JPH0873744A - Solidifying agent for silicone oil and cosmetic containing same - Google Patents

Abstract

PURPOSE: To obtain a solidifying agent for a silicone oil which has thixotropic properties and can gelatinize a silicone oil by using a specific organopolysiloxane having both molecular ends modified. CONSTITUTION: The agent contains an organopolysiloxane of the formula having both molecular ends modified. In the formula, R<1> to R<4> are each independently 1-6C alkyl, phenyl, or naphthyl; R<5> and R<6> are each independently a 16-600C linear or branched satd. hydrocarbon group; and r and s are each 0 or higher. Though the agent may comprise the organopolysiloxane alone, it may further contain other ingredients (e.g. a wax or an oil-gelatinizing agent) if necessary. A stable cosmetic excellent in persistence, feeling in use, etc., can be formed by incorporating the agent into a silicone oil liq. at normal temp.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicone oil solidifying agent capable of gelling silicone oil well. The present invention also relates to cosmetics containing the silicone oil-solidifying agent and having good cosmetic performance and stability.

[0002]

2. Description of the Related Art Generally, silicone oil has a high bond energy in the main chain and is excellent in heat resistance, acid resistance, weather resistance and the like, and has low surface tension and releasability, lubricity, water repellency and the like. Are known. Further, since the intermolecular force is small, the main chain is flexible, the gas permeability is high, and physiologically inactive, so that it has low toxicity and low irritation. From such things, electric appliances, electronics, automobiles, machines, medical care,
Various silicone oils are used in a wide range of fields such as cosmetics, fibers, paper, pulp, and building materials. Particularly in the field of cosmetics, silicone oils such as dimethylpolysiloxane and cyclic silicone, which have no stickiness and are highly safe, are widely used as a finishing agent for hair and as an oil component for various cosmetics.

As described above, although silicone oil is widely used for various purposes such as industrial use, there is still no agent for adjusting the viscosity of silicone oil. Therefore, when a large amount of silicone oil is contained, there are restrictions on the control of the viscosity, and in addition, the stability is poor,
There are many problems such as poor usability.

Therefore, as a solution to such a problem, it has been proposed to apply silicone oil to a cosmetic or a cosmetic base by making the best use of its characteristics (for example, JP-A-63). -152308, JP-A-1
-190757 and 1-207354).
They use organopolysiloxanes that are insoluble in silicone oil but swell in silicone oil as gelling agents. The gels formed in these gels have good stability but lack thixotropic rheological properties. There is a problem. This thixotropic rheological property is, for example, a “spread” when using cosmetics.
It is important for improving usability and usability.

Although silicone oil is widely used as an oil agent for cosmetics and cosmetics and is important, it has many problems when incorporated into cosmetics, especially oily solid cosmetics. That is, since silicone oil has poor compatibility with other cosmetic oils, it is difficult to dissolve it uniformly or to prepare a stable product based on silicone oil. There is a drawback that it will protrude and separate. Further, since there is still no agent that adjusts the viscosity of silicone oil, cosmetics containing a large amount of silicone oil generally have low viscosity, have poor stability, and have many problems such as dripping during use. ing. Furthermore, when silicone oil is used as an oil agent, it is difficult to stably disperse substances having different specific gravities in the composition over time.

Further, since polysiloxane having a long-chain alkyl group is superior in lubricity and miscibility with a hydrocarbon material to polydimethylsiloxane having only a methyl group as a substituent, it is used as a cosmetic raw material and a mold release agent. Used in a wide range of agents and lubricants.

For example, a method for treating dry skin using alkylmethylpolysiloxane as an active ingredient has been proposed (US Pat. No. 5,232,693). However, this is used only as a therapeutic agent for skin cracks, etc.
There is no description about a solidifying agent for silicone oil and cosmetics using it.

Thus, no agent has been found that can gel the silicone oil itself to adjust the viscosity, and the development of such an agent has been earnestly desired especially in the field of cosmetics and the like.

[0009]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a silicone oil solidifying agent which imparts thixotropic rheological properties and is capable of gelling silicone oil. Another object of the present invention is to provide a cosmetic composition containing the above-mentioned silicone oil solidifying agent, which is excellent in durability, feeling of use, and the like and has good stability.

