JP7558671B2 - Oil Gelling Agent - Google Patents

Description

The present invention relates to an oil gelling agent.

An oily solid obtained by gelling (solidifying) a liquid oil (oil) at room temperature using a solid oil (wax) is called an oil wax gel, and is used in the fields of cosmetics, quasi-drugs, household goods, etc. Oil wax gel is a hard solid, not a jelly, and has the property that when the surface is rubbed, only that part crumbles and becomes liquid, so it is widely used especially as a cosmetic base for lipstick, foundation, etc. (Patent Documents 1 to 4).

Meanwhile, the need for natural and organic cosmetics is growing against the backdrop of growing awareness of environmental issues and an increase in consumers seeking cosmetics that are less irritating to the skin. In recent years, the International Organization for Standardization (ISO) has issued "ISO 16128 Guidelines for technical definitions and criteria for natural and organic cosmetic ingredients" as an international standard for natural and organic cosmetics. In order to strongly appeal to consumers that a product is a natural cosmetic, it is necessary to increase the content of natural and naturally derived ingredients in the product.

However, the wax used to prepare oil wax gel is mainly polyethylene wax, which is a non-natural ingredient. Therefore, if a new oil gelling agent using natural ingredients could be provided instead of polyethylene wax, it could be used as a key material to create and expand the market for natural cosmetics based on oil wax gel.

JP 2015-193607 A JP 2015-174844 A JP 2010-265230 A Japanese Patent Application Publication No. 6-263618

The objective of the present invention is to provide a novel oil gelling agent that uses natural raw materials.

As a result of extensive research into the above-mentioned problems, the inventors discovered that the above-mentioned problems could be solved by using a specific type of wax in combination, and based on this knowledge, they developed the present invention.

That is, the present invention comprises the following [1] to [3].
[1] An oil gelling agent comprising the following components (A) and (B) as active ingredients:
(A) An aliphatic ester represented by the following general formula (1): R ¹ -COO-R ² (1)
[In the formula, ^R1 represents a linear alkyl group having 17 to 29 carbon atoms, and ^R2 represents a linear alkyl group having 20 to 30 carbon atoms.]
(B) Snow wax [2] The oil gelling agent described in [1] above, in which the amount of component (A) is 50 to 98 mass% and the amount of component (B) is 2 to 50 mass%, relative to 100 mass% of the total amount of components (A) and (B).
[3] An oil wax gel comprising an oil agent that is liquid at 25°C and the oil gelling agent according to either [1] or [2] above.

The oil gelling agent of the present invention utilizes snow wax, a natural raw material, as an active ingredient.
By using the oil gelling agent of the present invention, an oil wax gel with high hardness can be obtained.

The component (A) used in the present invention is an aliphatic ester represented by the following general formula (1).
R ¹ -COO-R ² (1)
[In the formula, ^R1 represents a linear alkyl group having 17 to 29 carbon atoms, and ^R2 represents a linear alkyl group having 20 to 30 carbon atoms.]

The number of carbon atoms in ^R1 in general formula (1) is preferably 17 or more and 27 or less. The number of carbon atoms in ^R2 in general formula (1) is preferably 20 or more and 26 or less, more preferably 22 or more and 24 or less.

Specific examples of component (A) include arachidyl stearate (an aliphatic ester of general formula (1) in which R ¹ has 17 carbon atoms and R ² has 20 carbon atoms. Hereinafter, this will be referred to as "C17-C20"). behenyl stearate (C17-C22), lignoceryl stearate (C17-C24), cellotyl stearate (C17-C26), montanyl stearate (C17-C28), melissyl stearate (C17-C30), arachidyl arachidate (C19-C20), behenyl arachidate (C19-C22), lignoceryl arachidate (C19-C24), cellotyl arachidate (C19-C26), montanyl arachidate (C19-C28), Melissyl arachidate (C19-C30), Arachidyl behenate (C21-C20), Behenyl behenate (C21-C22), Lignoceryl behenate (C21-C24), Cerotyl behenate (C21-C26), Montanyl behenate (C21-C28), Melissyl behenate (C21-C30), Arachidyl lignocerate (C23-C20), Behenyl lignocerate (C23-C22), Lignoceryl lignocerate (C23-C24), Lignoceryl Cerotyl cerotenate (C23-C26), Montanyl lignocerate (C23-C28), Melissyl lignocerate (C23-C30), Arachidyl cerotenate (C25-C20), Behenyl cerotenate (C25-C22), Lignoceryl cerotenate (C25-C24), Cerotyl cerotenate (C25-C26), Montanyl cerotenate (C25-C28), Melissyl cerotenate (C25-C30), Arachidyl montanate (C27-C20), Behenyl montanate (C2 Examples of the aliphatic esters include lignoceryl montanate (C27-C24), cerotoyl montanate (C27-C26), montanyl montanate (C27-C28), melissyl montanate (C27-C30), arachidyl melissate (C29-C20), behenyl melissate (C29-C22), lignoceryl melissate (C29-C24), cerotoyl melissate (C29-C26), montanyl melissate (C29-C28), and melissyl melissate (C29-C30). These aliphatic esters may be used alone or in any combination of two or more.

