JP2818887B2 - Gelling agent for oils - Google Patents

Description

Description: TECHNICAL FIELD The present invention can form an oily gel which is effective for various uses such as cosmetics by adding and compounding it to a gelling agent for oils, more specifically, silicone oil and other oils. The present invention relates to a new oil agent gelling agent, and a cosmetic or industrial oil agent containing the gelling agent.

Conventional technology and its problems Cosmetics and other external preparations and general industrial oils are often products in the form of gels, and their product gels have moderate gel strength and are stable, In particular, in the case of an external preparation such as cosmetics, it is required that the composition is further excellent in safety and can impart moisturizing property to the skin and the like, a soft feeling of use, and the like. Gelling agents for production have not yet been developed.

Means for Solving the Problems In view of the above situation, the present inventors have provided a gel product having a gelling ability with respect to such a base oil for cosmetics or industrial oil, and capable of providing a gel product satisfying the required performance. The intense research was conducted for the purpose of developing the agent.

As a result, they have found that dihydrolanosterol has the performance as the above-mentioned gelling agent, and have completed the present invention.

That is, the present invention The present invention relates to a gelling agent for an oil agent, comprising a dihydrolanosterol having the following structure as an active ingredient:

The gelling agent of the present invention can be added to cosmetics and other external preparations or industrial oils to make these products into an excellent gel form.

Dihydrolanosterol as an active ingredient of the gelling agent of the present invention is contained in isocholesterol obtained from lanolin alcohol in an amount of about 35% by weight as a mixture with lanosterol. It can be produced by partially reducing (hydrogenating) only the double bond. The production method can follow a conventionally known method. The gelling agent of the present invention may be in the form of high-purity dihydrolanosterol purified by the above-mentioned hydrogenation reaction or the like, or may be in the form of a mixture with lanosterol as it is, and may further contain other suitable additives May be added and mixed. Examples of the additives include liquid paraffin, petrolatum, white spindle oil, machine oil, heavy oil, mineral spirit, dry solvent, fog solvent, mineral oil such as kerosene, hexane, n-heptane, n-octane, isooctane, n
-Hydrocarbons such as pentane, n-nonane, n-decane, benzene, cyclohexane, animal and vegetable oils such as soybean oil, taro oil, castor oil, squalene, lanolin, liquid lanolin, olive oil, cetanol, oleyl alcohol,
Lanolin alcohol, squalane, oleic acid, palmitic acid, stearic acid, Nuka oil fatty acid methyl ester, lanolin fatty acid isopropyl alcohol ester,
Fatty oil derivatives such as octyldodecanol lanolin fatty acid ester and isopropyl myristate, sterols such as cholesterol, lanosterol and plant sterols and derivatives thereof can be exemplified. However, the content of the above-mentioned active ingredient in the gelling agent of the present invention is suitably at least 20% by weight. In some cases, the conversion cannot be sufficiently performed, which is not preferable. Incidentally, when using a mixture of the above dihydrolanosterol and lanosterol as the gelling agent of the present invention, the present inventors have found that the coexisting lanosterol promotes the excellent gelling ability unique to dihydrolanosterol as an active ingredient. Has been confirmed.

According to the study of the present inventors, the above-mentioned dihydrolanosterol as an active ingredient of the gelling agent of the present invention is responsible for the keratolytic action of the epidermal stratum corneum on the skin surface, similar to squalene present in sebum of the human body. Is considered to play a role in preventing skin keratinization and in maintaining the balance between the growth of skin from the dermis and the shedding of waste products from the stratum corneum and smoothly performing skin metabolism. Suitable for blending into etc.
Further, dihydrolanosterol as an active ingredient of the gelling agent of the present invention is excellent in oxidative stability, has no danger of skin irritation and the like, and is suitable for blending into the above-mentioned oil agent from the viewpoint of the above.

