and 150 ml of tetrahydrofuran in a nitrogen stream under heating and reflux stirring. A mixture of the above-mentioned and the above was added dropwise over a period of 4 hours. After the dropwise addition was completed, the mixture was allowed to stand for 2 hours to complete the reaction, and then 30 g of potassium carbonate was added, and the mixture was treated with alkali 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 is
Theoretical value as 83g and elemental analysis C ₅₅ H ₁₁₀ O ₁₈ :
Carbon, 62.38%, hydrogen 10.40%, actual value: carbon 62.29
%, hydrogen 10.32%. 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 does not have an ethylene oxide chain and has an HLB value of 7 or less. It can be effectively used as an emulsifier when mixed with an activator. Furthermore, polyglycerol poly(oxypolymethylene) 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, FIGS. 1 and 2 show the measurement results of formaldehyde elution over time for the polyglycerol compound of the present invention. 1st
The elution of formaldehyde from the emulsifier shown in the figure was measured using Sample A ₁ [1% aqueous solution of the emulsifier made of the polyglycerol compound of the present invention (polyglycerol (10) polyoxytrimethylene (8) stearate ester)] and Sample B. ₁ [Emulsifier consisting of a known hydrophilic nonionic surfactant (polyoxyethylene (20) sorbitan monooleate) 1%]
Aqueous solution], Sample C ₁ [Emulsifier consisting of a known hydrophilic nonionic surfactant (polyoxyethylene (20)
This figure shows the measured values of formaldehyde by the acetylacetone method when each of the sorbitan monostearate (1% aqueous solution) was left at 40°C for one month, and the elution of formaldehyde from the solubilizing agent shown in Figure 2 was measured. is Sample A ₂ [Solubilizer made of polyglycerol compound of the present invention (polyglycerol (14) polyoxytrimethylene (16) 2-octyldodecanoate ester) 1
% aqueous solution] and Sample B ₂ [a 1% aqueous solution of a solubilizer (polyoxyethylene (40) hydrogenated castor oil derivative) consisting of a known hydrophilic nonionic surfactant] were 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 (10) stearyl ether have high crystallinity and melting point.
Hardness suddenly changes around 40°C, and emulsions tend to solidify at low temperatures and flow at high temperatures. Further, conventional polyoxyethylene sorbitan monostearate has a low melting point and is difficult to obtain sufficient hardness 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 an 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, pearl-like crystals will precipitate, leading to instability of the product. However, in the present invention, the melting point is low, crystal precipitation does not occur, and solubilization is possible even with the use of a fatty acid with a long alkyl group.
Cosmetics with excellent safety and oxidative stability can be provided. (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, since the emulsifier made of the polyglycerol compound of the present invention does not have an ethylene oxide chain, the preservative effect is not reduced. To demonstrate this, Table 1 shows emulsifiers made of the polyglycerol compounds of the present invention (polyglycerol (12) polyoxytetramethylene (10) stearate and polyglycerol (3) polyoxytetramethylene (3) stearate). The emollient cream (O/W emulsion) shown in Example 1 below, which was produced using 5% by weight of ester, and the conventional emulsifier (sorbitan monostearate and polyoxyethylene (20) sorbitan monomonostearate) by weight The results show the results of testing the preservative power of a control product, emollient cream, with the addition of 0.3% by weight of preservatives (parabens (a mixture of methylparaben and butylparaben)). The number of bacteria per week is expressed as colony number, - is 0, ± is 1 to 4, + is 5 to less than 200,
indicates between 200 and less than 1000, and indicates between 1000 and less than ¹⁰⁴ .

【table】

[Table] According to Table 1, products using the emulsifier made of the polyglycerol compound of the present invention have superior preservative power compared to products using the conventionally used polyoxyethylene sorbitan emulsifier. I can see that you are doing it. Additionally, it has been reported that the fluorescence intensity increases when parabens are adsorbed to surfactants (34th Colloid Symposium). Therefore,
Emulsifier (polyglycerol (20) polyoxytetramethylene (10) consisting of the same amount of the polyglycerol compound of the present invention in a 4 ppm methylparaben aqueous solution
2-hexyl decanoic acid ester) and a commercially available emulsifier "Nitsukol HCO50" (trade name, manufactured by Nikko Chemicals, polyethylene oxide surfactant) was measured using a fluorometer (RF510 model, manufactured by Shimadzu Corporation). It was further demonstrated that the emulsifier made of the polyglycerol compound in the present invention has a low fluorescence intensity, and that the same effect can be obtained with a smaller amount of preservative. (Disappearance of Foam) Generally, solubilized lotion foams and does not disappear easily, but it is better to have less foam visually and tactilely. 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 A ₃ is a lotion solubilized with a solubilizer made of the polyglycerol compound of the present invention (polyglycerol (15) polyoxytrimethylene (16) 2-octyldodecanoate ester), and Comparative Example B ₃ is a lotion that is Comparative Example C ₃ is a lotion solubilized with a solubilizer (polyoxyethylene (20) oleyl ether), a comparative example _D3 is a lotion solubilized with a solubilizer (polyoxyethylene (50) hydrogenated castor oil), and 10ml of each of these is mixed into 30ml
The mixture was placed in a 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 solubilizing ability of surfactants is greatly influenced by the HLB value, and the optimal HLB value is
It is said to be 12 to 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 of a nonionic surfactant, it is sufficient to increase the number of moles of hydrophilic groups added, but if it is increased too much, 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 Liquid paraffin containing 20% by weight of each polyoxyethylene (20) sorbitan monostearate.
It is a simple emulsion consisting of water, and these
0.1 ml was applied to the skin of Angora rabbits three times at 24-hour intervals, and transdermal irritation was measured 4 days later. The evaluation is divided into 20 levels from 0 (no stimulation) to 3.0 (strong stimulation).
20 samples were measured and the average value was expressed.

