JP3274588B2 - Silicone oil solidifying agent - Google Patents

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 satisfactorily gelling silicone oil.

[0002]

2. Description of the Related Art In general, silicone oils have high binding energy of the main chain and are excellent in heat resistance, acid resistance, weather resistance and the like, and have low surface tension and have releasability, lubricity and water repellency. Are known. In addition, since the intermolecular force is small, the main chain is flexible, the gas permeability is high, and since it is physiologically inert, it has characteristics such as low toxicity and low irritation. Because of this, electrical appliances, electronics, automobiles, machinery, medical care,
Various silicone oils are used in a wide range of fields such as cosmetics, fibers, paper, pulp, and building materials. In particular, in the field of cosmetics, silicone oils such as dimethylpolysiloxane and cyclic silicone, which have no stickiness and high safety, are widely used as hair finishing agents and oils for various cosmetics.

[0003] As described above, although silicone oil is widely used for various uses such as industrial use, there is still no agent for adjusting the viscosity of silicone oil. For this reason, when a large amount of silicone oil is contained, there is generally a restriction in viscosity control, and furthermore, the stability is poor,
It has many problems such as poor usability.

In order to solve such a problem, there has been proposed a method in which silicone oil is gelled and applied to cosmetics and cosmetic bases by utilizing its properties (for example, Japanese Patent Application Laid-Open No. Sho 63). -152308, Japanese Unexamined Patent Application Publication No.
JP-A-190757 and JP-A-1-207354).
These use organopolysiloxanes, which are insoluble in silicone oil but swell in silicone oil, as gelling agents, but the gels formed in these have good stability but lack thixotropic rheological properties. There is a problem. This thixotropic rheological property is, for example, the "growth" during the use of cosmetics
It is important for improving the usability and the feeling of use.

[0005] In addition, silicone oil is widely used as an oil agent for cosmetics and cosmetics, and although it is important, there are many problems when blended in cosmetics, especially oily solid cosmetics. That is, since silicone oil has poor compatibility with other cosmetic oils, it is difficult to uniformly dissolve it or to prepare a stable product based on silicone oil. There is a drawback that separation occurs. In addition, since there is no agent for adjusting the viscosity of silicone oil, cosmetics containing a large amount of silicone oil generally have many problems such as low viscosity, poor stability, and dripping during use. ing. Further, when silicone oil is used as an oil agent, there is a disadvantage that it is difficult to stably disperse a substance having a specific gravity difference in a composition over time.

[0006] Polysiloxanes having a long-chain alkyl group are more excellent in lubricity and miscibility with hydrocarbon materials than polydimethylsiloxanes having only a methyl group as a substituent. It is widely used for agents and lubricants.

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

[0008] As described above, no agent capable of gelling the silicone oil itself and adjusting the viscosity has been found, and development of such an agent has been eagerly desired especially in the field of cosmetics and the like.

[0009]

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

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, when an organopolysiloxane having a long-chain saturated hydrocarbon group introduced into both terminals is used,
It has been found that a thixotropic rheological property can be imparted, a silicone oil solidifying agent that can be gelled while utilizing the properties of silicone oil can be obtained, and that this silicone oil solidifying agent can be applied to cosmetics. It was completed.

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

[0012]

Embedded image

(Wherein, R ^{1 to} R ⁴ represent an alkyl group having 1 to 6 carbon atoms which may be the same or different, phenyl group or naphthyl group, and R ⁵ and R ⁶ may be the same or different. Which is a linear or branched saturated hydrocarbon group having an average carbon number of 16 to 600, and r and s are numbers of 0 or more. An oil solidifying agent is provided.

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

In the general formula (1), among the groups represented by R ^{1 to} R ⁴ , the alkyl group having 1 to 6 carbon atoms includes methyl, ethyl, propyl, isopropyl, butyl, 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 preferred. 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 or R ⁶ has an average carbon number of 16 to 600. Preferably, 40-300 is more preferable. If the average carbon number is less than 16, the composition becomes oily and the compatibility with the hydrocarbon-based raw material is reduced. On the other hand, when it exceeds 600, the solubility with silicone oil at the time of heating is poor, and it cannot be gelled. In addition, properties specific to silicone such as heat resistance are lost. Examples of such a saturated hydrocarbon group having a branched chain include those having a short-chain branch having 1 to 5 carbon atoms at the fifth carbon atom counted from the terminal carbon atom of the saturated hydrocarbon group. Can be. In this case, examples of the short-chain branch 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, and in the case where the chain length of the saturated hydrocarbon group is short, the both-terminal-modified organopolysiloxane represented by the formula (1) has no influence on other physical properties. Can be lowered.