[0010]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that if an organopolysiloxane having long-chain saturated hydrocarbon groups introduced at both ends is used,
It was found that a thixotropic rheological property can be imparted, a silicone oil solidifying agent that can be gelled while taking advantage of the characteristics of silicone oil can be obtained, and that this silicone oil solidifying agent can be applied to cosmetics. It came to completion.

That is, the present invention provides the following general formula (1);

[0012]

Embedded image

(In the formula, R ^{1 to} R ⁴ may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms, a phenyl group or a naphthyl group, and R ⁵ and R ⁶ may be the same or different. A silicone containing a both-end modified organopolysiloxane represented by a linear or branched saturated hydrocarbon group having an average carbon number of 16 to 600, wherein r and s are 0 or more. An oil solidifying agent is provided.

The present invention also provides a cosmetic comprising the above-mentioned silicone oil solidifying agent and silicone oil which is liquid at room temperature.

In the above general formula (1), among the groups represented by R ^{1 to} R ⁴ , the alkyl group having 1 to 6 carbon atoms is methyl group, ethyl group, propyl group, isopropyl group, butyl group, s- Examples thereof include a butyl group, a t-butyl group, a pentyl group and a hexyl group. As R ^{1 to} R ⁴ , a methyl group, an ethyl group and a phenyl group are particularly preferable. These R ^{1 to} R ⁴ may be the same or different for each repeating unit.

In the general formula (1), the linear or branched saturated hydrocarbon group represented by R ⁵ and R ⁶ has an average carbon number of 16 to 600, but 27 to 300 40-300 are more preferable. When the average carbon number is less than 16, the mixture becomes oily and the compatibility with the hydrocarbon-based raw material decreases. On the other hand, when it exceeds 600, the solubility in silicone oil when heated is poor and gelation cannot be achieved. In addition, properties peculiar to silicone such as heat resistance are lost. Examples of the branched-chain saturated hydrocarbon group include those having a short-chain branched chain of 1 to 5 carbon atoms up to the fifth carbon atom counted from the terminal carbon atom of the saturated hydrocarbon group. You can Examples of the short-chain branch in this case include a 2-methyl group, a 3-methyl group, and a 2,2-dimethyl group. In the case of having such a short-chain branch, when the chain length of the saturated hydrocarbon group is short, both-end-modified organopolysiloxane represented by the formula (1) does not affect other physical properties at all. Can lower the melting point.

In the above general formula (1), both r and s are numbers of 0 or more, but both are preferably 100 to 3000, and more preferably 200 to 2000. Within this range, the effect of the long-chain alkyl group will be more exerted, and the lubricity and clogging properties will be good, and the miscibility will be good.

In the organopolysiloxane modified at both ends represented by the general formula (1), the weight ratio of the total of saturated hydrocarbon groups at both ends to the organopolysiloxane is 80:20 to 1: 1. Those having a ratio of 99 are preferable, and those having a ratio of 60:40 to 5:95 are particularly preferable because they have excellent solidifying power and stability.

The method for producing the both-end-modified organopolysiloxane represented by the general formula (1) is not particularly limited. For example, living polyethylene obtained after living polymerization of ethylene is reacted with a cyclic siloxane, and the cyclic siloxane and the terminal are further reacted. It can be produced by polymerizing a chain siloxane having a hydroxyl group or a mixture thereof in the presence of a catalyst. Hereinafter, this manufacturing method will be described.

First, as the first step, living anion polymerization is carried out by introducing ethylene into a solvent containing alkyllithium and tertiary diamine to obtain living polyethylene.

Alkyl lithium has 1 to 6 carbon atoms.
Is preferable, and examples thereof include methyllithium, ethyllithium, n-butyllithium, s-butyllithium, and t-butyllithium. As the tertiary diamine, those having 2 or 3 carbon atoms between nitrogen atoms are preferable, and those having 2 carbon atoms are more preferable. Tetramethylethylenediamine, dipiperidinoethane, dipyrrolidinoethane, sparteine, etc. Can be mentioned. These tertiary diamines are preferably used in an amount of 0.1 to 10 equivalents with respect to alkyllithium. When it is less than 0.1 equivalent, the polymerization rate becomes slow,
If it exceeds 10 equivalents, the living terminal may be inactivated, and the desired molecular weight may not be reached. Examples of the solvent include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclohexane and cyclopentane.