The oil agent gelled by the incorporation of the gelling agent of the present invention may be any of various cosmetic agents and other external preparations, industrial oil agents and various base oils conventionally known, and these are roughly classified into silicones. It is classified into synthetic oils including oils and general oils such as animal and vegetable oils and fats and their derivatives or mineral oils. More specifically, examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, silicone polyether copolymer oil, methyl hydrogen silicone oil, amino-modified silicone oil, and the like.
Oils may be used alone or as a mixture of two or more.

Examples of the oil agent other than the silicone oil include cosmetics, for example, liquid paraffin, mineral oil such as petrolatum, squalene, lanolin, liquid lanolin, animal and vegetable oils such as olive oil, cetanol, oleyl alcohol, lanolin alcohol, squalane, olein Fatty oil derivatives such as acid, palmitic acid, stearic acid, octyldodecanol lanolin fatty acid ester and myristic acid isopropyl ester, sterols such as cholesterol, lanosterol, and plant sterols and derivatives thereof can be exemplified. In the case of industrial oils, for example, liquid paraffin, white spindle oil, machine oil, heavy oil, mineral spirit, dry solvent, fog solvent, kerosene, insecticide solvent (Nippon Oil Co., Ltd.), No. 0 solvent (Nippon Oil Co., Ltd.), Mineral oil such as solvent naphtha, hexane,
hydrocarbons such as n-heptane, n-octane, isooctane, n-pentane, n-nonane, n-decane, benzene and cyclohexane; ketones and alcohols such as xylol, n-butanol, methyl ethyl ketone and methyl isobutyl ketone; Examples include animal and vegetable oils and fats such as soybean oil, tara oil and castor oil, and oil and fat derivatives such as stearic acid, oleic acid, nuka oil fatty acid methyl ester, and lanolin fatty acid isopropyl alcohol ester. One of these may be used alone as an oil agent to which the gelling agent of the present invention is applied, or two or more thereof may be used in combination as the same oil agent. It may be an oil agent to be converted.

The mixing ratio of the gelling agent of the present invention to the above various oils or their base oils can be appropriately determined according to the kind of the oiling agent, the active ingredient content of the gelling agent used, the required performance of the obtained gel, and the like, and is particularly limited. The amount of the active ingredient of the gelling agent is about 0.5 to 20% by weight based on the weight of the base oil
The gelling agent in this range can sufficiently gel the system.

Thus, a desired gel product effective for various uses can be easily produced by blending the gelling agent of the present invention.

The gelling agent of the present invention can also be used in the case where a crystalline substance is added to and blended with the oil agent in addition to the fact that the oil agent can be gelled by being blended with the oil agent as described above. It also has an action of preventing crystal precipitation that can prevent precipitation or maintain the size at a level at which there is no practical problem to obtain a desired gel in a uniform dispersion state. Examples of such crystalline substances include various substances which are generally known to be added to cosmetics and the like, for example, fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and lanolin fatty acid. Kind,
Examples thereof include aliphatic alcohols such as myristyl alcohol, cetyl alcohol, and stearyl alcohol. These are used in an amount of not more than 25% by weight of the total composition, generally about 0.
Suitably, it is about 1 to 25% by weight. Therefore, according to the use of the gelling agent of the present invention, it is possible to obtain a gel product which is very suitable for applications requiring the use of the crystalline substance in a relatively large amount.

Specific examples of gel products containing the gelling agent of the present invention include cosmetics and other external preparations such as gel lipstick,
Gel ointments and the like, as industrial oils, for example, floor wax,
Car wax, paint, printing ink and the like can be exemplified, and the present invention also provides such a gel product.

