JP5905838B2 - Silicone-modified wax, composition containing the same, cosmetic, and method for producing silicone-modified wax - Google Patents

Description

  The present invention relates to a silicone-modified wax, a composition containing the same, a cosmetic, and a method for producing a silicone-modified wax.

  Oily thickeners or gelling agents such as waxes (hereinafter collectively referred to as “thickeners”) increase the viscosity of oily components in cosmetics and improve the usability, stability, appearance, etc. of cosmetics. Used for purposes. As the oily thickener, hydrocarbon waxes such as ceresin, polyethylene and ozokerite, waxes such as carnauba wax and candelilla wax, polysaccharide fatty acid esters such as sucrose palmitate and the like are widely used.

  These thickeners usually need to be melted at a temperature equal to or higher than the melting point of the thickener when blended in cosmetics. Therefore, when a compound having a high melting point is blended, other components in the cosmetic may be deteriorated or decomposed. For this reason, it is desired that the melting point is low, particularly 100 ° C. or lower. However, a thickener having a low melting point generally has a low thickening effect, and may cause a decrease in viscosity or phase separation of the cosmetic in summer.

  Moreover, it is desired that the thickener has good compatibility with the low viscosity oil agent blended in the cosmetic. If the compatibility is poor, it may separate from the oil over time, or the crystal of the thickener may become large when cooled and the appearance and feel of the cosmetic may be impaired. Silicone oils are frequently used as cosmetic oils because of their excellent characteristics such as a smooth feel, good elongation and good water repellency. Of these, volatile silicone oils are frequently used to form cosmetics that are not sticky and feel light. However, silicone oil is poorly compatible with general oils and with thickeners, and easily causes the above-mentioned problems.

  In order to solve the above problems, thickeners capable of thickening volatile silicone oil have been developed (Patent Documents 1 and 2). However, it is difficult to smoothly thicken silicone oil alone, and the resulting thickened product lacks the smoothness required for cosmetics. Thus, silicone-modified olefin wax has been proposed as a solution to these problems. (Patent Document 3).

  When the above thickener is blended in a cosmetic, it is dissolved by heating together with the oil. The temperature for melting by heating is unknown, but it is usually above the melting point of the wax. When the silicone-modified olefin wax is dissolved by heating together with an oil agent and then cooled to room temperature, a silicone-based room temperature solidified composition having no fluidity is obtained, and the composition can be used as a cosmetic. (Patent Document 3, paragraph 0195). However, the composition has room for improvement in terms of extensibility and feel.

Japanese Patent No. 4664991 WO2004 / 110393 JP 2008-174571 A

  The present invention has been made in view of the above circumstances, and has high compatibility with oils such as volatile and non-volatile silicone oils, hydrocarbon oils, ester oils, natural animal and vegetable oils. It is an object of the present invention to provide a silicone-modified wax that can be made into a paste-like or solid composition that can be extended easily, a method for producing the same, a composition containing the silicone-modified wax, and a cosmetic.

  In order to solve the above-described problems, according to the present invention, a product having a urethane bond obtained from a polyhydric alcohol having one or two alkenyl groups in one molecule and an alkyl isocyanate is added to methyl hydrogen organo A silicone-modified wax obtained by subjecting polysiloxane to a hydrosilylation reaction and having a solid or thixotropic property at 25 ° C. is provided.

  Such a silicone-modified wax of the present invention is highly compatible with volatile and non-volatile silicone oils, hydrocarbon oils, ester oils, natural animal and vegetable oils and the like, and various oils are pasted or solidified. In particular, it is extremely useful as a thickener to be blended in cosmetics. The composition containing the silicone-modified wax of the present invention is a paste or solid composition that is smooth and has good elongation.

（Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４は、それぞれ独立に、水素原子、同一又は異種の、分岐ポリグリセロール鎖が結合した連結基若しくは置換基を有していてもよい、炭素数１〜２２の直鎖もしくは分岐鎖のアルキル基又はアルコシキ基、炭素数６〜２２のアリール基、及びフッ素置換アルキル基のいずれかを示す。但し、Ｒ^１、Ｒ^３のうち少なくとも１つは水素原子を示し、Ｒ^２、Ｒ^４のうち少なくとも１つはメチル基を示す。ｎは０〜５０の整数を示す。） The polyhydric alcohol is a compound having a linear or branched polyglycerin structure,
The alkyl isocyanate is a linear saturated alkyl isocyanate selected from carbon number 8 to 20,
The methyl hydrogen organopolysiloxane is a methyl hydrogen organopolysiloxane containing 1 to 5 hydrogen atoms (that is, SiH groups) bonded to a silicon atom represented by the following general formula (A) in one molecule. It is preferable.

(R ¹ , R ² , R ³ and R ⁴ each independently have a hydrogen atom, the same or different, a linking group or substituent to which the same or different branched polyglycerol chain is bonded, 22 represents a linear or branched alkyl group or alkoxy group, an aryl group having 6 to 22 carbon atoms, and a fluorine-substituted alkyl group, provided that at least one of R ¹ and R ³ represents a hydrogen atom. And at least one of R ² and R ⁴ represents a methyl group, and n represents an integer of 0 to 50.)

  If it is a silicone-modified wax using such a material, it is even more compatible with oils such as volatile and non-volatile silicone oils, hydrocarbon oils, ester oils, natural animal and vegetable oils, and various oils are surely used. Can be pasted or solidified.

  The silicone-modified wax preferably has a melting point (normal pressure) of 40 to 100 ° C.

  Such a silicone-modified wax is preferred because there is no risk of lowering the viscosity or phase separation of the cosmetic in summer and the like, and there is no risk of deterioration or decomposition of other components in the cosmetic.

  The present invention also provides a composition characterized in that it contains 5 to 40% by mass of the silicone-modified wax and is paste or solid at 25 ° C. and normal pressure.

  The silicone-modified wax of the present invention is highly compatible with oils such as silicone oils and has a high thickening effect, so that various oils are smooth and stretchable, and are paste or solid compositions (25 ° C. Normal pressure), and the composition can be suitably blended in cosmetics.

  The present invention also provides a cosmetic comprising the silicone-modified wax of the present invention.

  The silicone-modified wax of the present invention is suitable for cosmetics because it is highly compatible with various oils used in cosmetics, and can make various oils into a paste-like or solid composition that is smooth and stretchable. Used for. Furthermore, since the silicone-modified wax of the present invention can achieve a melting point of 40 to 100 ° C., and further 50 to 80 ° C., there is no risk of lowering the viscosity of the cosmetic or causing phase separation in summer, etc. There is no risk of degradation or decomposition of the other components in it.

Further, in the present invention, (I) a product having a urethane bond by urethanizing a polyhydric alcohol having one or two alkenyl groups in one molecule and an alkyl isocyanate in the absence of a catalyst or in the presence of a catalyst. Obtaining
(II) Provided is a method for producing a silicone-modified wax, comprising a step of hydrosilylating the urethanization reaction product and methylhydrogenorganopolysiloxane in the presence of a catalyst.

  According to such a method for producing a silicone-modified wax of the present invention, compatibility with oils such as volatile and non-volatile silicone oils, hydrocarbon oils, ester oils, natural animal and vegetable oils is high, and various oils are pasted. Or silicone modified waxes that can be solidified.

（Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４は、それぞれ独立に、水素原子、同一又は異種の、分岐ポリグリセロール鎖が結合した連結基若しくは置換基を有していてもよい、炭素数１〜２２の直鎖もしくは分岐鎖のアルキル基又はアルコキシ基、炭素数６〜２２のアリール基、及びフッ素置換アルキル基のいずれかを示す。但し、Ｒ^１、Ｒ^３のうち少なくとも１つは水素原子を示し、Ｒ^２、Ｒ^４のうち少なくとも１つはメチル基を示す。ｎは０〜５０の整数を示す。） Further, as the polyhydric alcohol, a compound having a linear or branched polyglycerin structure is used,
As the alkyl isocyanate, a linear saturated alkyl isocyanate having 8 to 20 carbon atoms is used,
As the methyl hydrogen organopolysiloxane, a methyl hydrogen organopolysiloxane containing 1 to 5 hydrogen atoms (that is, SiH groups) bonded to a silicon atom represented by the following general formula (A) in one molecule is used. It is preferable.

(R ¹ , R ² , R ³ and R ⁴ each independently have a hydrogen atom, the same or different, a linking group or substituent to which the same or different branched polyglycerol chain is bonded, 22 represents a linear or branched alkyl group or alkoxy group, an aryl group having 6 to 22 carbon atoms, or a fluorine-substituted alkyl group, provided that at least one of R ¹ and R ³ represents a hydrogen atom. And at least one of R ² and R ⁴ represents a methyl group, and n represents an integer of 0 to 50.)

  With such a method for producing a silicone-modified wax, the compatibility with oils such as volatile and non-volatile silicone oils, hydrocarbon oils, ester oils, natural animal and vegetable oils is high, and various oils are surely used. A silicone-modified wax that can be pasted or solidified can be produced.

  The silicone-modified wax of the present invention is highly compatible with oils such as volatile and non-volatile silicone oils, hydrocarbon oils, ester oils, natural animal and vegetable oils. It can be a thing. In addition, since it has a melting point of 40 to 100 ° C., it prevents viscosity reduction or phase separation of cosmetics in summer, etc., and can prevent deterioration and decomposition of other components when making a composition (during heating and melting), It can be suitably used as a cosmetic.

Hereinafter, the present invention will be described in more detail.
As described above, there is a demand for thickeners that are highly compatible with volatile and non-volatile silicone oils, hydrocarbon oils, ester oils, natural animal and vegetable oils, and that can paste or solidify various oils. It was.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have developed a product having a urethane bond obtained from a polyhydric alcohol having one or two alkenyl groups in one molecule and an alkyl isocyanate, with methyl A silicone-modified wax obtained by subjecting a hydrogen organopolysiloxane to a hydrosilylation reaction and having a solid or thixotropic property at 25 ° C. is a volatile and non-volatile silicone. It has been found that a paste-like or solid composition having high compatibility with oils, hydrocarbon oils, ester oils, natural animal and vegetable oils, etc., and thickening various oils can be made smooth and good.

  That is, the present invention comprises subjecting a methylhydrogenorganopolysiloxane to a hydrosilylation reaction with a product having a urethane bond obtained from a polyhydric alcohol having one or two alkenyl groups in one molecule and an alkyl isocyanate. And a silicone-modified wax characterized by being in the form of a grease having a solid or thixotropic property at 25 ° C.