The introduction pressure of ethylene is not particularly limited, but is preferably about 1 to 100 kg / cm ² . If the introduced pressure is less than 1 kg / cm ² , the polymerization reaction will be too slow, and 1
If it exceeds 00 kg / cm ² , the reaction speed becomes too fast,
It is not preferable because the reaction control becomes difficult. The polymerization temperature is not particularly limited, but is preferably 0 to 100 ° C and 20 to 8
0 ° C. is more preferable. If the temperature is lower than 0 ° C., the polymerization reaction becomes slow, and the living polyethylene produced is precipitated with a low molecular weight. If it exceeds 100 ° C., the living ends are deactivated, which is not preferable. The polymerization time varies depending on the polymerization temperature, the concentration of the tertiary diamine, the ethylene introduction pressure, etc., but is generally preferably 0.1 to 24 hours. However, as long as the heat of polymerization can be removed, it is preferable that the time is as short as possible in order to prevent deactivation of the living terminal. In the reaction at this stage, the average molecular weight of the produced polyethylene can be accurately controlled by appropriately setting the above-mentioned polymerization conditions.

Next, as a second step, the living polyethylene obtained in the first step is added to the following formula (2);

[0024]

[Chemical 3]

(In the formula, R ¹¹ and R ¹² represent an alkyl group having 1 to 6 carbon atoms, which may be the same or different, and p is 3 to
A cyclic siloxane represented by the formula (7) is reacted, and if necessary, acid treatment is performed to obtain a silanol-modified polyethylene having one terminal silanol.

The amount of the cyclic siloxane (2) used is not particularly limited as long as the molar amount of the repeating unit (silicon atom) of the siloxane is equal to or more than the molar amount of living polyethylene, but it is doubled in consideration of suppression of side reactions. It is preferably molar or higher. The cyclic siloxane (2) can be directly added to the living polyethylene solution as it is or as a hydrocarbon solution when it is quickly added with sufficient stirring. However, in order to avoid a side reaction in which two living polyethylenes react with one silicon atom, it is preferable to gradually add the living polyethylene solution to the cyclic siloxane that has been previously dissolved and diluted in a hydrocarbon solvent.

The reaction temperature is not particularly limited, but it is 0 to 1
The temperature is preferably 00 ° C, more preferably 20 to 80 ° C. When the temperature is lower than 0 ° C, living polyethylene is precipitated, and when the temperature is higher than 100 ° C, a side reaction is likely to occur, which is not preferable. Since the reaction proceeds rapidly in the above temperature range, a reaction time of several minutes is sufficient. However, when a product precipitates, it may take several hours, so that it is generally about 30 minutes to 5 hours. . The one-end silanol-modified polyethylene produced by the reaction at this stage is mainly a silanol having 1 to 4 siloxane units at the polyethylene end.

Next, in the third step, the one-end silanol-modified polyethylene obtained in the second step and the cyclic siloxane represented by the above formula (2) or the following formula (3);

[0029]

[Chemical 4]

(Wherein R ¹¹ and R ¹² have the same meanings as described above, and q represents an integer of 1 or more, preferably an integer of 1 to 3000) and a siloxane having hydroxyl groups at both terminals. Is subjected to equilibrium polymerization in the presence of an acid or base catalyst to obtain a crude organopolysiloxane modified at both ends.

The amount (mol number) of the one-terminal silanol-modified polyethylene and the compound of the formula (2) or (3) can be appropriately determined according to the molecular weight of the target both-end-modified organopolysiloxane. Examples of the acid catalyst include inorganic acids such as sulfuric acid, sulfonic acids such as methanesulfonic acid, and solid acids such as ion exchange resins. Examples of the base catalyst include hydroxides of alkali metals such as potassium hydroxide, tetraalkylammonium hydroxide, silanolates prepared from tetraalkylammonium hydroxide and cyclic siloxane, and the like. The amount of these catalysts used is not particularly limited, and usually about 0.01 to 1 mol% with respect to the repeating unit of siloxane is sufficient. In addition, in this reaction, a solvent such as an aromatic hydrocarbon such as toluene or an aliphatic hydrocarbon such as octane can be used in order to increase the solubility of the catalyst and the compatibility between the raw materials.