These gel products can be prepared basically in the same manner as conventional products of this type except that the gelling agent of the present invention is used. For example, a gel lipstick as a cosmetic is prepared by adding an appropriate amount of a bromo acid, a pigment, a fragrance, etc., together with the gelling agent of the present invention to an oily base material such as carnauba wax, beeswax, lanolin, cetyl alcohol, castor oil, etc. You. In particular, the lipstick obtained by using the gelling agent of the present invention is a softer and longer product. Gel ointment is
For example, bleached beeswax, paraffin, cetostearyl alcohol, and a liquid ointment base are prepared by adding the gelling agent of the present invention to an ointment base, and the resulting product has a transparent to translucent gel property, spreadability, and softness. The feeling is excellent. As base materials for various cosmetics, in addition to the components exemplified above, mineral oils such as petrolatum, squalane, lanolin, liquid lanolin, olive oil, castor oil, animal and vegetable oils such as lecithin, cetanol, oleyl alcohol, lanolin alcohol, squalane Alcohols or acids such as oleic acid, palmitic acid and stearic acid; esters such as octyldodecanol lanolin fatty acid ester and isopropyl myristate; sterols such as cholesterol, lanosterol and plant sterol.

For example, floor wax (liquid wax) as an industrial oil gel can be prepared by adding an appropriate amount of the gelling agent of the present invention to carnauba wax, paraffin, barium suarate, mineral spirit, mineral terpinene, etc., and thus is flexible. The result is a floor wax product with good elasticity and elongation. Ingredients that can be blended in such wax products include, in addition to the above, for example, montan wax, squalane, lanolin, liquid lanolin, olive oil, castor oil,
Animal or vegetable oils such as lecithin, cetanol, oleyl alcohol, lanolin alcohol, squalane, oleic acid, palmitic acid, alcohols or acids such as stearic acid, octyldodecanol lanolin fatty acid esters, esters such as isopropyl myristate, cholesterol, lanosterol, Sterols such as plant sterols can be exemplified. Further, the base agent for printing ink using the gelling agent of the present invention is, for example, after mixing components such as alkyd resin, xylene resin, ester rubber, cumarone, solvent naphtha, methyl isobutyl ketone, xylol, Is blended into a base agent, and then an ink agent containing a pigment is mixed and kneaded with a roll mill or the like, so that pigment dispersibility is excellent.
An ink product having good elongation and improved printing performance can be obtained.

The gel products thus obtained can exhibit various advantages as described below, based on the composition of the gel of the present invention. That is, in the cosmetics field, the system is oily transparent hairdressing agent,
An easy-to-handle product with fashionability, such as an oily transparent protective cream or a transparent lipstick, can be obtained. In addition, the gelling agent of the present invention itself has safety, which is a basic function of cosmetics, and functions as a humectant for the skin, and thus is particularly suitable for application in the cosmetics field. In addition, many oil-based oils are incompatible with each other, and in such mixed systems, separation often occurs in the system, which often causes product troubles, and particularly, those in which the above-mentioned poor compatibility is likely to occur. The gelling agent of the present invention can be effectively used as a gelling agent in a system in which such poor compatibility is likely to occur. Furthermore, there are many crystalline substances as well as compatibility in the compounding composition, and in cosmetics and the like, crystals are precipitated in the system, and when used, a trouble that feels like a foreign substance occurs, but the gelation of the present invention. In such a case, the agent has a function of gelling the whole or a part of the system, and at the same time, preventing the precipitation of crystals or keeping the size of the system to such an extent that does not hinder practical use. As described above, the gelling agent of the present invention has an advantage that its use range is very wide not only in the cosmetic field but also in the industrial field. The compounding range of the gelling agent of the present invention varies depending on the target system, and can be arbitrarily determined.
Generally, it is preferable to select from the range of about 0.5 to 20% by weight.

Examples Hereinafter, the present invention will be described in more detail with reference to preparation examples of the gelling agent of the present invention, production test examples of the gelling agent, and preparation examples of gel products using the same, as preparation examples. In addition,% in each example shows weight%.

Production Preparation Example 1 A commercially available isocholesterol product (manufactured by Yoshikawa Oil Co., Ltd., dihydrolanosterol content: about 35%) is used as it is. This will be referred to as "the present gelling agent 1".

