WO2012165227A1

WO2012165227A1 - Production method for low-odor, sugar alcohol-modified silicone

Info

Publication number: WO2012165227A1
Application number: PCT/JP2012/063072
Authority: WO
Inventors: 田村　誠基; さゆり澤山; 達央早田; 晴彦古川
Original assignee: 東レ・ダウコーニング株式会社
Priority date: 2011-05-30
Filing date: 2012-05-22
Publication date: 2012-12-06
Also published as: JP5809849B2; JP2012246445A

Abstract

The present invention relates to: a production method for a sugar alcohol-modified silicone comprising a step in which the sugar alcohol-modified silicone is treated using an acidic substance; an external preparation and/or cosmetic containing the sugar alcohol-modified silicone; and a method for measuring the carbonyl value of a sugar alcohol-modified silicone containing carbonyl compounds by using the absorbance of the reaction solution obtained by reacting the sugar alcohol-modified silicone with 2, 4-dinitrophenylhydrazine in a reaction medium containing a lower monovalent alcohol and water. The present invention enables: the production of a low-odor, sugar alcohol-modified silicone which is substantially odorless and in which the development of odors over time is restricted; the provision of an external preparation and/or cosmetic using such a sugar alcohol-modified silicone; and the simple and accurate quantification of carbonyl compounds, which are odor-causing agents, contained in sugar alcohol-modified silicone.

Description

Method for producing low odor sugar alcohol-modified silicone

This application claims priority based on Japanese Patent Application No. 2011-121094 filed in Japan on May 30, 2011, the contents of which are incorporated herein by reference. The present invention relates to low bromination of organopolysiloxanes modified with sugar alcohols.

Silicone having a hydrophilic group includes a silicone part that exhibits characteristics such as hydrophobicity, flexibility, lubricity, and chemical stability, and a hydrophilic group part that exhibits characteristics such as hydrophilicity, moisture retention, and adhesion. It has excellent surface-active ability due to the combination. For this reason, silicone having a hydrophilic group is widely used in foods, resins, paints, cosmetics and the like. In particular, in cosmetics, silicone oils such as low-molecular cyclic siloxanes are often blended for the purpose of improving the feeling of use, and because of their good compatibility with silicone oils, as cosmetic raw materials such as surfactants, for example, Many proposals have been made to use polyether-modified silicone (Patent Document 1, etc.).

However, in terms of hydrophilicity, polyether groups are insufficient, and (poly) glycerin-modified silicone and its application to cosmetics have been proposed for the purpose of improving hydrophilicity (Patent Documents 2 to 5). ). However, even in the (poly) glycerin group, the hydrophilicity is not yet sufficient, and for the purpose of further increasing the density of the hydroxyl group, a sugar alcohol-modified silicone using a sugar alcohol as a polyhydric alcohol, and its cosmetics. Applications have been proposed (Patent Documents 6 to 12).

Japanese Patent Laid-Open No. 61-293903 JP-A-57-149290 Japanese Patent Laid-Open No. 06-157236 Japanese Patent Application Laid-Open No. 09-071504 Japanese Patent Laying-Open No. 2005-042097 JP-A-62-068820 JP 63-139106 A JP 05-186596 A Japanese Patent Application Laid-Open No. 07-041417 JP 2002-11840 A JP 2008-274241 A JP 2002-179798 A

The sugar alcohol-modified silicone can be synthesized, for example, by a hydrosilylation reaction between an organohydrogenpolysiloxane having a silicon atom-bonded hydrogen group and a sugar alcohol group-containing compound having a carbon-carbon double bond.

However, the sugar alcohol-modified silicone thus obtained or a composition containing the same may have an odor, and in particular, since the odor tends to increase with time, the use of external preparations or cosmetics applied to the human body Use in is difficult. Moreover, even if it is a case where it can mix | blend with an external preparation or cosmetics, there exists a problem that the compounding quantity etc. are limited.

The present invention has been made to solve the above problems, and provides a method for producing a low-odor sugar alcohol-modified silicone that is substantially odorless and that suppresses the generation of odor over time. The purpose. And this invention makes it the 2nd objective to provide the external preparation or cosmetics using such low odor sugar alcohol modified silicone.

The odor of the sugar alcohol-modified silicone is considered to be one of the causes because of the internal transfer of the carbon-carbon double bond during the hydrosilylation reaction and the generation of a carbonyl compound such as propionaldehyde. The third object of the present invention is to provide a method for accurately and simply quantifying such carbonyl compounds.

As a result of intensive studies aimed at achieving the above object, the present inventors have reached the present invention. That is, the first object of the present invention is achieved by a method for producing a sugar alcohol-modified silicone, comprising a step of treating the sugar alcohol-modified silicone with at least one acidic substance. In particular, the first object of the present invention is to
(A) a sugar alcohol group-containing compound having a carbon-carbon double bond;
(B) A step [A] of synthesizing a sugar alcohol-modified silicone by hydrosilylation reaction with an organohydrogenpolysiloxane; and the synthesis step [A], or after the synthesis step [A].
Process of treating sugar alcohol-modified silicone in the presence of at least one acidic substance [B]
It is suitably achieved by a method for producing a sugar alcohol-modified silicone characterized by comprising:
Furthermore, it is more suitably achieved by a method for producing a sugar alcohol-modified silicone including a step of removing an odor-causing substance by heating and / or reducing pressure after the acid treatment step.

The sugar alcohol-modified silicone has the following general formula (1):

{Where,
R ¹ represents a monovalent organic group (excluding L and Q), a hydrogen atom or a hydroxyl group,
R ² is a substituted or unsubstituted, linear or branched monovalent hydrocarbon group having 9 to 60 carbon atoms, or the following general formula (2-1);

(Wherein R ¹¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, a hydroxyl group, or a hydrogen atom, and at least one of R ¹¹ is the monovalent hydrocarbon group. T Is a number in the range of 2 to 10, and r is a number in the range of 1 to 500) or the following general formula (2-2);

(Wherein R ¹¹ and r are as defined above), and represents a chain organosiloxane group,
L ¹ is the following general formula (3) when i = 1;

(Where
R ³ represents a substituted or unsubstituted, linear or branched monovalent hydrocarbon group having 1 to 30 carbon atoms,
Each R ⁴ independently represents an alkyl group having 1 to 6 carbon atoms or a phenyl group;
Z represents a divalent organic group,
i represents the generation of a silylalkyl group represented by L ^i, an integer from 1 to k when the generation number is the number of repetitions of the silylalkyl group is k, the number of layers k is an integer from 1 to 10, L ^{i + 1} is the silylalkyl group when i is less than k, R ⁴ when i = k, and h ⁱ is a number in the range of 0 to 3). Represents a silylalkyl group having
Q represents a sugar alcohol group-containing organic group,
a, b, c, and d are in the ranges of 1.0 ≦ a ≦ 2.5, 0 ≦ b ≦ 1.5, 0 ≦ c ≦ 1.5, and 0.0001 ≦ d ≦ 1.5, respectively. Is a number}.