The method for producing component (A) in the present invention may, for example, be a method that utilizes a dehydration condensation reaction between a monovalent linear saturated fatty acid having 18 to 30 carbon atoms and a monovalent linear saturated alcohol having 20 to 30 carbon atoms. A catalyst may be used to increase the reaction efficiency. The reaction temperature is preferably 180 to 250°C, and the reaction may be carried out under reduced pressure. After the reaction, the product may be purified by deacidification, washing with water, etc.

Examples of monovalent linear saturated fatty acids having 18 to 30 carbon atoms include stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, and melissic acid. These monovalent linear saturated fatty acids having 18 to 30 carbon atoms may be used alone or in any combination of two or more. The monovalent linear saturated fatty acids having 18 to 30 carbon atoms may also be mixed fatty acids mainly containing monovalent linear saturated fatty acids having 18 to 30 carbon atoms and containing monovalent linear saturated fatty acids having less than 18 carbon atoms or more than 30 carbon atoms, in which case the content of the monovalent linear saturated fatty acids having 18 to 30 carbon atoms is 50% by mass or more, preferably 70% by mass or more.

Examples of monohydric linear saturated alcohols having 20 to 30 carbon atoms include arachidyl alcohol, behenyl alcohol, lignoceryl alcohol, ceryl alcohol, montanyl alcohol, and melissyl alcohol. These monohydric linear saturated alcohols having 20 to 30 carbon atoms may be used alone or in any combination of two or more. The monohydric linear saturated alcohol having 20 to 30 carbon atoms may be a mixed alcohol mainly containing a monohydric linear saturated alcohol having 20 to 30 carbon atoms and containing a monohydric linear saturated alcohol having less than 20 carbon atoms or more than 30 carbon atoms, in which case the content of the monohydric linear saturated alcohol having 20 to 30 carbon atoms is 50% by mass or more, preferably 70% by mass or more.

Here, the international standard for natural and organic cosmetics, "ISO 16128 Guidelines for technical definitions and standards for natural and organic cosmetic ingredients" (hereinafter referred to as ISO 16128), defines "naturally derived raw materials" as raw materials made by chemical reaction between naturally derived parts obtained from plants, animals, etc. and non-naturally derived parts obtained from petroleum, etc., and whose molecular structure is made up of more than 50% naturally derived parts. Component (A) used in the present invention does not necessarily have to be a naturally derived raw material, but from the viewpoint of increasing the content of naturally derived raw materials in the oil wax gel, it is preferable that it is manufactured to be a naturally derived raw material.

The snow wax used as component (B) in the present invention is a white wax with a melting point of 80-85°C secreted by the scale insect, Coccidae. ISO 16128 defines "natural raw materials" as raw materials that originate from water, plants, animals, microorganisms, or minerals (excluding petroleum and natural gas) and are obtained by physical processing such as drying or crushing without chemical synthesis, and snow wax falls under this category of natural raw materials.

As an example of snow wax, deodorized refined snow wax No. 1 (product name; manufactured by Cerarica NODA) is commercially manufactured and sold, and this can be used in the present invention.

When using the oil gelling agent of the present invention, the amount of components (A) and (B) is preferably adjusted to 50 to 98% by mass, more preferably 65 to 95% by mass, even more preferably 75 to 95% by mass, and most preferably 87 to 93% by mass for component (A), and the amount of component (B) is preferably adjusted to 2 to 50% by mass, more preferably 5 to 35% by mass, even more preferably 5 to 25% by mass, and most preferably 7 to 13% by mass, relative to 100% by mass of the total amount of components (A) and (B).

The oil wax gel of the present invention contains an oil agent that is liquid at 25°C and components (A) and (B).

Examples of oils that are liquid at 25°C include hydrocarbon oils, branched fatty acids, branched alcohols, ester oils, ether oils, silicone oils, etc.

