JP2013129721A - Novel silicone derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel silicone derivative having high emulsion stability even in a water-containing composition, and having higher affinity to highly polar inorganic compounds, biological tissues such as hairs and skins, and various base materials such as fibers and the like in comparison with silicones.SOLUTION: There is provided the silicone derivative represented by general formula (1) or (2), wherein X represents a hydrocarbon having a nitrogen atom, and Z represents a polyalkylene oxide.

Description

  The present invention relates to silicone derivatives and compositions comprising silicone derivatives.

Silicone is a general-purpose material having various advantages such as low-molecular interaction, low reactivity, harmless and low irritation, low coefficient of friction, low viscosity, high lubricity, high spreadability, and high insulation. For this reason, silicones are used as fiber treatment agents, mold release agents, water-repellent agents, resin modifiers, paint additives, electrical insulation agents, heating media, grease compounds, machine oils, foam stabilizers, antifoaming agents, etc. It is used in various applications such as industrial supplies, pharmaceuticals, and cosmetics.
However, when silicone is used, there is a problem that it is difficult to prepare a stable emulsion. In addition, silicone has a problem that wettability and adsorptivity to a highly polar inorganic compound, a living tissue such as hair or skin, a substrate such as fiber, or a substrate surface are extremely low. For these problems, amino-modified silicones have been proposed and various studies have been made.

Patent Document 1 discloses an invention of a water-in-oil emulsion composition containing a specific lysine derivative-modified silicone, silicone oil, and water, and describes that emulsion stability is improved.
Patent Document 2 discloses an invention of a compound obtained by addition reaction of a polyoxyalkylene compound and a silicone compound, and describes that the emulsion stability with respect to silicone oil is excellent.
Patent Document 3 discloses an invention of a specific acyl acidic amino acid monosilicone sterol ester and describes that the touch is excellent.

JP 2006-169130 A JP 2001-039819 A International Publication No. 2010/114175 Pamphlet

However, in the compounds described in Patent Documents 1 and 2, the emulsion stability of silicone is not yet sufficient.
Furthermore, silicone compounds can be used for various applications and formulations as long as they are highly stable against alkalis and heat. For example, in general, when used for cosmetics, a weakly alkaline formulation may be used. Some ingredients may be heated. However, the compound described in Patent Document 3 has insufficient stability. In addition, a silicone compound having a high affinity for both water and oil has not yet been obtained. An object of the present invention is to provide a novel silicone derivative having high emulsion stability, high compound stability, high affinity for both water and oil, and low skin irritation.

（上記一般式（１）において、ｈ×ｎ個のＸのうち少なくとも一つは、下記一般式（３）で表わされ、その他のＸ及びＲは、それぞれ独立に炭素数１〜２２のアルキル基、若しくはアルコキシ基、炭素数２〜２２のアルケニル基、炭素数６〜２２のアリール基、ポリエーテル基、又は水酸基であり、Ｒ’’は炭素数１〜２２の炭化水素であり、Ｚはポリアルキレンオキシドであり、ｈは０〜３０００００であり、ｌは、０〜３０００００であり、ｎは０〜３０００００の整数である。）

（上記一般式（２）において、Ｘは、下記一般式（３）で表わされ、Ｒは、それぞれ独立に炭素数１〜２２のアルキル基、若しくはアルコキシ基、炭素数２〜２２のアルケニル基、炭素数６〜２２のアリール基、ポリエーテル基、又は水酸基である。）

（一般式（３）において、Ａは、窒素原子を有する炭化水素であり、Ｑは、下記一般式（４）で表わされ、ｍは１〜１０の整数である。）

（一般式（４）において、Ｒ^１は炭素数１〜２３の炭化水素基であり、Ｒ^２は水素又は炭素数１〜３の炭化水素であり、Ｙはカルボキシル基、スルホン酸基、硫酸エステル基、リン酸エステル基又はそれらの塩であり、ｊ、ｋはそれぞれ独立に０、１又は２のいずれかの整数であって、ｊ、ｋは同時に０ではない。）
［２］ 前記一般式（３）が、下記一般式（５）である［１］に記載のシリコーン誘導体。

（一般式（５）において、Ｒ^１、Ｒ^２、Ｙ、ｊ、ｋは一般式（４）と同様であり、Ｒ^３は炭素数１〜２２の炭化水素であり、−Ｚ−は−ＮＲ’−（Ｒ’は水素又は炭素数１〜１０の炭化水素である。）を示す。）
［３］ 前記一般式（３）が、下記一般式（６）である［１］に記載のシリコーン誘導体。

（一般式（６）において、Ｒ^１、Ｒ^２、Ｙ、ｊ、ｋは一般式（４）と同様であり、Ｒ^４及びＲ^５はそれぞれ独立に炭素数１〜２２の炭化水素である。）
［４］ Ｒ^２が水素であり、Ｙがカルボキシル基である［１］〜［３］のいずれか一項に記載のシリコーン誘導体。
［５］ ［１］〜［４］のいずれか一項に記載のシリコーン誘導体と、シリコーンとを含む組成物。
［６］ ［１］〜［４］のいずれか一項に記載のシリコーン誘導体と、Ｎ−アシルアミノ酸型界面活性剤とを含む組成物。 As a result of intensive studies on the above problems, the present inventors have found that a silicone derivative having a specific structure has high emulsification stability, high stability, high affinity for both water and oil, and skin irritation. As a result, the present invention was completed.
That is, the present invention is as follows.
[1] A silicone derivative represented by the following general formula (1) or (2).

(In the general formula (1), at least one of h × n X is represented by the following general formula (3), and the other X and R are each independently an alkyl having 1 to 22 carbon atoms. Or an alkoxy group, an alkenyl group having 2 to 22 carbon atoms, an aryl group having 6 to 22 carbon atoms, a polyether group, or a hydroxyl group, R ″ is a hydrocarbon having 1 to 22 carbon atoms, and Z is Polyalkylene oxide, h is 0 to 300,000, l is 0 to 300000, and n is an integer of 0 to 300000.)

(In the general formula (2), X is represented by the following general formula (3), and R is independently an alkyl group having 1 to 22 carbon atoms, an alkoxy group, or an alkenyl group having 2 to 22 carbon atoms. , An aryl group having 6 to 22 carbon atoms, a polyether group, or a hydroxyl group.)

(In General Formula (3), A is a hydrocarbon having a nitrogen atom, Q is represented by the following General Formula (4), and m is an integer of 1 to 10.)

(In General Formula (4), R ¹ is a hydrocarbon group having 1 to 23 carbon atoms, R ² is hydrogen or a hydrocarbon having 1 to 3 carbon atoms, and Y is a carboxyl group, a sulfonic acid group, or a sulfate ester. A group, a phosphate group or a salt thereof, j and k are each independently an integer of 0, 1 or 2, and j and k are not 0 at the same time.)
[2] The silicone derivative according to [1], wherein the general formula (3) is the following general formula (5).

(In General Formula (5), R ¹ , R ² , Y, j, and k are the same as in General Formula (4), R ³ is a hydrocarbon having 1 to 22 carbon atoms, and —Z— is —NR. '-(R' represents hydrogen or a hydrocarbon having 1 to 10 carbon atoms).)
[3] The silicone derivative according to [1], wherein the general formula (3) is the following general formula (6).

(In General Formula (6), R ¹ , R ² , Y, j, and k are the same as in General Formula (4), and R ⁴ and R ⁵ are each independently a hydrocarbon having 1 to 22 carbon atoms. )
[4] The silicone derivative according to any one of [1] to [3], wherein R ² is hydrogen and Y is a carboxyl group.
[5] A composition comprising the silicone derivative according to any one of [1] to [4] and silicone.
[6] A composition comprising the silicone derivative according to any one of [1] to [4] and an N-acylamino acid type surfactant.

  The silicone derivative of the present invention has the effects of high emulsion stability, high stability, high affinity for both water and oil, and low skin irritation.