The present invention also provides:
(I) a step of urethanating a polyhydric alcohol having 1 or 2 alkenyl groups in one molecule and an alkyl isocyanate in the absence of a catalyst or in the presence of a catalyst to obtain a product having a urethane bond;
(II) hydrosilylation reaction of the urethanization reaction product and methyl hydrogen organopolysiloxane in the presence of a catalyst;
A method for producing a silicone-modified wax is provided.

As the polyhydric alcohol having one or two alkenyl groups in one molecule used in the present invention, a straight chain having any one of the following structural formulas (B), (C), (D), and (E) Alternatively, branched one or two alkenyl group-containing polyglycerols can be mentioned.

（上記式中、ａ、ｂ、ｃ、ｄはそれぞれ２又は３である。） Further, those having an alkenyl group at the end can be preferably used. For example, the following triglycerin derivatives and tetraglycerin derivatives are preferable, and the following can be used.

(In the above formula, a, b, c and d are 2 or 3, respectively.)

  In addition, the structure of the polyhydric alcohol having one or two alkenyl groups used in the present invention may have a linear, branched, or cyclic ether structure.

  These alkenyl group-containing polyhydric alcohols can be obtained by reacting polyglycerin such as glycerin or diglycerin or triglycerine with allyl glycidyl ether in the presence of an alkali catalyst such as potassium hydroxide. it can. The reaction temperature is preferably controlled at 60 to 120 ° C. After the reaction, after neutralizing the alkali catalyst, the low-boiling component is distilled off to obtain the target product (polyhydric alcohol having one or two alkenyl groups).

  The alkyl group of the alkyl isocyanate used in the present invention is preferably an alkyl group having 8 to 20 carbon atoms. The alkyl group is octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl. The alkyl group may be a straight chain or a branched structure, but a straight chain alkyl group is preferred. These compounds may be used alone or in combination of two or more.

And the polyhydric alcohol which has the 1 or 2 alkenyl group in 1 molecule mentioned above, and alkyl isocyanate are prepared to reaction container, and it is about 5-10 hours at 30-100 degreeC in inert gas stream. A urethanization reaction product having a urethane bond can be obtained by performing a urethanization reaction and performing purification treatment such as decolorization and deodorization by a conventional method after completion of the urethanization reaction.
In the urethanization reaction, an acid catalyst, a metal catalyst, and a reflux solvent can be used as necessary.

（Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４は、それぞれ独立に、水素原子、同一又は異種の、分岐ポリグリセロール鎖が結合した連結基若しくは置換基を有していてもよい、炭素数１〜２２の直鎖もしくは分岐鎖のアルキル基又はアルコシキ基、炭素数６〜２２のアリール基、及びフッ素置換アルキル基のいずれかを示す。但し、Ｒ^１、Ｒ^３のうち少なくとも１つは水素原子を示し、Ｒ^２、Ｒ^４のうち少なくとも１つはメチル基を示す。ｎは０〜５０の整数を示す。） The methyl hydrogen organopolysiloxane to be hydrosilylated with the urethanization reaction product is an organopolysiloxane having at least one hydrogen atom directly bonded to a silicon atom and at least one methyl group directly bonded to a silicon atom in one molecule. And methylhydrogenorganopolysiloxane containing 1 to 5 hydrogen atoms (that is, SiH groups) bonded to a silicon atom represented by the following general formula (A) in one molecule.

(R ¹ , R ² , R ³ and R ⁴ each independently have a hydrogen atom, the same or different, a linking group or substituent to which the same or different branched polyglycerol chain is bonded, 22 represents a linear or branched alkyl group or alkoxy group, an aryl group having 6 to 22 carbon atoms, and a fluorine-substituted alkyl group, provided that at least one of R ¹ and R ³ represents a hydrogen atom. And at least one of R ² and R ⁴ represents a methyl group, and n represents an integer of 0 to 50.)

  Among these, Preferably, it is hydrogen organopolysiloxane which has one Si-H in a molecule | numerator, More preferably, it is (alpha) -hydrogen organopolysiloxane which has Si-H at the molecule | numerator piece terminal.

  As a synthesis method of methylhydrogensiloxane used in the present invention, hexamethylsiloxane, octamethylcyclotetrasiloxane (D4) and tetramethyltetrahydrogencyclotetrasiloxane (H4) are charged into a reaction vessel, an acid catalyst is added, After stirring at room temperature overnight, methylhydrogensiloxane can be obtained by performing purification treatment such as neutralization, decolorization, and deodorization.

  The methyl hydrogen organopolysiloxane and the glycerin derivative having an alkenyl group (the urethanization reaction product) in a molar ratio of Si-H group / alkenyl group of 0.5 or more and less than 1.5, preferably 0.8 Add less than 1.2 above.

The addition reaction is preferably performed in the presence of a platinum catalyst or a rhodium catalyst. Examples of preferable catalysts include chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid-vinylsiloxane complex, and the like.
The above addition reaction is carried out without solvent or in an organic solvent as necessary. Examples of the organic solvent include aliphatic alcohols such as methanol, ethanol, 2-propanol and butanol, aromatic hydrocarbons such as toluene and xylene, aliphatic or alicyclic carbonization such as n-pentane, n-hexane and cyclohexane. Examples thereof include halogenated hydrocarbons such as hydrogen, dichloromethane, chloroform, and carbon tetrachloride.

Although the addition reaction conditions are not particularly limited, since the obtained silicone wax is solid or grease-like at room temperature, the reaction at a reaction temperature higher than the melting point of the silicone wax makes the reaction system uniform. Preferably, when the reaction is performed in an organic solvent, the reaction is preferably performed under reflux for 5 to 10 hours.
After the addition reaction, removal of the allyl ether group with weak hydrochloric acid or alkylation by hydrogenation reaction may be performed by a known method. Moreover, you may add tocopherol and BHT (dibutylhydroxytoluene) as antioxidant.

  The silicone-modified wax of the present invention is in the form of a grease having a solid or thixotropy at 25 ° C., and the silicone-modified wax can achieve a melting point of 40 to 100 ° C., further 50 to 80 ° C. If the melting point is 40 ° C. or higher, the thickening effect is generally sufficient, and there is little risk of lowering the viscosity of cosmetics or causing phase separation in summer. Conversely, if it is 100 degrees C or less, since there is no possibility of causing deterioration and decomposition | disassembly of the other component in cosmetics, it is preferable.

  In addition, the silicone-modified wax of the present invention preferably has a polystyrene-equivalent weight average molecular weight of 500 to 10,000 as measured by gel permeation chromatography (GPC).

[Composition]
The composition according to the present invention contains 5 to 40% by mass of the silicone-modified wax of the present invention. Since the silicone-modified wax thickens various oils and the like, mixing with various oils provides a paste or solid composition that is smooth and stretchable at 25 ° C. and normal pressure, and has compatibility with various oils. It will be expensive. The composition is, for example, a mixture of the silicone-modified wax of the present invention and a silicone oil to be described later, and can be used for car wax, various mold release agents and the like in addition to a cosmetic to be described later.

[Cosmetics]
The silicone-modified wax having a urethane bond according to the present invention can be used in various cosmetics, and is particularly applied to skin and hair such as skin care products, makeup products, hair products, antiperspirant products, and UV control products. It is suitable as a raw material for cosmetics. The blending amount of the silicone-modified wax in the cosmetic is in the range of 0.5 to 95% by mass, preferably 1 to 70% by mass, based on the type of cosmetic and the type of silicone oil to be blended. Can be adjusted as appropriate. For example, in the case of a creamy cosmetic, in a solid or sticky cosmetic with 0.5 to 10% by mass, preferably 0.5 to 5% by mass of the total cosmetic, and with a powder component of 25% or less of the total formulation, When 2 to 70% by mass, preferably 2 to 50% by mass of the total cosmetic is suitable, and the powder component is a solid cosmetic of 80% or more of the total formulation, It is blended at 10% by mass, preferably 1-5% by mass.

（上式でＲ^５は、水素原子、水酸基又は炭素数１〜２０の１価の非置換又はフッ素置換されたアルキル基、アリール基、アミノ置換アルキル基、アルコキシ基及び一般式（ＣＨ_３）_３ＳｉＯ｛（ＣＨ_３）_２ＳｉＯ｝_ｓＳｉ（ＣＨ_３）_２ＣＨ_２ＣＨ_２−で示される基からなる群より選択される基である。ｍは０〜１０００の整数、ｌは０〜１０００の整数、ｌ＋ｍが１〜１０００の整数、ｘ、ｙは０、１、２又は３、ｐ及びｑは０〜８の整数で３≦ｐ＋ｑ≦８、ｒは１〜４の整数である。） The silicone-modified wax is preferably blended in a cosmetic together with silicone oil. In the present specification, the silicone oil includes not only a silicone compound that is liquid at room temperature (25 ° C.) but also a silicone resin that is resinous and gum-like at room temperature. What is dissolved or disperse | distributed in oil agents, such as hydrogen oil and ester oil, is also included. These silicone oils are mixed with the silicone-modified wax to give a paste or solid composition that is smooth and stretchable.
Preferred silicone oils include the following:

(In the above formula, R ⁵ represents a hydrogen atom, a hydroxyl group, or a monovalent unsubstituted or fluorine-substituted alkyl group having 1 to 20 carbon atoms, an aryl group, an amino-substituted alkyl group, an alkoxy group, and a general formula (CH ₃ ) _3. SiO {(CH ₃ ) ₂ SiO} _s Si (CH ₃ ) ₂ CH ₂ CH ₂ — is a group selected from the group consisting of: m is an integer from 0 to 1000, and l is from 0 to 1000. An integer, l + m is an integer of 1 to 1000, x and y are 0, 1, 2 or 3, p and q are integers of 0 to 8, 3 ≦ p + q ≦ 8, and r is an integer of 1 to 4.

Examples of R ⁵ include methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, trifluoropropyl group, nonafluorohexyl group, Heptadecylfluorodecyl group, phenyl group, aminopropyl group, dimethylaminopropyl group, aminoethylaminopropyl group, stearoxy group, butoxy group, ethoxy group, propoxy group, cetyloxy group, myristyloxy group, styryl group, α-methylstyryl group Hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, trifluoropropyl group, phenyl group, aminopropyl group, and aminoethylaminopropyl group are preferable.

Examples of silicone oils include low to high viscosity, preferably 0.65 to 1,000,000, such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, dimethylsiloxane / methylphenylsiloxane copolymer, etc. Organopolysiloxane, octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), tetramethyltetrahydrogencyclotetrasiloxane (D6), which is liquid at room temperature of 000 mm ² / s H4), cyclic siloxanes such as tetramethyltetraphenylcyclotetrasiloxane, tristrimethylsiloxysilane (M3T), tetrakistrimethylsiloxysilane (M4Q), tristrimethylsiloxyphenylsilane Branched siloxane emissions such, higher alkoxy-modified silicones such as stearoxysilicone silicones, alkyl-modified silicones, amino-modified silicones, fluorine-modified silicone, and the like.