Production Preparation Example 2 50 g of isocholesterol described in Production Preparation Example 1 above
Was dissolved in 500 ml of butanol, and charged with 0.5 g of a palladium catalyst (manufactured by Kawaken Fine Chemicals Co., Ltd.) in a 5 l autoclave at normal temperature under an initial pressure of 10 atm with hydrogen gas.
The reduction reaction was carried out at 30 ° C. and 30 atm for 20 hours. After completion of the reaction, the catalyst is separated and purified by recrystallization, etc.
Dihydrolanosterol having a purity of 95% or more was obtained in the yield of This is referred to as “the gelling agent of the present invention 2”.

Test Example 1 A predetermined amount (% by weight) of the gelling agent 2 of the present invention obtained in Production Example 2 was added to 10 g of each of various cosmetic oils and industrial oils shown in Tables 1 to 3 below. After heating and dissolving at ℃, it was allowed to cool to room temperature to gel.

The state of the mixture was observed over time from the start of cooling, and the gelling ability was evaluated based on the following criteria.

<Gelling ability evaluation criteria> S: The whole gelled within 30 minutes A: The whole gelled in 30 minutes to 1 hour B: The whole gelled in 1 to 5 hours C: The whole in 5 hours or more Is gelled. D: 50% or more gels in 5 hours or more. E: Only less than 50% gels in 5 hours or more. However, as liquid paraffin a, "Smoyl P-60" manufactured by Matsumura Sekiyu KK (specific gravity (15/4 ° C): 0.835 / 0.845, flash point (C.
OC): 145 ° C or higher, viscosity (37.8 ° C): 8.86 / 11.7 cSt, pour point: -10 ° C or lower. As liquid paraffin b, "Smoyl P-80" (specific gravity (15/4 ° C): 0.8
40 / 0.850, flash point (COC): 160 ° C or higher, viscosity (37.8
C): 14.4 / 16.9 cSt, pour point: -10C or less.
As liquid paraffin c, "Smoyl P-10" manufactured by Dojo
0 "(specific gravity (15/4 ° C): 0.850 / 0.860, flash point (COC):
170 ° C or higher, viscosity (37.8 ° C): 19.4 / 21.6cSt, pour point:-
10 ° C or less). As liquid paraffin d, "Smoyl P-200" (specific gravity (15/4 ° C): 0.875 / 0.88)
5. Flash point (COC): 190 ° C or higher, viscosity (37.8 ° C): 41.9
/44.1 cSt, pour point: -15 ° C or lower). As turbine oil, "Turbine Oil 68" manufactured by Nippon Oil Co., Ltd. (petroleum hydrocarbon 100%, pale yellow, flash point (COC): 200 ° C or higher, density: 0.86 to 0.89 g / cm ³ , pour point: -12.5 Below 4 ° C, Class 4 Petroleum / III) was used. The term "insolubles" in the table means that the amount of the gelling agent added is too large beyond its saturation solubility.

In addition, as O-solvent, Nippon Oil Co., Ltd. O-solvent L (specific gravity (15/4 ° C): 0.745, aniline point: 80.4)
° C, fractionation properties Initial distillation: 182 ° C, 50%: 194 ° C and end point: 212
° C, flash point: 65 ° C (Penschmartens type), aromatic content: 0.0% by volume). Heavy oil (Special A) is JIS K2
It corresponds to Type 1 No. 1 (Heavy Fuel Oil A) specified in 205, and is “Stan Fuel A-01” manufactured by Esso Oil Co., Ltd. (density (15 ° C.): 0.8479, flash point: 68 ° C., pour point: − 25 ° C., sulfur content: 0.06% by weight).

Naphtha No. 3 in the above table refers to an aliphatic solvent manufactured by Exxon (Exxon Naphtha No. 3, aniline point: 58 ° C.,
Distillation range Initial boiling point: 85 ° C, 50%: 95 ° C, 95%: 118 ° C, dry point: 124 ° C, average molecular weight: 99, specific gravity (15/4 ° C): 0.72, aromatic content: 6% by volume No. 5 is an aliphatic solvent manufactured by the company (Exxon Naphtha No. 5, aniline point: 55 ° C, flash point (TCC): 42 ° C, distillation range Initial boiling point: 152 ° C, 50% : 16
7 ° C, 95%: 190 ° C, dry point: 197 ° C, average molecular weight: 143, specific gravity (15/4 ° C): 0.78, aromatic content: 16% by volume).