In the general formula (1), the monovalent organic group represented by R ¹ is a substituted or unsubstituted linear or branched monovalent hydrocarbon group having 1 to 8 carbon atoms, —R ⁵ O ( AO) _n R ⁶ (wherein AO represents an oxyalkylene group having 2 to 4 carbon atoms, and R ⁵ is a substituted or unsubstituted, linear or branched divalent group having 3 to 5 carbon atoms) R ⁶ represents a hydrocarbon group, R ⁶ is a hydrogen atom, a substituted or unsubstituted, straight-chain or branched monovalent hydrocarbon group having 1 to 24 carbon atoms, or a substituted group having 2 to 24 carbon atoms Or a polyoxyalkylene group, an alkoxy group, a hydroxyl group, or a hydrogen atom represented by an unsubstituted, linear or branched acyl group, where n = 1 to 100 (provided that R ¹ is all a hydroxyl group, A hydrogen atom, the alkoxy group or the polyoxyalkylene group; Can not be).

In the general formula (1), Q is the following general formula (4-1):

(Where
R represents a divalent organic group,
e is 1 or 2, or the following general formula (4-2):

(Where
R is as described above,
e 'is preferably a sugar alcohol group-containing organic group represented by 0 or 1.

In the general formula (4-1) or (4-2), the divalent organic group represented by R is a substituted or unsubstituted, linear or branched divalent hydrocarbon group having 3 to 5 carbon atoms. Can be.

In the general formula (1), the silylalkyl group having a siloxane dendron structure represented by L ¹ is represented by the following general formula (3-1):

Or the following general formula (3-2):

(Where
R ³ , R ⁴ and Z are as described above,
h ¹ and h ² each independently represents a functional group represented by a number ranging from 0 to 3.

The sugar alcohol-modified silicone has the following structural formula (1-1):

(Where
R ² , L ¹ and Q are as described above,
X is a group selected from the group consisting of a methyl group, R ² , L ¹ and Q;
n1, n2, n3 and n4 are each independently a number in the range of 0 to 2,000, and n1 + n2 + n3 + n4 is a number in the range of 1 to 2,000. However, when n4 = 0, at least one of X is Q).

The sugar alcohol-modified silicone has the following structural formula (1-1-1):

Or the following structural formula (1-1-2):

(Where
R ² , Q, X, Z, n1, n2, n3 and n4 are as described above)
The thing represented by these is preferable.

In the structural formula (1-1-1) or the structural formula (1-1-2), each Z independently represents the following general formula:

(Where
R ⁷ each independently represents a substituted or unsubstituted, linear or branched alkylene group or alkenylene group having 2 to 22 carbon atoms, or an arylene group having 6 to 22 carbon atoms. ,
R ⁸ is

A group selected from the group consisting of: a divalent organic group represented by:

The acidic substance may be selected from the group consisting of inorganic acids, organic acids, acidic inorganic salts, solid acids, and acidic platinum catalysts.

The acidic substance is preferably a water-soluble acidic inorganic salt that is solid at 25 ° C. and has an aqueous solution having a pH of 4 or less at 25 ° C. when 50 g is dissolved in 1 L of ion-exchanged water.

The second object of the present invention is to provide an external preparation or cosmetic raw material containing the low odor sugar alcohol-modified silicone obtained by the above production method, or an external preparation or makeup containing the low odor sugar alcohol modified silicone. Achieved by a fee.

A third object of the present invention is to react carbonyls in sugar alcohol-modified silicone with 2,4-dinitrophenylhydrazine in a reaction medium containing at least one monohydric lower alcohol having 1 to 4 carbon atoms. This is achieved by a method for measuring the carbonyl value of the sugar alcohol-modified silicone from the absorbance of the reaction solution obtained in this manner.

The sugar alcohol-modified silicone or sugar alcohol-modified silicone-containing composition obtained by the present invention preferably has a carbonyl value measured by the above method of 2.5 Abs / g or less.

The present invention provides a sugar alcohol-modified silicone or a sugar alcohol-modified silicone-containing composition that is substantially odorless and that suppresses the generation of odor over time by a simple process of acid treatment. Can do. That is, one aspect of the present invention is a method for reducing the odor of a sugar alcohol-modified silicone including a step of treating the sugar alcohol-modified silicone with an acidic substance.

The odor reducing effect of the sugar alcohol-modified silicone according to the present invention is extremely high, and the odor reducing effect obtained in the present invention cannot be obtained even if other modified silicones are acid-treated in the same manner as the present invention. In addition, it is possible to obtain an odor reducing effect as obtained in the present invention by performing hydrogenation treatment on the other modified silicones, but the hydrogenation treatment is complicated in steps, and is a relatively expensive reagent. And special equipment is required. In the present invention, since it is not necessary to carry out such a hydrogenation treatment, it is advantageous for implementation on an industrial scale, and it is also possible to provide a sugar alcohol-modified silicone that is easily and inexpensively non-brominated. it can.

Moreover, although this invention is sugar alcohol modified silicone or a composition containing it, the raw material for external preparations or cosmetics by which the odor was reduced can be provided. Therefore, in the present invention, it is possible to provide a low odor external preparation or cosmetic while containing a sugar alcohol-modified silicone.

Since the odor of the sugar alcohol-modified silicone of the present invention or a composition containing the sugar is reduced, it is not necessary to mask the odor when blended into an external preparation or cosmetic, and the formulation of the external preparation or cosmetic formulation is designed. High degree of freedom. This is particularly advantageous in cosmetics where odor-containing functionality is important, and it is easy to design an unscented cosmetic, a slightly scented cosmetic, or a cosmetic with a desired fragrance.

And in this invention, the carbonyl compound considered to be one of the causes of the odor of sugar alcohol modified silicone can be quantified accurately and simply. In addition, since it is not necessary to conduct a sensory test, the degree of low bromide can be quantified safely and objectively, and the product is reduced in the amount of external preparations or cosmetic products. It can be clearly shown.

(Method for producing low-odor sugar alcohol-modified silicone)
The present invention relates to a method for producing a sugar alcohol-modified silicone, comprising a step of treating the sugar alcohol-modified silicone with at least one acidic substance. In particular, from the viewpoint of industrially obtaining a low bromide external preparation or cosmetic raw material (sugar alcohol-modified silicone), which reduces odor more effectively,
(A) a sugar alcohol group-containing compound having a carbon-carbon double bond;
(B) A step [A] of synthesizing a sugar alcohol-modified silicone by hydrosilylation reaction with an organohydrogenpolysiloxane; and the synthesis step [A], or after the synthesis step [A].
Process of treating sugar alcohol-modified silicone in the presence of at least one acidic substance [B]
It is preferable that it is a manufacturing method of the sugar alcohol modified silicone characterized by including this. Moreover, it is more preferable that it is a manufacturing method of the sugar alcohol modified silicone including the process of removing an odor causative substance by heating and / or pressure-reducing after the said acid treatment process.