The reaction temperature is not particularly limited, but is 20 to 20.
300 degreeC is preferable and 60-200 degreeC is more preferable.
When the temperature is lower than 20 ° C, the reaction system becomes heterogeneous, and when the temperature is higher than 300 ° C, by-products such as cyclic siloxane are likely to occur, which is not preferable. The reaction time will differ depending on the conditions such as the amount of raw materials and the temperature, but is usually 8 hours to 7 days.

Next, in the fourth step, the product obtained in the third step is neutralized, dehydrated, and if necessary, purified by reprecipitation or the like, and finally the both ends represented by the formula (1). A modified organopolysiloxane can be obtained. By the third stage, polysiloxanes with acid or base catalyst remaining at the terminals have been formed, so neutralization is performed to make all the remaining terminals of the catalyst into neutral silanols. It may be neutralized by adding a base calculated from the amount of catalyst or an acid. However, it can also be removed by filtration when a solid acid is used; and by thermal decomposition treatment when a tetraalkylammonium salt is used as a base. Next, the silanol thus produced is heated and dehydrated by an apparatus equipped with a dehydration tube to cause a coupling reaction to obtain a product. The dehydration reaction is carried out neat when the polysiloxane has a low molecular weight and the viscosity is low, but when the viscosity is high, it is dehydrated by refluxing it in a hydrocarbon solvent such as toluene. The product is obtained by distilling off the solvent.

Further, the organopolysiloxane modified at both ends represented by the formula (1) can be prepared by the method described in US Pat.
No. 232,693, the method described in Example 1 in the fourth column,
That is, it can also be obtained by a method of reacting an α-olefin with a methylhydrogenpolysiloxane having a Si—H group at the end in the presence of a platinum-charcoal catalyst.

The silicone oil solidifying agent of the present invention has the formula (1)
Can be composed of both-end modified organopolysiloxane represented by, but other components as necessary, for example, carnauba wax, beeswax, candelilla wax, paraffin wax, microcrystalline wax, montan wax, ozokerite, Various waxes such as ceresin, polyethylene wax, Fischer-Tropsch wax and ethylene propylene copolymer; oil gelling agents such as 12-hydroxystearic acid, metal soap, sucrose fatty acid ester and the like can be blended. Also,
When the silicone oil is solidified using the silicone oil solidifying agent of the present invention, the amount of the organopolysiloxane modified with both ends represented by the formula (1) is 1 to 900 parts by weight based on 100 parts by weight of the silicone oil. Is preferable, and 5-200
More preferably parts by weight. By using the silicone oil solidifying agent of the present invention, various silicone oils that are liquid at room temperature can be solidified well.

The cosmetic of the present invention contains the above-mentioned silicone oil solidifying agent and silicone which is liquid at room temperature. The silicone oil solidifying agent used in the present invention is as described above, and the compounding amount of the silicone oil solidifying agent in the cosmetic is 0.1 as the both-end modified organopolysiloxane represented by the formula (1).
It is preferably from 50 to 50% by weight, more preferably from 0.5 to 40% by weight, and further preferably from 3 to 30% by weight, because it is more stable, spreads well at the time of use, and is excellent in usability.

The silicone oil liquid at room temperature used in the present invention is not particularly limited as long as it is a liquid silicone oil used in ordinary cosmetics and used, transported, stored, and the like. For example, dimethylpolysiloxane, octane Examples thereof include methylcyclotetrasiloxane, decamethylcyclopentasiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane and methylethylpolysiloxane. These silicone oils can be used singly or in combination of two or more kinds.
It is preferable to add 99% by weight, particularly 10 to 90% by weight.

The cosmetics of the present invention include oils, waxes, powders, and powders within the qualitative and quantitative ranges that do not impair the object of the present invention.
Pigments, dyes, fragrances, surfactants, preservatives, drugs, moisturizers, thickeners, cosmetic ingredients, water and the like can be added.

The cosmetics of the present invention can be produced according to a conventional method, such as sticks, pastes, creams,
It may be in any form such as gel or liquid.
In addition, oily solid cosmetics such as makeup cosmetics such as foundations, lipsticks, blushers, eyebrows, eye shadows, eyeliners; emulsion type cosmetics such as emulsions and creams; liquid cosmetics such as lotions and cleansing oils. can do.