One of the preferable silicone resins used by dissolving or dispersing in a low-viscosity oil agent is an alkyl hydrogen polysiloxane and a crosslinking agent having at least two reactive vinyl unsaturated groups in the molecular chain. And a cross-linked organopolysiloxane obtained by reacting with swelled with an oil agent having a weight higher than its own weight, particularly a silicone oil having a viscosity of 0.65 to 10.0 mm ² / s higher than its own weight. Examples of the alkyl hydrogen polysiloxane include a methyl hydrogen polysiloxane having a linear or partially branched unit, a methyl hydrogen polysiloxane grafted with an alkyl chain having 6 to 20 carbon atoms, and a methyl hydrogen poly grafted with a polyoxyethylene chain. Genpolysiloxane and the like can be mentioned. Two or more hydrogen atoms bonded to silicon atoms are required on average in the molecule. Examples of the crosslinking agent include methyl vinyl polysiloxane, α, ω-alkenyl diene, glyceryl triallyl ether, polyoxyalkynylated glyceryl triallyl ether, trimethylolpropane triallyl ether, polyoxyalkynylated trimethylolpropane triallyl ether and the like. Thus, there may be mentioned those having two or more vinylic reactive sites in the molecule.

  Furthermore, the crosslinked organopolysiloxane contains in the crosslinked molecule at least one selected from the group consisting of a polyoxyalkylene moiety, a polyglycerin moiety, an alkyl moiety, an alkenyl moiety, an aryl moiety, and a fluoroalkyl moiety. Is preferred. Specific examples include JP-A-2-43263, JP-A-2-214775, JP-A-26131772, JP-A-9-136815 (KSG30), JP-A-2001-342255, International Publication WO03 / 20828 (KSG210), Those described in International Publication WO 03/24413 (KSG40) are preferred. By using this cross-linked organopolysiloxane, it can be expected that the anti-lighting effect, the matte feeling imparting effect, the adhesion improving effect, and the color transfer preventing effect are imparted.

  Specific examples of the composition comprising the cross-linked organopolysiloxane and an oil agent such as silicone oil, hydrocarbon oil, ester oil and the like include KSG-15, 16, 17, 18, 21, 210, 31, 32, 33, 34. , 310, 320, 330, 340, 41, 42, 43, 44, 710, 810, 820, 830, 840 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.).

A second preferable silicone resin used by dissolving or dispersing in a low-viscosity oil is a silicone resin that is in the form of gum or solid at room temperature and preferably dissolved in decamethylcyclopentasiloxane. Gum-like silicone resin, in the general formula _{(CH 3) 3 SiO {(} CH 3) 2 SiO} t linear silicone represented by _{{(CH 3) R 6 SiO} } u Si (CH 3) 3, R 6 Is selected from the group consisting of an alkyl group having 6 to 20 carbon atoms, an amino group-containing alkyl group having 3 to 15 carbon atoms, a fluorine-substituted alkyl group, and a quaternary ammonium base-containing alkyl group, t is 1001 to 20000, and u is 0 ˜5000, t + u is preferably 1001 to 25000.

  The solid silicone resin is an MQ comprising any combination of trialkylsiloxy units (M units), dialkylsiloxy units (D units), monoalkylsiloxy units (T units), and tetrafunctional siloxy units (Q units). A silicone network compound which is a resin, MDQ resin, MTQ resin, MDTQ resin, TD resin, TQ resin, or TDQ resin is preferable. Particularly preferred is a silicone network compound containing in the molecule at least one part selected from the group consisting of a pyrrolidone moiety, a long-chain alkyl moiety, a polyoxyalkylene moiety and a fluoroalkyl moiety (Japanese Patent Laid-Open No. 2000-234062, Patent No. 32188872).

  A third preferable silicone resin used by dissolving or dispersing in a low-viscosity oil is a volatile silicone, a volatile hydrocarbon oil, a nonvolatile silicone, a nonvolatile silicone resin that is semi-solid to solid at room temperature. It is dissolved in a basic hydrocarbon oil. This acrylic silicone resin is particularly preferably an acrylic silicone resin containing in its molecule at least one moiety selected from the group consisting of a pyrrolidone moiety, a long-chain alkyl moiety, a polyoxyalkylene moiety and a fluoroalkyl moiety. The structure of the acrylic silicone resin may be a silicone chain, or one of the acrylic chains may be in the form of a graft, or may be in the form of a block of a silicone chain and an acrylic chain (Japanese Patent Laid-Open No. 1-319518, Japanese Patent No. 2704730). No. 2,767,633, Japanese Patent No. 2,767,636, and Japanese Patent Laid-Open No. 2000-344829).

Of the silicone oils described above, preferably, dimethylpolysiloxane, decamethylcyclopentasiloxane having a viscosity of 1 to 30 mm ² / s (25 ° C.), silicone having a viscosity of 0.65 to 10.0 mm ² / s that is higher than its own weight. Cross-linked dimethylpolysiloxane, cross-linked polyether-modified silicone, and acrylic silicone resin dissolved in volatile oil are used. Each of these silicone oils may be used alone or as a mixture.

  The silicone modified wax of the present invention and the silicone oil are mixed in a weight ratio of 1: 0.01 to 1:45, preferably 1: 0.5 to 1:20. It is preferable to mix so that it may contain the mass%, and to mix | blend with cosmetics as a uniform paste-form, gel-form, or solid composition. The blending amount of the silicone oil in the entire cosmetic can be appropriately adjusted according to the type of the cosmetic, but is typically in the range of 1 to 70% by mass, preferably 3 to 60% by mass. Here, the mass of the silicone oil is an amount including the solvent.

  In addition to silicone oil, the cosmetic of the present invention may contain one or more oil agents depending on the purpose. As long as it is used for normal cosmetics, any oil agent of solid, semi-solid and liquid can be used. Examples of such oils include natural animal and plant oils and semi-synthetic oils, hydrocarbon oils, higher alcohol oils, ester oils, and fluorine oils.

  For example, natural animal and vegetable oils and semi-synthetic fats and oils include avocado oil, linseed oil, almond oil, ibotarou, eno oil, olive oil, cacao fat, kapok wax, kaya oil, carnauba wax, liver oil, candelilla wax, beef tallow, beef leg fat , Beef bone fat, hydrogenated beef tallow, kyounin oil, whale wax, hydrogenated oil, wheat germ oil, sesame oil, rice germ oil, rice bran oil, sugarcane wax, sasanqua oil, safflower oil, shea butter, cinnamon oil, cinnamon oil, jojo Barrow, shellac wax, turtle oil, soybean oil, tea seed oil, camellia oil, evening primrose oil, corn oil, lard, rapeseed oil, Japanese kiri oil, nukarou, germ oil, horse fat, persic oil, palm oil, palm kernel oil , Castor oil, hydrogenated castor oil, castor oil fatty acid methyl ester, sunflower oil, grape oil, bayberry wax, jojoba oil, macadamia Ritz oil, beeswax, mink oil, cottonseed oil, cotton wax, owl, owl kernel oil, montan wax, coconut oil, hardened coconut oil, tricoconut oil fatty acid glyceride, sheep oil, peanut oil, lanolin, liquid lanolin, reduced lanolin, lanolin alcohol Hard lanolin, lanolin acetate, lanolin fatty acid isopropyl, hexyl laurate, POE lanolin alcohol ether, POE lanolin alcohol acetate, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, egg yolk oil and the like. However, POE means polyoxyethylene.

  As hydrocarbon oils, ozokerite, squalane, squalene, ceresin, paraffin, paraffin wax, polyethylene wax, polyethylene-polypropylene copolymer, liquid paraffin, pristane, polyisobutylene, microcrystalline wax, petrolatum, etc .; as higher fatty acid, lauric acid , Myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), isostearic acid, 12-hydroxystearic acid, etc. Is mentioned.

  As higher alcohols, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol, hexyl decanol, octyldodecanol, cetostearyl alcohol, 2-decyltetradecinol, Examples include cholesterol, phytosterol, POE cholesterol ether, monostearyl glycerin ether (batyl alcohol), monooleyl glyceryl ether (ceracyl alcohol), and the like.

  Examples of ester oils include diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, N-alkyl glycol monoisostearate, isocetyl isostearate, trimethylolpropane triisostearate, isotridecyl isononanoate, isononane Isononyl acid, ethylene glycol di-2-ethylhexanoate, cetyl 2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, cetyl octanoate, octyldodecyl gum ester, Oleyl oleate, octyldodecyl oleate, decyl oleate, neopentyl glycol dicaprate, triethyl citrate, 2-ethylhexyl succinate, amyl acetate, Ethyl acetate, butyl acetate, isocetyl stearate, butyl stearate, diisopropyl sebacate, di-2-ethylhexyl sebacate, cetyl lactate, myristyl lactate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, palmitate 2-heptylundecyl acid, cholesteryl 12-hydroxystearylate, dipentaerythritol fatty acid ester, isopropyl myristate, octyldodecyl myristate, 2-hexyldecyl myristate, myristyl myristate, hexyldecyl dimethyloctanoate, ethyl laurate, Hexyl laurate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, diisostearyl malate, etc .; Glyceryl triisooctanoate glyceryl triisostearate, glyceryl triisopalmitate, glyceryl monostearate, di-2-heptyl undecanoic acid, glyceryl trimyristate, diglyceryl, and the like myristyl isostearate.

  Examples of the fluorinated oil include perfluoropolyether, perfluorodecalin, and perfluorooctane.

  The blending amount of these oils is preferably in the range of 5 to 95% by mass of the entire cosmetic. In particular, when the cosmetic is in the form of a solid or stick, the blending amount is preferably 10 to 50% by mass of the entire cosmetic.

  In the cosmetic of the present invention, one or more compounds having an alcoholic hydroxyl group in the molecular structure may be used depending on the purpose. Examples of the compound having an alcoholic hydroxyl group which can be added in the present invention include lower alcohols such as ethanol and isopropanol, sugar alcohols such as sorbitol and maltose, sterols such as cholesterol, sitosterol, phytosterol and lanosterol, butylene glycol, There are polyhydric alcohols such as propylene glycol, dibutylene glycol and pentylene glycol. As a compounding quantity, the range of 0.1-98 mass% of the whole cosmetics is suitable.

  Water can be blended in the cosmetic of the present invention depending on the purpose. The blending amount is preferably in the range of 1 to 95% by mass of the entire cosmetic.

  In the cosmetic of the present invention, one or more compounds having a powder and / or a colorant may be used depending on the purpose.

