JPS5931485B2 - Synthetic oil composition for cosmetics - Google Patents

Description

Detailed Description of the Invention The present invention is a low molecular weight polymer obtained by polymerizing isoprene with a catalyst mainly consisting of an organometallic compound and a nickel compound, and is a chain polymer having a number average molecular weight of 150 to 3000. This is a cosmetic composition containing synthetic oil obtained by hydrogenation.

There are many types of synthetic oils that have traditionally been used in cosmetics, including liquid paraffin, glycerin, and polyethylene glycol, but squalene, which is obtained by refining shark oil obtained from sharks, has been found to be useful for human skin. Because squalene has better permeability and absorption than synthetic products, and because squalene is obtained from sharks, it is known to be not only harmless to the human body but also a beneficial compound.

It is known that this compound has an isoprene skeleton, is formed into a hexamer by polymerizing isoprene in the 1-4 type, and the double bond is also an all-trans structure. However, it has become clear that oils like squalene, which have many residual double bonds, can become rancid, meaning they can be severely oxidized by air, producing a foul odor or turning into substances harmful to the human body. Therefore, it has become clear that squalane, which is made by hydrogenating squalene and has completely zero unsaturation, has excellent weather resistance, permeability into the skin, and non-toxicity. However, since squalene is extracted from sharks, as the amount of shark fish caught has decreased, it has inevitably become a valuable and expensive item. In Japan, the amount of fish caught is limited, and attempts have been made to synthesize synthetic oil to replace it. Among these, Japanese Patent Publication 1973
-35984, Published Patent Publication 1986-85243, Published Patent Publication 1974-117413, Published Patent Publication 1977-
-133302, etc., a new synthesis method is described.
However, it has become clear that these methods have the following drawbacks. The method of patent publication No. 49-35984 is as follows:
In order to heat-polymerize isoprene with a solid acid catalyst, isoprene is not subjected to 1.4-type polymerization, but instead undergoes cyclization polymerization or 3-type polymerization.
In order to make a type 4 bond or a type 1/2 bond,
Because it has a structure in which isopropenyl groups, vinyl groups, and 6-membered ring groups are bonded to the side chain, it is much more powerful than oil obtained by hydrogenating natural linear terpenes (squalene) at the same molecular weight. It became clear that skin permeability to the human body was insufficient due to the increased viscosity and different molecular structure. Also, published patent publication 1985-85
243 is a method in which synthetic oil is produced by further hydrogenating a low polymer obtained by polymerizing isobutylene, butadiene, butene-1, etc.; Therefore, even though its molecular weight is small, its viscosity is high, its fluidity is not as good as that of squalane, and its molecular structure and three-dimensional structure are different, so its permeability into human skin is insufficient. Ta. Furthermore, published patent publications 11743/1982 and 133302/1987 disclose a method for synthesizing squalane by coupling geranyl acetone and hexahydropseudoid ionone, further dehydration reaction, and further hydrogenation. is listed.

However, although this method exhibits flow characteristics similar to squalane obtained by hydrogenating squalene obtained from natural products, the starting materials geranylacetone and hexahydropsoidionone are themselves expensive. , these must be further dimerized and coupled, then subjected to dehydration reaction, and then hydrogenated, so there are many steps, and the yield in each step is less than 90%, resulting in a high price. It was hot. However, according to the method of the present invention, in order to homopolymerize isoprene and perform 1.4-type polymerization, it has a structure very similar to squalene, which is further hydrogenated, and then fractionated by vacuum distillation to produce squalane. Compounds with almost the same structure as can be synthesized. Therefore, the viscosity characteristics, skin permeability, non-toxicity, and non-irritating properties are also the same. As a method for obtaining a low polymer of isoprene used in the present invention with a number average molecular weight of 150 to 3000, for example, published patent publication No. 49-11151
There are 89 methods.

In this method, isoprene is polymerized in the presence of an .alpha.-olefin using an organometallic compound and a nickel compound catalyst, or a catalyst prepared by adding an electron donating compound to the above catalyst system. The molecular weight can be easily controlled by adjusting the amount of d-olefin, organometallic compound, nickel compound, and electron donating compound. Next, the polymer thus obtained is prepared by deactivating the polymerization catalyst with methanol, ethanol, propanol, n-amyl alcohol, water, etc., and removing the catalyst with an acidic aqueous solution such as hydrochloric acid, sulfuric acid, or nitric acid, or with formic acid, acetic acid, or the like. Remove by mixing with an aqueous solution of an organic acid such as oxalic acid. Further, the polymer is neutralized with an alkaline aqueous solution, washed with water, and the solution used for polymerization is removed under reduced pressure to obtain a liquid polymer.

To hydrogenate the liquid polymer obtained in this way, alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, and aliphatic hydrocarbon solvents such as heptane, hexane, pentane, and cyclohexane are usually used. It can be carried out by dissolving it in a solvent or a mixed solvent, or without a solvent.

