JPH0635372B2 - Cosmetics - Google Patents

Description

The present invention relates to cosmetics containing a novel epoxy resin branched higher fatty acid ester.

BACKGROUND ART Conventionally, various substances have been used for cosmetics represented by nail lacquers, lipsticks, mascaras, hair styling agents, etc. for the purpose of improving their adhesiveness and stickiness and forming a film. For example, natural products include rosin, rosin acid esters, and natural gums, and synthetic products include cellulose-based resins, acrylic acid-based resins, polyvinylpyrrolidone, and carboxyvinyl polymers. Was there. Similarly, the epoxy resin oleic acid ester has been a raw material that has been blended into cosmetics for a long time by taking advantage of its adhesiveness, stickiness and film-forming property.

However, this product has an unsaturated bond in the acyl group, and due to oxidative deterioration, changes in color and odor occur over a period of time after production. It was not possible to raise the blending concentration so as to make full use of the above. In addition, it was feared that this product could easily generate hydroperoxide by heat and light, which could lead to skin troubles. In recent years, refining technology has improved, and oleic acid, which has almost no color or odor and contains almost no linoleic acid or linolenic acid, can be obtained.Epoxy resin oleic acid ester using this can also be synthesized. But in this case
Although the improvement effect on color and odor was observed, it was not effective on deterioration stability against light and heat.

On the other hand, an epoxy resin ricinoleic acid ester is also commercially available as a raw material similar to the epoxy resin oleic acid ester, but this also has the same problem as oleic acid ester because it has an unsaturated bond.

Further, these two kinds of esters have poor compatibility with pristane, a low boiling point hydrocarbon and the like, which are main blending components in cosmetics, and there is a drawback that separation occurs when these are mixed at a high concentration.

Furthermore, epoxy resin stearic acid ester was developed to improve the oxidative stability and poor compatibility of the above two types of ester, and it was already used in some products. ) Significantly changes and the melting point is near room temperature (19 to 14 ° C). Since the viscosity of the product formulation system remarkably changes with temperature, there are cases where the product does not have a sufficient function, for example, the formulation system becomes highly viscous at low temperatures and usability deteriorates.

2. Phase transition occurs near room temperature and separation easily occurs.

However, there are drawbacks such as the above, and special measures are required for its use, and the amount or range of use is limited to a part.

Therefore, the present inventors have solved the problems of the above-mentioned conventional epoxy resin fatty acid ester, and
As a result of intensive research to obtain a material that takes advantage of film-forming properties, we focused on branched higher fatty acids that have recently been synthesized, improved, and are now available at low cost. When an ester was synthesized, it was found that not only the above-mentioned problems were solved but also a cosmetic containing this ester had excellent properties. The present invention has been completed based on such findings.

The present invention will be described in detail below.

The epoxy resin branched higher fatty acid ester applied to the present invention is a resin ester having a structure shown below.

(However, R ₁ represents an acyl residue of a branched fatty acid having 8 to 20 carbon atoms, R ₂ represents hydrogen and / or the same acyl residue as R _1. ) As described above, the present resin ester is an epoxy resin. A compound having a resin as a main skeleton and partially acylated. The fatty acid component applied to acylation is a branched fatty acid having 8 to 20 carbon atoms, for example, 2-ethylhexanoic acid having 8 carbon atoms, 2-hexyldecanoic acid having 16 carbon atoms, and 18 carbon atoms. Methyl branched chain fatty acid (manufactured by Emery Co.) 5.7.7-trimethyl-
2- (1.3.3-Tributyl) -octanoic acid (for example, Fineoxocol manufactured by Nissan Chemical Co., Ltd.), 2-heptylundecanoic acid (for example, Diadol manufactured by Mitsubishi Kasei Co., Ltd.), etc. -Octyldodecanoic acid and the like, which are appropriately selected according to the properties required for the cosmetics to be blended and are subjected to esterification, but in consideration of the versatility of the obtained resin ester, isostearic acid Is the most useful. When a branched fatty acid having a carbon number of less than 8 is used as an acylating agent, the solubility is insufficient even when the degree of esterification is considerably increased, and it becomes difficult to add it to a formulation system. When a larger branched fatty acid is used, the oil solubility is improved but the original adhesiveness and sticking property of the epoxy resin are reduced, which is not preferable.

Then, as a method for industrially obtaining the present resin ester, a conventional esterification reaction can be applied as it is. That is, the general manufacturing process is as shown below.

Epoxy resins have high reactivity, which a branched higher fatty acid (C ₈ -C ₂₀₎ were mixed, heating in the presence or absence of a nitrogen stream and a catalyst (such as an inorganic acid) (Example: 200 ° C. or higher) Can be easily obtained.