  As powder, if it is used for normal cosmetics, its shape (spherical, needle-like, plate-like, etc.), particle size (smoke-like, fine particles, pigment grade, etc.), particle structure (porous, Any one can be used regardless of non-porous or the like). Examples thereof include inorganic powders, organic powders, surfactant metal salt powders, colored pigments, pearl pigments, metal powder pigments, tar dyes, natural dyes, and the like.

  Specific examples of the inorganic powder include titanium oxide, zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, mica, kaolin, sericite, muscovite. , Synthetic mica, phlogopite, saucite, biotite, lithia mica, silicic acid, anhydrous silicic acid, aluminum silicate, magnesium silicate, magnesium aluminum silicate, calcium silicate, barium silicate, strontium silicate, tungstic acid Examples thereof include metal salts, hydroxyapatite, vermiculite, hydrite, bentonite, montmorillonite, hectorite, zeolite, ceramic powder, dicalcium phosphate, alumina, aluminum hydroxide, boron nitride, and silica.

  Specific examples of organic powders include polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane, benzoguanamine powder, polymethylbenzoguanamine powder, tetrafluoroethylene powder, polymethylmethacrylate powder, cellulose, silk powder, nylon Powder, 12 nylon, 6 nylon, crosslinked silicone fine powder having a structure in which dimethyl silicone is crosslinked, fine powder of polymethylsilsesquioxane, composite powder in which polymethylsilsesquioxane is bonded to crosslinked silicone, Styrene / acrylic acid copolymer, divinylbenzene / styrene copolymer, vinyl resin, urea resin, phenol resin, fluororesin, silicon resin, acrylic resin, melami Resins, epoxy resins, polycarbonate resin, microcrystalline fiber powder, starch powder, and lauroyl lysine.

  Specific examples of the surfactant metal salt powder (metal soap) include zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc myristate, magnesium myristate, zinc cetyl phosphate, calcium cetyl phosphate, and zinc cetyl phosphate. Sodium etc. are mentioned.

  Specific examples of colored pigments include inorganic red pigments such as iron oxide, iron hydroxide, and iron titanate, inorganic brown pigments such as γ-iron oxide, inorganic yellow pigments such as yellow iron oxide and loess, black iron oxide, Inorganic black pigments such as carbon black, inorganic purple pigments such as manganese violet and cobalt violet, inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide and cobalt titanate, inorganic blue pigments such as bitumen and ultramarine, tar Examples include raked pigments, raked natural pigments, and synthetic resin powders obtained by combining these powders.

  Specific examples of pearl pigments include titanium oxide coated mica, titanium oxide coated mica, bismuth oxychloride, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, fish scale foil, titanium oxide coated colored mica, etc .; Examples thereof include aluminum powder, copper powder, and stainless steel powder.

  As tar pigments, Red No. 3, Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 227, Red No. 228, Red 230, Red 401, Red 505, Yellow 4, Yellow 5, Yellow 202, Yellow 203, Yellow 204, Yellow 401, Blue 1, Blue 2, Blue 201, Blue 404 Green No. 3, Green No. 201, Green No. 204, Green No. 205, Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 206, Orange No. 207, etc .; natural pigments include carminic acid, laccaic acid, and calsamine , A powder selected from brazirin, crocin and the like.

  These powders can be used in combination with powders or those treated with general oils, silicone oils, fluorine compounds, surfactants, etc., and can be used alone or in combination of two or more as required. Can do. Moreover, as a compounding quantity, the range of 0.1-99 mass% of the whole cosmetics is suitable. In particular, the blending amount in the case of a powdered solid cosmetic is preferably in the range of 80 to 99% by mass of the entire cosmetic.

  In the cosmetic of the present invention, one or more surfactants can be used depending on the purpose. Such surfactants include anionic, cationic, nonionic and amphoteric active agents, but are not particularly limited, and any surfactant can be used as long as it is used in normal cosmetics. Things can also be used.

  Examples of anionic surfactants include fatty acid soaps such as sodium stearate and triethanolamine palmitate, alkyl ether carboxylic acids and salts thereof, condensates of amino acids and fatty acids, alkane sulfonates, and alkene sulfones. Acid salt, sulfonate of fatty acid ester, sulfonate of fatty acid amide, formalin condensation sulfonate, alkyl sulfate ester, secondary higher alcohol sulfate, alkyl and allyl ether sulfate, sulfuric acid of fatty acid ester Ester salts, sulfate esters of fatty acid alkylolamides, sulfate esters such as funnel oil, alkyl phosphates, ether phosphates, alkyl allyl ether phosphates, amide phosphates, N-acyl amino acid based activators, etc .; As a cationic surfactant The alkylamine salts, polyamines and amine salts such as an amino alcohol fatty acid derivatives, alkyl quaternary ammonium salts, aromatic quaternary ammonium salts, pyridinium salts and imidazolium salts.

  Nonionic surfactants include sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, poly Oxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene glyceryl glycerin fatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene castor oil, Polyoxyethylene hydrogenated castor oil, polyoxyethylene phytostanol ether, polyoxyethylene N-phytosterol ether, polyoxyethylene cholestanol ether, polyoxyethylene cholesteryl ether, polyoxyalkylene-modified organopolysiloxane (see Japanese Patent No. 2137062, JP-A-7-330907), polyglycerin-modified organopolysiloxane (Japanese Patent Publication No. 62) -34039, Japanese Patent No. 2613124, Japanese Patent No. 2844453, Japanese Patent Laid-Open No. 2002-179798), polyoxyalkylene / alkyl co-modified organopolysiloxane (Japanese Patent Laid-Open No. 61-90732, Japanese Patent Laid-Open No. 9-59386) Reference), alkanolamides, sugar ethers, sugar amides, and the like. Examples of amphoteric surfactants include betaines, aminocarboxylates, imidazoline derivatives, and amidoamine types. Moreover, as a compounding quantity, 0.1-20 mass% of the whole cosmetics, Especially preferably, the range of 0.2-10 mass% is suitable.

  Furthermore, the cosmetics of the present invention include components used in ordinary cosmetics, such as oil-soluble gelling agents, organically modified clay minerals, resins, antiperspirants, UV absorbers, UV absorbers, humectants, antiseptics. Agent, antibacterial agent, fragrance, salt, antioxidant, pH adjuster, chelating agent, refreshing agent, anti-inflammatory agent, skin beautifying agent (whitening agent, cell activator, rough skin improving agent, blood circulation promoter, skin astringent, Antiseborrheic agents, etc.), vitamins, amino acids, nucleic acids, hormones, inclusion compounds, hair solidifying agents and the like can be added.

Examples of oil-soluble gelling agents include metal soaps such as aluminum stearate, magnesium stearate, zinc myristate, amino acid derivatives such as N-lauroyl-L-glutamic acid, α, γ-di-n-butylamine, and dextrin palmitate Dextrin stearate, dextrin fatty acid ester such as dextrin 2-ethylhexanoic acid palmitic acid ester, fructooligosaccharide fatty acid ester such as fructooligosaccharide stearic acid ester, inulin 2-ethylhexanoic acid stearic acid ester, sucrose palmitic acid ester, Sucrose fatty acid esters such as sugar stearate, benzylidene derivatives of sorbitol such as monobenzylidene sorbitol, dibenzylidene sorbitol, dimethylbenzyl dodecyl an Examples thereof include gelling agents selected from organically modified clay minerals such as monium montmorillonite clay and dimethyl dioctadecyl ammonium montmorillonite clay.
Examples of the resin include resins selected from poly (meth) acrylate, polyethylene, polyester, polypropylene, polystyrene, polyurethane, polyamide (for example, nylon (registered trademark), epoxy resin, urea resin, acrylic resin, and the like).

  Examples of the antiperspirant include an antiperspirant selected from aluminum chlorohydrate, aluminum chloride, aluminum sesquichlorohydrate, zirconyl hydroxychloride, aluminum zirconium hydroxychloride, aluminum zirconium glycine complex, and the like.

  Examples of UV absorbers include benzoic acid UV absorbers such as paraaminobenzoic acid, anthranilic UV absorbers such as methyl anthranilate, salicylic acid UV absorbers such as methyl salicylate, and cinnamon such as octyl paramethoxycinnamate. Acid UV absorbers, benzophenone UV absorbers such as 2,4-dihydroxybenzophenone, urocanic acid UV absorbers such as ethyl urocanate, dibenzoyl such as 4-t-butyl-4'-methoxy-dibenzoylmethane Methane-based ultraviolet absorbers and the like, and examples of the ultraviolet absorption and scattering agent include powders that absorb and scatter ultraviolet rays, such as fine particle titanium oxide, fine particle iron-containing titanium oxide, fine particle zinc oxide, fine particle cerium oxide, and composites thereof. It is done.

  Moisturizers include glycerin, sorbitol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, pentylene glycol, glucose, xylitol, maltitol, polyethylene glycol, hyaluronic acid, chondroitin sulfate, pyrrolidone carboxylate, polyoxy Examples include ethylene methyl glucoside and polyoxypropylene methyl glucoside.

  Antibacterial and antiseptics include paraoxybenzoic acid alkyl esters, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol, etc., and antibacterial agents include benzoic acid, salicylic acid, carboxylic acid, sorbic acid, paraoxybenzoic acid alkyl ester , Parachlorometacresol, hexachlorophene, benzalkonium chloride, chlorhexidine chloride, trichlorocarbanilide, photosensitizer, phenoxyethanol and the like.

  Perfumes include aloe, turmeric, oolong tea, olive, orange, licorice, raspberry, keihi, salvia, perilla, peony, carrot, loquat, safflower, peppermint, peach, lime, lavender, green tea, rosemary, royal jelly, wild thyme, etc. There are extract liquids.

  Examples of the salts include inorganic salts, organic acid salts, amine salts, and amino acid salts. Examples of inorganic salts include sodium salts, potassium salts, magnesium salts, calcium salts, aluminum salts, zirconium salts, zinc salts, and the like of inorganic acids such as hydrochloric acid, sulfuric acid, carbonic acid, and nitric acid; Salts of organic acids such as dehydroacetic acid, citric acid, malic acid, succinic acid, ascorbic acid, stearic acid; amine salts and amino acid salts include, for example, salts of amines such as triethanolamine, and amino acids such as glutamic acid There is salt. In addition, a salt such as hyaluronic acid and chondroitin sulfate, an aluminum zirconium glycine complex, etc., and an acid-alkali neutralized salt used in cosmetic formulations can also be used.

  Antioxidants include tocopherol, butylhydroxyanisole, dibutylhydroxytoluene, phytic acid, etc. pH adjusters include lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, dl-malic acid, potassium carbonate, sodium bicarbonate , Ammonium bicarbonate, etc., as a chelating agent, alanine, sodium edetate, sodium polyphosphate, sodium metaphosphate, phosphoric acid, etc., as a cooling agent, L-menthol, camphor, etc., as an anti-inflammatory agent, allantoin, Examples include glycyrrhizic acid and salts thereof, glycyrrhetinic acid and stearyl glycyrrhetinate, tranexamic acid, and azulene.