Specific examples of hydrocarbon oils include squalane, squalene, liquid paraffin, α-olefin oligomer, hydrogenated polyisobutene, isoparaffin, etc. Examples of branched fatty acids include 2-ethylhexanoic acid, isononanoic acid, isopalmitic acid, isostearic acid, isobehenic acid, etc. Examples of branched alcohols include isostearyl alcohol, octyldodecanol, hexyldecanol, decyltetradecanol, oleyl alcohol, etc. Examples of ester oils include 2-ethylhexyl 2-ethylhexanoate, isononyl 2-ethylhexanoate, diisobutyl adipate, di-2-ethylhexyl succinate, cetyl 2-ethylhexanoate, 2-hexyldecyl 2-ethylhexanoate, neopentyl glycol di-2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, medium-chain fatty acid triglyceride, neopentyl glycol dicaprate, 2-ethylhexyl isononanoate, isononyl isononanoate, isodecyl isononanoate, isotridecyl isononanoate, hexyl laurate, isopropyl myristate, and 2-hexyl myristate. decyl, 2-octyldodecyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl stearate, ethyl isostearate, isopropyl isostearate, 2-hexyldecyl isostearate, isostearyl isostearate, isodecyl neopentanoate, isostearyl neopentanoate, octyldodecyl neopentanoate, 2-octyldodecyl dimethyloctanoate, 2-ethylhexyl hydroxystearate, 2-octyldodecyl 12-stearolylstearate, oleyl oleate, 2-ethylhexyl salicylate, dialkyl carbonate, etc. Examples of ether oils include dioctyl ether, polyoxyethylene-polyoxypropylene dimethyl ether, etc. Examples of silicone oils include octamethyltrisiloxane, decamethyltetrasiloxane, decamethylcyclopentasiloxane, caprylmethicone, and methylpolysiloxane.

These oils that are liquid at 25°C may be used alone or in any combination of two or more.

The content of components (A) and (B) and the oil agent that is liquid at 25°C in the entire oil wax gel of the present invention varies depending on the application of the oil wax gel, the intended hardness, etc., and is not particularly limited, but the total amount of components (A) and (B) is 1 to 30% by mass, preferably 5 to 20% by mass, of 100% by mass of the oil wax gel of the present invention, and the remainder can be adjusted to be an oil agent that is liquid at 25°C.

There are no particular limitations on the method for producing the oil wax gel of the present invention, but for example, a method can be carried out in which components (A) and (B) are added to an oil agent that is liquid at 25°C, and these are heated to a temperature above their melting points (e.g., 80 to 120°C) to mix uniformly, and the resulting mixture is poured into a mold and cooled and solidified.

The oil wax gel of the present invention can be used, for example, in cosmetics, medicines, quasi-drugs, and household goods, and is particularly preferably used in cosmetics. Specific examples of cosmetics include solid oil-based cosmetics such as oil-based foundations, lipsticks, and lip glosses, as well as solid oil-based cleansing cosmetics.

When the oil wax gel of the present invention is used in cosmetics, the oil wax gel can contain, in addition to the above-mentioned components, components that are typically used in cosmetics, such as color pigments, dyes, body pigments, surfactants, antioxidants, fragrances, UV absorbers, moisturizers, etc.

The present invention will be specifically explained below with reference to examples, but the present invention is not limited to these.

[Synthesis Example 1]
In a 2L four-necked separable flask equipped with a stirrer, a thermometer, a gas inlet tube, and a water separator, 718 g of behenic acid (2.2 mol; trade name: RADIACID0560; manufactured by Oleon), 700 g of behenyl alcohol (2.1 mol; trade name: GINOL-22 (98%); manufactured by GODREJ), and 0.1 wt% stannous oxide (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) as a catalyst were charged, and an esterification reaction was carried out in a nitrogen gas stream at 230°C for 5 hours until no decrease in acid value was observed. After completion of the reaction, neutralization treatment was carried out with 0.18 wt% phosphoric acid (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and filtration was carried out using a Buchner funnel to obtain 1340 g of an esterification product (behenyl behenate). The behenyl behenate thus obtained corresponds to a naturally derived raw material defined by ISO16128.

[Synthesis Example 2]
A 500 mL four-necked separable flask equipped with a stirrer, a thermometer, a gas inlet tube, and a water separator was charged with 163.5 g of montanic acid (0.42 mol; trade name: HOE WAX S; manufactured by Hoechst Japan Co., Ltd.), 137.6 g of behenyl alcohol (0.42 mol; trade name: GINOL-22 (98%); manufactured by GODREJ Co., Ltd.), and 0.1 wt% stannous oxide (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) as a catalyst, and an esterification reaction was carried out in a nitrogen gas stream at 230° C. for 6 hours until no decrease in acid value was observed. After completion of the reaction, the mixture was neutralized with 0.18 wt% phosphoric acid (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and filtered to obtain 278 g of an esterification product (behenyl montanate).