[Table] According to Table 2, it has been demonstrated that the polyglycerol compound of the present invention is extremely safe, with skin irritation comparable to or less than that of sorbitan fatty acid ester, which has been said to be extremely safe. Ta. As described above, the polyglycerol compound of the present invention is extremely safe and secure, and in the case of cosmetics, it is blended according to various dosage forms.For example, in lotions, it is used as a solubilizer at 0.1
-10% by weight, and in cosmetic creams, it is blended in an optimum range of 0.5-60% by weight as an emulsifier. [Example] Next, examples of cosmetics that are one of the present invention will be listed. The numerical value of each component indicates weight %.

[Example 1] Emollient cream Polyglycerol (12) Polyoxytetramethylene (10) Stearate 3.0 Polyglycerol (3) Polyoxytetramethylene (3) Stearate 2.0 Stearic acid 5.0 Component A Setanol 3.0 Squalane 10.0 Beeswax 2.0 Whale wax 1.0 Lanolin 2.0 Parabens (methylparaben, butylparaben mixture) 0.3 Antioxidant Appropriate amount Fragrance Appropriate amount Propylene glycol 7.0 Component B Glycerin 4.0 Purified water 60.7 Stir component B heated to 70℃ into component A heated to 70℃. After the reaction, the product is uniformly emulsified using a homomixer and cooled to 30°C using a heat exchanger.

[Example 2] Emollient lotion Polyglycerol (6) Polyoxytetramethylene (4) Stearic acid ester 3.0 Stearic acid 2.0 Setanol 1.5 Component A Lanolin 2.0 Squalane 10.0 Preservative Appropriate amount Antioxidant Appropriate amount Fragrance Appropriate amount Propylene glycol 4.0 Ingredient B Sorbitol 4.0 Carboxyvinyl polymer 0.1 Purified water 63.4 Component C 10% triethanolamine aqueous solution 10.0 Component B heated to 70°C is added to component A heated to 70°C with stirring, and after the reaction is uniformly emulsified with a homomixer. Next, component C is slowly added while stirring to neutralize the mixture, and the mixture is cooled to 30°C using a heat exchanger to obtain a product.

[Example 3] Cream foundation Polyglycerol (5) Polyoxytetramethylene (6) Palmitic acid ester 3.0 Stearic acid 4.0 Glycerin monostearate 3.0 Component A Setanol 1.0 Liquid paraffin 7.0 Glycerin tri-2-ethylhexanoate 7.0 Preservative Appropriate amount Purified water 55.0 Component B Triethanolamine 1.0 Sorbitol 3.0 Titanium oxide 8.0 Component C Kaolin 5.0 Talc 2.0 Bentonite 1.0 Coloring fragrance Appropriate amount Component D Perfume Appropriate amount Heat component B to 80℃, mix it with pigment, and grind it. Add and disperse component C. Component A, which had been heated and dissolved at 80°C, was gradually added to this mixture while stirring and emulsified. Next, cool while stirring and add component D. The product is further cooled to 30°C.

[Example 4] Lotion polyglycerol (14) Polyoxytrimethylene (16)-2-octyldodecanoic acid ester 1.0 Fragrance 0.4 1,3-butylene glycol 2.5 Sorbitol 2.5 Ethanol 5.0 Distilled water 88.6 Methylparaben Appropriate amount Polyglycerol (14 ) Polyoxytrimethylene (16)-2-octyldodecanoate, fragrance, 1,3-butylene glycol, and methylparaben are uniformly dissolved, and distilled water is added thereto with stirring at room temperature. Further, sorbitol and ethanol are added and dissolved to obtain a product. This lotion is 5~
It remained stable for 3 months at 40°C.

[Example 5] Solubilized polyglycerol (8) polyoxytetramethylene in jojoba oil
(8) Eicosenoic acid ester 1.0 Jojoba oil 0.3 Fragrance 0.4 1,3-butylene glycol 5.0 Distilled water 88.3 Ethanol 5.0 Preservative appropriate amount Polyglycerol (8) Polyoxytetramethylene
(8) Eicosenoic acid ester, jojoba oil, fragrance, 1,
3-Butylene glycol and a preservative are uniformly dissolved, distilled water is added while stirring at room temperature, and ethanol is further added. This product was stable for 3 months at 5-40°C. [Effects of the Invention] The polyglycerol compound and cosmetics of the present invention having the above configuration are safe without eluting formaldehyde even under severe temperature conditions, and have short defoaming time in the solubilized 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. It is something.

[Brief explanation of drawings]

Figures 1 and 2 are graphs showing changes in formaldehyde elution over time for emulsifiers and solubilizers made of the polyglycerol compound of the present invention, together with known emulsifiers and solubilizers, and Figure 3 is a graph of the present invention. FIG. 2 is a graph showing measured values of the foam disappearance rate when fragrances are solubilized for the invention and comparative examples. FIG.

Claims (1)

[Claims] 1 General formula RCOO(X)m[-Y]-nH (wherein R is a linear or branched saturated or unsaturated fatty acid residue having 7 to 35 carbon atoms, and X is
_{CH2CH2CH2CH2O} or _{CH2CH2CH2CH2CH2O} 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 RCOO(X)m[-Y]-nH (In the formula, R is a linear or branched saturated or unsaturated fatty acid residue having 7 to 35 carbon atoms, and X is
CH ₂ CH ₂ CH ₂ O or a mixture of CH ₂ CH ₂ CH ₂ CH ₂ O or both, Y represents a glyceryl group, m = 1 to 60, and n = 3 to 60, respectively. ) A cosmetic comprising at least one polyglycerol compound represented by the following.