  As skin beautifying ingredients, placenta extract, whitening agents such as arbutin, glutathione, and yukinoshita extract, royal jelly, photosensitizer, cholesterol derivatives, cell activators such as calf blood extract, rough skin improver, nonyl acid wallenylamide, Nicotinic acid benzyl ester, nicotinic acid β-butoxyethyl ester, capsaicin, zingerone, cantalis tincture, ictamol, caffeine, tannic acid, α-borneol, tocopherol nicotinate, inositol hexanicotinate, cyclandrate, cinnarizine, trazoline, Examples thereof include blood circulation promoters such as acetylcholine, verapamil, cephalanthin and γ-oryzanol, skin astringents such as zinc oxide and tannic acid, and antiseborrheic agents such as sulfur and thianthol.

  Vitamins such as vitamin A oil, retinol, retinol acetate, retinol palmitate, etc., vitamin B2 such as riboflavin, riboflavin butyrate, flavin adenine nucleotide, pyridoxine hydrochloride, pyridoxine dioctanoate, pyridoxine tripalmi Vitamin B6 such as tate, vitamin B12 and derivatives thereof, vitamin B such as vitamin B15 and derivatives thereof, L-ascorbic acid, L-ascorbic acid dipalmitate, L-ascorbic acid-2-sodium sulfate, L- Vitamin C such as ascorbic acid phosphoric acid diester dipotassium, vitamin D such as ergocalciferol, cholecalciferol, α-tocopherol, β-tocopherol, γ-tocopherol, dl-α-tocopherol acetate , Vitamin E such as dl-α-tocopherol nicotinate, dl-α-tocopherol succinate, nicotinic acids such as vitamin H, vitamin P, nicotinic acid, benzyl nicotinate, nicotinamide, calcium pantothenate, D-pant There are pantothenic acids such as tenenyl alcohol, pantothenyl ethyl ether, acetyl pantothenyl ethyl ether, biotin and the like.

  As amino acids, glycine, valine, leucine, isoleucine, serine, threonine, phenylalanine, arginine, lysine, aspartic acid, glutamic acid, cystine, cysteine, methionine, tryptophan, etc., nucleic acid, deoxyribonucleic acid, etc., hormone, estradiol , Etenyl estradiol and the like.

  Examples of the inclusion compound include cyclodextrins and crown ethers.

  Examples of the hair fixing polymer compound include amphoteric, anionic, cationic, and nonionic polymer compounds, such as polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymer, Acid vinyl ether polymer such as methyl vinyl ether / maleic anhydride alkyl half ester copolymer, acid polyvinyl acetate polymer such as vinyl acetate / crotonic acid copolymer, (meth) acrylic acid / alkyl (meth) acrylate Copolymer, acidic acrylic polymer such as (meth) acrylic acid / alkyl (meth) acrylate / alkylacrylamide copolymer, N-methacryloylethyl-N, N-dimethylammonium / α-N-methylcarboxybetaine / Alkyl (meth) acrylate copolymer, H Rokishipuropiru (meth) acrylate / butylaminoethyl methacrylate / amphoteric acrylic polymer compounds such as acrylic acid octyl amide copolymers. In addition, naturally-derived polymer compounds such as cellulose or derivatives thereof, keratin and collagen or derivatives thereof can also be suitably used.

  In the present invention, cosmetics include skin lotions, emulsions, creams, cleansings, packs, oil liquids, massage agents, cleaning agents, deodorants, hand creams, lip balms and other skin care cosmetics, makeup bases, white powder, liquid foundations. Makeup cosmetics such as oily foundation, blusher, eye shadow, mascara, eyeliner, eyebrow, lipstick, hair cosmetics such as shampoos, rinses, treatments, set agents, antiperspirants, sunscreen emulsions and sunscreen creams, etc. UV protection cosmetics and the like.

  In addition, these cosmetics have various shapes such as liquid, emulsion, cream, solid, paste, gel, powder, press, multilayer, mousse, spray, stick, pencil, etc. However, a solid form or a stick form is particularly preferable.

  Synthesis Examples, Synthesis Comparative Examples, Examples and Comparative Examples are shown below to describe the present invention more specifically, but the present invention is not limited thereto. In the present specification, Me represents a methyl group, and Bu represents a butyl group.

(Synthesis Example 1)
A three-necked flask was charged with 1.0 mol of glycerin monoallyl ether having the following structure and 1.96 mol of octadecyl isocyanate, and urethanated at a temperature of 100 ° C. for 8 hours in a nitrogen stream without a catalyst. A compound of the following structural formula (I) having a urethane bond was obtained. As a silicone modification of compound (I), 30% by weight of isopropanol as a solvent, compound (I) (double bond 1.0 mol) and methyl hydrogen organopolysiloxane (Si-H 1.2 mol) having the following structure were added, 0.02% by mass of a 3% ethanol solution of chloroplatinic acid was added as a catalyst, and an addition reaction was carried out at 100 ° C. for 8 hours under a nitrogen stream. Thereafter, the solvent was heated and stripped under reduced pressure to obtain a white solid product of the following structural formula (J) at room temperature.

Glycerin monoallyl ether:

（式（Ｉ）中のＷは下記構造式（Ｗ）である。）

(W in formula (I) is the following structural formula (W).)

Methyl hydrogen organopolysiloxane:

（式（Ｊ）中のＷは下記構造式（Ｗ）である。）

(W in formula (J) is the following structural formula (W).)

（式（Ｗ）中のＸは下記構造式（Ｘ）である。）

(X in the formula (W) is the following structural formula (X).)

(Synthesis Example 2)
A three-necked flask was charged with 1.0 mol of glycerin monoallyl ether and 1.96 mol of octadecyl isocyanate, and urethanated at a temperature of 100 ° C. for 8 hours in a nitrogen stream without a catalyst. A compound of the above structural formula (I) was obtained. As a silicone modification of Compound (I), 30% by weight of isopropanol as a solvent, Compound (I) (1.0 mol of double bond) and 1.2 mol of methyl hydrogen organopolysiloxane having the following structure were added, and platinum chloride as a catalyst. 0.02% by mass of a 3% ethanol solution of acid was added, and an addition reaction was performed at a temperature of 100 ° C. for 8 hours under a nitrogen stream. Thereafter, the solvent was heated and stripped under reduced pressure to obtain a white solid product of the following structural formula (K) at room temperature.

Methyl hydrogen organopolysiloxane:

（式（Ｋ）中のＷは上記構造式（Ｗ）である。）

(W in formula (K) is the above structural formula (W).)

(Synthesis Example 3)
A three-necked flask was charged with 1.0 mol of glycerin monoallyl ether and 1.96 mol of octadecyl isocyanate, and 0.05% by mass of triethylamine as a catalyst was subjected to a urethanization reaction at a temperature of 100 ° C. for 8 hours under a nitrogen stream. The compound of the above structural formula (I) having a white solid urethane bond was obtained. As a silicone modification of compound (I), 30% by weight of isopropanol as a solvent, compound (I) (double bond 1.0 mol) and methyl hydrogen organopolysiloxane (Si-H 1.2 mol) having the following structure were added, 0.02% by mass of a 3% ethanol solution of chloroplatinic acid was added as a catalyst, and an addition reaction was carried out at 100 ° C. for 8 hours under a nitrogen stream. Thereafter, the solvent was heated and stripped under reduced pressure to obtain a white solid product of the above structural formula (J) at room temperature.

Methyl hydrogen organopolysiloxane:

(Synthesis Example 4)
A three-necked flask was charged with 1.0 mol of glycerin monoallyl ether and 1.96 mol of octadecyl isocyanate, and urethanated at a temperature of 100 ° C. for 8 hours in a nitrogen stream without a catalyst. A compound of the above structural formula (I) was obtained. As a silicone modification of compound (I), 30% by weight of isopropanol as a solvent, compound (I) (double bond 1.0 mol) and methyl hydrogen organopolysiloxane (Si-H 1.0 mol) having the following structure were added, 0.02% by mass of a 3% ethanol solution of chloroplatinic acid was added as a catalyst, and an addition reaction was carried out at 100 ° C. for 8 hours under a nitrogen stream. Thereafter, the solvent was heated and stripped under reduced pressure to obtain a white solid product of the following structural formula (L) at room temperature.

（式（Ｌ）中のＷは上記構造式（Ｗ）である。） Methyl hydrogen organopolysiloxane:

(W in the formula (L) is the above structural formula (W).)

(Synthesis Example 5)
A three-necked flask was charged with triglycerin monoallyl ether (OH 4.0 mol) having the following structure and 3.92 mol of octadecyl isocyanate, and subjected to a urethanization reaction at a temperature of 100 ° C. for 8 hours in a nitrogen stream without using a catalyst. The compound of the above structural formula (I) having a white solid urethane bond was obtained. As a silicone modification of the compound (I), 30% by weight of isopropanol as a solvent, a product (1.0 mol of a double bond) and methyl hydrogen organopolysiloxane (Si-H 1.2 mol) having the following structure were added as a catalyst. 0.02% by mass of a 3% ethanol solution of chloroplatinic acid was added, and an addition reaction was performed at 100 ° C. for 8 hours under a nitrogen stream. Thereafter, the solvent was stripped by heating under reduced pressure to obtain a white solid product of the following structural formula (M) at room temperature.

Triglycerin monoallyl ether:

Methyl hydrogen organopolysiloxane:

（式（Ｍ）中のＹは下記構造式（Ｙ）である。）

(Y in the formula (M) is the following structural formula (Y).)

（式（Ｙ）中のＷは上記構造式（Ｗ）である。）

(W in the formula (Y) is the above structural formula (W).)

(Synthesis Example 6)
A three-necked flask was charged with triglyceryl diallyl ether (OH 3.0 mol) having the following structure and 2.94 mol of octadecyl isocyanate, and subjected to a urethanization reaction at a temperature of 100 ° C. for 8 hours in a nitrogen stream under a non-catalytic condition. A white solid compound having a urethane bond was obtained. As a silicone modification of the obtained urethane compound, 30% by weight of isopropanol as a solvent, a urethane compound (double bond 1.0 mol) and methyl hydrogen organopolysiloxane (Si-H 1.2 mol) having the following structure were added, and a catalyst was added. As an addition, 0.02% by mass of a 3% ethanol solution of chloroplatinic acid was added, and an addition reaction was carried out at 100 ° C. for 8 hours under a nitrogen stream. Thereafter, the solvent was heated and stripped under reduced pressure to obtain a white solid product of the following structural formula (N) at room temperature.