(Sugar alcohol-modified silicone)
The sugar alcohol-modified silicone has the following general formula (1):

{Where,
R ¹ represents a monovalent organic group (excluding R ² , L ¹ and Q), a hydrogen atom or a hydroxyl group,
R ² is a substituted or unsubstituted, linear or branched monovalent hydrocarbon group having 9 to 60 carbon atoms, or the following general formula (2-1);

(Wherein R ¹¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, a hydroxyl group or a hydrogen atom, and at least one of R ¹¹ is the monovalent hydrocarbon group. T is 2 is a number in the range of 2 to 10, and r is a number in the range of 1 to 500) or the following general formula (2-2);

The monovalent organic group represented by R ¹ in the general formula (1) is not particularly limited as long as it is not a functional group corresponding to R ² , L ¹ and Q, but is substituted or substituted with 1 to 8 carbon atoms. An unsubstituted, linear or branched monovalent hydrocarbon group, —R ⁵ O (AO) _n R ⁶ (wherein AO represents an oxyalkylene group having 2 to 4 carbon atoms, and R ⁵ represents carbon Represents a substituted or unsubstituted, straight-chain or branched divalent hydrocarbon group having 3 to 5 atoms, wherein R ⁶ is a hydrogen atom, a substituted or unsubstituted straight-chain having 1 to 24 carbon atoms A branched or branched monovalent hydrocarbon group, or a substituted or unsubstituted, linear or branched acyl group having 2 to 24 carbon atoms, and n = 1 to 100). Polyoxyalkylene group, alkoxy group, (meth) acryl group, amide group, carbino Group, or is preferably a phenol group. However, R ¹ does not all become a hydroxyl group, a hydrogen atom, the alkoxy group or the polyoxyalkylene group.

Examples of the monovalent hydrocarbon group having 1 to 8 carbon atoms include, for example, alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl; cyclopentyl, cyclohexyl Cycloalkyl groups such as vinyl groups, allyl groups, butenyl groups, etc .; aryl groups such as phenyl groups, tolyl groups; aralkyl groups such as benzyl groups; and hydrogen atoms bonded to carbon atoms of these groups At least partially a halogen atom such as fluorine, or a group substituted with an organic group including an epoxy group, glycidyl group, acyl group, carboxyl group, amino group, methacryl group, mercapto group, etc. (however, the total number of carbon atoms is 1 to 8). The monovalent hydrocarbon group is preferably a group other than an alkenyl group, and particularly preferably a methyl group, an ethyl group, or a phenyl group. The alkoxy group is a lower alkoxy group such as methoxy group, ethoxy group, isopropoxy group, butoxy group, lauryl alkoxy group, myristyl alkoxy group, palmityl alkoxy group, oleyl alkoxy group, stearyl alkoxy group, behenyl alkoxy group. Illustrative are higher alkoxy groups.

In particular, R ¹ is preferably a monovalent hydrocarbon group or monovalent fluorinated hydrocarbon group having 1 to 8 carbon atoms that does not have an aliphatic unsaturated bond. Examples of the monovalent hydrocarbon group having no aliphatic unsaturated bond belonging to R ¹ include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group; phenyl group, tolyl group, xylyl group Aryl groups such as benzyl groups, etc., and monovalent fluorinated hydrocarbon groups include perfluoroalkyl groups such as trifluoropropyl groups and pentafluoroethyl groups. Industrially, R ¹ is preferably a methyl group, an ethyl group, or a phenyl group. Particularly, 90 mol% to 100 mol% of all R ¹ are a methyl group, an ethyl group, or a phenyl group. Is preferably a group selected from:

The sugar alcohol-modified silicone has a modified group other than the hydrophilic group (-Q), particularly a short-chain or medium-chain hydrocarbon-based group, introduced as R ¹ or designed for the purpose of imparting further functionality. Is possible. That is, when R ¹ is a substituted monovalent hydrocarbon group, the substituent can be appropriately selected according to the characteristics to be imparted and the application. For example, when used as a cosmetic raw material, an amino group, an amide group, an aminoethylaminopropyl group, a carboxyl group, or the like is used as a substituent for a monovalent hydrocarbon group for the purpose of improving the feeling of use, feel or sustainability. Can be introduced.

The substituted or unsubstituted, linear or branched monovalent hydrocarbon group of 9 to 60 carbon atoms of R ^{2 in} the general formula (1) is a long chain hydrocarbon group or the above general formula (2-1 ) Or (2-2) is a chain-like organosiloxane group, and is introduced into the main chain and / or side chain of the polysiloxane, so that it can be blended in an external preparation or cosmetic. The emulsifiability and dispersibility for various components such as the body, and the feeling of use can be further improved. Furthermore, since the monovalent long-chain hydrocarbon group or the chain-like organopolysiloxane group is a hydrophobic functional group, the compatibility and blending stability with respect to organic oils having a high alkyl group content are further improved. All of R ² may be the monovalent long-chain hydrocarbon group or the chain-like organopolysiloxane group, or may be a functional group of both of them. In the sugar alcohol-modified silicone, in particular, part or all of R ² is preferably a monovalent long chain hydrocarbon group, and the sugar has a monovalent long chain hydrocarbon group. Alcohol-modified silicones exhibit superior compatibility with not only silicone oils but also non-silicone oils with a high alkyl group content. For example, non-silicone oils with excellent thermal stability and stability over time Products and dispersions can be obtained.

The substituted or unsubstituted, straight-chain or branched monovalent hydrocarbon groups having 9 to 60 carbon atoms and represented by R ² in the general formula (1) may be the same as each other. Further, the structure may be selected from linear, branched and partially branched. In the present invention, an unsubstituted and linear monovalent hydrocarbon group is particularly preferably used. Examples of the unsubstituted monovalent hydrocarbon group include an alkyl group, an aryl group, and an aralkyl group having 9 to 60 carbon atoms, preferably 9 to 30 carbon atoms, more preferably 10 to 25 carbon atoms. On the other hand, examples of the substituted monovalent hydrocarbon group include a perfluoroalkyl group, an aminoalkyl group, and an amidoalkyl group having 9 to 30 carbon atoms, preferably 9 to 30 carbon atoms, and more preferably 10 to 25 carbon atoms. Group and carbinol group. Moreover, a part of carbon atoms of the monovalent hydrocarbon group may be substituted with an alkoxy group, and examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group. Such a monovalent hydrocarbon group is particularly preferably an alkyl group having 9 to 30 carbon atoms, and represented by the general formula: — (CH ₂ ) _v —CH ₃ (v is a number in the range of 8 to 30). The group represented by these is illustrated. An alkyl group having 10 to 25 carbon atoms is particularly preferred.

Unlike the silylalkyl group having a siloxane dendron structure, the chain organosiloxane group represented by the general formula (2-1) or (2-2) has a linear polysiloxane chain structure. In the general formula (2-1) or (2-2), each R ¹¹ is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, a hydroxyl group, or a hydrogen atom. The substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms is preferably an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl having 6 to 30 carbon atoms. A cycloalkyl group having 6 to 30 carbon atoms, and an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group; a cyclopentyl group, a cyclohexyl group A cycloalkyl group such as a group; an aryl group such as a phenyl group and a tolyl group is exemplified, and a hydrogen atom bonded to a carbon atom of these groups is at least partially a halogen atom such as fluorine, an epoxy group, an acyl group, It may be substituted with an organic group including a carboxyl group, amino group, methacryl group, mercapto group and the like. Particularly preferred as R ¹¹ is a form in which a methyl group, a phenyl group or a hydroxyl group is raised, a part of R ¹¹ is a methyl group, and a part is a long-chain alkyl group having 8 to 30 carbon atoms. Is preferred.