In the above general formula (1), r and s are each a number of 0 or more, and preferably a number of 100 to 3000, and more preferably a number of 200 to 2000. When it is within this range, the effect of the long-chain alkyl group is more exerted, and the lubricating property and the plugging property are further improved.

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

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

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

The alkyl lithium may have 1 to 6 carbon atoms.
Is preferred, 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, such as tetramethylethylenediamine, dipiperidinoethane, dipyrrolidinoethane, and sparteine. Can be mentioned. These tertiary diamines are preferably used in an amount of 0.1 to 10 equivalents to the alkyl lithium. If it is less than 0.1 equivalent, the polymerization rate becomes slow,
If it exceeds 10 equivalents, the living terminal may be inactivated and may not reach the target molecular weight. Examples of the solvent include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclohexane, and cyclopentane.

The pressure for introducing ethylene is not particularly limited, but is preferably about 1 to 100 kg / cm ² . When the introduction pressure is less than 1 kg / cm ² , the polymerization reaction becomes too slow.
If it exceeds 00 kg / cm ² , the reaction speed becomes too fast,
It is not preferable because reaction control becomes difficult. Although the polymerization temperature is not particularly limited, it is preferably 0 to 100 ° C., and 20 to 8 ° C.
0 ° C. is more preferred. When the temperature is lower than 0 ° C., the polymerization reaction is slowed, and the resulting living polyethylene is precipitated with a low molecular weight. When the temperature is higher than 100 ° C., the living terminal is inactivated, which is not preferable. The polymerization time varies depending on the polymerization temperature, the concentration of the tertiary diamine, the pressure for introducing ethylene, and the like, but is generally preferably 0.1 to 24 hours. However, as long as the heat of polymerization can be removed, the time is preferably as short as possible from the viewpoint of preventing inactivation 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 polymerization conditions.

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

[0024]

Embedded image

(Wherein, 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
(Indicating an integer of 7), and then, if necessary, an acid treatment to obtain a one-terminal silanol-modified polyethylene.

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 not less than the molar amount of the living polyethylene. More than moles are preferred. When the cyclic siloxane (2) is added quickly with sufficient stirring, it can be directly added to the living polyethylene solution as it is or as a hydrocarbon solution. However, in order to avoid a side reaction in which two living polyethylenes react with one silicon atom, it is preferable to gradually add a living polyethylene solution to a cyclic siloxane previously dissolved and diluted in a hydrocarbon solvent.

The reaction temperature is not particularly limited, but may be from 0 to 1
00 ° C is preferred, and 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 easily occurs, which is not preferable. The reaction proceeds quickly within the above-mentioned temperature range, so that the reaction time is several minutes. However, when the product precipitates, it may take several hours, and therefore the reaction time is generally about 30 minutes to 5 hours. . The one-terminal silanol-modified polyethylene produced by the reaction at this stage is mainly a silanol having 1 to 4 siloxane units at the polyethylene terminal.

Next, as a third step, 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]

Embedded image

Wherein R ¹¹ and R ¹² have the same meaning as described above, and q is an integer of 1 or more, preferably an integer of 1 to 3000. Is subjected to equilibration polymerization in the presence of an acid or base catalyst to obtain a crude organopolysiloxane modified at both ends.

The amount (molar number) of the silanol-modified polyethylene at one end and the compound of the formula (2) or (3) can be appropriately determined according to the desired molecular weight of the organopolysiloxane modified at both ends. 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 use amount of these catalysts is not particularly limited, and usually about 0.01 to 1 mol% is sufficient for the repeating unit of siloxane. In this reaction, a solvent such as an aromatic hydrocarbon such as toluene and 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,
300 ° C is preferable, and 60 to 200 ° C is more preferable.
When the temperature is lower than 20 ° C., the reaction system becomes non-uniform, and when the temperature is higher than 300 ° C., by-products such as cyclic siloxane are easily generated, which is not preferable. The reaction time varies depending on the conditions such as the amount of the raw materials and the temperature, but is usually 8 hours to 7 days.

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

The organopolysiloxane modified at both ends represented by the formula (1) is prepared by the method described in US Pat.
No. 232,693, the method described in Example 1 in column 4,
That is, it can also be obtained by a method in which an α-olefin is reacted with methyl hydrogen polysiloxane having a terminal Si—H group in the presence of a platinum-carbon catalyst.