（一般式（１）において、ｈ×ｎ個のＸのうち少なくとも一つは、下記一般式（３）で表わされ、その他のＸ及びＲは、それぞれ独立に炭素数１〜２２のアルキル基、若しくはアルコキシ基、炭素数２〜２２のアルケニル基、炭素数６〜２２のアリール基、ポリエーテル基、又は水酸基であり、Ｒ’’は炭素数１〜２２の炭化水素であり、Ｚはポリアルキレンオキシドであり、ｈは０〜３０００００の整数であり、ｌは０〜３０００００の整数であり、ｎは０〜３０００００の整数である。）
（一般式（２）において、Ｘは、下記一般式（３）で表わされ、Ｒは、それぞれ独立に炭素数１〜２２のアルキル基、若しくはアルコキシ基、炭素数２〜２２のアルケニル基、炭素数６〜２２のアリール基、ポリエーテル基、又は水酸基である。）

（一般式（３）において、Ａは、窒素原子を有する炭化水素であり、Ｑは、下記一般式（４）で表わされ、ｍは１〜１０の整数である。）

（一般式（４）において、Ｒ^１は炭素数１〜２３の炭化水素基であり、Ｒ^２は水素又は炭素数１〜３の炭化水素であり、Ｙはカルボキシル基、スルホン酸基、硫酸エステル基、リン酸エステル基又はそれらの塩であり、ｊ、ｋはそれぞれ独立に０、１又は２のいずれかの整数であって、ｊ、ｋは同時に０ではない。） Hereinafter, the present invention will be described in detail.
The present invention is a silicone derivative represented by the following general formula (1) or (2).

(In General Formula (1), at least one of h × n X is represented by the following General Formula (3), and the other X and R are each independently an alkyl group having 1 to 22 carbon atoms. Or an alkoxy group, an alkenyl group having 2 to 22 carbon atoms, an aryl group having 6 to 22 carbon atoms, a polyether group, or a hydroxyl group, R ″ is a hydrocarbon having 1 to 22 carbon atoms, and Z is a poly An alkylene oxide, h is an integer from 0 to 300000, l is an integer from 0 to 300000, and n is an integer from 0 to 300000.)
(In the general formula (2), X is represented by the following general formula (3), and each R is independently an alkyl group having 1 to 22 carbon atoms, or an alkoxy group, an alkenyl group having 2 to 22 carbon atoms, (It is a C6-C22 aryl group, a polyether group, or a hydroxyl group.)

(In General Formula (3), A is a hydrocarbon having a nitrogen atom, Q is represented by the following General Formula (4), and m is an integer of 1 to 10.)

(In General Formula (4), R ¹ is a hydrocarbon group having 1 to 23 carbon atoms, R ² is hydrogen or a hydrocarbon having 1 to 3 carbon atoms, and Y is a carboxyl group, a sulfonic acid group, or a sulfate ester. A group, a phosphate group or a salt thereof, j and k are each independently an integer of 0, 1 or 2, and j and k are not 0 at the same time.)

First, general formulas (1) and (2) will be described.
In the general formula (1), one or more of h × n Xs are represented by the general formula (3). X other than X represented by the general formula (3) (hereinafter referred to as other X) and R are an alkyl group having 1 to 22 carbon atoms or an alkoxy group, and 2 to 22 carbon atoms. An alkenyl group, an aryl group having 6 to 22 carbon atoms, a polyether group, or a hydroxyl group.
R ″ is a hydrocarbon having 1 to 22 carbon atoms.
Z is a polyalkylene oxide.
Moreover, in General formula (2), X is represented by General formula (3), R is respectively independently a C1-C22 alkyl group or an alkoxy group, C2-C22 alkenyl group, An aryl group, a polyether group, or a hydroxyl group having 6 to 22 carbon atoms is represented.
Specific examples of the alkyl group having 1 to 22 carbon atoms or the alkoxy group, the alkenyl group having 2 to 22 carbon atoms, the aryl group having 6 to 22 carbon atoms, and the polyether group are as follows.
Examples of the alkyl group having 1 to 22 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, trifluoropropyl and the like.
Examples of the alkoxy group having 1 to 22 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and phenoxy groups.
Examples of the alkenyl group having 2 to 22 carbon atoms include a vinyl group and an allyl group.
Examples of the aryl group having 6 to 22 carbon atoms include a phenyl group, a benzyl group, a tolyl group, and a xylyl group.
The polyether group is a general term for linear polymers having an ether bond in the main chain, and examples thereof include polyalkylene oxide and polyphenylene oxide.
In addition, when there are a plurality of X, R, and R ″ in the general formulas (1) and (2), they may be different or the same.

Other X and R in the general formula (1) and R in the general formula (2) are alkyl groups having 1 to 12 carbon atoms, alkoxy groups, alkenyl groups having 2 to 12 carbon atoms, or 6 to 6 carbon atoms. Twelve aryl groups, polyalkylene oxide are preferred. More preferably, they are a C1-C3 alkyl group or a phenyl group, More preferably, they are a methyl group, a propyl group, or a phenyl group. Among these, a methyl group is particularly preferable from the viewpoint of versatility and price. A phenyl group is particularly preferable from the viewpoint of heat resistance.
Further, in the other X and R in the general formula (1) and R in the general formula (2), hydrogen may be substituted with fluorine. In addition, other X and R in the general formula (1) and R in the general formula (2) have a substituent such as a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group, or a salt thereof. The solubility in weak acidity is improved by having these substituents.
Furthermore, other X and R in the general formula (1) and R in the general formula (2) are a phenyl group, a phenol group, a hydroxy group, a carboxy group, an amino group (0 to 14 carbon atoms), an imino group, ( It may have a substituent such as aminoethyl) amino group, (dimethylaminoethyl) amino group, polyoxyalkylene group, mercapto group, and epoxy group. These substituents are the functional groups of the modified organopolysiloxane that remain unreacted in the production method described later.
In the general formula (1), h is an integer of 0 to 300000, and l is an integer of 0 to 300000. N is an integer of 0 to 300,000.
Moreover, as molecular weight of the silicone derivative represented by General formula (1), it is 50-10,000,000 normally.

Next, general formula (3) will be described.
In the general formula (3), A is a hydrocarbon having a nitrogen atom. A in the general formula (3) corresponds to a bonding part for bonding Q represented by the general formula (4) to the silicone compound. The nitrogen atom of A is directly bonded to Q. Since the nitrogen atom is directly bonded to Q, the bond is strong and the stability as a compound is high. Therefore, the silicone derivative of the present invention can exhibit high emulsification stability even at high temperatures and in an acid / alkali environment. In General formula (3), m is 1-10. In other words, m Qs are bonded to A. As a specific example, the case where m is 1 (formula (3-1)) and the case where m is 2 (formula (3-2)) are shown below. In addition, m is preferably 1 to 3. More preferably, m is 1 or 2. In addition, when there are a plurality of Q, they may be different from each other.

一般式（４）において、Ｒ^１は、炭素数１〜２３の炭化水素基を表わす。好ましくは、炭素数が７から１７の炭化水素基であり、より好ましくは、炭素数が１１から１７の炭化水素基である。Ｒ^１は、直鎖、分岐鎖、又は環状鎖（芳香族炭化水素鎖）のいずれでもよく、置換基を有していてもよい。好ましくは、直鎖である。また、当該炭化水素基は飽和でも不飽和でも使用できるが、飽和であるのが好ましい。
一般式（４）中のＲ^２は、水素、又は炭素数１〜３の炭化水素を表わす。Ｒ^２が炭素数１〜３の炭化水素の場合、置換基としてカルボキシル基又はスルホン酸基を有してもよい。炭素数１〜３の炭化水素の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシ（イソ）プロピル基、ジヒドロキシ（イソ）プロピル基、カルボキシメチル基、カルボキシエチル基、カルボキシプロピル基及びスルホエチル基等を挙げることができる。好ましくは、水素である。なお、分子内にＲ^１、Ｒ^２が複数ある場合は、それぞれ異なっていても、同一でもよい。 Next, general formula (4) will be described.