In general formula (2-1) or (2-2), t is a number in the range of 2 to 10, r is a number in the range of 1 to 500, and r is a number in the range of 2 to 500. It is preferable. Such a linear organosiloxane group is hydrophobic, and from the viewpoint of compatibility with various oils, r is preferably a number in the range of 1 to 100, and a number in the range of 2 to 30. Particularly preferred.

The silylalkyl group having a siloxane dendron structure represented by the general formula (3) is a functional group exhibiting high water repellency, including a structure in which carbosiloxane units spread in a dendrimer shape, and is a combination of a hydrophilic group and a hydrophilic group. When using an external preparation or cosmetic containing the sugar alcohol-modified silicone, the balance is excellent, and an unpleasant sticky feeling can be suppressed and a refreshing natural feel can be given. Furthermore, the silylalkyl group having a siloxane dendron structure is a functional group that imparts an advantageous property that it can be used in combination with a wide range of components because it is chemically stable.

Examples of the substituted or unsubstituted, linear or branched monovalent hydrocarbon group represented by R ³ in the general formula (3) include, for example, a methyl group, an ethyl group, Alkyl groups such as propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkenyl groups such as vinyl group, allyl group and butenyl group; phenyl group and tolyl Aryl groups such as groups; aralkyl groups such as benzyl groups; and hydrogen atoms bonded to carbon atoms of these groups are at least partially halogen atoms such as fluorine, or epoxy groups, glycidyl groups, acyl groups, carboxyl groups , Groups substituted with an organic group including an amino group, a methacryl group, a mercapto group and the like (provided that the total number of carbon atoms is 1 to 30).

Of the alkyl group having 1 to 6 carbon atoms or the phenyl group represented by R ⁴ in the general formula (3), examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, i- Examples include linear, branched or cyclic alkyl groups such as propyl, n-butyl, i-butyl, s-butyl, pentyl, neopentyl, cyclopentyl, hexyl and the like.

In general formula (3), when i = k, R ⁴ is preferably a methyl group or a phenyl group. In particular, when i = k, a methyl group is preferable.

The number of hierarchies k is industrially preferably an integer of 1 to 3, more preferably 1 or 2. In each layer number, the group represented by L ¹ is represented as follows. In the formula, R ³ , R ⁴ and Z are the same groups as described above.

When the number of hierarchies is k = 1, L ¹ is represented by the following general formula (3-1).

When the number of hierarchies is k = 2, L ¹ is represented by the following general formula (3-2).

When the number of hierarchies is k = 3, L ¹ is represented by the following general formula (3-3).

In the structure represented by the general formulas (3-1) to (3-3) when the number of layers is 1 to 3, h ¹ , h ² and h ³ are each independently a number in the range of 0 to 3. These h ⁱ are particularly preferably numbers in the range of 0 to 1, and h ⁱ is particularly preferably 0.

In the general formulas (3) and (3-1) to (3-3), each Z is independently a divalent organic group, specifically, a silicon-bonded hydrogen atom, an alkenyl group, an acryloxy group, Examples include divalent organic groups formed by the addition reaction of a functional group having an unsaturated hydrocarbon group at the end, such as a methacryloxy group, depending on the method for introducing a silylalkyl group having a siloxane dendron structure. The functional group is not limited to this, and can be selected as appropriate. Preferably, each Z independently represents the following general formula:

Is a group selected from divalent organic groups represented by the formula: In particular, Z in L ¹ is preferably a divalent organic group represented by the general formula —R ⁷ — introduced by the reaction of a silicon-bonded hydrogen atom and an alkenyl group. Similarly, Z is preferably a divalent organic group represented by —R ⁷ —COO—R ⁸ — introduced by reaction of a silicon-bonded hydrogen atom with an unsaturated carboxylic ester group. On the other hand, it is the hierarchical number k is 2 or more, the silylalkyl group represented by L is a 2 ^~ L ^k L ^i, Z is preferably an alkylene group having 2 to 10 carbon atoms, an ethylene group, a propylene group , A methylethylene group or a hexylene group is particularly preferable, and an ethylene group is most preferable.

In the general formula, each R ⁷ independently represents a substituted or unsubstituted, linear or branched alkylene group or alkenylene group having 2 to 22 carbon atoms, or 6 to 22 carbon atoms. Represents an arylene group. More specifically, R ⁷ is a linear alkylene group such as ethylene group, propylene group, butylene group, hexylene group; methylmethylene group, methylethylene group, 1-methylpentylene group, 1,4-dimethylbutylene group. are branched alkylene groups exemplified etc., R ⁷ is an ethylene group, a propylene group is preferably a group selected from methyl ethylene group or a hexylene group.

In the above general formula, R ⁸ is a group selected from divalent organic groups represented by the following formula.

In the general formula (1), Q is a sugar alcohol-containing organic group and constitutes a hydrophilic portion of the sugar alcohol-modified silicone. The structure of Q is not limited as long as it has a sugar alcohol moiety, but it is preferable that the sugar alcohol residue is bonded to the silicon atom via a divalent organic group.

Therefore, Q is preferably the following general formula (4-1):

(Where
R represents a divalent organic group,
e is 1 or 2, and h is the following general formula (4-2):

(Where
R is as described above,
e ′ is 0 or 1).

The sugar alcohol-modified silicone is characterized in that at least one of the sugar alcohol-containing organic groups represented by the general formula (4-1) or (4-2) is bonded to a silicon atom. Further, it may be an organopolysiloxane having two or more types of sugar alcohol-containing organic groups selected from these sugar alcohol-containing organic groups in the same molecule. Similarly, mixtures of organopolysiloxanes having different sugar alcohol-containing organic groups may be used.

The divalent organic group represented by R in the general formula (4-1) or (4-2) is not particularly limited. For example, the divalent organic group having 1 to 30 carbon atoms, substituted or unsubstituted, A linear or branched divalent hydrocarbon group may be mentioned. A substituted or unsubstituted, linear or branched divalent hydrocarbon group having 3 to 5 carbon atoms is preferable. Examples of the substituted or unsubstituted, linear or branched divalent hydrocarbon group having 1 to 30 carbon atoms include, for example, methylene group, dimethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene A linear or branched alkylene group having 1 to 30 carbon atoms, such as a group, heptamethylene group, octamethylene group, etc .; Bonded to carbon atoms of 30 alkenylene groups; arylene groups having 6 to 30 carbon atoms such as phenylene groups and diphenylene groups; alkylene arylene groups having 7 to 30 carbon atoms such as dimethylenephenylene groups; A hydrogen atom is at least partially a halogen atom such as fluorine, or a carbinol group, an epoxy group, a glycidyl group, Sill group, a carboxyl group, an amino group, a methacryl group, a mercapto group, an amide group, and substituted groups in the organic group containing an oxyalkylene group or the like. The divalent hydrocarbon group is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 3 to 5 carbon atoms.