The silicone oil solidifying agent of the present invention has the formula (1)
Can be composed of the both-terminal-modified organopolysiloxane alone, but if necessary, other components such as 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 soaps, sucrose fatty acid esters, 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 used is 1 to 900 parts by weight, based on 100 parts by weight of the silicone oil, as a double-ended organopolysiloxane represented by the formula (1). Is preferred, and 5-200
Part by weight is more preferred. When the silicone oil solidifying agent of the present invention is used, various types of 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 normal temperature. The silicone oil solidifying agent used in the present invention is as described above, and the compounding amount thereof is 0.1% as a double-ended organopolysiloxane represented by the formula (1) in the cosmetic.
The content is preferably from 50 to 50% by weight, particularly preferably from 0.5 to 40% by weight, and more preferably from 3 to 30% by weight, because it is more stable, has good spreadability in use, and is excellent in usability.

The silicone oil which is liquid at ordinary temperature used in the present invention is not particularly limited as long as it is used in ordinary cosmetics and is a silicone oil which is liquid at the time of use, transportation, storage and the like. Examples thereof include methylcyclotetrasiloxane, decamethylcyclopentasiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane, and methylethylpolysiloxane. These silicone oils can be used alone or in combination of two or more.
99% by weight, particularly preferably 10 to 90% by weight is blended.

The cosmetic of the present invention contains oils, waxes, powders, and the like within a qualitative and quantitative range that does not impair the object of the present invention.
Pigments, dyes, fragrances, surfactants, preservatives, drugs, humectants, thickeners, cosmetic ingredients, water and the like can be added.

[0039] The cosmetic of the present invention can be produced according to a usual method, and includes a stick, a paste, a cream,
It can be in any form, such as gel or liquid.
Also, oily solid cosmetics such as makeup cosmetics such as foundation, lipstick, blusher, eyebrows, eye shadow, eyeliner, etc .; emulsified cosmetics such as emulsions and creams; liquid cosmetics such as lotions and cleansing oils; can do.

In the case of a foundation or a makeup cosmetic, a cosmetic powder is mixed and dispersed in a gelled oily base containing a silicone oil solidifying agent and silicone oil, and the mixture is solidified and molded. It is manufactured by
Further, these oil phases can be emulsified with an appropriate aqueous phase and used. As the powder used here, known pigments commonly used in cosmetics can be used, for example, talc, sericite, mica, kaolin, silica,
Extenders such as nylon powder, polyethylene powder, cellulose powder; coloring agents such as carbon black, titanium oxide, iron oxide, zinc oxide, ultramarine, navy blue, chromium oxide, organic tar pigments, lakes, etc .; titanium mica, iron oxide coated mica And the like. Also,
Those pigments which have been surface-treated with silicone, higher fatty acids, higher alcohols, fatty acid esters, metal soaps, amino acids, alkyl phosphates and the like, or those which are encapsulated in organic or inorganic microcapsules can also be used. These pigments can be used alone or in combination of two or more kinds, and it is preferable to mix 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 imparts thixotropic rheological properties to the silicone oil by being blended with the silicone oil, and easily forms a gel while utilizing the properties of the silicone oil. Can be
This gel is highly stable and has no spinnability. The silicone oil solidifying agent of the present invention is useful not only for cosmetics but also for materials such as pharmaceuticals and crayons. Further, the cosmetic containing the silicone oil solidifying agent can impart thixotropic rheological properties to the silicone oil in the cosmetic, so that the stability is improved and the persistence after application to the skin is good. It is excellent in sustainability and feeling of use. The cosmetic of the present invention is particularly suitable as an oily solid cosmetic, and when used as an oily solid cosmetic, has high stability over time, and does not cause dripping or oil floating due to the blended silicone oil, and Because it has excellent spreadability and adhesion on the skin, it has good makeup performance such as long lasting and covering power,
No oil seepage occurs.

[0042]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 (First stage) 400 ml of dry cyclohexane, 3 ml of tetramethylethylenediamine, and n-butyllithium (1.6 mol /
12.5 ml (0.02 mol) of a solution of l) in cyclohexane
, 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 was placed in a 1-liter eggplant flask in advance.
8g, 10ml dry cyclohexane solution prepared,
It was added dropwise to the reaction system under a nitrogen stream. After completion of the dropwise addition, the mixture was reacted at 30 ° C. for 1 hour, and then the reaction mixture was poured into 2 liters of methanol. After stirring for one hour,
The resulting solid was collected by filtration under reduced pressure, 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. GPC analysis (using an analyzer made by Waters; ortho-dichlorobenzene, 135 ° C, calibration with a polyethylene standard sample) showed a number average molecular weight of 610 and a molecular weight distribution of 1.03. In addition, ¹ H
-NMR analysis (using a Bruker analytical instrument; 200 MHz
z, chloroform-d, 50 ° C, standard uses TMS)
As a result, a methyl group bonded to a silyl group at -0.05 ppm (singlet), a methylene group bonded to a silyl group at 0.4 ppm (triplet), a starting methyl group at 0.8 ppm (triplet), A signal of a 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 end.