In the case of foundations, makeup cosmetics, etc., a powder for cosmetics is mixed and dispersed in a gelled oily base containing a silicone oil solidifying agent and silicone oil, and then solidified and molded. Manufactured by.
Further, these oil phases may be emulsified together with an appropriate water phase and used. As the powder used here, known pigments usually used in cosmetics can be used, and for example, talc, sericite, mica, kaolin, silica,
Extender pigments such as nylon powder, polyethylene powder, cellulose powder; colorants such as carbon black, titanium oxide, iron oxide, zinc oxide, ultramarine blue, dark blue, chromium oxide, organic tar dyes, lakes; titanium mica, iron oxide coated mica And the like. Also,
It is also possible to use those obtained by surface-treating these pigments with silicone, higher fatty acid, higher alcohol, fatty acid ester, metal soap, amino acid, alkyl phosphate or the like, or those encapsulated in organic or inorganic microcapsules. These pigments may be used alone or in combination of two or more, and it is preferable to add 0.1 to 80% by weight, particularly 5 to 70% by weight in the total composition.

[0041]

The silicone oil solidifying agent of the present invention, when added to silicone oil, imparts thixotropic rheological properties to the silicone oil, and easily forms a gel while utilizing the properties of the silicone oil. Can
This gel is highly stable and has no spinnability. The silicone oil-solidifying agent of the present invention is useful not only as a cosmetic but also as a material for medicines, crayons and the like. Further, the cosmetic containing the silicone oil-solidifying agent can impart the thixotropic rheological property to the silicone oil in the cosmetic, so that the stability is improved and the residual property after application to the skin is good, It has excellent durability and feeling of use. The cosmetic of the present invention is particularly suitable as an oily solid cosmetic, and when it is an oily solid cosmetic, it has high stability over time and does not cause dripping or oil floating due to the blended silicone oil, and Since it is excellent in spreadability and adhesion on the skin, it has good makeup performance such as makeup retention and covering power,
No oil bleeding, etc.

[0042]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1 (Step 1) 400 ml of dry cyclohexane, 3 ml of tetramethylethylenediamine, and n-butyllithium (1.6 mol / l) were placed in a 1 liter allclave purged with nitrogen.
12.5 ml (0.02 mol) of a solution of l) in cyclohexane
Was charged, the temperature of the reaction system was maintained at 30 ° C., and the introduction pressure was 2
8.2 liters of ethylene gas were introduced at kg / cm ² .

(Second Step) Next, octamethylcyclotetrasiloxane 11.
Prepare a solution of 8g and 10ml of dry cyclohexane.
It was added dropwise to the reaction system under a nitrogen stream. After completion of the dropping, the mixture was reacted at 30 ° C. for 1 hour, and then the reaction mixture was added to 2 liters of methanol. After stirring for 1 hour,
The solid produced by vacuum filtration was collected and dried in an oven at 50 ° C. under vacuum for 24 hours to obtain a white waxy solid. The yield was 12.0 g. As a result of GPC analysis (using an analyzer manufactured by Waters; ortho-dichlorobenzene, 135 ° C., calibrated with polyethylene standard sample), the number average molecular weight was 610 and the molecular weight distribution was 1.03. Also, ¹ H
-NMR analysis (using an analytical instrument manufactured by Bruker; 200MH
z, chloroform-d, 50 ° C, standard uses TMS)
As a result, a methyl group bonded to the silyl group at -0.05 ppm (singlet), a methylene group bonded to the silyl group at 0.4 ppm (triplet), a starting terminal methyl group at 0.8 ppm (triplet), A signal of the main chain methylene group was observed at around 1.2 ppm. From the integral ratio of each signal, it was found that the terminal silanol group introduction rate was 99%. The number of siloxane units introduced was 1.4 per polyethylene terminal.

(Third stage) Next, 12.0 g of the polyethylene containing a terminal silanol group, 88 g of octamethylcyclotetrasiloxane and 100 ml of toluene were placed in a 1 liter separable flask equipped with a condenser, and toluene was refluxed. Heated on an oil bath until.
When all the raw materials were uniformly dissolved, 0.01 g of potassium hydroxide was added, and reflux was continued for 48 hours.