As the sugar alcohol-containing organic group, it is particularly preferable that R is a propylene group and e = 1 in the general formula (4-1). Similarly, as the sugar alcohol-containing organic group, it is particularly preferable that R is a propylene group and e ′ = 0 in the general formula (4-2). In this case, the sugar alcohol-containing organic group has the structural formula: —C ₃ H ₆ —OCH ₂ [CH (OH)] ₃ CH ₂ OH, corresponding to the general formula (4-1) or the general formula (4-2). Or a xylitol residue represented by the structural formula: —C ₃ H ₆ —OCH {CH (OH) CH ₂ OH} ₂ (hereinafter, simply referred to as “xylitol residue” or “xylitol modifying group”).

The bonding position of the sugar alcohol-containing organic group may be either the side chain or the terminal of polysiloxane, which is the main chain, and has a structure having two or more sugar alcohol-containing organic groups in one molecule of sugar alcohol-modified silicone. May be. Further, these two or more sugar alcohol-containing organic groups may be the same or different sugar alcohol-containing organic groups. These two or more sugar alcohol-containing organic groups may have a structure in which only the side chain of the polysiloxane that is the main chain, only the terminal, or the side chain and the terminal are bonded.

The sugar alcohol-modified silicone represented by the general formula (1) having a sugar alcohol group-containing organic group (-Q) is represented by the following structural formula (1-1):

(Where
R ² , L ¹ and Q are each independently as described above,
X is a group selected from the group consisting of a methyl group, R ² , L ¹ and Q;
n1, n2, n3 and n4 are each independently a number in the range of 0 to 2,000, and n1 + n2 + n3 + n4 is a number in the range of 0 to 2,000. However, when n4 = 0, at least one of X is Q), and is preferably a sugar alcohol-modified silicone having a linear polysiloxane structure.

In formula (1-1), (n1 + n2 + n3 + n4) is preferably a number in the range of 10 to 2,000, more preferably in the range of 25 to 1500, and particularly preferably in the range of 50 to 1000. n1 is preferably a number in the range of 10 to 2,000, more preferably in the range of 25 to 1500, and still more preferably in the range of 50 to 1000. n2 is preferably a number in the range of 0 to 250, and more preferably a number in the range of 0 to 150.

When R ² is the above-mentioned long-chain alkyl group, it is particularly preferable that n2> 1 from the viewpoint of surface activity and compatibility with oil agents other than silicone. n3 is preferably a number in the range of 0 to 250, particularly preferably n3> 1 and having at least ^one silylalkyl group (—L ¹ ) having a siloxane dendron structure in the side chain portion. n4 is a number in the range of 0 to 100, and preferably a number in the range of 0 to 50. However, when n4 = 0, at least one of X needs to be Q.

In the structural formula (1-1), each Q independently represents a sugar alcohol-containing organic group represented by the general formula (4-1) or the general formula (4-2). In the sugar alcohol-modified silicone, , Q may be a sugar alcohol-containing organic group represented by the general formula (4-1) or the general formula (4-2), and a part of Q in one molecule may be represented by the general formula (4- The sugar alcohol-containing organic group represented by 1), and the remaining Q may be a sugar alcohol-containing organic group represented by the general formula (4-2).

Furthermore, the sugar alcohol-modified silicone may be a mixture of one or more sugar alcohol-modified silicones represented by the general formula (1).

In particular, the sugar alcohol-modified silicone is preferably a sugar alcohol-containing organic group in which Q is a xylitol residue in the general formula (1).

As described above, the xylitol residue has the structural formula: —C ₃ H ₆ —OCH ₂ [CH (OH)] ₃ CH ₂ OH, or the structural formula: —C ₃ H ₆ —OCH {CH (OH) CH ₂ it is a group represented by OH} _2, in the sugar alcohol-modified silicones, these xylitol residues may be two even one. Therefore, in the general formula (1), all of Qs are represented by the structural formula: —C ₃ H ₆ —OCH ₂ [CH (OH)] ₃ CH ₂ OH, or the structural formula: —C ₃ H ₆ —OCH { It may consist only of xylitol residues represented by CH (OH) CH ₂ OH} ₂ , or Q may be represented by the structural formula: —C ₃ H ₆ —OCH ₂ [CH (OH)] ₃ CH ₂ It may be composed of OH and two types of xylitol residues represented by the structural formula: —C ₃ H ₆ —OCH {CH (OH) CH ₂ OH} ₂ . In the latter case, the constitutional ratio (substance ratio) is preferably in the range of 5: 5 to 10: 0, particularly preferably in the range of 8: 2 to 10: 0. In the case of 10: 0, Q substantially consists only of a xylitol residue represented by the structural formula: —C ₃ H ₆ —OCH ₂ [CH (OH)] ₃ CH ₂ OH.

Further, when the sugar alcohol-modified silicone is a mixture of two or more types of sugar alcohol-modified silicone, Q in the general formula (1) is a structural formula: —C ₃ H ₆ —OCH in the mixture. Sugar alcohol-modified silicone consisting only of xylitol residues represented by ₂ [CH (OH)] ₃ CH ₂ OH, Q in the above general formula (1) is the structural formula: —C ₃ H ₆ —OCH {CH (OH) A sugar alcohol-modified silicone consisting only of a xylitol residue represented by CH ₂ OH} ₂ and Q in the general formula (1) are represented by the structural formula: —C ₃ H ₆ —OCH ₂ [CH (OH)] ₃ CH ₂ OH and a sugar alcohol-modified silicone composed of two types of xylitol residues represented by the structural formula: —C ₃ H ₆ —OCH {CH (OH) CH ₂ OH} ₂ (component ratio (substance ratio) ) Is 5: 5 It is preferably in the range of ˜10: 0, and particularly preferably in the range of 8: 2 to 10: 0), and can contain at least two sugar alcohol-modified silicones selected from the group consisting of: Further, in the sugar alcohol-modified silicone, Q in the general formula (1) is a structural formula: —C ₃ H ₆ —OCH ₂ [CH (OH)] ₃ CH ₂ OH, and a structural formula: —C ₃ It is composed of two types of xylitol residues represented by H ₆ —OCH {CH (OH) CH ₂ OH} ₂ (the composition ratio (substance ratio) is preferably in the range of 5: 5 to 10: 0, : A range of 2 to 10: 0 is particularly preferable), and may be a mixture of at least two sugar alcohol-modified silicones having different constituent ratios.

Examples of the sugar alcohol-modified silicone include the following structural formula (1-1-1):

(Where
R ² , Q, X, Z, n1, n2, n3 and n4 are as described above), or the following structural formula (1-1-2):

(Where
R ² , Q, X, Z, n1, n2, n3 and n4 are as described above, and a sugar alcohol-modified silicone represented by

The modification rate of the organopolysiloxane with the sugar alcohol-containing organic group is preferably in the range of 0.001 to 50 mol% of all functional groups bonded to the polysiloxane as the main chain, and 0.01 to 30 mol. % Is more preferable, and a range of 0.1 to 10 mol% is even more preferable. In the sugar alcohol-modified silicone represented by the structural formula (1-1), the modification rate (mol%) due to the sugar alcohol-containing organic group is expressed by the following formula:

Modification rate (mol%) = (Number of sugar alcohol-containing organic groups bonded to silicon atoms per molecule) / {6 + 2 × (n1 + n2 + n3 + n4)} × 100

Indicated by For example, in the case of a sugar alcohol-modified silicone composed of trisiloxane having one sugar alcohol-containing organic group, one of eight silicon atom-bonded functional groups is modified with the sugar alcohol-containing organic group. The modification rate due to the sugar alcohol-containing organic group is 12.5 mol%.