The gasoline used was Esso Sekiyu's automotive gasoline (regular, product name: Esso Gasoline). Typical properties are: density (15 ° C): 0.7236 g / cm ³ , octane number (research method): 90, vapor pressure (37.8 ° C, KPA) 7
0.5, oxidation stability: 690 minutes, benzene: 0.8% by volume, methanol: 0.5 (-)% by volume, kerosene: 1.0 (-)% by volume,
MTBE: 0.5 (-)% by volume.

As the insecticide solvent, A solvent and K solvent, those manufactured by Nippon Oil Co., Ltd. (petroleum solvents) were used, respectively. The properties of each are as follows.

Insecticide solvent (specific gravity (15/4 ° C): 0.796, aniline point: 72.0 ° C, fractionation properties Initial distillation: 199 ° C, 50%: 218 ° C and end point: 249 ° C, flash point: 80 ° C (Penschaltense type) ,
Aromatic content: 7.0% by volume) A solvent (specific gravity (15/4 ° C): 0.790, aniline point: 4
4.5 ° C, Kauributanol value: 42.5, fractional distillation properties Initial distillation: 154
° C, 50%: 165 ° C and end point: 195 ° C, flash point: 41 ° C (tag closed type), aromatic content: 28.0% by volume) K solvent (specific gravity (15/4 ° C): 0.800, aniline point: 3
7.3 ° C, Kauributanol value: 46.3, Fractionation properties Initial distillation: 152
° C, 50%: 163 ° C and end point: 193 ° C, flash point: 41 ° C (tag closed type), aromatic content: 34.1% by volume) Test Example 2 Dimethyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd.)
KF96 • 100CS) and the oils were prepared according to Production Examples 1 and 2 of the present invention.
1% and 3% of the gelling agents 1 and 2 of the present invention obtained in
The mixture was added, mixed and dissolved at the following ratio, and the mixture was gelled in the same manner as in Test Example 1.

For comparison, a comparative test was carried out using the same amount of dextrin palmitic acid ester (comparative gelling agent) as a gelling agent.

In each of the above tests, the observation results of the dissolution state of the gelling agent and the gelling ability (gelation time) by cooling at room temperature, and
Table 4 shows the results obtained by measuring the state and consistency after the time using a 1/4 scale consistency meter manufactured by Tokyo Keiki Seisakusho in accordance with "Consistency Test Method" of JIS-K2220.

Test Example 3 The same test as Test Example 2 was repeated using methylphenyl silicone (KF56, manufactured by Shin-Etsu Chemical Co., Ltd.) as the target oil agent.

 The results are shown in Table 5 below.

Formulation Example 1 Preparation of cosmetic cream (A) Oil phase Squalane 20% Liquid paraffin ^{* 1} 30% Vaseline 10% Cetanol 1% Sorbitan sesquiolate 3% Gelling agent of the present invention 2 3% (B) Water phase Water 33% Preservative Appropriate amount As liquid paraffin ^{* 1} , "Smoyl P-70" manufactured by Matsumura Sekiyu KK was used.

The oil phase (A) and the water phase (B) are each heated to 70 to 75 ° C. to make them homogeneous, and the water phase (B) is gradually added to the oil phase (A) while stirring, and then homomixed. The emulsion was uniformly emulsified and cooled to room temperature to obtain a good cosmetic cream having an appropriate thixotropy.

Formulation Example 2 Preparation of cosmetic cream (A) Oil phase Squalane 20% Liquid paraffin ^{* 1} 30% Vaseline 10% Cetanol 1% Sorbitan sesquiolate 3% Dimethyl silicone ^{* 2} 10% Gelling agent of the present invention 2 3% (B) Water Phase water 23% Preservative appropriate amount In addition, "Smoyl P-70" manufactured by Matsumura Sekiyu KK was used as liquid paraffin ^{* 1} , and "KF96-100CS" manufactured by Shin-Etsu Chemical Co., Ltd. was used as dimethyl silicone ^{* 2} .