[Synthesis Example 3]
A 2 L four-neck separable flask equipped with a stirrer, a thermometer, a gas inlet tube, and a water separator was charged with 695 g of stearic acid (2.5 mol; product name: Lunac S-98; manufactured by Kao Corporation), behenyl alcohol (2.5 mol; product name: GINOL-22 (98%); manufactured by GODREJ), and 0.1 wt % stannous oxide (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) as a catalyst, and an esterification reaction was carried out in a nitrogen gas stream at 230° C. for 5 hours until no decrease in acid value was observed. After completion of the reaction, the mixture was neutralized with 0.18 wt % phosphoric acid (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and filtered to obtain 1,398 g of an esterification product (behenyl stearate).

[Preparation of Oil Gelling Agent]
(1) Raw materials for oil gelling agent 1) Behenyl behenate (Synthesis Example 1; C21-C22; melting point: 73°C)
2) Behenyl montanate (Synthesis Example 2; C27-C22; melting point: 75°C)
3) Behenyl stearate (Synthesis Example 3; C17-C22; melting point: 68°C)
4) Snow wax (product name: Deodorized and refined Snow wax No. 1; melting point: 81° C.; manufactured by Cerarica NODA Co., Ltd.)
5) Candelilla Wax (Product name: Refined Candelilla Wax MK-2; melting point: 70°C; manufactured by Yokoseki Oil Industries Co., Ltd.)
6) Hydrogenated jojoba oil (product name: Jojoba wax; melting point: 68°C; manufactured by Nikko Chemicals Co., Ltd.)
7) Carnauba wax (product name: refined carnauba wax R-100; melting point: 83°C; manufactured by Yokoseki Oils and Fat Industries Co., Ltd.)
8) Beeswax (product name: food additive beeswax; melting point: 64°C; manufactured by Miki Chemical Industry Co., Ltd.)
9) Rice bran wax (product name: Rice Wax SSI; melting point: 78°C; manufactured by Boso Oil Co., Ltd.)

The formulations of oil gelling agents 1 to 13 prepared using the above raw materials are shown in Tables 1 and 2. Of these, oil gelling agents 1 to 6 shown in Table 1 are examples of the present invention, and oil wax gels 7 to 13 shown in Table 2 are comparative examples.

(2) Preparation method of oil gelling agents Each wax was placed in a 50 mL beaker according to Tables 1 and 2, heated to 90°C, and thoroughly shaken until the contents were homogenized. The resulting mixture was cooled and solidified at 25°C for 30 minutes to obtain 10 g each of oil gelling agents 1 to 11. Note that oil gelling agents 12 and 13 consisted of only one type of raw material, and therefore the raw material itself was used as the oil gelling agent.

[Test Example 1]
[Production and Evaluation of Oil Wax Gel Using Cetyl 2-Ethylhexanoate]
(1) Preparation of Oil Wax Gels 20 g of 2-ethylhexanoate cetyl (trade name: NIKKOL CIO; oil agent liquid at 25°C; manufactured by Nikko Chemicals Co., Ltd.) and 2.2 g of an oil gelling agent according to Table 3 were placed in a 100 mL beaker, heated to 90°C, and thoroughly shaken until the contents were homogenized. The resulting mixture was poured into a cylindrical metal mold (inner diameter x height: 50 mm x 15 mm), cooled and solidified at 25°C for 30 minutes, and oil wax gels 1 to 9 (22.2 g each) were obtained. Note that when oil gelling agents 7 and 9 to 11 were used, gelation did not occur and no oil wax gels were obtained.

(2) Measurement of hardness Oil wax gels 1 to 9 were removed from the mold, and their hardness was measured in an environment of 25°C using a texture analyzer (product name: Ez Test; manufactured by Shimadzu Corporation). In the measurement, a cylindrical jig with a diameter of 14 mm was lowered toward the oil wax gel at a speed of 5 mm/min to compress the oil wax gel, and the yield point (point at which the increase in stress is alleviated: peak or inflection point) was taken as the hardness (N), which was symbolized according to the following evaluation criteria. The results are shown in Table 3.
<Evaluation criteria>
◎: 13.0N or more ○: 8.0N or more, less than 13.0N △: 5.0N or more, less than 8.0N ×: Less than 5.0N

As is clear from the results in Table 3, oil wax gels 1 to 6, which contained oil gelling agents 1 to 6 that combined components (A) and (B), achieved results of "○" or better. However, when oil gelling agents 7 to 13, which did not contain components (A) and (B), were added, they either did not gel or, even if an oil wax gel was obtained, achieved a result of "×," which was inferior to the examples of the present invention.