(Third Step) Next, 12.0 g of the above-mentioned polyethylene having a silanol group at the terminal, 88 g of octamethylcyclotetrasiloxane and 100 ml of toluene are placed in a 1-liter separable flask equipped with a condenser, and the toluene is refluxed. Until heated on an oil bath.
When all the raw materials were uniformly dissolved, 0.01 g of potassium hydroxide was added, and reflux was continued for 48 hours.

(Fourth Step) Thereafter, 0.18 ml of a 1N alcoholic hydrochloric acid solution was added, and the mixture was sufficiently stirred. Add water,
After confirming that the pH was 7, the generated inorganic salt was extracted with water. Washing was performed three times while heating, and a Dean-Stark tube was attached in place of the condenser, and toluene was refluxed until complete dehydration. The toluene was distilled off to obtain a brittle rubbery white wax product. The yield was 96 g. 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. ¹ H-NMR (using an analytical instrument manufactured by Bruker; 200 MHz, chloroform-d, 50 ° C., standard is T
Using MS), the result was -0.05 ppm (singlet)
A methyl group bonded to a silyl group; 0.4 ppm (triplet) a methylene group bonded to a silyl group;
8 ppm (triplet) starting terminal methyl group, 1.2 pp
A methylene group signal of the polyethylene chain was observed around m. From the integration ratio of each signal, it was found that the weight ratio of the polyethylene portion to the siloxane portion was 10:90. The organopolysiloxane modified at both ends thus obtained was used as a silicone oil solidifying agent.

Example 2 The procedure of Example 1 was repeated except that the amount of octamethylcyclotetrasiloxane used in the third stage was changed to 10 g.
A wax-like organopolysiloxane modified at both ends was obtained (yield: 21 g, weight average molecular weight: 2,100, weight ratio of polyethylene portion to siloxane portion: 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 to silicone oil was tested by the following method. (Test Method) Each of the solidifying agents shown in Table 1 was added to three types of silicone oil so as to be 10% by weight, and then heated to 90 ° C. and mixed and dissolved. Next, the mixture was sufficiently stirred so as to be uniform, then cooled, and the state of the gel in that case was visually evaluated according to the following criteria. Table 1 shows the results. ：: A thixotropic gel is formed. Δ: A gel is formed, but does not exhibit thixotropic properties. X: No gel is formed.

[0049]

[Table 1]

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

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

[0052]

(Composition) (% by weight) (1) Dimethylpolysiloxane Remaining (2) Solidifying agent of Example 1 10.0 (3) Candelilla wax 3.0 (4) Preservative proper amount (5) Oxidation Titanium 15.0 (6) Bengala 0.8 (7) Yellow iron oxide 2.5 (8) Black iron oxide 0.2 (9) Mica 31.5 (10) Fragrance trace

(Production method) Components (1) to (4) were heated at 90 ° C.
And mixed and dissolved. Further, the components (5) to (9) were added, and sufficiently stirred and mixed so as to be uniform while maintaining the temperature at 90 ° C. After the component (10) was added to the mixture and mixed, the mixture was filled in a metal dish and cooled to obtain an oily solid foundation.

Example 4 (Oily solid foundation) An oily 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 component (2).

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

[0056]

(Table 3) (Composition) (% by weight) (1) Remaining liquid isoparaffin (2) Aluminum dicetyl phosphate 2.0 (3) Candelilla wax 3.0 (4) Titanium oxide (water-repellent) 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) 31.5 (9) Preservative appropriate amount (10) Fragrance trace amount

Comparative Example 2 (Oilic 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]

(Composition) (% by weight) (1) Residual amount of dimethylpolysiloxane (2) Aluminum dicetyl phosphate 2.0 (3) Candelilla wax 3.0 (4) Titanium oxide (water-repellent) 15 0.0 (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) 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 spreading, make-up and covering power, oil exudation and shape retention by the following methods.
Table 5 shows the results.

(Expansion, long-lasting and covering power) 20 to 5
Twenty women in their 0s were used as test subjects to actually use each of the oily solid foundations, and the sensory evaluation of each item was evaluated on a five-point scale (very good, excellent, indecidable, inferior, (Very poor) and evaluated according to the following criteria. ：: Excellent if very good, but 60% of all subjects
More than that. Δ: Similarly, a case of 40% or more and less than 60%. X: Similarly, when it is less than 40%.