In general formula (4), ^{R 1} represents a hydrocarbon group having 1 to 23 carbon atoms. Preferred is a hydrocarbon group having 7 to 17 carbon atoms, and more preferred is a hydrocarbon group having 11 to 17 carbon atoms. R ¹ may be any of a straight chain, a branched chain, or a cyclic chain (aromatic hydrocarbon chain), and may have a substituent. Preferably, it is a straight chain. The hydrocarbon group may be saturated or unsaturated, but is preferably saturated.
R ² in the general formula (4) represents hydrogen or a hydrocarbon having 1 to 3 carbon atoms. When R ² is a hydrocarbon having 1 to 3 carbon atoms, it may have a carboxyl group or a sulfonic acid group as a substituent. Specific examples of the hydrocarbon having 1 to 3 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, hydroxymethyl group, hydroxyethyl group, hydroxy (iso) propyl group, dihydroxy (iso) propyl group, carboxymethyl A group, a carboxyethyl group, a carboxypropyl group and a sulfoethyl group. Preferably, it is hydrogen. In addition, when there are a plurality of R ¹ and R ² in the molecule, they may be different or the same.

Y in the general formula (4) represents a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group or a salt thereof. Preferably, it is a carboxyl group or a salt thereof.
When Y is a salt, examples of the basic substance that forms a salt together with the carboxyl group, sulfonic acid group, sulfate ester group, or phosphate ester group include alkyl metals, alkaline earth metals, and the like. Examples thereof include metals such as sodium, potassium and lithium, and examples of the alkaline earth metal include metals such as calcium and magnesium. Other metals include aluminum, zinc, iron, cobalt, titanium, zirconium, and silver.

Examples of basic substances other than metals include, but are not limited to, organic amine salts and basic amino acid salts. Examples of organic amine salts include ammonia, monoethanolamine, diethanolamine, triethanolamine, and triisopropanolamine. The basic amino acid salts include arginine and lysine salts. Other examples include ammonium salts and polyvalent metal salts.
Y can include two or more salts arbitrarily selected from the salts described above. When there are a plurality of Y, they may be different from each other or the same.
In the general formula (4), j and k each independently represent 0, 1, or 2, but j and k are not 0 at the same time.

The silicone derivative of the present invention is represented by the general formula (1) or (2), and m Qs bonded to A each have Y which is a hydrophilic group. Therefore, the silicone derivative of the present invention has a silicone property and has a high affinity for water. Therefore, the silicone derivative of the present invention has high emulsion stability even in a composition containing water.
In addition, the silicone derivative of the present invention has a higher affinity for various substrates such as highly polar inorganic compounds, living tissues such as hair and skin, and fibers, compared to silicone. Below, the preferable aspect of the silicone derivative of this invention is demonstrated.

（一般式（５）において、Ｒ^１、Ｒ^２、Ｙ、ｊ、ｋは一般式（４）と同様であり、Ｒ^３は炭素数１〜２２の炭化水素基であり、−Ｚ−は−ＮＲ’’’−（Ｒ’’’は水素又は炭素数１〜１０の炭化水素である。）を示す。）
一般式（５）は、一般式（３）において、Ａとｍを特定したものである。ｍは１である。
Ｒ^３は、炭素数１〜２２の炭化水素を表わし、好ましくは炭素数１〜１８の炭化水素である。Ｒ^３は直鎖、分枝鎖、環状鎖のいずれでもよく、置換基を有していてもよい。また、Ｒ^３はフッ素置換されていてもよい。 The general formula (5) will be described.
In the present invention, the general formula (3) is preferably a silicone derivative represented by the following general formula (5).

(In General Formula (5), R ¹ , R ² , Y, j, and k are the same as in General Formula (4), R ³ is a hydrocarbon group having 1 to 22 carbon atoms, and —Z— is — NR ′ ″ — (R ′ ″ represents hydrogen or a hydrocarbon having 1 to 10 carbon atoms.)
General formula (5) specifies A and m in general formula (3). m is 1.
R ³ represents a hydrocarbon having 1 to 22 carbon atoms, preferably a hydrocarbon having 1 to 18 carbon atoms. R ³ may be a straight chain, a branched chain, or a cyclic chain, and may have a substituent. R ³ may be fluorine-substituted.

  -Z- is -NR ""-(R "" represents hydrogen or a hydrocarbon having 1 to 10 carbon atoms). Since —Z— is —NR ″ ″ —, the bond is strong, and thus the stability as a compound is high. Therefore, the bond does not break even at high temperatures or in an acid / alkali environment, and the silicone derivative of the present invention can exhibit high emulsification stability and can also suppress odor. In particular, -Z- is preferably -NH-, from the viewpoint of the stability of the compound and the stability to acid and alkali.

  The silicone derivative represented by the general formula (1) or (2) has the characteristics of silicone and has high affinity with water, and thus has high emulsification stability, and a highly polar inorganic compound or High affinity to various tissues such as living tissue such as hair and skin, and fibers.

（一般式（６）において、Ｒ^１、Ｒ^２、Ｙ、ｊ、ｋは一般式（４）と同様であり、Ｒ^４及びＲ^５はそれぞれ独立に炭素数１〜２２の炭化水素である。） Next, general formula (6) will be described.
In the present invention, the general formula (3) is preferably a silicone derivative represented by the following general formula (6).

(In General Formula (6), R ¹ , R ² , Y, j, and k are the same as in General Formula (4), and R ⁴ and R ⁵ are each independently a hydrocarbon having 1 to 22 carbon atoms. )

General formula (6) specifies A and m in general formula (3). m is 2.
In the general formula (6), R ¹ , R ² , Y, j, and k are as described in the general formula (4). R ^{4, R 5} are, in the general formula (5) is the same as ^{R 3.}
The silicone derivative represented by the general formula (1) or (2) including the portion of the general formula (6) has a silicone property and has a hydrophilic group, and thus has a high affinity with water. Therefore, it has high emulsification stability and high affinity for various substrates such as highly polar inorganic compounds, living tissues such as hair and skin, and fibers.

Next, the composition containing the silicone derivative of the present invention will be described.
The composition of this invention contains the silicone derivative represented by the said General formula (1) or (2), and silicone. Since the silicone derivative of the present invention has high affinity with silicone, silicone can be stably emulsified in a composition containing silicone. Further, even in a composition containing water, the silicone derivative of the present invention has a hydrophilic group, so that silicone can be stably emulsified. Therefore, the composition of the present invention has extremely high emulsion stability.

  Silicone (oil) includes linear polysiloxanes (for example, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.), cyclic polysiloxanes (for example, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexane). And silicone resins that form a three-dimensional network structure, various modified polysiloxanes (amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, etc.) It is done.

In addition, a composition comprising (A) the silicone derivative of the present invention and (B) an N-acylamino acid type surfactant has little skin irritation and has a very excellent surfactant effect even at a low concentration. Have
In the present invention, (B) the N-acylamino acid of the N-acylamino acid type surfactant is an acyl group derived from a saturated or unsaturated fatty acid having 2 to 24 carbon atoms into the amino group of the amino acid. Is. The amino acid residue in the N-acyl amino acid is various amino acids such as α-amino acid, β-amino acid, γ-amino acid and ω-amino acid, and the amino group may be N-methyl or N-ethyl. Any of optical isomers, that is, D-form, L-form, and racemate may be used.

  Specific examples of amino acids include glutamic acid, aspartic acid, glycine, alanine, lanthionine, β-methyllanthionine, cystathionine, diencholic acid, ferrinin, aminomalonic acid, β-oxyaspartic acid, α-amino-α-methylsuccinic acid , Β-oxyglutamic acid, γ-oxyglutamic acid, γ-methylglutamic acid, γ-methyleneglutamic acid, γ-methyl-γ-oxyglutamic acid, α-aminoadipic acid, α, α'-diaminoadipic acid, β, β'- Diaminoadipic acid, α-amino-γ-oxyadipic acid, α-aminopimelic acid, α-amino-γ-oxypimelic acid, β-aminopimelic acid, α-aminosuberic acid, α-aminosebacic acid, pantothenic acid, etc. .

  Specific examples of the acyl group may be those derived from a saturated or unsaturated fatty acid having 2 to 24 carbon atoms, and may be linear, branched or cyclic.

The N-acylamino acid is preferably an N-acyl-L-amino acid from the viewpoint of biodegradability.
In the composition of the present invention, (A) the silicone derivative of the present invention and (B) the N-acylamino acid type surfactant have a mass ratio of (A) / (B) of 1/100 to 100/1. What is contained in the composition is preferable. If it is the said range, the irritation | stimulation to skin etc. is smaller, and there exists an even more excellent surface active effect | action also in low concentration.