Triglyceryl diallyl ether:

Methyl hydrogen organopolysiloxane:

（式（Ｎ）中のＺは下記構造式（Ｚ）であり、Ｗは上記構造式（Ｗ）である。）

(Z in the formula (N) is the following structural formula (Z), and W is the above structural formula (W).)

(Synthesis Comparative Example 1)
A three-necked flask was charged with 1.0 mol of glyceryl monoallyl ether and 1.96 mol of octadecyl isocyanate, and urethanated at a temperature of 100 ° C. for 8 hours in a nitrogen stream without a catalyst. The product of the above structural formula (I) having a urethane bond was obtained.

(Synthesis Comparative Example 2)
A three-necked flask was charged with 1.0 mol of glycerin monoallyl ether and 1.96 mol of behenic acid, and 0.05% by mass of p-toluenesulfonic acid as a catalyst, at a temperature of 190 ° C. for 10 hours in a nitrogen stream. Went. Thereafter, an aqueous sodium hydrogen carbonate solution was added as a neutralizing agent, a neutralization reaction was performed at a temperature of 70 ° C. for 1 hour, cooled, dissolved in tetrahydrofuran, filtered, and the solvent was stripped by heating under reduced pressure to form the following structure. A pale yellow solid product of formula (O) was obtained. (V in the formula (O) is C (═O) C ₂₁ H _43. ) As a silicone modification of the compound (O), 30% by weight of isopropanol as a solvent, compound (O) (1.0 mol of double bond) ) And methylhydrogenorganopolysiloxane (Si-H1.2 mol) having the following structure, 0.02% by mass of a 3% ethanol solution of chloroplatinic acid as a catalyst, and a nitrogen stream at 8O 0 C for 8 hours. The addition reaction was performed. Thereafter, the solvent was heated and stripped under reduced pressure to obtain a white solid product of the following structural formula (P) at room temperature.

Methyl hydrogen organopolysiloxane:

（式（Ｐ）中のＱは下記構造式（Ｑ）である。）

(Q in Formula (P) is the following structural formula (Q).)

  Table 1 below shows the melting points and weight average molecular weights of the compounds described in Synthesis Examples 1 to 6 and Synthesis Comparative Examples 1 and 2, respectively.

合成実施例１と合成比較例２は、それぞれウレタン結合、エステル結合を含有するシリコーンワックスである。エステル結合よりもウレタン結合がより強い分子間力であるため、合成実施例１の方がより高い融点になったと考えられる。

Synthetic Example 1 and Synthetic Comparative Example 2 are silicone waxes containing a urethane bond and an ester bond, respectively. Since the urethane bond is a stronger intermolecular force than the ester bond, the synthesis example 1 is considered to have a higher melting point.

Compatibility of thickener with oil and evaluation of composition In order to evaluate the compatibility with various oils in Synthesis Examples 1 to 6 and Synthesis Comparative Examples 1 and 2, each thickener was added to 9 g of various oils. After adding 1 g, heating and dissolving at 80 ° C., and cooling at room temperature, the state of the composition was evaluated.

The compatibility was evaluated as follows.
○: dissolved, Δ: slightly turbid, ×: insoluble

ジメチルポリシロキサンは信越化学工業（株）製のＫＦ−９６−２ｃｓ、６ｃｓ、
メチルフェニルポリシロキサンは信越化学工業（株）製のＫＦ−５６Ａ

Dimethylpolysiloxane is KF-96-2cs, 6cs, manufactured by Shin-Etsu Chemical Co., Ltd.
Methylphenylpolysiloxane is KF-56A manufactured by Shin-Etsu Chemical Co., Ltd.

The evaluation of the thickening effect was as follows.
◎: Solidified, ○: Viscosity, Δ: Partial separation, ×: Separation

表２、３に示した通り、合成比較例１の増粘剤はシリコーン未変性であるため、シリコーン油との相溶性が低く、油剤が湧き出し、十分な増粘効果が得られなかった。これに対し、合成実施例１〜６の増粘剤はシリコーン変性により、シリコーン油への相溶性が高く、増粘又は固化した。
合成比較例２はエステル結合を有するシリコーンワックスであり、合成実施例１と比較すると、増粘効果が低かった。合成実施例１はウレタン結合を有するため、エステル結合よりも分子間力が強固となり、増粘効果が高くなったためと考えられる。

As shown in Tables 2 and 3, since the thickener of Synthesis Comparative Example 1 is unmodified with silicone, the compatibility with silicone oil is low, the oil agent springs up, and a sufficient thickening effect cannot be obtained. On the other hand, the thickeners of Synthesis Examples 1 to 6 were highly compatible with silicone oil and thickened or solidified by silicone modification.
Synthetic Comparative Example 2 was a silicone wax having an ester bond, and the thickening effect was low as compared with Synthetic Example 1. Since Synthesis Example 1 has a urethane bond, it is considered that the intermolecular force is stronger than the ester bond and the thickening effect is increased.

Using the thickeners of Synthesis Examples 1 to 6 and Synthesis Comparative Examples 1 and 2, cosmetics were evaluated.
(Example 1) Emulsion (component) Mass (%)
1. Silicone-modified wax obtained in Synthesis Example 1 2.0
2. Dimethylpolysiloxane 2cs 30.0
3. Decamethylcyclopentasiloxane 10.0
4). Glyceryl trioctanoate 5.0
5. Polyether-modified silicone (Note 1) 5.0
6.1,3-Butylene glycol 5.0
7). Preservative appropriate amount 8. Perfume appropriate amount 9. Purified water 43.0
(Note 1) Shin-Etsu Chemical Co., Ltd .: KF-6017 (trade name)
(Production method)
A) Components 1 to 5 are dissolved by heating.
B) After mixing components 6 to 7 and 9, add A) and emulsify.
C) B) above is cooled and component 8 is added to obtain an emulsion.
The emulsion of the present invention obtained as described above had no stickiness and good elongation. Also, a glossy finish was obtained when applied to the skin.

(Example 2) Water-in-oil cream (component) Mass (%)
1. Squalane 10.0
2. Decamethylcyclopentasiloxane 7.0
3. Dimethylpolysiloxane 2cs 5.0
4). Polyether-modified branched silicone (Note 1) 2.0
5. Silicone modified wax obtained in Synthesis Example 2 1.0
6). Dipropylene glycol 7.0
7). Preservative appropriate amount 8. Perfume appropriate amount 9. Purified water 68.0
(Note 1) Shin-Etsu Chemical Co., Ltd .: KF-6028 (trade name)
(Production method)
A) Components 1 to 5 are heated and mixed.
B) Components 6 to 9 are mixed and added to A) and emulsified with stirring.
The water-in-oil cream of the product of the present invention obtained as described above was a water-in-oil cream with no stickiness and good spread.

(Example 3) Water-in-oil cream (component) Mass (%)
1. Silicone-modified wax obtained in Synthesis Example 3 2.0
2. Dimethylpolysiloxane 6cs 10.0
3. Cross-linked polyether-modified silicone (Note 1) 5.0
4). Dipropylene glycol 10.0
5. Sodium citrate 0.2
6). Ethanol 5.0
7). Preservative appropriate amount 8. Perfume appropriate amount 9. Purified water 67.8
(Note 1) Shin-Etsu Chemical Co., Ltd .: KSG-21 (trade name)
(Production method)
A) Components 1 to 3 are dissolved by heating.
B) Components 4 to 9 are mixed and dissolved, and added to A) and emulsified with stirring.
The water-in-oil cream of the product of the present invention obtained as described above had no oiliness and stickiness, and spread well. Also, a matte finish was obtained.

(Example 4) Water-in-oil cream makeup base (component) Mass (%)
1. Cross-linked polyether-modified silicone (Note 1) 4.0
2. Cross-linked dimethylpolysiloxane (Note 2) 1.0
3. Polyether-modified silicone (Note 3) 0.5
4). Dimethylpolysiloxane (6 mm ² / sec (25 ° C.)) 6.0
5. Dimethylpolysiloxane (20 mm ² / sec (25 ° C.)) 2.0
6). Decamethylcyclopentasiloxane 3.0
7). Titanium oxide / cyclopentasiloxane dispersion (Note 4) 10.0
8). Silicone modified wax obtained in Synthesis Example 2 1.0
9. Dipropylene glycol 5.0
10. Sodium citrate 0.2
11. Methylcellulose (2% aqueous solution) (Note 5) 2.5
12 Ethanol 3.0
13. Preservative appropriate amount14. Perfume appropriate amount 15. Purified water 61.8
(Note 1) Shin-Etsu Chemical Co., Ltd .: KSG-21 (trade name)
(Note 2) Shin-Etsu Chemical Co., Ltd .: KSG-15 (trade name)
(Note 3) Shin-Etsu Chemical Co., Ltd .: KF-6017 (trade name)
(Note 4) Shin-Etsu Chemical Co., Ltd .: SPD-T1S (trade name)
(Note 5) Shin-Etsu Chemical Co., Ltd .: Metroz 65-SH4000 (trade name)
(Production method)
A) Components 1 to 8 are heated and mixed.
B) Components 9 to 15 are mixed and dissolved, and added to A) and emulsified with stirring.
The water-in-oil makeup base of the product of the present invention obtained as described above was not oily, non-sticky, and spread well. Furthermore, it has a fresh and refreshing usability and a matte finish.

(Example 5) Oil-in-water cream (ingredient) Mass (%)
1. Silicone-modified wax obtained in Synthesis Example 4 2.0
2. Cross-linked dimethylpolysiloxane (Note 1) 15.0
3. Decamethylcyclopentasiloxane 10.0
4). Dimethylpolysiloxane 20cs 18.0
5. Polyether-modified silicone (Note 2) 0.7
6). Propylene glycol 3.0
7). Polyacrylamide mixture (Note 3) 0.8
8). Xanthan gum (2% aqueous solution) 8.0
9. Preservative appropriate amount10. Perfume proper amount11. Purified water 42.5
(Note 1) Shin-Etsu Chemical Co., Ltd .: KSG-16 (trade name)
(Note 2) Shin-Etsu Chemical Co., Ltd .: KF-6011 (trade name)
(Note 3) Made by SEPIC: Sepigel 305 (trade name)
(Production method)
A) Components 1 to 4 are heated and mixed.
B) Components 5 to 11 are mixed and dissolved.
C) The above A) is added to the above B) and emulsified with stirring.
It was found that the oil-in-water water-type cream of the present invention obtained as described above was an excellent oil-in-water cream having a light and easy-to-use ease.