The sugar alcohol-modified silicone includes, for example, (a) an organopolysiloxane having a silicon atom-bonded hydrogen atom in the presence of a hydrosilylation reaction catalyst, and (b) an organic compound having one reactive unsaturated group per molecule. And (c) a sugar alcohol functional organic compound having one reactive unsaturated group in one molecule, and (d) a siloxane dendron compound having one reactive unsaturated group in one molecule as required. And / or (e) a long-chain hydrocarbon compound or a chain organopolysiloxane compound having one reactive unsaturated group in one molecule can be obtained. The reactive unsaturated group is preferably an alkenyl group or an unsaturated fatty acid ester group which is an unsaturated functional group having a carbon-carbon double bond. -R ¹ is introduced by component (b), -L ¹ is introduced by component (d), and -R ² is introduced by component (e).

More specifically, the sugar alcohol-modified silicone can be obtained as follows, for example.

The sugar alcohol-modified silicone is an unsaturated organic compound having a carbon-carbon double bond at one end of a molecular chain, and a carbon-carbon double bond in the molecule relative to an organopolysiloxane having a silicon-hydrogen bond. It can be obtained by addition reaction of an unsaturated ether compound of a sugar alcohol having A siloxane dendron compound having a carbon-carbon double bond at one end of the molecular chain and / or an unsaturated long-chain hydrocarbon compound having a carbon-carbon double bond at one end of the molecular chain or a piece of molecular chain A chain organopolysiloxane having a carbon-carbon double bond at the terminal may be further subjected to an addition reaction.

In the above case, the sugar alcohol-modified silicone comprises the unsaturated organic compound, the unsaturated ether compound of the sugar alcohol, and optionally the siloxane dendron compound and / or the unsaturated long chain hydrocarbon compound or It can be obtained as a hydrosilylation reaction product of a chain organopolysiloxane having a carbon-carbon double bond at one end of the molecular chain and a SiH group-containing siloxane. Thereby, an organic group and a sugar alcohol-containing organic group, and optionally a silylalkyl group having a siloxane dendron structure, and / or a long-chain hydrocarbon group or a chain organopolysiloxane group, are added to the sugar alcohol-modified silicone. It can be introduced into the polysiloxane chain. This reaction can be carried out collectively or in the form of a sequential reaction, but the sequential reaction is preferred from the viewpoints of safety and quality control.

For example, the sugar alcohol-modified silicone is represented by the following general formula (1 ′) in the presence of a hydrosilylation reaction catalyst:

(Where
R ¹ , a, b, c and d are as described above) (a ′) an organohydrogensiloxane and (c) a sugar alcohol function having one reactive unsaturated group in one molecule It can be obtained by reacting at least a reactive organic compound. (D) a siloxane dendron compound having one reactive unsaturated group in one molecule, and / or (e) a hydrocarbon compound or reactive unsaturated group having one reactive unsaturated group in one molecule. It is preferable to further react a chain organopolysiloxane having one molecule per molecule.

The sugar alcohol-modified silicone comprises (c) a sugar alcohol functional organic compound having one reactive unsaturated group per molecule, and optionally (d) one reactive unsaturated group per molecule. The siloxane dendron compound and / or (e) the hydrocarbon compound having one reactive unsaturated group in one molecule or the chain organopolysiloxane having one reactive unsaturated group in one molecule coexist. Whether the (c) component, the (d) component and / or the (e) component, and (a ′) the organohydrogensiloxane represented by the general formula (1 ′) are reacted together as a state Alternatively, after the (a ′) organohydrogensiloxane and optionally the component (d) and / or the component (e) are sequentially subjected to an addition reaction, the component (c) is further subjected to an addition reaction. The preparative like, can be suitably produced.

Examples of (a) organopolysiloxane having a silicon atom-bonded hydrogen atom and (a ′) organohydrogensiloxane include the following structural formula (1-1) ′:

(Where
Each R ¹ is independently as described above;
X ′ is a group selected from R ¹ or a hydrogen atom,
n1, n2, n3 and n4 are as described above. However, when n2 + n3 + n4 = 0, at least one of X ′ is a hydrogen atom).

(D) As a siloxane dendron compound having one reactive unsaturated group in one molecule, the following general formula (3 ′):

{Where
R ³ and R ⁴ are as described above,
Z ′ represents a divalent organic group,
h ¹ is a number in the range 0-3,
L ′ ¹ is R ⁴ or the following general formula (3 ″) when j = 1:

(Wherein R ³ and R ⁴ are as described above,
Z represents a divalent organic group,
j represents a hierarchy of the silylalkyl group represented by L ^j , and when the hierarchy number that is the number of repetitions of the silylalkyl group is k ′, it is an integer of 1 to k ′, and the hierarchy number k ′ is an integer of 1 to 9 L ^{j + 1} is the silylalkyl group when j is less than k ′, and R ⁴ when j = k ′. a compound having a siloxane dendron structure having one carbon-carbon double bond at the end of the molecular chain represented by: h ^j represents a silylalkyl group represented by the following formula: .

(C) The sugar alcohol functional organic compound having one reactive unsaturated group in one molecule includes the following general formula (4′-1):

(Where
R ′ represents an unsaturated organic group,
e is 1 or 2, preferably 1), or the following general formula (4′-2):

(Where
R ′ represents an unsaturated organic group,
A monounsaturated ether compound of a sugar alcohol represented by e ′ is 0 or 1, preferably 0) is preferable.

The unsaturated organic group is not particularly limited as long as it has an unsaturated group, but a substituted or unsubstituted, linear or branched unsaturated hydrocarbon group having 3 to 5 carbon atoms is preferable. Examples of the unsaturated hydrocarbon group having 3 to 5 carbon atoms include alkenyl groups such as vinyl group, allyl group and butenyl group. An allyl group is preferred.

The monounsaturated ether compound of the sugar alcohol, monoallyl ethers are preferred sugar alcohol, the structural _{_{formula: CH 2 = CH-CH 2}} -OCH 2 [CH (OH)] 3 CH 2 OH, or the structural formula: _{_{CH 2 = CH-CH 2 -OCH}} {CH (OH) CH 2 OH} xylitol monoallyl ether represented by ₂ (hereinafter, referred to as "xylitol monoallyl ether") is more preferable. Xylitol monoallyl ether can be synthesized by a known method, and some are commercially available.