Next, the aqueous solution of the silicone derivative of the present invention will be described.
The silicone derivative of the present invention can be used as it is depending on the application, but can also be used in the form of an aqueous solution. Depending on the nature and state of the composition, it may be difficult to handle it as a solid at room temperature, in which case it is preferable to handle it as an aqueous solution. The aqueous solution containing the silicone derivative of the present invention can be prepared (neutralized) by forming a salt between the silicone derivative and the basic substance.
The content (concentration) of the silicone derivative in the aqueous solution of the silicone derivative of the present invention can be appropriately adjusted according to the application. The concentration range is preferably 0.001 to 99.999 wt%, more preferably 0.01 to 80 wt%.
Further, the aqueous solution of this silicone derivative further contains other surfactants, for example, surfactants such as anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants as appropriate. May be.

（一般式（７）において、Ｒ^１は炭素数１〜２３の炭化水素基を表わし、Ｒ^２は水素又は炭素数１〜３の炭化水素を表わし、ｊ、ｋは０、１、２のいずれかであり、かつｊ、ｋは同時に０ではない。） Below, the manufacturing method of the silicone derivative of this invention is demonstrated.
As a method for producing the silicone derivative represented by the general formula (1), an N-acyl acidic amino acid anhydride represented by the following general formula (7) and a modified organopolysiloxane compound having one or more amino groups, It can be obtained by reacting at room temperature to 250 ° C. without solvent or in the presence of a solvent.

(In the general formula (7), R ¹ represents a hydrocarbon group having 1 to 23 carbon atoms, R ² represents hydrogen or a hydrocarbon having 1 to 3 carbon atoms, and j and k are 0, 1, or 2) And j and k are not 0 at the same time.)

The N-acyl acidic amino acid anhydride represented by the general formula (7) used as a raw material is an anhydride in which an acidic amino acid is N-acylated. The N-acyl acidic amino acid anhydride may be any of D-form, L-form, and racemate which are optical isomers. In particular, an L-acidic amino acid which is an L-form is preferable because of its excellent biodegradability.
Acidic amino acids are those having more carboxyl groups than amino groups in the molecule. For example, monoaminodicarboxylic acid having 2 and 1 carboxyl groups and amino groups, respectively, can be mentioned. The hydrogen of the amino group may be substituted with a hydrocarbon group having 1 to 3 carbon atoms.
Specific examples of acidic amino acids include N-acyl glutamic acid, aspartic acid, lanthionine, β-methyllanthionine, cystathionine, diencholic acid, ferrinin, aminomalonic acid, β-oxyaspartic acid, α-amino-α-methylsuccinic acid , Β-oxyglutamic acid, γ-oxyglutamic acid, γ-methylglutamic acid, γ-methyleneglutamic acid, γ-methyl-γ-oxyglutamic acid, α-aminoadipic acid, α-amino-γ-oxyadipic acid, α-aminopimelic acid , Α-amino-γ-oxypimelic acid, β-aminopimelic acid, α-aminosuberic acid, α-aminosebacic acid, pantothenic acid and the like. Among these, the case where the acidic amino acid is an L-acidic amino acid is preferable because biodegradability is particularly excellent.

Examples of the modified organopolysiloxane compound having one or more amino groups used as a raw material include amino-modified organopolysiloxane. When amino-modified organopolysiloxane is used, the production purity and stability of the silicone derivative of the present invention are improved. The denaturation site may be of either end, one end, side chain type, or side chain both end type.
The modified organopolysiloxane compound can make a bond derived from an amino group, and an acid amide bond is made by the amino group. This bond corresponds to -A- in the general formula (3).
Further, the modified organopolysiloxane compound may have a substituent other than the functional group described above. Further, the modified organopolysiloxane compound may be an optical isomer of D-form, L-form, and racemate, or may be each isomer.

  Specific examples of modified organopolysiloxane compounds having one or more functional groups selected from amino groups include amino-modified organopolysiloxanes (FZ-3789; Toray Dow Silicone, TSF4702, TSF4703; Momentive Performance Materials, etc.), etc. Is mentioned.

When reacting the N-acyl acidic amino acid anhydride and the modified organopolysiloxane compound, a solvent may be used. Examples of the solvent used in the reaction include water, a mixed solvent of water and an organic solvent, or an inert solvent such as tetrahydrofuran, benzene, toluene, xylene, carbon tetrachloride, chloroform, and acetone. The reaction temperature is preferably −5 ° C. to 200 ° C. and mixed and reacted at a temperature equal to or higher than the melting point of the above compound.
As another method for producing the compound represented by the general formula (1) or (2), not an N-acyl acidic amino acid anhydride but an N-acyl acidic amino acid mono-lower ester (for example, methyl ester, ethyl ester), It can also be obtained by reacting with a modified organopolysiloxane compound.
An N-acyl acidic amino acid mono-lower ester and a modified organopolysiloxane compound are dissolved in a suitable solvent such as dimethylformamide, a catalyst such as potassium carbonate is added, and the mixture is heated at -5 ° C to 250 ° C under reduced pressure. Then, it is obtained by removing the reaction solvent. Or it can also obtain by carrying out heat-melting without a solvent without using a solvent, adding a catalyst, such as sodium hydroxide, and carrying out transesterification at room temperature-250 degreeC. The N-acyl acidic amino acid mono-lower ester used in this case is preferably N-acyl-L-acidic amino acid mono-lower ester.

Alternatively, the silicone derivative may be an N-acyl acidic amino acid anhydride represented by the general formula (7) and a modified organopolysiloxane compound at a temperature equal to or higher than any melting point, or tetrahydrofuran, benzene, toluene, xylene, four It can also be obtained by mixing and reacting at −5 to 200 ° C. using an inert solvent such as carbon chloride, chloroform or acetone.
The N-acyl acidic amino acid anhydride used in this case is also preferably N-acyl-L-acidic amino acid anhydride. Here, the N-acyl acidic amino acid anhydride can be obtained by reacting an N-acyl acidic amino acid with a dehydrating agent such as carboxylic anhydride such as acetic anhydride.

Another method for producing the compound represented by the general formula (1) or (2) is to react an N-acyl acidic amino acid instead of an N-acyl acidic amino acid anhydride with the modified organopolysiloxane compound. Can also be obtained.
The N-acyl acidic amino acid and the modified organopolysiloxane compound are dissolved in an appropriate solvent such as toluene, a catalyst is added if necessary, and the mixture is heated at -5 ° C to 250 ° C, and then the reaction solvent is removed. Can be obtained. Alternatively, it can also be obtained by heating and melting without solvent without using a solvent, adding a catalyst as necessary, and reacting at room temperature to 250 ° C. The N-acyl acidic amino acid used in this case is preferably an N-acyl-L-acidic amino acid.

Furthermore, the alkali salt can be obtained by neutralizing the silicone derivative obtained by the above-mentioned method with an alkali. From the silicone derivatives obtained by these methods, the silicone derivative represented by the general formula (1) or (2) can be isolated by appropriate purification means.
Hereinafter, the reaction in the production of the silicone derivative of the present invention will be described with specific examples.
For example, the silicone derivative represented by the following general formula (8) can be produced by reacting the N-acyl acidic amino acid anhydride of the general formula (7) with an amino-modified organopolysiloxane.

Representative examples of the use of the silicone derivative of the present invention and the composition thereof include, for example, industrial detergents and treatment materials, household (clothing, kitchen, dwelling, tableware, etc.) detergent raw materials, cosmetic raw materials, skin external ingredients ( Refining agents, dyeing assistants, softeners, water repellents), antifouling agents, concrete admixtures, printing ink raw materials, lubricating oil raw materials, antistatic agents, antifogging agents, lubricants, dispersants, deinking. Agents, surface treatment agents and the like.
These applications can be said to be useful applications utilizing the low irritation to the skin and the like, which are one of the features of the present invention, and the surface activity and biodegradability at a low concentration. When used in these applications, the present invention is prepared as a blended composition (such as a cleaning composition or a cosmetic composition) depending on the application. The blending amount of the product of the present invention in the blending composition is not particularly limited, and blended according to the use. Preferably, it is 0.001-99.999 wt%, More preferably, it is the range of 0.01-80 wt%.