(Oil Exudation and Shape Retention) Each oily solid foundation was stored in a constant temperature and humidity room at 40 ° C. and 70% humidity for one month, and the oil exudation on the surface was visually observed. Was evaluated according to the following criteria. ：: No seepage of oil was observed. ×: Seepage of oil is observed. The shape retention was evaluated by visually observing the shape retention when the surface was rubbed with an application sponge as in actual use, and evaluated according to the following criteria. ：: The shape retention is excellent. ×: Poor shape retention.

[0062]

[Table 5]

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

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

[0065]

(Composition) (% by weight) (1) Dimethylpolysiloxane remaining amount (2) Solidifying agent of Example 1 15.0 (3) Paraffin wax 8.0 (4) Celesin 3.0 (5) Preservation (6) Titanium oxide 2.5 (7) Pearl pigment 0.8 (8) Red No. 202 5.0 (9) Fragrance trace amount

(Preparation method) Components (1) to (4) were heated at 90 ° C.
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. The component (9) was added to the mixture and mixed to obtain a lipstick.

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

[0068]

(Composition) (% by weight) (1) Dimethylpolysiloxane remaining amount (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) 15.0 (7) Bengala (water-repellent) 2.0 (8) Yellow iron oxide (water-repellent) 1.0 (9) ) Fragrance trace

(Preparation method) Components (1) to (4) were heated at 90 ° C.
And mixed and dissolved. Further, components (5) to (8) were added and mixed for about 5 minutes, followed by finish pulverization. next,
It was pressed on a gold plate with a press machine to obtain blush.

When the lipstick of Example 5 and the blusher of Example 6 were tested in accordance with Test Example 2, the lipstick had excellent spreadability, long-lasting and covering power, and exudation of oil and excellent shape retention.

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

[0072]

(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 (20EO) 1.2 (8) Methyl paraben 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) were added to component (14).
1) was added and mixed by heating to obtain an aqueous phase. Further, the lipophilic components of components (1) to (7) were mixed. This oil phase was added to the aqueous phase for pre-emulsification. After the component (12) was added and uniformly mixed, the component (13) was added for neutralization. Next, the mixture was uniformly emulsified by 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]

(Composition) (% by weight) (1) Dimethylpolysiloxane 5.0 (2) Solidifying agent of Example 1 1.0 (3) Squalane 5.0 (4) Stearic acid 2.0 (5) Stearyl alcohol 7.0 (6) Reduced lanolin 1.0 (7) Octyl dodecanol 6.0 (8) Polyoxyethylene cetyl ether (25EO) 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) Component (10) to component (14)
(13) was added thereto, followed by heating and mixing to obtain an aqueous phase. Further, other oil phase components were mixed by heating. The oil phase was added to the aqueous phase to perform preliminary emulsification, and then uniformly emulsified by a homogenizer, and then cooled to room temperature to obtain a cream.

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

[0078]

(Composition) (% by weight) (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) Components (6) to (8) are added to component (9).
Was added and mixed by heating to obtain an aqueous phase. Further, other oil phase components were mixed by heating. The aqueous phase was added to the oil phase to perform preliminary emulsification, and then uniformly emulsified by 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 emulsification stability, good in persistence after application to the skin, and excellent in persistence and usability.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI A61K 7/031 A61K 7/031 C08G 77/04 C08G 77/04 // C07F 7/04 C07F 7/04 N (72) Inventor Motoichi Nakamura Kinomoto 950-14, Wakayama City, Wakayama Prefecture 950-14 (72) Inventor Yasushi Ito 1450-235 Nishihama, Wakayama City, Wakayama Prefecture (56) References JP-A-3-264510 (JP, A) (58) Fields investigated (Int. ⁷ , DB name) C08L 83/04 A61K 7/00 A61K 7/02 A61K 7/027 A61K 7/031 C08G 77/04

Claims (3)

(57) [Claims] 1. The following general formula (1): (Wherein, 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 represent an average carbon number which may be the same or different. A linear or branched saturated hydrocarbon group of from 16 to 600, and r and s each represent a number of 0 or more). . 2. The silicone oil solidifying agent according to claim 1, wherein in the general formula (1), R ⁵ and R ⁶ are a linear or branched saturated hydrocarbon group having an average of 40 to 300 carbon atoms. 3. In the general formula (1), r and s are 10
The silicone oil solidifying agent according to claim 1 or 2, wherein the number is from 0 to 3000.