[Test Example 2]
[Production and evaluation of oil wax gel using liquid paraffin]

(1) Preparation of oil wax gels 20 g of liquid paraffin (product name: liquid paraffin; oil agent liquid at 25°C; Fujifilm Wako Pure Chemical Industries, Ltd.) and 2.2 g of an oil gelling agent according to Table 4 were placed in a 100 mL beaker, heated to 90°C, and thoroughly shaken until the contents were homogenized. The resulting mixture was poured into a cylindrical metal mold (inner diameter x height: 50 mm x 15 mm), cooled and solidified at 25°C for 30 minutes, and oil wax gels 10 to 18 (22.2 g each) were obtained. Note that when oil gelling agents 7 and 9 to 11 were used, gelation did not occur and no oil wax gels were obtained.

(2) Measurement of hardness Oil wax gels 10 to 18 were removed from the mold, and their hardness was measured in an environment of 25°C using a texture analyzer (product name: Ez Test; manufactured by Shimadzu Corporation). In the measurement, a cylindrical jig with a diameter of 14 mm was lowered toward the oil wax gel at a speed of 5 mm/min to compress the oil wax gel, and the yield point (point at which the increase in stress is alleviated: peak or inflection point) was taken as the hardness (N), which was symbolized according to the following evaluation criteria. The results are shown in Table 4.
<Evaluation criteria>
◎: 10.0N or more ○: 8.0N or more, less than 10.0N △: 5.0N or more, less than 8.0N ×: Less than 5.0N

As is clear from the results in Table 4, oil wax gels 10 to 15, which contained oil gelling agents 1 to 6 containing components (A) and (B) in combination, achieved results of "○" or better. However, when oil gelling agents 7 to 13 were added without the use of components (A) and (B), they did not gel, or, even if an oil wax gel was obtained, it was only a result of "△" or worse, which was inferior to the examples of the present invention.

[Test Example 3]
[Production and Evaluation of Oil Wax Gel Using Medium Chain Triglyceride]
(1) Preparation of oil wax gels 20 g of medium chain triglyceride (product name: Actor M1; oil solution liquid at 25°C; manufactured by Riken Vitamin Co., Ltd.) and 2.2 g of oil gelling agent according to Table 5 were placed in a 100 mL beaker, heated to 90°C, and thoroughly shaken until the contents were homogenized. The resulting mixture was poured into a cylindrical metal mold (inner diameter x height: 50 mm x 15 mm), cooled and solidified at 25°C for 30 minutes, and oil wax gels 19 to 27 (22.2 g each) were obtained. Note that when oil gelling agents 7 and 9 to 11 were used, gelation did not occur and no oil wax gel was obtained.

(2) Measurement of hardness Oil wax gels 19 to 27 were removed from the mold, and their hardness was measured in an environment of 25°C using a texture analyzer (product name: Ez Test; manufactured by Shimadzu Corporation). In the measurement, a cylindrical jig with a diameter of 14 mm was lowered toward the oil wax gel at a speed of 5 mm/min to compress the oil wax gel, and the yield point (point at which the increase in stress is alleviated: peak or inflection point) was taken as the hardness (N), which was symbolized according to the following evaluation criteria. The results are shown in Table 5.
<Evaluation criteria>
◎: 30.0N or more ○: 15.0N or more, less than 30.0N △: 10.0N or more, less than 15.0N ×: Less than 10.0N

As is clear from the results in Table 5, oil wax gels 19-24, which contained oil gelling agents 1-6 containing components (A) and (B) in combination, achieved results of "○" or better. However, when oil gelling agents 7-13 were added without the use of components (A) and (B), they did not gel, or, even if an oil wax gel was obtained, it was inferior to the examples of the present invention.

Claims (2)

An oil gelling agent containing the following components (A) and (B) as active ingredients, in which the amount of component (A) is 85-95 % by mass and the amount of component (B) is 5-15 % by mass relative to 100% by mass of the total amount of components (A) and (B) (excluding those containing candelilla wax).
(A) one or more selected from the group consisting of behenyl behenate, behenyl montanate, and behenyl stearate; (B) snow wax; An oil wax gel containing an oil agent that is liquid at 25°C and the oil gelling agent described in claim 1.