Here, the molecular weight of the epoxy resin used is approximately 1,000.
Those having a range of up to 2,000 are preferably used, and the molecular weight in a resin esterified state is about 2,000.
The type and degree of esterification of the branched higher fatty acid are adjusted so as to be in the range of 0 to 4,000, but as described above, the resin ester of the present invention is adjusted according to the purpose for which it is used, and the above range is not always required. Not deterministic. Each of the obtained epoxy resin esters is a pale yellow to yellowish brown highly viscous liquid or pasty substance.

Epoxy resin branched higher fatty acid ester according to the present invention,
It has the following features.

1. All of these products have excellent compatibility with cosmetic oil agents, such as ester oil agents such as 2-ethylhexanoate and IPM, and triglycerides such as Nomcoat TIO and castor oil, as well as pristane and low boiling point carbonization. It also has a compatibility with hydrogen of 10% or more.

2. This product is not susceptible to oxidative deterioration due to heat and light and has excellent stability.

3. A product obtained by dissolving this product in an oil agent has mild temperature-viscosity characteristics, that is, the viscosity does not increase or decrease between seasons, and the product stability is excellent.

4. Excellent in adhesion and film formation.

5. Since it is a highly viscous liquid or paste, it does not need to be heated and melted when the product is manufactured, and it is easy to handle and industrially advantageous.

The epoxy resin branched higher fatty acid ester of the present invention can be added as one component of an oil agent for cosmetics when it is mixed with cosmetics. Further, the compounding amount may be arbitrarily compounded according to the dosage form, but generally, the range of 0.1 to 25% by weight is selected. Furthermore, there are no particular restrictions on the method of blending.

The cosmetics obtained by the present invention include lipsticks,
In addition to blusher, eyeliner, mascara, nail lacquer, powdery cosmetics such as eye shadow, solid powder powder, etc., are mainly shown to improve the adhesiveness, and also hair liquid, hair spray, set lotion. With such hair styling products, products having a natural finish and a sufficient hair styling property can be obtained.

Next, the results of evaluating the epoxy resin branched higher fatty acid ester according to the present invention will be shown. As the evaluation method, the results of synthesizing epoxy resin fatty acid esters of various fatty acids and measuring the oxidation stability and photooxidation stability thereof are shown in Table 1. Similarly, the viscosity temperature dependence of the resin ester was measured, and the results are shown in Table 2.

The test method is as follows.

A. Oxidation stability test ○ Samples oleic acid ester (A), purified oleic acid ester (B),
Ricinoleic acid ester (C), methyl branched chain (C ₁₈ ) fatty acid ester (D), 2-heptylundecanoic acid ester (E),
2-octyldodecanoic acid ester (F), ○ method Take 20 g of each sample in a 20 ml screw tube,
The peroxide value (POV) was measured by leaving the sample in a thermostat bath at 90 ° C. for 16 hours without opening the stopper.

The measurement was carried out according to the standard test method for fats and oils, the number of samples was 3, and the POV in Table 1 was shown as the average value.

B. Photo-oxidation stability test ○ Samples Same as those used in the oxidation stability test ○ Method 1.0 g of each sample was weighed on a 4 cmφ mini-dishes and kept at 40 ° C without the lid, After irradiating with xenon lamp light for 16 hours, the peroxide value was measured. The xenon lamp light used had a spectrum similar to that of sunlight, and the amount of ultraviolet irradiation energy was almost the same as that of sunlight.
The number of samples was 3, and the POV in Table 1 was shown as the average value.

C. Viscosity temperature dependence test ○ Reagents Epoxy resin stearic acid ester (conventional product) Epoxy resin isostearic acid ester (product of the present invention) (Methyl branched chain) ○ Method 40% sample, low boiling point hydrocarbon 60% Simple formulation prepared Then, the system viscosity at 40 ° C., 20 ° C. and 5 ° C. was measured.

As described above, the epoxy resin branched higher fatty acid ester applied to the present invention is excellent in oxidative stability against heat and light, and there are few safety problems associated therewith, and
The formulation system containing the product of the present invention is capable of providing a cosmetic composition which has a gentle change in system viscosity with respect to temperature changes and is excellent in stability over time.

Next, the present invention will be described in more detail with reference to examples.
The blending amount is% by weight.

Example 1. Hairdressing tic castor oil 59 Beeswax 12 Gelow 5 2-Ethylhexanoic acid trigly 10 Paraffin wax 5 Polyoxypropylene butyl ether 3 Epoxy resin isostearic acid ester 3 (Emery) Antioxidant proper amount pf 3 (value) The present invention in Example 1 Compared to the conventional epoxy resin stearic acid instead of the substance, Good adherence to hair 2. Light and soft finish 3. The result is that the hair is shiny, and in comparison with the one in which the conventional isostearic acid triglyceride is replaced, 1. It was evaluated as having great hair styling power.