Hereinafter, the use of the silicone derivative of the present invention will be described in more detail.
The cosmetic raw material and the skin external preparation raw material which are uses of the present invention will be described.
The cosmetic product in the present invention is a general term for quasi-drugs and cosmetics referred to in the Pharmaceutical Affairs Law. Specific examples include quasi-drugs, cosmetics, cleansing cosmetics, hair cosmetics, basic cosmetics, makeup cosmetics, perfumes, sunscreen / sunscreen cosmetics, nail cosmetics, lip cosmetics, oral cosmetics, and bath cosmetics. .
Examples of quasi-drugs include mouth refreshing agents, odor control agents, tempering powders, hair nourishing agents, hair removal agents, hair dyes, permanent wave agents, bath preparations, medicated cosmetics, and medicated toothpastes. .
Examples of cosmetics include cleansing cosmetics, hair cosmetics, basic cosmetics, makeup cosmetics, perfumes, sunscreen / sunscreen cosmetics, nail cosmetics, lip cosmetics, oral cosmetics, bath cosmetics, and the like.

Examples of cleaning cosmetics include cosmetic soaps, facial cleansers (cream / paste, liquid / gel, granules / powder, aerosol use, etc.), shampoos, rinses, and the like.
Cosmetics for hair include hair dyes, hair treatments (including cream, mist, oil, gel and other forms and split coats), hair set (hair oil, set lotion, curler lotion) , Pomade, tic, bottle oil, hair spray, hair mist, hair liquid, hair foam, hair gel, water grease) and the like.
Basic cosmetics include general cream, milky lotion (cleansing cream, cold cream, burnishing cream, hand cream, etc.), shaving cream (after shaving cream, shaving cream, etc.), lotion (hand lotion, general lotion, etc.), Cologne, shaving lotion (after shaving lotion, shaving lotion, etc.), cosmetic oil, pack and the like.
As makeup cosmetics, there are as follows: creamy, creamy, solid, powdery, talcum powder, kneaded, baby powder, body powder, watery, etc., powder, foundation (creamy, liquid, solid, etc.), blusher, eyebrows Examples include eye cream, eye cream, eye shadow mascara, and eyeliner.

Examples of perfumes include general perfumes, kneaded perfumes, and powdered perfumes.
Examples of the tan / sunscreen cosmetics include tan / sunscreen cream, tan / sunscreen lotion, tan / sunscreen oil and the like.
Examples of nail cosmetics include nail cream, enamel, enamel remover and the like.
Examples of lip cosmetics include lipstick and lip balm.
Examples of oral cosmetics include toothpaste.
Examples of bath makeup include bath salt, bath oil, bubble bath and the like.

In particular, the present invention is preferably used for cleaning cosmetics, hair cosmetics, basic cosmetics, and makeup cosmetics.
Moreover, this invention can be used together with the various additives normally used for cosmetics. Additives include anionic surfactants, amphoteric surfactants, nonionic surfactants, cationic surfactants, polymeric surfactants, fats and oils, hydrocarbons, waxes, higher fatty acids, higher alcohols, ester oils, Volatile or non-volatile oils, humectants, water-soluble and oil-soluble polymers, thickening / foaming ingredients, sequestering agents, preservatives, pH adjusters, anti-dandruff / itching agents, UV absorbers, whitening agents , Blood circulation promoters, local stimulants, anti-inflammatory agents, astringents, refreshing agents, and antioxidants. Specific examples include the following.

Anionic surfactants include fatty acid salts (soaps), alkyl sulfates (AS), polyoxyethylene alkyl ether sulfates (AES), alpha-olefin sulfonates (AOS), alkyl benzene sulfonates, alkyls Naphthalene sulfonate, alkyl sulfonate (SAS), dialkyl sulfosuccinate, alpha-sulfonated fatty acid salt, N-acyl amino acid salt, N-acyl-N-methyl taurate salt, sulfated oil and fat, polyoxyethylene styrenated phenyl Examples thereof include ether sulfate, alkyl phosphate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether phosphate, naphthalene sulfonate formalin condensate and the like.
Examples of amphoteric surfactants include alkylbetaines, alkylamidobetaines, alkylsulfobetaines, imidazolinium betaines and the like.

Nonionic surfactants include fatty acid alkylolamide, alkylamine oxide, polyoxyethylene alkyl ether (AE), polyoxyethylene alkyl phenyl ether, polyoxyethylene polystyryl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene Oxyethylene polyoxypropylene alkyl ether, polyhydric alcohol fatty acid partial ester, polyoxyethylene polyhydric alcohol fatty acid partial ester, polyoxyethylene fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, triethanol Examples include amine fatty acid partial esters.
Examples of cationic surfactants include primary to tertiary fatty amine salts, alkylammonium chlorides, tetraalkylammonium salts, trialkylbenzylammonium salts, alkylpyridinium salts, alkylhydroxyethyl imidazolinium salts, dialkylmorpholiniums. Examples include salts.
Examples of the polymer surfactant include sodium alginate, starch derivatives, tragacanth rubber and the like. Examples of natural surfactants include lecithin, lanolin, cholesterol, saponin and the like.

As fats and oils, avocado oil, almond oil, olive oil, cacao oil, sesame oil, safflower oil, soybean oil, coconut oil, persic oil, castor oil, mink oil, cottonseed oil, owl, palm oil, egg yolk oil, palm oil, palm kernel oil And synthetic triglycerides.
Examples of the hydrocarbon include liquid paraffin, petrolatum, ceresin, microcrystalline wax, and isoparaffin.
Examples of the wax include beeswax, whale wax, lanolin, carnauba wax, candelilla wax and derivatives thereof.
Examples of the higher fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, behenic acid, undecylenic acid, lanolin fatty acid, hard lanolin fatty acid, soft lanolin fatty acid and the like.
Examples of the higher alcohol include lauryl alcohol, cetanol, cetostearyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, hexyl decanol, and octyldodecanol.
Examples of ester oils include isopropyl myristate and butyl stearate.

Examples of the volatile or non-volatile oil include silicones such as metal soap, straight silicone oil, and modified silicone oil.
Examples of polyols include glycerin, 1,3-butanediol, propanediol, and polyethylene glycol.
Examples of the humectant include trimethylglycine, sorbitol, pyrrolidone carboxylates, lactates, hyaluronates, and the like.
Examples of water-soluble and oil-soluble polymers include hydroxyethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose hydroxypropyl trimethyl ammonium chloride ether, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, methyl hydroxypropyl cellulose, soluble starch, carboxymethyl starch, methyl starch, propylene alginate Glycol ester, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, carboxyvinyl polymer, polyacrylate, guar gum, locust bin gum, quince seed, carrageenan, galactan, gum arabic, pectin, mannan, starch, xanthan gum, dextran, succinoglucan , Card run, hi Ruronic acid, gelatin, casein, albumin, collagen, methoxyethylene maleic anhydride copolymer, amphoteric methacrylate copolymer, polydimethylmethylenepiperidinium chloride, polyacrylate copolymer, polyvinyl acetate, nitrocellulose And silicone resin.

Examples of the thickening / foaming component include polyethylene glycol fatty acid ester, polyoxyethylene fatty acid ester methyl glycoside, and tetradecene sulfonate.
Examples of the sequestering agent include ethylenediaminetetraacetic acid and its salts, hydroxyethylenediaminetriacetic acid and its salts, phosphoric acid, ascorbic acid, succinic acid, gluconic acid, polyphosphates, metaphosphates, hinokitiles and the like.
Examples of the preservative include p-hydroxybenzoates, benzoic acid and salts thereof, phenoxyethanol, hinokitiol and the like.
Examples of the pH adjuster include citric acid, malic acid, adipic acid, glutamic acid, aspartic acid and the like.

Examples of the dandruff / itch prevention agent include trichlorocarbanilide, salicylic acid, zinc pyrithione, and isopropylmethylphenol.
Examples of the ultraviolet absorber include benzophenone derivatives, paraaminobenzoic acid derivatives, paramethoxycinnamic acid derivatives, salicylic acid derivatives, and the like.
Examples of the whitening agent include arbutin, kojic acid, ascorbic acid, hinokitile and derivatives thereof.