Xylitol monoallyl ether, the structural _{_{formula: CH 2 = CH-CH 2}} -OCH 2 [CH (OH)] 3 CH 2 OH, or the structural _{_{formula: CH 2 = CH-CH 2}} -OCH {CH (OH) CH Only one of the compounds represented by ₂ OH} ₂ may be used, and even a mixture thereof can be used without particular limitation. In particular, the structural _{_{formula: CH 2 = CH-CH 2}} -OCH 2 [CH (OH)] 3 CH 2 OH, or the structural _{_{formula: CH 2 = CH-CH 2}} -OCH {CH (OH) CH 2 OH} 2 or used as a raw material either xylitol monoallyl ether represented in purified, or the structural _{_{formula: CH 2 = CH-CH 2}} -OCH 2 [CH (OH)] 3 CH 2 OH, and the structural formula : in _{_{CH 2 = CH-CH 2 -OCH}} {CH (OH) CH 2 OH} substance amount ratio of xylitol monoallyl ether represented by _2, 5: 5-10: xylitol mono comprising in the range of 0 Allyl ether is preferably used as a raw material. In the latter case, xylitol monoallyl ether containing 8: 2 to 10: 0 is more preferable. Incidentally, 10: 0, the raw material is substantially the structural _{_{formula: CH 2 = CH-CH 2}} -OCH 2 [CH (OH)] from xylitol monoallyl ether represented by the ₃ CH ₂ OH Is a purified product.

(E) The hydrocarbon compound having one reactive unsaturated group in one molecule or the chain organopolysiloxane having one reactive unsaturated group in one molecule has the following general formula:

Wherein R ′ is as described above,
R ^{2 ′} is a substituted or unsubstituted, linear or branched monovalent hydrocarbon group having 7 to 58 carbon atoms, or the following general formula (2-1);

(Wherein R ¹¹ , t and r are as defined above) or the following general formula (2-2);

A monounsaturated organic compound represented by the formula (wherein R ¹¹ and r are as defined above represents a chain organosiloxane group) is preferred.

(E) The hydrocarbon compound having one reactive unsaturated group per molecule is preferably a monounsaturated hydrocarbon having 9 to 30 carbon atoms, more preferably 1-alkene. Examples of 1-alkene include 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-hexadecene, 1-octadecene and the like. Examples of the chain organopolysiloxane having one reactive unsaturated group per molecule include one-end vinyl group-capped dimethylpolysiloxane and one-end vinyl group-capped methylphenyl polysiloxane.

The hydrosilylation reaction is preferably performed in the presence of a catalyst, and examples thereof include platinum, ruthenium, rhodium, palladium, osmium, iridium, and the like, and the platinum compound is particularly effective because of its high catalytic activity. Examples of platinum compounds include: chloroplatinic acid; metal platinum; a metal platinum supported on a carrier such as alumina, silica, carbon black; platinum-vinylsiloxane complex, platinum-phosphine complex, platinum-phosphite complex And platinum complexes such as platinum alcoholate catalysts. The amount of the catalyst used is about 0.5 to 1000 ppm as platinum metal when using a platinum catalyst.

Further, the sugar alcohol-modified silicone may be subjected to a hydrogenation treatment for the purpose of improving the odor after the reaction due to the residual unsaturated compound. The hydrogenation treatment includes a method using pressurized hydrogen gas and a method using a hydrogenation agent such as a metal hydride. Further, the hydrogenation treatment includes a homogeneous reaction and a heterogeneous reaction. One of these can be performed alone, or a combination of these can also be performed. However, considering the advantage that the used catalyst does not remain in the product, the heterogeneous catalytic hydrogenation reaction using a solid catalyst is most preferable.

As the solid catalyst (hydrogenation catalyst), a general noble metal catalyst such as a platinum catalyst and a palladium catalyst, and a nickel catalyst can be used. More specifically, nickel, barium, platinum, rhodium, cobalt and the like alone and a combination of a plurality of metals such as platinum-palladium, nickel-copper-chromium, nickel-copper-zinc, nickel-copper tungsten and nickel-molybdenum are combined. The catalyst can be illustrated. Examples of the catalyst carrier used arbitrarily include activated carbon, silica, silica alumina, alumina, zeolite and the like. In addition, copper-containing hydrogenation catalysts such as Cu—Cr, Cu—Zn, Cu—Si, Cu—Fe—Al, and Cu—Zn—Ti are listed. The form of the hydrogenation catalyst cannot be generally determined, but can usually be appropriately selected from powders, granules, tablets and the like. Also, the platinum catalyst used in the synthesis step (hydrosilylation reaction) can be used as it is. These hydrogenation catalysts can be used alone or in combination of two or more.

The hydrogenation treatment can also be used for purifying a crude product of sugar alcohol-modified silicone obtained by the above addition reaction. Specifically, in the presence of a hydrogenation catalyst, it can be purified by performing no bromination by a hydrogenation treatment in a solvent or in the absence of a solvent, further reducing odors with time after blending into cosmetics, etc. Such a refined product can be used in an external preparation or cosmetic application that requires compatibility with the above components. In addition, as a pre-process or post-process without bromide, a stripping treatment may be performed on a crude product or hydrogenated product of a sugar alcohol-modified silicone by contacting nitrogen gas under reduced pressure to distill off a light product. preferable. However, the hydrogenation treatment is economically disadvantageous in view of cost effectiveness.

The low odor sugar alcohol-modified silicone according to the present invention is obtained in the form of a composition containing sugar alcohol-modified silicone alone or a sugar alcohol-modified silicone and an acidic substance. Low bromide can be achieved by acid treatment. In the case of a composition containing a sugar alcohol-modified silicone and an acidic substance, the amount of the sugar alcohol-modified silicone is not particularly limited, but is 1 to 99 weight (mass) based on the total weight (mass) of the composition. )%, Preferably 5 to 95% by weight, more preferably 10 to 90% by weight, even more preferably 20 to 80% by weight, even more preferably 30 to 70% by weight. % Range.

(Acid substance)
The acidic substance used in the present invention is not particularly limited, and may meet any definition of Lewis acid, Bronsted acid, or Arrhenius acid. The acidic substance used in the present invention is preferably a water-soluble acid. Therefore, the acidic substance used in the present invention is preferably Arrhenius acid that releases protons in an aqueous solution. An acidic substance may be used individually by 1 type, and may use 2 or more types. In the present invention, by using such an acidic substance, sugar alcohol-modified silicone is substantially non-brominated without causing breakage of carbon-oxygen bond or silicon-oxygen bond, and odor generation with time is almost complete. Can be suppressed.

The inorganic acid is not particularly limited, and examples thereof include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, boric acid, sulfonic acid, and sulfinic acid. In addition, what contains organic groups, such as benzenesulfonic acid, is not preferable as an inorganic acid.

