JPH0798727B2 - External skin preparation - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to tetrahydroabietic acid and alcohol (s).
The present invention relates to a skin external preparation containing an ester of

[Prior Art] Rosin is derived from gum rosin, tall rosin,
It is roughly divided into wood rosin and is sometimes called resin acid.

Esters of these rosins with alcohols such as glycerin and pentaerythritol have various useful physical properties, but in the field of external preparations for skin, for example, adhesiveness and luster to nail enamel and hair spray of cosmetics, etc. It is only used for giving purposes.

The cause is that rosin ester has a problem that it is inferior in oxidative stability and has a sensitizing effect on the skin.

[Problems to be Solved by the Invention] As a result of intensive studies on the above problems, the present inventors have found that the alcohol ester of tetrahydroabietic acid derived from abietic acid, which is a main component of rosin, causes the above problems. It was found that the rosin ester retained the useful physical properties, and based on this finding, the present invention was completed.

[Means for Solving Problems] That is, the present invention is an external preparation for skin characterized by containing an ester of tetrahydroabietic acid and alcohol.

The alcohol ester of tetrahydroabietic acid according to the present invention may be obtained by any method, but it is general to purify rosin to obtain abietic acid, which is hydrogenated and then converted to an ester with an alcohol. .

Isolation of abietic acid from rosin is not limited to a particular method, but generally, under reflux, hydrochloric acid is used as a catalyst to isomerize other isomers to abietic acid, followed by cooling to obtain crystals that precipitate.

The hydrogenation reaction (hereinafter referred to as hydrogenation reaction) is not limited to a particular method, but is usually carried out at room temperature to 300 ° C. using a metal catalyst such as palladium, platinum or nickel.

The reaction is carried out at a hydrogen pressure of 1 to 300 kg / cm ² , although the conditions vary depending on the presence or absence of a solvent and the substance used.

The ester of the present invention can be obtained by esterifying the tetrahydroabietic acid thus obtained with an alcohol.

The alcohol used here is a monohydric alcohol or a polyhydric alcohol, and means the following.

The monohydric alcohol is a saturated linear aliphatic alcohol having 1 to 22 carbon atoms (methanol, ethanol, n-propanol, n-butanol, n-octanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, etc.). , Palmitrail alcohol, oleyl alcohol, erucyl alcohol and other monoene linear aliphatic alcohols, carbon number 3
~ 36 saturated branched aliphatic alcohols (isopropyl alcohol, isobutanol, sec-butanol, 2 ethylbutanol, 2-ethylhexanol, 3,5,5-trimethylhexanol, 2-hexyldecanol, isostearyl alcohol, 2-octyldodeca). Nol, 2-decyl tetradecanol, 2-hexadecyl eicosanol and the like), cholesterol, cholestanol, phytosterol and the like.

The polyhydric alcohol refers to a polyhydric alcohol having two or more alcohols. As the dihydric alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol,
Dipropylene glycol, tripropylene glycol,
Polypropylene glycol, 1,3-propanediol,
1,3-butylene glycol, 1,2-butylene glycol,
Examples thereof include dibutylene glycol, tributylene glycol, polybutylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol and 1,2-hexadecanediol.

Examples of the trihydric alcohol include glycerin, trimethylolethane, trimethylolpropane, 1,2,6-hexanetriol and the like.

Examples of tetrahydric or higher alcohols include polyglycerin such as pentaerythritol, diglycerin, and triglycerin, dipentaerythritol, and polyvinyl alcohol.

The esterification reaction may be a dehydration reaction between tetrahydroabietic acid and an alcohol by heating, or tetrahydroabietic acid may be induced into an acid chloride and reacted with an alcohol. Further, there is also a method in which an alkali salt of tetrahydroabietic acid, for example, in the case of a monohydric alcohol, is converted into an alkyl halide and then reacted. Alternatively, an alkylene oxide such as ethylene oxide or propylene oxide may be reacted. A solvent or catalyst may be used if necessary. Of course, the invention is not limited to the method described above.

The degree of esterification in the case of a polyhydric alcohol of a dihydric alcohol or more may be a full ester or a partial ester. That is, one or two or more hydroxyl groups in the polyhydric alcohol may be esterified.

Representative esters are exemplified below.

2-Hexyldecyl tetrahydroabietic acid, isostearyl tetrahydroabietic acid, ethylene glycol mono- or di-tetrahydroabietic acid, propylene glycol mono- or di-tetrahydroabietic acid, polyethylene glycol mono- or di-tetrahydroabietic acid (average molecular weight 500), mono To tri-tetrahydroabietic acid glycerin, mono to tetra-tetrahydroabietic acid diglycerin, mono to octa-tetrahydroabietic acid hexaglycerin, mono to dodeca-tetrahydroabietic acid decaglycerin, mono to tri-tetrahydroabietic acid trimethylolpropane, mono To tetra-tetrahydroabietic acid pentaerythritol, mono to hexa-tetrahydroabietic acid dipentaethyl ester Suritoru and the like.