Examples of the blood circulation promoter include assembly extract, cephalanthin, vitamin E and derivatives thereof, gamma oryzanol and the like.
Examples of the local stimulant include chili tincture, ginger tincture, cantharis tincture, nicotinic acid benzyl ester and the like.
Examples of the anti-inflammatory agent include glycyrrhetinic acid, glycyrrhizic acid derivatives, allantoin, azulene, aminocaproic acid, hydrocortisone, and the like.
Examples of the astringent include zinc oxide, zinc sulfate, allantoin hydroxyaluminum, aluminum chloride, zinc sulfocolate, and tannic acid.
Examples of the refreshing agent include menthol and camphor.
Examples of the antioxidant include silicone materials such as polymer silicone and cyclic silicone, tocopherols, BHA, BHT, gallic acid, NDGA, and the like.

In addition, nutrients such as various vitamins and amino acids, antihistamines, female hormone agents, hair root activators, purified water, and the like can be included.
In particular, combined use with fatty acid diethanolamide, polyoxyethylene dioleic acid methyl glucoside, polyethylene glycol distearate, tetradecene sulfonate, myristic acid salts, myristyl dimethylamine is useful in terms of increasing viscosity and foaming power. . Further, the combined use of the present invention and each amphoteric surfactant is extremely useful in that the irritation is further reduced. In addition, those described in the cosmetic raw material standards and the cosmetic varieties component composition standards can be used in combination. Moreover, the above-mentioned additives can be used in combination of two or more as appropriate.
The topical skin preparation in the present invention means a composition applied to the skin in the fields of pharmaceuticals, quasi drugs, cosmetics and the like. The dosage form is not limited as long as the effect of the present invention is not lost. Specific examples of the external preparation for skin may be any ointment, cream, milky lotion, lotion, pack, bath preparation, etc. as long as they are conventionally used for external preparations for skin. Moreover, what was carry | supported by the sheet-like base is also included. In the external preparation for skin, the silicone derivative of the present invention is used by blending with the base of the external preparation for skin.
The external preparation for skin in the present invention is produced according to the intended dosage form by appropriately blending the components used in the external preparation for skin as necessary. In addition to the above-mentioned additives, the components used in the external preparation for skin include ultraviolet absorbers, ultraviolet scattering agents, liquid fats and oils, waxes, solid fats and oils, hydrocarbon oils, solid fats and oils, higher fatty acids, higher alcohols, and synthetic ester oils. Is mentioned.

As the ultraviolet absorber, paraaminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester, N, N-dimethyl PABA ethyl ester, N, Benzoic acid UV absorbers such as N-dimethyl PABA butyl ester and N, N-dimethyl PABA methyl ester, anthranilic acid UV absorbers such as homomenthyl-N-acetylanthranilate, amyl salicylate, menthyl salicylate, homomenthyl salicylate , Salicylic acid UV absorbers such as octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate, octyl cinnamate, ethyl-4-isopropyl cinnamate Methyl-2,5-diisopropylcinnamate, ethyl-2,4-diisopropylcinnamate, methyl-2,4-diisopropylcinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p- Methoxycinnamate, octyl-p-methoxycinnamate (2-ethylhexyl-p-methoxycinnamate), 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β- Cinnamon such as phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl-diparamethoxycinnamate, trimethoxycinnamate methylbis (trimethylsiloxane) silylisopentyl Acid UV absorber, 3- (4′-methylbenzylidene) -d, 1-camphor, 3-benzylidene-d, 1-camphor, urocanic acid, urocanic acid ethyl ester, 2-phenyl-5-methylbenzoxazole 2,2′-hydroxy-5-methylphenylbenzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenylbenzotriazole), Dibenzalazine, dianisoylmethane, 4-methoxy-4′-t-butyldibenzoylmethane, 5- (3,3-dimethyl-2-norbornylidene) -3-pentan-2-one, dimorpholinopyridazinone and the like It is done.
Examples of the ultraviolet scattering agent include powders such as titanium oxide, fine particle titanium oxide, zinc oxide, fine particle zinc oxide, iron oxide, fine particle iron oxide, and cerium oxide.
As these ultraviolet scattering agents, needle-like, spindle-like, spherical and granular powders are usually used. A fine particle powder having a particle size of 0.1 μm or less is preferred.

UV scattering agent that has been hydrophobized by silicone treatment such as methylhydrogenpolysiloxane and silane coupling agent, metal soap treatment, fluorine treatment such as perfluoroalkyl phosphate diethanolamine salt and perfluoroalkylsilane, and dextrin fatty acid ester treatment Is also preferable.
Liquid oils include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, sasanqua oil, castor oil, flaxseed oil, saury Examples thereof include flower oil, cotton seed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnagiri oil, Japanese kiri oil, jojoba oil, germ oil, triglycerin and the like.
Solid fats and oils include cocoa butter, coconut oil, horse fat, hydrogenated coconut oil, palm oil, beef tallow, sheep fat, hardened beef tallow, palm kernel oil, pork fat, beef bone fat, owl kernel oil, hydrogenated oil, and cow leg fat. , Mole, hardened castor oil, and the like.

The waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibota wax, whale wax, montan wax, nuka wax, lanolin, kapok wax, lanolin acetate, liquid lanolin, sugar cane wax, lanolin fatty acid isopropyl, lauryl hexyl, reduced lanolin, jojojo Examples thereof include a wax, hard lanolin, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, and the like.
Examples of the hydrocarbon oil include liquid paraffin, ozokerite, squalane, pristane, paraffin, ceresin, squalene, petrolatum, microcrystalline wax, polyethylene wax, and Fischer-Tropsch wax.

Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, toluic acid, linoleic acid, linolenic acid, eicosapentaenoic acid (EPA), and docosahexaenoic acid (DHA). It is done.
As higher alcohols, straight chain alcohols (for example, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, etc.), branched chain alcohols (for example, monostearyl glycerin ether (batyl alcohol), 2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyldodecanol, octyldodecanol, etc.).
Synthetic ester oils include isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, cetyl lactate, myristyl lactate Lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, neopentyl glycol dicaprate, apple Acid diisostearyl, di-2-heptylundecanoic acid glycerin, tri-2-ethylhexanoic acid trimethylolpropane, Trimethylolpropane phosphate, pentaerythritol tetra-2-ethylhexanoate, glycerin tri-2-ethylhexanoate, glycerin trioctanoate, glyceryl triisopalmitate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glyceryl trimyristate, tri-2-heptylundecanoic acid glyceride, castor oil fatty acid methyl ester, oleyl oleate, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L -Glutamic acid-2-octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyl myristate Sill, palmitic acid 2-hexyl decyl, 2-hexyldecyl adipate, 2-ethylhexyl succinate, triethyl citrate, polyoxyethylene-polyoxypropylene random polymer methyl ether.
Others include lower alcohols such as ethanol, antioxidants such as butylhydroxytoluene, tocopherol, and phytin, antibacterial agents such as benzoic acid, sorbic acid, paraoxybenzoic acid alkyl ester, hexachlorophene, acyl sarcosine acid (for example, lauroyl sarcosine sodium) ), Organic acids such as glutathione, vitamin A and its derivatives, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 and its derivatives, vitamin B such as vitamin B12, vitamin B15 and its derivatives, ascorbine Acid, ascorbic acid sulfate (salt), ascorbic acid phosphate (salt), vitamin C such as ascorbic acid dipalmitate, α-tocopherol, β-tocopherol, δ-tocophero , Vitamin E such as tocopherol acetate, vitamin D, vitamin H, pantothenic acid, pantethine and other vitamins, nicotinamide, benzyl nicotinate, γ-oryzanol, allantoin, glycyrrhizic acid (salt), glycyrrhetinic acid and its Derivatives, hinokitiol, bisabolol, thymol, inositol, saikosaponin, carrot saponin, hechisaponin, muclodisaponin and other saponins, pantothenyl ethyl ether, ethinyl estradiol, tranexamic acid, arbutin, cephalanthin, placenta extract and other various drugs, Clara, Kouhone, orange, sage, yarrow, mallow, assembly, thyme, spruce, spruce, birch, horsetail, loofah, maronier, yukinoshita, arnica, lily, Artemisia, Peonies, Aloe, Gardenia, Sawara, Hawthorn extract, Hypericum perforatum extract, Iris in extract, Acacia extract, Ginkgo biloba extract, Eustoma biloba extract, Fennel extract, Oolong tea extract, Water lily extract, Ages extract, Enmeisou Extracts, plant extracts such as extract, green grass extract, grasshopper extract, licorice extract, licorice extract, gardenia extract, black tea extract, sesame extract, tormentilla extract, rose extract, loofah extract, peppermint extract, rosemary extract, royal jelly extract, Pigment, sorbitan monolaurate, sorbitan monopalmitate, sorbitan sesquioleate, sorbitan trioleate, polyoxyethylene sorbate monolaurate , Polysoxyethylene sorbitan monostearate, polyethylene glycol monooleate, polyoxyethylene alkyl ether, polyglycol diether, lauroyl diethanol amide, fatty acid isopropanol amide, maltitol hydroxy fatty acid ether, alkylated polysaccharide, alkyl glucoside, sugar ester, etc. Nonionic activators, stearyltrimethylammonium chloride, cationic surfactants such as benzalkonium chloride, laurylamine oxide, sodium palmitate, sodium laurate, sodium laurate, potassium lauryl sulfate, triethanolamine ether of alkyl sulfate , Funnel oil, linear dodecyl benzene sulfate, polyoxyethylene hydrogenated castor oil maleic acid, acylmethyl Anionic surfactants such as phosphorus, amphoteric surfactants, antioxidants such as δ-tocopherol and butylhydroxytoluene, preservatives such as phenoxyethanol and paraben, α-hydroxy acids, N, N, N-trimethylglycine (TMG ), An exfoliating agent such as L-serine, malonic acid, or succinic acid.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the examples. The evaluation means used in the examples of the present invention are as follows.
1) Confirmation of reaction products
^The reaction product was confirmed using ¹ H-NMR and ¹³ C-NMR.