(Fourth stage) After that, 0.18 ml of 1N alcoholic hydrochloric acid solution was added and sufficiently stirred. Add water,
It was confirmed that the pH was 7, and the produced inorganic salt was extracted with water. It was washed three times with heating, a Dean-Stark tube was attached instead of the condenser, and toluene was refluxed until completely dehydrated. Toluene was distilled off to give a brittle, rubbery white wax product. The yield was 96g. G
As a result of PC analysis (using an analyzer manufactured by Waters; orthodichlorobenzene, 135 ° C., polystyrene conversion), the weight average molecular weight was 18,600 and the molecular weight distribution was 2.03. Also, ¹ H-NMR (using an analytical instrument manufactured by Bruker; 200 MHz, chloroform-d, 50 ° C., standard is T
As a result of using MS), -0.05 ppm (singlet)
A methyl group bonded to the silyl group, 0.4 ppm (triplet) a methylene group bonded to the silyl group, 0.
Starting terminal methyl group at 8ppm (triplet), 1.2pp
A signal of the methylene group of the polyethylene chain was observed near m. From the integral ratio of each signal, it was found that the weight ratio of the polyethylene part and the siloxane part was 10:90. The both-end modified organopolysiloxane thus obtained was used as a silicone oil solidifying agent.

Example 2 In the same manner as in Example 1 except that the amount of octamethylcyclotetrasiloxane used in the third step was 10 g,
A waxy organopolysiloxane modified at both ends was obtained (yield 21 g, weight average molecular weight 2100, weight ratio of polyethylene part to siloxane part 51:49), and this was used as a silicone oil solidifying agent.

Test Example 1 The gel-forming ability of the silicone oil solidifying agents obtained in Examples 1 and 2 for silicone oil was tested by the following method. (Test Method) Each solidifying agent shown in Table 1 was added to 3 kinds of silicone oils so as to be 10% by weight, and then heated to 90 ° C. to be mixed and dissolved. Next, the mixture was sufficiently stirred so as to be uniform and then cooled, and the state of the gel in that case was visually evaluated according to the following criteria. The results are shown in Table 1. ◯: A thixotropic gel is formed. Δ: A gel is formed, but does not exhibit thixotropy. X: No gel is formed.

[0049]

[Table 1]

As is clear from Table 1, the solidifying agents of Examples 1 and 2 all formed gels having good thixotropic properties.

Example 3 (oily solid foundation) An oily solid foundation having the following composition was produced by the following production method.

[0052]

[Table 2] (Composition) (% by weight) (1) Dimethyl polysiloxane remaining amount (2) Solidifying agent of Example 1 10.0 (3) Candelilla wax 3.0 (4) Preservative proper amount (5) Oxidation Titanium 15.0 (6) Red iron oxide 0.8 (7) Yellow iron oxide 2.5 (8) Black iron oxide 0.2 (9) Mica 31.5 (10) Perfume Trace amount

(Production method) Components (1) to (4) are heated to 90 ° C.
It was heated to and mixed and dissolved. Furthermore, the components (5) to (9) were added, and sufficiently stirred and mixed so as to be uniform while maintaining the temperature at 90 ° C. The component (10) was added to this mixture, mixed, filled in a gold plate and cooled to obtain an oily solid foundation.

Example 4 (Oil-based solid foundation) An oil-based solid foundation was obtained by the same composition and production method as in Example 1 except that the solidifying agent obtained in Example 2 was used instead of the component (2).

Comparative Example 1 (oily solid foundation) An oily solid foundation having the following composition was obtained in the same manner as in the production method of Example 1.

[0056]

(Table 3) (Composition) (wt%) (1) Liquid isoparaffin residual amount (2) Aluminum dicetylphosphate 2.0 (3) Candelilla wax 3.0 (4) Titanium oxide (water repellent treated) 15. 0 (5) Red iron oxide (water repellent) 0.8 (6) Yellow iron oxide (water repellent) 2.5 (7) Black iron oxide (water repellent) 0.2 (8) Mica (water-repellent treated) 31.5 (9) Preservatives proper amount (10) Fragrance trace amount

Comparative Example 2 (oily solid foundation) An oily solid foundation having the following composition was obtained in the same manner as in the production method of Example 1.