Any one kind or two or more kinds of the above-mentioned esters are appropriately selected and mixed in the external preparation for skin of the present invention. The compounding amount is 0.1 to 70% by weight, preferably 1 to 50% by weight, based on the total amount of the external preparation for skin.

Many of these esters have a high melting point, but they are easy to use when dissolved in a liquid substance used in an external preparation for skin. For example, liquid paraffin, glycerin tri-2-ethylhexanoate, olive oil, macadamia nut oil, castor oil, sunflower oil, oleyl oleate, orange luffy oil, glyceryl triisostearate,
Glycerin diisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, neopentyl glycol dicaprate, isostearyl alcohol,
2-octyldodecyl alcohol and the like can be mentioned.

In addition, in the external preparation for skin of the present invention, other than the above ester,
Usually, other components used in the external preparation for skin can be appropriately blended as necessary. For example, liquid paraffin,
Squalane, petrolatum, microcrystalline wax, ozokerite, ceresin, cetyl alcohol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-octyldodecyl alcohol, 2
-Decyltetradecyl alcohol, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, 2-octyldodecyl myristate, 2-octyldodecyl oleate, isopropyl myristate, neopentyl glycol di2-ethylhexanoate, neocaprylate neo Pentyl glycol, neopentyl glycol dicaprate, glyceryl triisooctylate, glyceryl triisostearate, olive oil, macadamia nut oil, avocado oil, sunflower oil, mink oil, lanolin, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid , Various kinds of hydrocarbons such as beeswax, higher alcohols,
Ester, oils and fats, waxes and other oily components, silicones, organic solvents such as acetone, toluene, butyl acetate, ethyl acetate, alkyd resins, resins such as urea resins, camphor, plasticizers such as acetyltributyl citrate, Examples thereof include ultraviolet absorbers, surfactants, humectants, vitamins, fragrances, water, alcohols, thickeners, inorganic powders, organic powders, pigments, thickeners and the like.

The external preparation for skin according to the present invention may be in the form of liquid, emulsion, cream, ointment, powder, cake, pencil, stick or the like.

[Effects of the Invention] The ester of tetrahydroabietic acid and alcohol according to the present invention has no sensitization to the skin, has good stability, is glossy, and when applied to the skin, sticks, has a moisturizing effect, It is suitable for use as a raw material for external preparations for skin such as cosmetics, quasi-drugs, and pharmaceuticals, because it is easy to use for familiar use. In the case of a partial ester, it can be used as a surfactant such as an emulsifier and a solubilizer.

[Examples] Hereinafter, the present invention will be described in more detail with reference to production examples, test examples, and examples.

Production Example-1 Abietic acid 2 kg of Chinese gum rosin (acid value 170, softening point 81 ° C) was dissolved in 2 kg of ethanol, 20 ml of hydrochloric acid was added, and the mixture was reacted under reflux for 1 hour. After standing overnight, the crystals were filtered and recrystallized three times with 1 kg of ethanol, and the obtained crystals were dried under reduced pressure. The obtained abietic acid has an acid value of 184.6 and a melting point of 169.
It was ~ 174 ° C.

Production Example-2 Tetrahydroabietic acid 60 g of abietic acid obtained in Production Example-1 and cyclohexane 1
20 g, 1.5 g of nickel-diatomaceous earth N-103 (nickel 50 to 52%, manufactured by JGC Chemical Co., Ltd.) as a catalyst was charged into an autoclave, and after hydrogen substitution, 100 kg / cm.
^The pressure of hydrogen was increased to ² and the reaction was carried out at 250 ° C. for 4 hours. After completion of the reaction, the reaction mixture was cooled, unreacted hydrogen was removed, the catalyst was removed by filtration, and the mixture was treated with dilute hydrochloric acid. The crude tetrahydroabietic acid thus obtained was concentrated, recrystallized twice in acetone and dried in vacuum. The obtained tetrahydroabietic acid had an acid value of 183 and a melting point of 170 ° C.

Comparative Production Example-1 Glycerin triabietic acid Abietic acid (acid value 184.6, melting point 169 to 174 ° C) 596 g and glycerin 78.1 g were charged into a 4-necked flask equipped with a nitrogen introducing tube, a stirrer, and a water separation tube with a cooling tube. The reaction was carried out at 230 ° C. for 3 hours and then at 260 ° C. for 10 hours to obtain glycerin triabietic acid. The acid value of this product was 5.5 and the softening point was 86 ° C.