2) Evaluation of Silicone Derivative (A) Reaction Rate The content ratio of the silicone derivative represented by the general formula (1) contained in those obtained in Examples was determined and used as the reaction rate. When the N-acyl acidic amino acid derivative and the modified organopolysiloxane compound are all reacted, the reaction rate is 100%. When there is an unreacted N-acyl acidic amino acid derivative, the reaction rate is lower than 100%. Measurement was performed by the following method.
In high performance liquid chromatography (HPLC) equipped with a GPC column (manufactured by Tosoh Corporation, TSK-GEL G2000HXL (7.8 mm × 300 mm) + TSK-GEL G1000HHR (7.8 mm × 300 mm)), differential refraction using THF as an eluent Each component was analyzed using a rate detector (manufactured by Shimadzu Corporation; RID-10A).

(B) Odor of silicone derivative Ten panelists of healthy men performed sensory evaluation. The evaluation criteria are described below.
If there are more than 7 people who have no odor: ○ (good)
If there are 4-6 people who have no odor: △ (possible)
If there are 3 or less people who have no odor: × (impossible)

(C) Skin Irritation of Silicone Derivatives The panel of 10 healthy boys was used continuously for 1 week, and then the presence or absence of skin irritation was evaluated. The evaluation criteria are described below.
If there are more than 7 people who are not irritating: ○ (good)
If 4 to 6 people are not irritating: △ (possible)
If there are 3 or less people who are not irritating: × (impossible)

(D) Compound stability A sodium hydroxide aqueous solution was added to the silicone derivative to adjust the solid content of the silicone derivative to 1% and pH 9, and stored at 40 ° C for 1 month. Then, each component was analyzed using high performance liquid chromatography (HPLC).
Since the N-acyl acidic amino acid derivative increases when the stability of the silicone derivative is lost, the stability of the compound was evaluated by a change in the ratio of the peak area corresponding to the N-acyl acidic amino acid derivative with respect to the total peak area. The criteria for evaluation are as follows.
The ratio of the peak area corresponding to the N-acyl acidic amino acid derivative after storage increases by 0 to 10% with respect to the initial value: ○ (good)
The ratio of the peak area corresponding to the N-acyl acidic amino acid derivative after storage increases by more than 10% with respect to the initial value: x (impossible)

(E) Coloring degree of silicone derivative Ten panelists of healthy men evaluated visually. The evaluation criteria are described below.
When there are 7 or more people in white to light yellow: ○ (good)
When 4 to 6 people are white to pale yellow: △ (possible)
When the number of white to light yellow people is 3 or less: × (impossible)

(F) Emulsification stability An aqueous solution of 50% polydimethylsiloxane (6 cst), 49.97% purified water and 0.03% test emulsifier was adjusted to a total of 150 g, and 5 at 10,000 rpm using a homomixer. Minute emulsification. The emulsion was left at 50 ° C. for 3 days, and the emulsified state was observed. When two layers of an aqueous layer and an emulsified layer were observed, the emulsification stability was evaluated according to the following criteria.
A cloudy emulsion can be confirmed, and no oil is confirmed in the aqueous layer: ○ (Emulsified)
A state where a small amount of clear oil can be confirmed at the top of the emulsified layer: △ (Emulsification is broken)
A state where a large amount of transparent oil can be confirmed at the top of the emulsified layer: × (not emulsified)

Example 1
Side chain amino-modified silicone (Toray Dow Silicone; FZ-3789) 120.0 g was mixed in acetone 355.6 g. While stirring this mixed solution, 32.4 g of N-lauroyl-L-glutamic anhydride was added over 30 minutes at room temperature, and the reaction was carried out for 3 hours. After stirring for 24 hours, the solvent was removed from the reaction solvent to obtain 150.9 g of a silicone derivative. The reaction product was confirmed by NMR. The analysis and evaluation results are shown in Table 1.

Example 2
120.0 g of side chain type amino-modified silicone (Toray Dow Silicone; FZ-3789) was mixed in 314.9 g of acetone. While stirring this mixed solution, 14.9 g of N-lauroyl-L-glutamic anhydride was added over 30 minutes at room temperature, and the reaction was carried out for 3 hours. After stirring for 24 hours, the solvent was removed from the reaction solvent to obtain 133.6 g of a silicone derivative. The reaction product was confirmed by NMR. The analysis and evaluation results are shown in Table 1.

Example 3
In Example 1, the reaction step was carried out under the same conditions as in Example 1 except that N-lauroyl-L-glutamic anhydride was changed to N-lauroyl-D-glutamic anhydride, and 149.3 g of silicone derivative was obtained. Obtained. The reaction product was confirmed by NMR. The analysis and evaluation results are shown in Table 1.

Example 4
Side chain type amino-modified silicone (Toray Dow Silicone; FZ-3789) 120.0 g was mixed in acetone 365.7 g. While stirring this mixed solution, 36.7 g of N-palmitoyl-L-glutamic anhydride was added over 30 minutes at room temperature, and the reaction was carried out at 50 ° C. for 3 hours. Further, stirring was continued at room temperature for 24 hours, and then the solvent was removed from the reaction solvent to obtain 155.2 g of a silicone derivative. The reaction product was confirmed by NMR. The analysis and evaluation results are shown in Table 1.

Example 5
Side chain type amino-modified silicone (Toray Dow Silicone; FZ-3789) 120.0 g was mixed in 372.3 g of acetone. While stirring this mixed solution, 39.5 g of N-stearoyl-L-glutamic anhydride was added over 30 minutes at room temperature, and the reaction was carried out at 50 ° C. for 5 hours. Further, stirring was continued at room temperature for 24 hours, and then the solvent was removed from the reaction solvent to obtain 156.3 g of a silicone derivative. The reaction product was confirmed by NMR. The analysis and evaluation results are shown in Table 1.

Example 6
30.0 g of one-terminal amino-modified silicone (Momentive Performance Materials; TSF4700) was mixed in 77.3 g of acetone. While stirring this mixed solution, 3.1 g of N-lauroyl-L-glutamic anhydride was added over 10 minutes at room temperature, and the reaction was carried out at 50 ° C. for 5 hours. Furthermore, after continuing stirring for 24 hours at normal temperature, the solvent was removed from the reaction solvent to obtain 32.8 g of a silicone derivative. The reaction product was confirmed by NMR. The analysis and evaluation results are shown in Table 1.