Catalysts for hydrogenation include Raney nickel,
A nickel catalyst such as nickel on soil or nickel on lacquer, or a commonly used catalyst such as palladium or platinum. After the reaction, the catalyst and solvent are removed from the reaction solution using a conventional method.Then, the hydrogenated liquid polymer is distilled under reduced pressure using the molecular distillation method. A distillate, a middle distillate with an appropriate viscosity, and a residual fraction with a high viscosity can be obtained, and these can be used as emulsions, creams, etc. depending on each fraction.
Used in cosmetics such as ticks and pomades. The aforementioned Japanese Patent Publication No. 49-35984 and Japanese Patent Application Laid-Open No. 49-852
Using the liquid polymer obtained by the method described in Publication No. 43 as a synthetic saturated oil by hydrogenating it as a raw material, a cold cream was prepared according to the formulation described in Example 1 below, and the product of the present invention and the product of the present invention were prepared. In comparison, the so-called sensory characteristics such as the cream's spreadability, texture, and texture are inferior. Also, JP-A-49-117413 and JP-A-49-1333
Since the synthetic oil obtained in Publication No. 02 has a structure similar to that of aqualane obtained by hydrogenating natural squalene, its cream formulation also exhibits the same performance as a cream containing natural squalane. As shown in Example 1 below, this is equivalent to the performance of the product of the present invention. The significance of the present invention is to provide a compound that uses synthetic oil obtained through simple and inexpensive raw materials and processes and has the same performance as the synthetic oil obtained through complex and expensive raw materials and processes as described above. It's because I was able to do it. Next, specific examples of the present invention will be shown, but the present invention is not limited to the following specific examples. Example 1 1.5. equipped with a stirring bar. A stainless steel autoclave (withstand pressure 20k9/0d) was purged with nitrogen, and 300ml of anhydrous toluene was added with 11 dehydrated and distilled anhydrous isoprene 1367 under a nitrogen stream, cooled to -5°C, and heated to 0.
．． 1m01/l toluene solution of nickel naphthenate 4
4 ml of a toluene solution of ethylaluminum sesquichloride (m111 m01/l), 4 ml of a toluene solution of triphenylphosphine (0.02 m01/l), and 4 ml of propylene 647 are added and polymerized at 60'C for 6 hours.

To terminate the polymerization, use a toluene solution of isopropyl alcohol (1
Add 10ml of 0% solution) under pressure and stir for 10 minutes.
After that, unreacted propylene and butadiene are purged in the fume hood. Next, PHL. 800 ml of hydrochloric acid aqueous solution of PH-12 and the above polymerization solution were washed in a glass flask of No. 21 for 5 hours, and after standing still, the aqueous layer was separated, and 800 ml of caustic soda aqueous solution of PH-12 and the oil layer were mixed for 1 hour, and left standing. After separating the aqueous layer, the oil layer was optically mixed with 800 ml of ion-exchanged water for 1 hour, and then left to stand to separate the aqueous layer. The oil layer is concentrated under reduced pressure using a rotary evaporator. In this way, a colorless and transparent low viscosity liquid 103y was obtained.

The viscosity was 24 centipoise at 30°C. When the molecular weight was measured using a vapor pressure permeability meter, the number average molecular weight was 410. This liquid polyisoprene was hydrogenated as follows.

An activated product of Raney Nickel R-200 manufactured by Nikko Rikagaku Sangyo Co., Ltd. is degassed, dehydrated, stored in nitrogen, and placed in a Schlenk tube.

Of these, 20 ml of Raney Nickel R-20057, 75 ml of the above liquid polyisoprene, and 75 ml of cyclohexane were added.
Add it to a 0ml stainless steel autoclave and introduce hydrogen from a hydrogen cylinder to 25kg/C7? Add until gauge pressure of L is reached. Mix by heating to 150°C using an oil bath. Pressure 25k9/? hold at 15
Mixing was continued at 0'C for 30 hours to complete hydrogenation and after cooling, the mixture was brought to normal pressure and the catalyst was removed using a centrifugal separator to obtain a colorless and transparent liquid. To remove the solvent, the mixture was concentrated under reduced pressure using a rotary evaporator to obtain 74 ml of a colorless and transparent liquid. The viscosity was 35 centipoise at 30°C. The liquid polyisoprene hydrogenated in this manner showed almost the same chart as squalane in both the Nosaka infrared spectrum. When compared with Raccoon Chart, the signal area of the proton of the methyl group of squalane/the area of the signal of the total proton - 0.39, but the proton of the methyl group of the hydrogenated liquid polyisoprene by the method of the present invention/total proton = 0.40, and it became clear that since the liquid polyisoprene obtained by the method of the present invention is of the 1,4-bond type, the hydrogenated material also has almost the same structure as squalane. Furthermore, this hydrogenated product was fractionally distilled using a molecular distillation apparatus.

When 107 samples were fractionated, 12
The first fraction with a boiling point below 0°C is 3.57 and 1 mmH
0.2m77 from 140℃ at a vacuum degree of g! Hgl25O
The second fraction of boiling point in °C is 3.27 and the remainder is 3.37
It was hot.

The physical properties of the second fraction are shown in Table 1 in comparison with squalane.

A cold cream was prepared by blending the hydrogenated polyisoprene used in the present invention shown in Table 1 as follows.

Of this composition, it exhibited the same color, odor, long-term stability, non-irritability, spreadability, stiffness, and texture as the one in which the polyisoprene hydrogenated product of the present invention was replaced with squalane.

Example 2 A lipstick was prepared as a prototype by blending the same hydrogenated polyisoprene of the present invention as in Example 1.

Of this formulation, a lipstick with a gloss and good spreadability was obtained, which was equivalent to the lipstick of the present invention in which the hydrogenated polyisoprene was replaced with squalane.

Example 3 The hydrogenated polyisoprene obtained in Example 1 was blended as follows to prepare a Hygiene cream.

This formulation had the same spreadability and smoothness as when the hydrogenated polyisoprene was replaced with squalane.

Claims (1)

[Claims] 1 A low molecular weight polymer obtained by polymerizing isoprene with a catalyst consisting of a nickel compound, an organoaluminium compound, and an electron donating compound, using an α-olefin as a molecular weight regulator, and having a number average molecular weight of 150 to 3000.
A cosmetic composition containing fully saturated synthetic oil obtained by hydrogenating chain polymers.