(Example 6) Water-in-oil type solid cream (component) Mass (%)
1. Silicone modified wax 30.0 obtained in Synthesis Example 2
2. Dimethylpolysiloxane 20cs 24.0
3. Decamethylcyclopentasiloxane 24.0
4). Polyether-modified silicone (Note 1) 2.0
5.1,3-Butylene glycol 2.0
6). Preservative appropriate amount 7. Perfume appropriate amount 8. Purified water 18.0
(Note 1) Shin-Etsu Chemical Co., Ltd .: KF-6017 (trade name)
(Production method)
A) Components 1 to 4 were dissolved by heating.
B) Components 5 to 8 were mixed and dissolved and added to A) and emulsified with stirring.
C) The above B) was filled into a product.
The water-in-oil solid cream of the product of the present invention obtained as described above had no oiliness, stickiness and good spread despite the large amount of oil.

(Example 7) Lipstick (component) Mass (%)
1. Silicone-modified wax obtained in Synthesis Example 1 35.0
2. Polyethylene wax 5.0
3. Squalane 30.0
4). Decamethylcyclopentasiloxane 26.0
5. Acrylic silicone resin (Note 1) 4.0
6). Appropriate amount of pigment 7. Preservative appropriate amount 8. Perfume appropriate amount (Note 1) Shin-Etsu Chemical Co., Ltd .: KP-545 (trade name)
(Production method)
A) Components 1 to 4 were dissolved by heating.
B) Components 5 to 7 were mixed and dispersed and added to A) above and stirred uniformly.
C) Component 8 was added to B) and filled into a product.
The lipstick of the product of the present invention obtained as described above did not have oiliness and stickiness, and also spread well with light sliding.

(Example 8) Powder foundation (component) Mass (%)
1. Sericite 40.0
2. Mica 10.0
3. 3. Talc remaining amount Titanium oxide 10.0
5. Fine particle titanium oxide 5.0
6). Magnesium stearate 3.0
7). Pigment 4.2
8). Silicone-modified wax obtained in Synthesis Example 3 1.0
9. Squalane 3.0
10. Preservative appropriate amount11. Perfume appropriate amount (production method)
A) Components 8 to 11 are mixed.
B) After mixing the components 1 to 7, the above A) is added and mixed uniformly.
C) The above B) is press-molded into a mold to obtain a powder foundation.
The powder foundation of the present invention obtained as described above had no stickiness and spread well. Moreover, it was found to be a powder foundation that gives a glossy finish.

(Example 9) Cream foundation (component) Mass (%)
1. Cross-linked polyether-modified silicone (Note 1) 4.0
2. Glyceryl trioctanoate 3.0
3. Diisostearyl malate 5.0
4). Decamethylcyclopentasiloxane 6.0
5. Silicone-modified wax obtained in Synthesis Example 5 2.0
6). Fluorine-modified hybrid silicone composite powder (Note 2) 2.5
7). Pigment 8.0
8). Acrylic silicone resin (Note 3) 5.0
9. Dipropylene glycol 5.0
10. Sodium citrate 0.2
11. Preservative appropriate amount 12. Perfume appropriate amount13. Purified water 59.3
(Note 1) Shin-Etsu Chemical Co., Ltd .: KSG-21 (trade name)
(Note 2) Shin-Etsu Chemical Co., Ltd .: KSP-200 (trade name)
(Note 3) Shin-Etsu Chemical Co., Ltd .: KP-545 (trade name)
(Production method)
A) Components 1 to 6 are heated and mixed.
B) Components 9 to 13 are mixed and dissolved, and added to A) and emulsified with stirring.
C) Components 7-8 are mixed and added to B) above to make it uniform.
It was found that the cream foundation of the present invention obtained as described above has no stickiness, good stretch, and a matte finish.

(Example 10) Solid foundation (component) Mass (%)
1. Silicone modified wax 30.0 obtained in Synthesis Example 1
2. Polyethylene wax 5.0
3. Diisostearyl malate 32.5
4). Decamethylcyclopentasiloxane 28.5
5. Acrylic silicone resin (Note 1) 4.0
6). Appropriate amount of pigment 7. Preservative appropriate amount 8. Perfume appropriate amount (Note 1) Shin-Etsu Chemical Co., Ltd .: KP-545 (trade name)
(Production method)
A) Components 1 to 4 were dissolved by heating.
B) Components 5 to 7 were mixed and dispersed and added to A) above and stirred uniformly.
C) Component 8 was added to B) and filled into a product.
It was found that the solid foundation of the product of the present invention obtained as described above has no oiliness and stickiness and has a good elongation.

(Example 11) Water-in-oil compact foundation (component) Mass (%)
1. Silicone-modified wax obtained in Synthesis Example 5 25.0
2. Candelilla wax 5.0
3. Glyceryl tri-2-ethylhexanoate 24.0
4). Decamethylcyclopentasiloxane 22.0
5. Acrylic silicone resin (Note 1) 4.0
6). Trimethylsiloxysilicic acid (Note 2) 1.0
7). Polyether-modified silicone (Note 3) 2.0
8). Pigment proper amount 9.1,3-butylene glycol 2.0
10. Preservative appropriate amount11. Perfume appropriate amount 12. Purified water 15.0
(Note 1) Shin-Etsu Chemical Co., Ltd .: KP-545 (trade name)
(Note 2) Shin-Etsu Chemical Co., Ltd .: KF-7312J (trade name)
(Note 3) Shin-Etsu Chemical Co., Ltd .: KF-6017 (trade name)
(Production method)
A) Components 1 to 4 and 7 were dissolved by heating.
B) Components 9, 10 and 12 were mixed and dissolved, and added to A) and emulsified with stirring.
C) Components 5, 6, and 8 were mixed and dispersed and added to B) above and stirred uniformly.
D) Component 11 was added to C) and filled into a product.
The water-in-oil compact foundation of the product of the present invention obtained as described above had good oiliness, no stickiness and good spread despite the large amount of oil agent.

(Example 12) Eye shadow (component) Mass (%)
1. Sericite 40.0
2. Mica 10.0
3. 3. Talc remaining amount Titanium oxide 10.0
5. Fine particle titanium oxide 5.0
6). Magnesium stearate 3.0
7). Appropriate amount of pigment 8. Octyldodecanol 3.0
9. Glyceryl tri-2-ethylhexanoate 8.0
10. Silicone-modified wax obtained in Synthesis Example 3 2.0
11. Preservative appropriate amount 12. Perfume appropriate amount (production method)
A) Components 8 to 11 are heated and mixed.
B) After mixing the components 1 to 7, the above A) is added and mixed uniformly.
C) Add component 12 to B) above.
It was found that the eye shadow of the product of the present invention obtained as described above has no stickiness, good stretch, and a glossy finish.

(Example 13) Powder eyebrow (component) Mass (%)
1. Silicone-modified wax obtained in Synthesis Example 2 3.0
2. Jojoba oil 5.0
3. Glyceryl trioctanoate 2.0
4). Silicone-treated mica 40.0
5. Silicone-treated barium sulfate 15.0
6). Silicone-treated titanium oxide 10.0
7). Silicone-treated pigment appropriate amount 8. Hybrid silicone composite powder (Note 1) 1.5
9. Spherical polymethylsilsesquioxane powder (Note 2) 2.5
10. Silicone-treated talc remaining amount 11. Preservative appropriate amount 12. Perfume Appropriate amount (Note 1) Shin-Etsu Chemical Co., Ltd .: KSP-100 (trade name)
(Note 2) Shin-Etsu Chemical Co., Ltd .: KMP-590 (trade name)
(Production method)
A) Components 4 to 12 are mixed and made uniform.
B) Components 1 to 3 are mixed and dissolved, and added to A) to make it uniform.
C) The above B) is press-molded into a mold to obtain a powder eyebrow.
It was found that the eyebrow of the product of the present invention obtained as described above has no stickiness, good stretch, and a glossy finish.

(Example 14) Pencil-shaped eyebrow (component) Mass (%)
1. Silicone-modified wax obtained in Synthesis Example 4 40.0
2. Polyethylene wax 10.0
3. Jojoba oil 40.0
4). Decamethylcyclopentasiloxane 5.0
5. Acrylic silicone resin (Note 1) 5.0
6). Appropriate amount of pigment 7. Preservative appropriate amount 8. Perfume appropriate amount (Note 1) Shin-Etsu Chemical Co., Ltd .: KP-545 (trade name)
(Production method)
A) Components 1 to 4 were dissolved by heating.
B) Components 5 to 7 were mixed and dispersed and added to A) above and stirred uniformly.
C) Component 8 was added to B) and filled into a product.
The pencil-shaped eyebrow of the present invention obtained as described above was excellent in slipperiness and good elongation without powder scattering.

(Example 15) Hair cream (ingredient) Mass (%)
1. Silicone-modified wax obtained in Synthesis Example 4 2.0
2. Diglyceryl monoisostearate 5.0
3. Decamethylcyclopentasiloxane 8.0
4). Stearyltrimethylammonium chloride 1.5
5. Glycerin 3.0
6). Propylene glycol 5.0
7). Hydroxyethyl cellulose 0.2
8). Preservative appropriate amount 9. Perfume appropriate amount10. Purified water 75.3
(Production method)
A) Components 1 to 3 are dissolved by heating.
B) Components 4-8 and 10 are mixed and dissolved uniformly.
C) The above B) is added to the above A) and emulsified, then cooled and component 9 is added.
The hair cream of the present invention obtained as described above exhibits extremely excellent effects in elongation at the time of application, flexibility of hair after use, smoothness, moist feeling, gloss, It turned out to be a very good hair cream.

(Example 16) Conditioning mousse (component) Mass (%)
1. Silicone modified wax obtained in Synthesis Example 2 0.5
2. Diglyceryl monoisostearate 2.0
3. Cross-linked dimethylpolysiloxane (Note 1) 0.5
4). Glyceryl trioctanoate 1.5
5. Glycerin 3.0
6). Stearyldimethylbenzylammonium chloride 0.5
7). Polyoxyethylene hydrogenated castor oil 0.5
8). Ethanol 7.0
9. Preservative appropriate amount10. Perfume proper amount11. Purified water remaining amount 12. Liquefied petroleum gas 5.0
(Note 1) Shin-Etsu Chemical Co., Ltd .: KSG-16 (trade name)
(Production method)
A) Components 1 to 4 are dissolved by heating.
B) Components 5-9 and 11 are mixed and dissolved uniformly.
C) The above B) is added to A) above and emulsified, and then cooled and component 10 is added.
D) C) above is packed in an aerosol can and filled with component 12 to obtain a conditioning mousse.
The conditioning mousse of the present invention obtained as described above has a moist feeling, flexibility and smoothness, has a good feel without oily feeling, and has a matte finish. It turned out to be a honning mousse.