Example 7
25.0 g of single-terminal amino-modified silicone (Momentive Performance Materials; TSF4701) was mixed in 65.6 g of acetone. While stirring this mixed solution, 3.1 g of N-lauroyl-L-glutamic anhydride was added over 10 minutes at room temperature, and the reaction was carried out at 50 ° C. for 5 hours. Further, stirring was continued at room temperature for 24 hours, and then the solvent was removed from the reaction solvent to obtain 27.8 g of a silicone derivative. The reaction product was confirmed by NMR. The analysis and evaluation results are shown in Table 1.

Comparative Example 1
90.3 g of both terminal carbinol-modified silicone (Shin-Etsu Silicone; KF-6001) was mixed in 289.9 g of acetone. While stirring this mixed solution, 33.9 g of N-myristoyl-L-glutamic anhydride was added at 50 ° C. over 30 minutes, and the reaction was carried out for 5 hours. Furthermore, after continuing stirring for 24 hours at normal temperature, the solvent was removed from the reaction solvent to obtain 123.0 g of a silicone derivative. The reaction product was confirmed by NMR. The analysis and evaluation results are shown in Table 1.

Comparative Example 2
One-terminal carbinol-modified silicone (Shin-Etsu Silicone; X-22-170BX) 28.0 g was mixed in acetone 73.9 g. While stirring this mixed solution, 3.7 g of N-palmitoyl-L-glutamic anhydride was added at 50 ° C. over 10 minutes, and the reaction was carried out for 5 hours. Furthermore, after continuing stirring for 24 hours at normal temperature, the solvent was removed from the reaction solvent to obtain 31.0 g of a silicone derivative. The reaction product was confirmed by NMR. The analysis and evaluation results are shown in Table 1.

Comparative Example 3
19.0 g of side chain mercapto-modified silicone (Shin-Etsu Silicone; KF-2001) was mixed in 51.6 g of acetone. While stirring this mixed solution, 3.1 g of N-lauroyl-L-glutamic anhydride was added at 50 ° C. over 10 minutes, and the reaction was carried out for 5 hours. Further, stirring was continued at room temperature for 24 hours, and then the solvent was removed from the reaction solvent to obtain 21.9 g of a silicone derivative. The reaction product was confirmed by NMR. The analysis and evaluation results are shown in Table 1.

Using the silicone derivative obtained in Example 1 and the silicone derivative obtained in Example 2, the N-acyl acidic amino acid derivative / silicone functional group molar ratio was calculated and the degree of coloration was evaluated. The results are shown in Table 2.
The N-acyl acidic amino acid derivative / silicone functional group molar ratio represents the ratio between the functional group of silicone and the acylamino acid. A molar ratio greater than 1 indicates that the acylamino acid is higher than the functional group of the silicone.
In Example 1, since the N-acyl acidic amino acid derivative / silicone functional group molar ratio is about 1 and the reaction rate is 97%, almost all of the functional groups of both terminal amino-modified silicones are reacted. On the other hand, in Example 2, since the N-acyl acidic amino acid derivative / silicone functional group molar ratio is about 0.5 and the reaction rate is 92%, among the functional groups possessed by the side chain amino-modified silicone, It can be seen that half, that is, one functional group reacts with an acylamino acid.
From the evaluation result of the coloring degree, it can be seen that the silicone derivative of Example 1 in which almost all the functional groups of the silicone have reacted has a better coloring degree.

Examples 8-14
The compositions obtained in Examples 1 to 7 were completely neutralized with an aqueous sodium hydroxide solution, and then dried to obtain a neutralized silicone derivative powder. Emulsion stability was evaluated using the silicone derivative as an emulsifier. The results are shown in Table 3.

Comparative Examples 4-6
The compositions obtained in Comparative Examples 1 to 3 were completely neutralized with an aqueous sodium hydroxide solution, and then dried to obtain a neutralized silicone derivative powder. Emulsion stability was evaluated using the silicone derivative as an emulsifier. The results are shown in Table 3.

Comparative Examples 7-12
The modified silicone used in the reactions in Examples 1, 6, 7 and Comparative Examples 1 to 3 was used as an emulsifier as it was to evaluate the emulsion stability. The results are shown in Table 3.

Example 15
A styling spray composition having the following composition was prepared. Raw materials other than the propellant were dissolved by adding ethanol, filtered and filled into cans, and after the valve was attached, the propellant was filled. The styling spray composition was low in skin irritation and excellent in touch.

Example 16
A styling lotion composition having the following composition was prepared by adding the raw materials to ethyl alcohol and uniformly dissolving and mixing them. The styling lotion composition had little skin irritation and good touch.

Example 17
A styling mousse composition having the following composition was uniformly emulsified with a homomixer except for the propellant, filled into a can, and after mounting the valve, the propellant and gas were filled. The styling mousse had low skin irritation and excellent touch.

Example 18
A hair wax composition having the following composition was prepared by uniformly emulsifying with a homomixer. The hair wax composition had a good feel and low skin irritation.

  The silicone derivative of the present invention has high emulsification stability, low skin irritation, and high affinity for various base materials, so that it can be used for industrial detergents and treatment materials, household use (clothing, kitchen, dwelling, tableware). Etc.) Detergent raw materials, cosmetic raw materials, skin external preparation raw materials, food raw materials, pharmaceutical raw materials, emulsion (polymerization) raw materials, agricultural chemical raw materials, textile processing raw materials (refining agents, dyeing aids, softeners, water repellents) Agent), antifouling agent, concrete admixture, printing ink raw material, lubricating oil raw material, antistatic agent, antifogging agent, lubricant, dispersant, deinking agent, surface treatment agent and the like.

Claims (6)

A silicone derivative represented by the following general formula (1) or (2).

(In the general formula (1), at least one of h × n X is represented by the following general formula (3), and the other X and R are each independently an alkyl having 1 to 22 carbon atoms. Or an alkoxy group, an alkenyl group having 2 to 22 carbon atoms, an aryl group having 6 to 22 carbon atoms, a polyether group, or a hydroxyl group, R ″ is a hydrocarbon having 1 to 22 carbon atoms, and Z is Polyalkylene oxide, h is 0 to 300,000, l is 0 to 300000, and n is an integer of 0 to 300000.)

(In the general formula (2), X is represented by the following general formula (3), and R is independently an alkyl group having 1 to 22 carbon atoms, an alkoxy group, or an alkenyl group having 2 to 22 carbon atoms. , An aryl group having 6 to 22 carbon atoms, a polyether group, or a hydroxyl group.)

(In General Formula (3), A is a hydrocarbon having a nitrogen atom, Q is represented by the following General Formula (4), and m is an integer of 1 to 10.)

(In General Formula (4), R ¹ is a hydrocarbon group having 1 to 23 carbon atoms, R ² is hydrogen or a hydrocarbon having 1 to 3 carbon atoms, and Y is a carboxyl group, a sulfonic acid group, or a sulfate ester. A group, a phosphate group or a salt thereof, j and k are each independently an integer of 0, 1 or 2, and j and k are not 0 at the same time.) The silicone derivative according to claim 1, wherein the general formula (3) is the following general formula (5).

(In General Formula (5), R ¹ , R ² , Y, j, and k are the same as in General Formula (4), R ³ is a hydrocarbon having 1 to 22 carbon atoms, and —Z— is —NR. '-(R' represents hydrogen or a hydrocarbon having 1 to 10 carbon atoms).) The silicone derivative according to claim 1, wherein the general formula (3) is the following general formula (6).

(In General Formula (6), R ¹ , R ² , Y, j, and k are the same as in General Formula (4), and R ⁴ and R ⁵ are each independently a hydrocarbon having 1 to 22 carbon atoms. ) The silicone derivative according to any one of claims 1 to 3, wherein R ² is hydrogen and Y is a carboxyl group.   The composition containing the silicone derivative as described in any one of Claims 1-4, and silicone.   A composition comprising the silicone derivative according to any one of claims 1 to 4 and an N-acylamino acid type surfactant.