Production Example-3 Glycerin tritetrahydroabietic acid This was carried out in substantially the same manner as Comparative Production Example-1 except that 600 g of tetrahydroabietic acid and 78.7 g of glycerin were used. The acid value of the product was 5.9 and the softening point was 92 ° C.

Production Example-4 2-octyldodecyl tetrahydroabietic acid The procedure of Comparative Production Example-1 was repeated except that 593 g of tetrahydroabietic acid and 452 g of 2-octyldodecyl alcohol were used. The acid value of the product was 4.7.

Production Example-5 Tetra (tetrahydroabietic acid) pentaerythritol Tetrahydroabietic acid 604 g, pentaerythritol
The procedure of Comparative Production Example-1 was repeated except that 88 g was used. The acid value of the product was 15.7 and the softening point was 107 ° C.

Production Example-6 Methyl tetrahydroabietic acid Tetrahydroabietic acid (50 g) was dissolved in benzene (150 ml), 38 g of phosphorus pentachloride was added thereto, and the mixture was reacted under a nitrogen stream at room temperature for 1 hour and further under reflux for 2 hours, and then under reduced pressure. Vacuum distillation at 145-180 ℃ / 1mmHg except hydrogen chloride and phosphoryl chloride, and tetrahydroabietoyl chloride 37
got g. Dissolve this in 100 ml of benzene and add 10 parts of pyridine.
g, 4.5 g of methanol was added, and the mixture was reacted at room temperature for 1 hour and further refluxed for 2 hours, washed with water, dried, and 160 to 165 ° C /
It was distilled under reduced pressure at 3.0 mmHg. The product thus obtained was a white solid with an acid value of 1.3 and a melting point of 97-98 ° C.

Production Example-7 Polyethylene glycol monotetrahydroabietic acid 300 g of tetrahydroabietic acid and 1 g of potassium hydroxide were charged into an autoclave equipped with a blowing tube and a stirrer, and reacted at 210 ° C. under pressure from the blowing tube to 600 g of ethylene oxide under pressure. . The product was liquid and had an acid value of 0.4.

Although typical production examples have been described above, according to the present invention, various forms of ester from liquid to solid can be obtained according to need.

Next, the sensitizing property and stability of the ester obtained by the present invention were examined.

Test Example 1 Guinea pig sensitization test Using a healthy Hartley albino guinea pig with a body weight of 380 to 450 g, the Modified Maximization Test (Sato, Y.et
al: A modified technique of guinea pig testing to i
dentify delayed hypersensitivity allergens; Contact
Darmatitis, 7, 225-237, 1981).

First, sensitization treatment was performed as follows. Freund's Complete adjuvant Difco:
(Hereinafter abbreviated as FCA) to the shaved guinea pig neck with 0.1 ml.
Four intradermal injections were made. The stratum corneum at the injection site was injured in a “#” type, and 0.1 ml of the test substance was taken on a lint cloth (a patch for the Torii patch test) and applied to the four sites at the injection site for 72 hours.

Seven days after the intradermal injection, the injection site was shaved, and 0.2 g of white petrolatum containing 10% by weight sodium lauryl sulfate was applied. next day,
0.2 ml of a 10% by weight test substance acetone solution was applied to the injection site and left under occlusion for 48 hours to complete the sensitization treatment. 21 days after the intradermal injection, the induction test was carried out by applying 10 μl of the acetone solution of the test substance of each concentration to the shaved back skin in an open state.

In each test, FCA was used as a control animal during sensitization treatment.
The same provocation test as described above was simultaneously carried out on an animal which had been intradermally injected only with an emulsion obtained by emulsifying the same with water to distinguish the non-specific skin irritation reaction of the test substance.

The sensitization was evaluated according to the following criteria.

++: Strong sensitization.

 +: There is clear sensitization.

 -: No sensitization.

Test Example 2 Stability Test 20 g of the sample was put into a 100 ml screw tube, left at 50 ° C. for 1 month, and then 10 female panels evaluated the odor based on whether or not the odor was changed.

○ There is no odor.

× It has a strange odor.

As described above, the obtained ester was subjected to a sensitizing test and a stability test according to the above-mentioned test method, and as a result, any ester using tetrahydroabietic acid as an acid part had no sensitizing property and was stable. It was confirmed to be good.

The results are shown in the table below.

Examples will be shown below.

Example-1 Lipstick <Manufacturing method> is dissolved by heating at 85 to 95 ° C, and is added to disperse it. Immediately, the mixture was degassed under reduced pressure, transferred to a predetermined container, cooled and solidified to obtain lipstick.

When the glycerin tritetrahydroabietate of Example-1 was blended, it had a good feel when used on the skin and no sensitization was observed. In addition, as a result of a sensory evaluation of the odor of 10 women left at 50 ° C. for 1 month, no odor was found.