[0058]

(Table 4) (Composition) (% by weight) (1) Remaining amount of dimethylpolysiloxane (2) Aluminum dicetylphosphate 2.0 (3) Candelilla wax 3.0 (4) Titanium oxide (water repellent treated) 15 0.0 (5) Red iron oxide (water repellent treated) 0.8 (6) Yellow iron oxide (water repellent treated) 2.5 (7) Black iron oxide (water repellent treated) 0.2 (8 ) Mica (water repellent treated) 31.5 (9) Preservative appropriate amount (10) Fragrance trace amount

Test Example 2 The oily solid foundations of Examples 3 and 4 and Comparative Examples 1 and 2 were tested for spreadability, makeup retention and covering power, and oil exudation and shape retention by the following methods.
The results are shown in Table 5.

(Spreading, holding makeup and covering power) 20-5
We asked 20 women in their 0s to actually use their respective oily solid foundations, and evaluated the sensory evaluation for each item on a 5-point scale (very excellent, excellent, neither can be said, inferior, It was considerably inferior) and evaluated according to the following criteria. ○: 60% of all subjects, but very good
In the above case. Δ: Similarly, in the case of 40% or more and less than 60%. X: Similarly, when less than 40%.

(Exudation and Shape Retention of Oil) Each oily solid foundation was visually observed for oil exudation on the surface when the oily solid foundation was stored in a constant temperature and humidity chamber at 40 ° C. and 70% humidity for 1 month. The following criteria were used for evaluation. ◯: No oil oozing was observed. X: Oil oozing is recognized. The shape-retaining property was evaluated by visually observing the shape-retaining property when the surface was rubbed with a coating sponge as in actual use, and evaluated according to the following criteria. ◯: Excellent shape retention. X: Shape retention is inferior.

[0062]

[Table 5]

As is clear from Table 5, the foundations of Examples 3 and 4 were excellent in all test items.

Example 5 (Lipstick) A lipstick having the following composition was produced by the following production method.

[0065]

[Table 6] (Composition) (wt%) (1) Remaining amount of dimethylpolysiloxane (2) Solidifying agent of Example 1 15.0 (3) Paraffin wax 8.0 (4) Ceresin 3.0 (5) Preservative Agents Appropriate amount (6) Titanium oxide 2.5 (7) Pearl pigment 0.8 (8) Red No. 202 5.0 (9) Perfume Trace amount

(Production method) Components (1) to (4) were heated to 90 ° C.
It was heated to and mixed and dissolved. Further, the components (5) to (8) were added and sufficiently stirred and mixed so as to be uniform while maintaining the temperature at 90 ° C. Component (9) was added to this mixture and mixed to obtain a lipstick.

Example 6 (Blusher) A blusher having the following composition was produced by the following production method.

[0068]

[Table 7] (Composition) (% by weight) (1) Remaining amount of dimethylpolysiloxane (2) Solidifying agent of Example 2 5.0 (3) Paraffin wax 20.0 (4) Preservative proper amount (5) Sericite 30.0 (6) Titanium oxide (water repellent treated) 15.0 (7) Red iron oxide (water repellent treated) 2.0 (8) Yellow iron oxide (water repellent treated) 1.0 (9 ) Fragrance

(Manufacturing method) Components (1) to (4) were heated to 90 ° C.
It was heated to and mixed and dissolved. Further, the components (5) to (8) were added and mixed for about 5 minutes, and then finish pulverized. next,
Pressed on a gold plate with a press machine to obtain a blusher.

When the lipstick of Example 5 and the blusher of Example 6 were tested according to Test Example 2, the spreadability, makeup retention and covering power were excellent, and oil exudation and shape retention were also excellent.

Example 7 (Emulsion) An emulsion having the following composition was produced by the following production method.