Using the oil phase (A) and the aqueous phase (B), a cosmetic cream having excellent dispersion stability of dimethyl silicone and having a smooth and comfortable feeling was obtained in the same manner as in Preparation Example 1.

The cosmetics of the present invention obtained in Formulation Examples 1 and 2 and Comparative Creams 1 and 2 prepared in the same manner without blending the gelling agent of the present invention in each example for comparison (however, only the amount of the gelling agent of the present invention is added) The amount of liquid paraffin was increased), each of them was left in a constant temperature bath at 40 ° C. for a predetermined time, and a stability test was performed to observe whether or not the oil layer had separated.

 The results are shown in Table 6 below.

From the above table, it can be seen that the cosmetic cream of the present invention is excellent in stability.

Formulation Example 3 Preparation of floor wax The following components were mixed, heated to 75 to 80 ° C, uniformly dissolved, and then cooled to room temperature to obtain a cloudy liquid floor wax. Ingredient Amount (%) Carnauba wax 3.7 Paraffin 3.8 Mineral spirits 69.5 Mineral terpinene 10.0 dimethylsilicone 10.0 present invention gelling agents 2 5.0 this compound, when construction to the floor, there is gloss, liquid elongation of the crystal has a poor The grains were inconspicuous and smooth.

On the other hand, the comparative floor wax without the gelling agent of the present invention (however, the amount of mineral spirit was increased by that amount) had a glossy floor, no liquid elongation, and conspicuous crystal grains. there were.

Formulation Example 4 Preparation of gel lipstick The following components were mixed, and 1 to 5% of bromoacid, 5 to 10% of pigment, and an appropriate amount of fragrance were added to the mixture to prepare a gel lipstick. Ingredient Amount (%) Carnauba wax 8 beeswax 10 Lanolin 4 Cetyl alcohol 5 Castor oil 65 present invention gelling agent 2 8 thereof was intended quality excellent with growth in soft.

Formulation Example 5 Preparation of gel ointment The following components were blended to prepare a gel ointment. Ingredient Amount (%) bleached beeswax 5 Liquid paraffin 90 present invention gelling agent 2 5 thereof was intended quality excellent with growth in soft.

Formulation Example 6 Preparation of Liquid Wax A liquid wax product having flexibility, good elongation and gloss was obtained by mixing the following components. Ingredient composition (%) Carnauba wax 3.7 Paraffin 3.8 Mineral spirit 77.5 Mineral terpinene 10.0 Gelling agent of the present invention 2 5.0 Formulation example 7 Preparation of base for printing ink Preparation of base for printing ink did. Ingredient Amount (%) Alkyd resin 10 xylene resin 5 Esztergom 5 coumarone 2 solvent naphtha 40 methyl isobutyl ketone 20 xylol 15 present invention gelling agent 2 5 This material is kneaded in a roll mill and subsequently mixing the pigment ink agent This makes it possible to obtain a printing ink having good pigment dispersibility, good elongation, and improved printing performance.

────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Shiro Yoshikawa 10-3 Kitakawabori-cho, Tennoji-ku, Osaka-shi, Osaka Inside Yoshikawa Refinery Co., Ltd. (58) Field surveyed (Int.Cl. ⁶ , DB name) C09K 3 / 00 A61K 7/00 C08K 5/05 C08L 83/06 C11B 5/00 CA (STN)

Claims (5)

(57) [Claims] [1] The following equation A gelling agent for oils, comprising dihydrolanosterol having the following structure as an active ingredient: 2. The gelling agent according to claim 1, wherein the oil agent is a silicone oil. 3. The gelling agent according to claim 2, wherein the oil agent is selected from animal and vegetable oils, sterols, fats and oils derivatives, mineral oils and hydrocarbons. 4. A cosmetic comprising the gelling agent according to claim 4. 5. An industrial oil containing the gelling agent according to claim 5.