On the other hand, when the glycerin triabietic acid of Comparative Example-1 was blended, when it was applied to the skin, the feeling of use was good, but the weak sensitization was recognized. In addition, as a result of sensory odor evaluation by 10 female panelists, the one left at 50 ° C. for 1 month was found to have changed odor.

Example-2 Lipstick <Manufacturing method> is dissolved by heating at 85 to 95 ° C, and is added and dispersed. Immediately, the mixture was degassed under reduced pressure, transferred to a predetermined container, cooled and solidified to obtain lipstick.

When applied to the skin, the lipstick of Example-2 was glossy, had a good feeling in use, and had no sensitizing property. A female panel 10 was left at 50 ° C for 1 month.
As a result of sensory odor evaluation by name, no odor was observed.

On the other hand, the lipstick of Comparative Example-2 had gloss when applied to the skin and had a good feeling in use, but a weak sensitizing property was observed. In addition, as a result of sensory odor evaluation by 10 female panelists after leaving at 50 ° C. for 1 month, a strange odor was observed.

Example-3 Eye Shadow Talc to 100% Mica 10 Mica Titanium Synthetic Pearl 60 Red No. 226 0.1 Blue No. 404 1 Liquid Paraffin 6 Tetra (pentaerythritol tetrahydroabietate (Production Example-5) 2 Sorbitan sesquioleate 1 Preservative A suitable perfume Mix an appropriate amount from <Production method> with a Henschel mixer and
Wiping is done by heating and melting at 80 ℃, and further mixed with a Henschel mixer. Then, the mixture was crushed with an atomizer, sieved, and compression-molded in an inner plate to obtain a pressed eye shadow.

The eye shadow obtained in Example-3 had a strong impact resistance, and when applied to the skin, it had a good feeling in use and no sensitizing property was observed. No odor was observed even after standing at 50 ° C for 1 month.

Example-4 Massage cream Paraffin 4.0% Microcrystalline wax 6.0 Beeswax 6.0 Vaseline 14.0 Liquid paraffin 37.5 Glycerol tritetrahydroabietate (Production Example-3) 5.0 Sorbitan sesquioleate 3.7 Polyoxyethylene (20) sorbitan monooleate 0.8 Perfume 0.5 Preservative, antioxidant Proper amount Soap powder 0.3% Purified water 22.2 <Manufacturing method> Add soap powder to purified water and heat to 70 ℃. Mix other ingredients and heat to melt to 70 ° C. The above-mentioned aqueous phase portion is added to this oil phase portion to carry out preliminary emulsification, then uniformly emulsified with a homomixer and cooled to near room temperature by a heat exchanger.

Example-5 Emulsion Tetrahydroabietic acid 2-octyldodecyl (Production Example-4) 2.0% Mink oil 3.0 Myristyl alcohol 1.5 Dimethylpolysiloxane (20 cps) 1.0 Polyoxyethylene 2-octyldodecyl ether (20 mol) 2.5 Glyceryl monostearate 0.5 Isostearic acid 0.3 Isopalmitic acid 0.2 Behenic acid 0.3 Carboxyvinyl polymer 0.2 Gelatin 0.1 Carrageenan 0.1 Hyaluronic acid 0.1 Tragant gum 0.1 Dextrin 0.1 Caustic potassium 0.08 Dipropylene glycol 3 Polyethylene glycol 4 Purified water 80.92 <Production method> Mix and heat to 70 ℃ Hold and call this Phase A.
Is added to and dissolved with stirring, and is added, and immediately before emulsification is added and dissolved, and the temperature is maintained at 70 ° C., and this is referred to as phase B. Phase A was added to phase B and pre-emulsified, then emulsified with a homomixer and then cooled to 30 ° C. to obtain an emulsion.

Example-6 Oily ointment type foundation Liquid paraffin to 100.0% Isopropyl palmitate 17.0 Tetra (tetrahydroabietic acid) pentaerythritol (Production Example-5) 2.0 Microcrystalline wax 8.0 Ozokerite 9.0 Candelilla wax 0.5 Preservative / antioxidant proper amount Titanium oxide 15.0 Kaolin 15.0 Talc 6.0 Coloring pigment 4.0 Perfume Appropriate amount <Production method> Are mixed with a Hellshell mixer to form Part B. After adding part B to part A and mixing with stirring, was added with mixing with stirring to obtain an oily ointment type foundation.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hideyuki Ichikawa 1-64 Futamatagawa, Asahi-ku, Yokohama-shi, Kanagawa Mine Corp. No. 514 Examiner Masato Ikeda

Claims (1)

[Claims] 1. A skin external preparation containing an ester of tetrahydroabietic acid and an alcohol.