[0072]

[Table 8] (Composition) (% by weight) (1) Dimethylpolysiloxane 5.0 (2) Solidifying agent of Example 2 1.0 (3) Squalane 5.0 (4) Paraffin wax 1.0 (5) Beeswax 0.5 (6) Sorbitan sesquioleate 0.8 (7) Polyoxyethylene oleyl ether (20 EO) 1.2 (8) Methylparaben 0.2 (9) 1,3-butylene glycol 5. 0 (10) Glycerin 4.0 (11) Ethanol 2.0 (12) Carboxyvinyl polymer (1.0% aqueous solution) 20.0 (13) Potassium hydroxide 0.1 (14) Purified water 54.2

(Production method) Components (8) to (1) are added to the component (14).
1) was added and mixed by heating to obtain an aqueous phase part. Further, the lipophilic components (1) to (7) were mixed. This oil phase part was added to the water phase part to carry out preliminary emulsification, and after adding the component (12) and mixing them uniformly, the component (13) was added to neutralize. Then, the mixture was uniformly emulsified with a homogenizer and then cooled to room temperature to obtain an emulsion.

Example 8 (Cream) A cream having the following composition was produced by the following production method.

[0075]

[Table 9] (Composition) (wt%) (1) Dimethylpolysiloxane 5.0 (2) Solidifying agent of Example 1.0 1.0 (3) Squalane 5.0 (4) Stearic acid 2.0 (5) Stearyl alcohol 7.0 (6) Reduced lanolin 1.0 (7) Octyldodecanol 6.0 (8) Polyoxyethylene cetyl ether (25 EO) 3.0 (9) Lipophilic glyceryl monostearate 2. 0 (10) propylparaben 0.2 (11) glycerin 3.0 (12) propylene glycol 2.0 (13) 1,3-butylene glycol 1.0 (14) purified water 61.8

(Production method) Ingredient (14) to ingredient (10)
(13) was added and mixed by heating to obtain an aqueous phase portion. Further, other oil phase components were heated and mixed. This oil phase part was added to the water phase part for preliminary emulsification, and then homogenized with a homogenizer, followed by cooling to room temperature to obtain a cream.

Example 9 (Cream) A cream having the following composition was produced by the following production method.

[0078]

[Table 10] (Composition) (wt%) (1) Dimethylpolysiloxane 10.0 (2) Solidifying agent of Example 2 1.0 (3) Vaseline 3.0 (4) Dextrin fatty acid ester 2.0 (5 ) Polydimethylsiloxane-methyl (polyoxyalkylene) siloxane copolymer 7.0 (6) Methylparaben 0.1 (7) Glycerin 10.0 (8) 1,3-butylene glycol 2.0 (9) Purified water 64 .9

(Production method) Ingredients (6) to (8) are added to ingredient (9).
Was added and mixed by heating to obtain an aqueous phase portion. Further, other oil phase components were heated and mixed. A water phase portion was added to this oil phase portion to carry out preliminary emulsification, and then the mixture was uniformly emulsified with a homogenizer and then cooled to room temperature to obtain a cream.

The emulsions or creams obtained in Examples 7 to 9 were all excellent in emulsion stability, had good persistence after application to the skin, and were excellent in durability and usability.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location A61K 7/031 // C07F 7/04 N (72) Inventor Motoichi Nakamura 950 Kinomoto, Wakayama City, Wakayama Prefecture −14 (72) Inventor Yasushi Ito 1450-235 Nishihama, Wakayama, Wakayama Prefecture

Claims (5)

[Claims] 1. The following general formula (1): (In the formula, R ^{1 to} R ⁴ represent an alkyl group having 1 to 6 carbon atoms which may be the same or different, a phenyl group or a naphthyl group, and R ⁵ and R ⁶ may have the same or different average carbon number. A silicone oil solidifying agent characterized by containing 16-600 linear or branched saturated hydrocarbon groups, and r and s each representing a number of 0 or more). . 2. The silicone oil-solidifying agent according to claim 1, wherein R ⁵ and R ⁶ in the general formula (1) are linear or branched saturated hydrocarbon groups having an average carbon number of 40 to 300. 3. In the general formula (1), r and s are 10
The silicone oil solidifying agent according to claim 1 or 2, which has a number of 0 to 3000. 4. A cosmetic containing the silicone oil solidifying agent according to any one of claims 1 to 3 and a silicone oil that is liquid at room temperature. 5. An oily solid cosmetic containing the silicone oil solidifying agent according to any one of claims 1 to 3 and a silicone oil that is liquid at room temperature.