Example 2. Hair spray Ethyl acrylate / methacrylic acid copolymer 1.2 Epoxy resin Octyldodecanoic acid ester 0.3 Dimethylpolysiloxane 0.4 2-Ethylhexanoic acid triglycerine 0.1 Pristane 0.1 Ethanol 96.5 Fragrance 1 0.0 Polyoxyethylene octyl phenyl ether 0.4 (evaluation) The same evaluation as in Example 1 was obtained.

Example 3. Liquid hair styling agent Ethanol 64.3 Polyoxypropylene butyl ether 9 Propylene glycol 2 Polyoxypropylene glycerin 7 Epoxy resin isostearic acid ester 1 (Diadol) Pristane 0.1 Water 12.5 Fragrance 2 Cetyltrimethylammonium chloride 0.1 Polyoxy Ethylene octyl phenyl ether 2 (evaluation) The same evaluation as in Example 1 was obtained.

Example 4. Lipstick Castor oil 47.7 Octyldodecyl myristate 3.5 Triethyl 2-ethylhexanoate 15 Microcrystalline wax 9 Epoxy resin isostearic acid ester 3 (Emery) Candelilla wax 1 Cetyl 4-ethylhexanoate 4 Methylpolysiloxane 1. 5 Tar-based pigment 2 Iron oxide 0.5 Titanium oxide 1.0 Sericite 11 Polyoxyethylene cetyl ether 0.8 Antioxidant Appropriate amount (evaluation) The substance according to the present invention in Example 4 was treated with conventional epoxy resin stearin. Compared with what replaced with acid ester, 1. Good spread during application 2. The result is that the gloss after application is good, and in comparison with the conventional one substituted with triglyceride isostearate, 1. It was evaluated that the makeup would not easily come off.

Example 5. Rod-shaped eye shadow ceresin 17 pristane 17 octyldodecyl myristate 13 triethyl 2-ethylhexanoate 1 gungzhou 8 chromium oxide 3.5 iron oxide 1.5 epoxy resin isostearate 3 (emery) polyethylene powder 15 mica titanium 19 sorbitan sesquistearate 2.3 Antioxidant Appropriate amount (Evaluation) The same evaluation as in Example 4 was obtained.

Example 6. Stain concealing cosmetic ceresin 20 microcrystalline wax 4.5 pristane 6.5 cetyl 2-ethylhexanoate 13.5 carnauba wax 0.4 sorbitan sesquioleate 1.5 mica titanium 5 titanium oxide 30.5 iron oxide 7.5 talc 8.5 Perfume 0.2 Epoxy resin isostearic acid ester 2 (Emery) (Evaluation) When carried out in the same manner as in Example 4, as compared with the case where the epoxy resin stearic acid ester was replaced, 1. Good spreadability during application In addition, compared with the case where isostearic acid triglyceride is replaced, 1. We received the evaluation that the makeup does not easily come off.

Example 7. Hoho Red Tar Dye Appropriate amount Mica Titanium 10.3 Gunjou 1.4 Pristane 5.1 Dimethylpolysiloxane 2.1 Talc 63 Aluminum stearate 3.2 Epoxy resin isostearate 1.8 (Emery) Cericide 10.8 Fragrance 0 .2 Octyldodecyl myristate 2 (evaluation) When carried out in the same manner as in Example 4, as compared with the one in which the epoxy resin stearic acid ester was replaced, 1. Good attachment to makeup puff. 2. Good spreadability during application In addition, as compared with the case where isostearic acid triglyceride is replaced, 1. It was evaluated that the makeup would not easily come off.

Example 8. Pressed Powder Talc 84 Iron Oxide 1 Sericite 6 Magnesium Carbide 1 Zinc myristate 2 Aluminum myristate 1 Myristyl myristate 0.5 Fragrance 2 Octyldecyl myristate 2 Epoxy resin isostearate 1 (Emery) (value) Conducted The same evaluation as in Example 7 was obtained.

Example 9. Base cream Jojoba oil 5 Liquid paraffin 2 Pristane 10 Methylphenylsilicone 5 Microcrystalline wax 6 Polyethylene powder 17 Sorbitan monooleate 2 Polyoxyethylene sorbitan monooleate 16 Sericite 8 Iron oxide 5 Talc 7 Titanium oxide 12 Fragrance 0.5 0.5 Epoxy resin isostearic acid ester 4.5 (Fineoxochol)) (Evaluation) When the same procedure as in Example 4 was carried out, 1. Good spread during application 2. Excellent viscosity stability at low temperature In addition, as compared with the one in which isostearic acid triglyceride is replaced, 1. It was evaluated that the makeup would not easily come off.

Claims (2)

[Claims] 1. A cosmetic comprising an epoxy resin branched higher fatty acid ester. 2. The cosmetic according to claim 1), wherein the fatty acid component of the branched higher fatty acid ester of epoxy resin is 2-ethylhexanoic acid, 2-hexyldecanoic acid, isostearic acid, 2-octyldodecanoic acid. .