(Example 17) Roll-on type antiperspirant (component) Mass (%)
1. Silicone-modified wax obtained in Synthesis Example 1 5.0
2. Cross-linked polyether-modified silicone (Note 1) 20.0
3. Liquid paraffin 10.0
4). Cross-linked dimethylpolysiloxane (Note 2) 15.0
5. Decamethylcyclopentasiloxane 30.0
6). Aluminum zirconium tetrachlorohydrate 20.0
7). Perfume Appropriate amount (Note 1) Shin-Etsu Chemical Co., Ltd .: KSG-21 (trade name)
(Note 2) Shin-Etsu Chemical Co., Ltd .: KSG-15 (trade name)
(Production method)
A) Components 1 to 5 are heated and mixed.
B) Add components 6 and 7 to A and disperse uniformly.
The roll-on type antiperspirant obtained as described above has good spread, no stickiness or oily feeling, no change with temperature and time, and excellent usability and stability. .

(Example 18) Water-in-oil type antiperspirant (component) Mass (%)
1. Silicone-modified wax obtained in Synthesis Example 3 2.0
2. Cross-linked polyether-modified silicone (Note 1) 7.0
3. Decamethylcyclopentasiloxane 7.0
4). Liquid paraffin 8.0
5.1,3-Butylene glycol 5.0
6). Sodium citrate 0.2
7). Aluminum chlorohydrate 20.0
8). Perfume appropriate amount 9. Purified water 50.8
(Note 1) Shin-Etsu Chemical Co., Ltd .: KSG-21 (trade name)
(Production method)
A) Components 1 to 4 are heated and mixed.
B) Components 5 to 6 and 8 are mixed, and components 7 and 9 are added and dissolved.
C) The above B) is added to the above A) and stirred to emulsify.
The water-in-oil type antiperspirant obtained as described above has good spread, no stickiness or oily feeling, no change with temperature and time, and excellent usability and stability. It was a medium water type antiperspirant.

(Example 19) Solid antiperspirant (component) Mass (%)
1. Silicone-modified wax obtained in Synthesis Example 5 22.0
2. Polyethylene-polypropylene copolymer 4.0
3. Dimethylpolysiloxane (6 mm ² / sec (25 ° C.)) 22.0
4). Decamethylcyclopentasiloxane 22.0
5. Cross-linked dimethylpolysiloxane (Note 1) 15.0
6). Aluminum zirconium tetrachlorohydrate 15.0
7). Perfume appropriate amount (Note 1) Shin-Etsu Chemical Co., Ltd .: KSG-16 (trade name)
(Production method)
A) Components 1 to 5 were heated and made uniform.
B) Components 6 and 7 were mixed and dispersed in A).
C) The above B) was filled into a product.
The solid antiperspirant obtained as described above is a solid antiperspirant that has good spread, no stickiness or oily feeling, no change with temperature and time, and excellent usability and stability. It was.

(Example 20) Solid antiperspirant (component) Mass (%)
1. Silicone-modified wax obtained in Synthesis Example 4 25.0
2. Polyethylene wax 8.0
3. Dimethylpolysiloxane (6 mm ² / sec (25 ° C.)) 25.0
4). Decamethylcyclopentasiloxane 22.0
5. Cross-linked dimethylpolysiloxane (Note 1) 5.0
6). Aluminum zirconium tetrachlorohydrate (glycine salt) 15.0
7). Perfume appropriate amount (Note 1) Shin-Etsu Chemical Co., Ltd .: KSG-16 (trade name)
(Production method)
A) Components 1 to 5 were heated and made uniform.
B) Components 6 and 7 were mixed and dispersed in A).
C) The above B) was filled into a product.
The solid antiperspirant obtained as described above is a solid antiperspirant that has good spread, no stickiness or oily feeling, no change with temperature and time, and excellent usability and stability. It was.

(Example 21) UV-cut water-in-oil cream (component) Mass (%)
1. Silicone-treated zinc oxide 20.0
2. Acrylic modified silicone resin (Note 1) 12.0
3. Decamethylcyclopentasiloxane 20.0
4). Glyceryl trioctanoate 3.0
5. Silicone-modified wax obtained in Synthesis Example 2 2.0
6). Cross-linked polyether-modified silicone (Note 2) 5.0
7). Polyether-modified silicone (Note 3) 1.0
8). Alkyl / polyether co-modified silicone (Note 4) 1.0
9. Octyl methoxycinnamate 6.0
10. Sodium citrate 0.2
11. Dipropylene glycol 3.0
12 Preservative appropriate amount13. Perfume appropriate amount14. Purified water 26.8
(Note 1) Shin-Etsu Chemical Co., Ltd .: KP-545 (trade name)
(Note 2) Shin-Etsu Chemical Co., Ltd .: KSG-21 (trade name)
(Note 3) Shin-Etsu Chemical Co., Ltd .: KF-6017 (trade name)
(Note 4) Shin-Etsu Chemical Co., Ltd .: KF-6026 (trade name)
(Production method)
A) A part of component 3 and 4 to 9 are heated and mixed.
B) Components 10 to 12 and 14 are mixed and added to A) and emulsified with stirring.
C) The remaining components 1, 2 and 3 are mixed and dispersed, and component 13 is added to B) to make it uniform.
The water-in-oil type UV cut cream obtained as described above has good spread, no stickiness or oily feeling, clearness, no change over time and temperature, and very easy to use and stable. It was an excellent UV cut cream.

(Example 22) UV-cut water-in-oil emulsion (component) Mass (%)
1. Dimethylpolysiloxane (6 mm ² / sec (25 ° C.)) 5.0
2. Cross-linked polyether-modified silicone (Note 1) 5.0
3. Glyceryl trioctanoate 2.0
4). Silicone wax (C) obtained in Synthesis Example 6 1.0
5. Polyether-modified silicone (Note 2) 1.0
6). Titanium oxide / decamethylcyclopentasiloxane dispersion (Note 3)
30.0
7). Zinc oxide / decamethylcyclopentasiloxane dispersion (Note 4) 30.0
8). Dipropylene glycol 3.0
9. Sodium citrate 0.2
10. Preservative appropriate amount11. Perfume appropriate amount 12. Purified water 22.8
(Note 1) Shin-Etsu Chemical Co., Ltd .: KSG-21 (trade name)
(Note 2) Shin-Etsu Chemical Co., Ltd .: KF-6017 (trade name)
(Note 3) Shin-Etsu Chemical Co., Ltd .: SPD-T1S (trade name)
(Note 4) Shin-Etsu Chemical Co., Ltd .: SPD-Z1 (trade name)
(Production method)
A) Components 1 to 5 are heated and mixed.
B) Components 8 to 10 and 12 are mixed and dissolved, and added to A) and emulsified with stirring.
C) Ingredients 6, 7, and 11 are added to B) and made uniform.
The water-in-oil type UV-cut emulsion obtained as described above has good spread, no stickiness or oily feeling, transparency, good makeup, no change over time and temperature, and usability It was a UV-cut emulsion with very good stability.

(Example 23) UV cut oil-in-water cream (ingredient) Mass (%)
1. Cross-linked organopolysiloxane (Note 1) 5.0
2. Cetyl isooctanoate 5.0
3. Silicone modified wax obtained in Synthesis Example 5 1.0
4). Titanium oxide / decamethylcyclopentasiloxane dispersion (Note 2) 15.0
5. Polyether-modified silicone (Note 3) 1.0
6). Polyether-modified silicone (Note 4) 1.0
7). Acrylic acid amide based mixture (Note 5) 2.0
8). Propylene glycol 5.0
9. Methylcellulose (2% aqueous solution) (Note 6) 5.0
10. Preservative appropriate amount11. Perfume appropriate amount 12. Purified water 60.0
(Note 1) Shin-Etsu Chemical Co., Ltd .: KSG-18 (trade name)
(Note 2) Shin-Etsu Chemical Co., Ltd .: SPD-T1S (trade name)
(Note 3) Shin-Etsu Chemical Co., Ltd .: KF-6027 (trade name)
(Note 4) Shin-Etsu Chemical Co., Ltd .: KF-6011 (trade name)
(Note 5) Sepic: Sepigel 305 (trade name)
(Note 6) Shin-Etsu Chemical Co., Ltd .: Metroles SM-4000 (trade name)
(Production method)
A) Components 5-8 and 10, 12 are mixed.
B) Components 1 to 3 are heated and mixed and added to A) and emulsified with stirring.
C) Add component 4 to B) above and add components 9 and 11 to make it uniform.
The oil-in-water type UV cut cream obtained as described above has good spread, no stickiness or oily feeling, transparency, good makeup, no change over time and temperature, and stable use. It was a UV cut cream with excellent properties.

(Comparative Example 1) Solid Foundation In Example 10, a solid foundation was prepared in the same manner as in Example 10 except that the thickener obtained in Synthesis Comparative Example 1 was used instead of the silicone-modified wax of Component 1. It was. The obtained solid foundation was sticky and poorly spread compared to the foundation of Example 10.

(Comparative Example 2) Solid Antiperspirant A solid antiperspirant was prepared in the same manner as in Example 19 except that the thickener obtained in Synthesis Comparative Example 2 was used in place of the silicone-modified wax of Component 1. Made a sweat agent. The obtained solid antiperspirant was softer and less stable than the antiperspirant of Example 19.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. It is contained in the technical range.

Claims (2)

(I) a step of urethanating a polyhydric alcohol having 1 or 2 alkenyl groups in one molecule and an alkyl isocyanate in the absence of a catalyst or in the presence of a catalyst to obtain a product having a urethane bond;
(II) hydrosilylation reaction of the urethanization reaction product and methyl hydrogen organopolysiloxane in the presence of a catalyst;
A process for producing a silicone-modified wax characterized by comprising: As the polyhydric alcohol, a compound having a linear or branched polyglycerol structure is used,
As the alkyl isocyanate, a linear saturated alkyl isocyanate having 8 to 20 carbon atoms is used,
As the methyl hydrogen organopolysiloxane, a methyl hydrogen organopolysiloxane containing 1 to 5 hydrogen atoms (that is, SiH groups) bonded to a silicon atom represented by the following general formula (A) in one molecule is used. The method for producing a silicone-modified wax according to claim 1 .

(R ¹ , R ² , R ³ and R ⁴ each independently have a hydrogen atom, the same or different, a linking group or substituent to which the same or different branched polyglycerol chain is bonded, 22 represents a linear or branched alkyl group or alkoxy group, an aryl group having 6 to 22 carbon atoms, or a fluorine-substituted alkyl group, provided that at least one of R ¹ and R ³ represents a hydrogen atom. And at least one of R ² and R ⁴ represents a methyl group, and n represents an integer of 0 to 50.)