The organic acid is not particularly limited, but monocarboxylic acid (including monohydroxymonocarboxylic acid and dihydroxymonocarboxylic acid), dicarboxylic acid (including monohydroxydicarboxylic acid and dihydroxydicarboxylic acid), polycarboxylic acid, and the like. Can be used, for example
Linear saturated aliphatic monocarboxylic acids (alkanoic acids) such as formic acid, acetic acid, trifluoroacetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid;
Branched saturated aliphatic monocarboxylic acids (alkanoic acids) such as 2-methylpropanoic acid, 2-methylbutanoic acid, trimethylpropanoic acid, 2-methylpentanoic acid, trimethylacetic acid;
Unsaturated aliphatic monocarboxylic acids (alkenoic acids) such as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, acetovinyl acid, acetoallylic acid, hexenoic acid, heptenoic acid, octenoic acid;
Unsaturated aliphatic monocarboxylic acids (alkyne acids) such as propiolic acid, tetrolic acid, allylic acetic acid, hexynic acid, octynic acid;
Polyunsaturated aliphatic monocarboxylic acids such as pentadienoic acid and sorbic acid;
Α-hydroxymonocarboxylic acids such as citric acid, lactic acid, glycolic acid, α-oxybutyric acid;
Β-hydroxymonocarboxylic acids such as 2-hydroxyvaleric acid, 2-hydroxycaproic acid, β-oxybutyric acid;
γ-hydroxymonocarboxylic acids such as γ-oxybutyric acid;
Dihydroxymonocarboxylic acids such as glyceric acid;
Other hydroxymonocarboxylic acids such as hydroxy (meth) acrylic acid;
Saturated aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid;
Monohydroxy saturated aliphatic dicarboxylic acids such as tartronic acid, malic acid, etc. dihydroxy saturated aliphatic dicarboxylic acids such as tartaric acid;
Unsaturated aliphatic dicarboxylic acids such as maleic acid and fumaric acid;
Aromatic monocarboxylic acids such as benzoic acid;
Aromatic dicarboxylic acids such as phthalic acid;
Amino acids such as glycine, alanine, valine, leucine, glutamic acid, aspartic acid, PL-pyrrolidone carboxylic acid;
Examples thereof include polycarboxylic acids such as gallic acid.

Further, as the organic acid, alkyl sulfuric acid, alkyl phosphoric acid, phenol and the like can be used. Higher fatty acids or salts thereof are not preferred as organic acids.

The acidic inorganic salt is not limited, but is preferably water-soluble. In particular, the pH at 25 ° C. of the aqueous solution when it is solid at 25 ° C. and 50 g is dissolved in 1 L of ion-exchanged water is 4 Hereinafter, a water-soluble acidic inorganic salt that is preferably 3.5 or less, more preferably 2.0 or less is preferable. When the acidic inorganic salt is solid at room temperature (25 ° C.), it can be easily removed by filtration, if necessary. Further, when the acidic inorganic salt is water-soluble, it can be easily washed away with water as necessary. In addition, the value of pH in this invention is the value which measured the sample aqueous solution using the pH meter provided with the glass electrode at room temperature (25 degreeC).

As the acidic inorganic salt, for example, an acidic inorganic salt in which at least a monovalent hydrogen atom of a divalent or higher-valent inorganic acid is neutralized with a base can be used. Examples of the divalent or higher inorganic acid include sulfuric acid and sulfurous acid. Examples of the base include alkali metals and ammonia.

More specifically, the acidic inorganic salt is one or more acidic inorganic salts composed of hydrogen sulfate ion (HSO ₄ ⁻ ) or hydrogen sulfite ion (HSO ₃ ⁻ ) and a monovalent cation (M ⁺ ). Are preferable, and examples of the monovalent cation (M ⁺ ) include alkali metal ions and ammonium ions. Particularly preferably, one or more monovalent cations selected from the group consisting of sodium ion, potassium ion and ammonium ion are preferred.

Examples of acidic inorganic salts include lithium hydrogen sulfate, sodium hydrogen sulfate, potassium hydrogen sulfate, rubidium hydrogen sulfate, cesium hydrogen sulfate, ammonium hydrogen sulfate, sodium hydrogen sulfite, or hydrates thereof, and AlCl ₃ , FeCl. ₃ , Lewis acids such as TiCl ₄ and BF ₃ .Et ₂ O are specifically exemplified. The pH of the aqueous solution when 50 g of some acidic inorganic salts are dissolved in 1 L of ion exchange water is as illustrated in the table below. Due to the technical effect of low bromide, one or more acidic inorganic salts selected from the group consisting of sodium hydrogen sulfate, potassium hydrogen sulfate and ammonium hydrogen sulfate are used as water-soluble acidic inorganic salts having a pH of 2.0 or less. Use is most preferred.

Examples of the solid acid include acidic solid materials such as activated clay, acidic clay, solid acidic zirconium oxide, strongly acidic cation exchange resin, fluorinated sulfonic acid resin, alumina, silica alumina, and zeolite. Solid acidic zirconium oxide is preferred. Examples of the solid acidic zirconium oxide include those prepared by treating a zirconium hydroxide with sulfuric acid and then at 300 ° C. or more, more specifically, aluminum hydroxide or hydrated oxide, zirconium hydroxide or hydrated oxide. A solid acidic zirconium prepared by calcining a molded product obtained by kneading and molding a product and a sulfuric acid-containing compound at a temperature at which tetragonal zirconia is obtained, specifically, at 300 ° C. or higher. Specific examples include zirconia sulfate. As a solid acidic zirconium oxide, SZA-60 manufactured by Japan Energy Co., Ltd. is commercially available. The strongly acidic cation exchange resin is, for example, a cation exchange resin whose functional group is a sulfonic acid group (—SO ₃ H), and commercially available products such as Amberlist 15 and Amberlist 16 sold by Organo Corporation, There are an amber list 31, an amber list 35, and the like. The fluorinated sulfonic acid resin is a perfluorinated polymer having a pendant sulfonic acid group bonded to a polymer chain. Specific examples thereof include those described in Japanese Patent Publication No. 59-4446. Is mentioned.

Examples of the acidic platinum catalyst that can be used include chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid olefin complexes, chloroplatinic acid ketone complexes, chloroplatinic acid vinylsiloxane complexes, and platinum tetrachloride. . Chloroplatinic acid is preferred.

(Acid treatment of sugar alcohol-modified silicone and reduction of odor)
The method for producing a sugar alcohol-modified silicone according to the present invention includes an acid treatment step of treating the sugar alcohol-modified silicone with at least one acidic substance, whereby the odor of the sugar alcohol-modified silicone is greatly reduced. For this reason, the production method of the present invention has an aspect of “odor reduction method”. Details are shown below.

The kind and production method of the sugar alcohol-modified silicone are as described above. That is, the sugar alcohol-modified silicone can be obtained, for example, by hydrosilylation reaction of at least one sugar alcohol group-containing compound having a carbon-carbon double bond and at least one organohydrogenpolysiloxane. . Only one type of sugar alcohol group-containing compound may be used, or two or more types of sugar alcohol group-containing compounds may be used in combination. Moreover, the kind of the acidic substance, the production method, and the like are as described above. Only one kind of acidic substance may be used, or two or more kinds of acidic substances may be used in combination.

The acid treatment step can be performed by bringing the sugar alcohol-modified silicone into contact with the acidic substance in any manner.

Specifically, the acid treatment step includes, for example, at least one kind of the acidic substance, and optionally water, alcohol, etc. in a reaction system (for example, a reaction vessel such as a flask) containing the sugar alcohol-modified silicone. It can carry out by operation, such as adding the organic solvent of and stirring.

In particular, it is preferable to add at least one kind of the acidic substance and water to the reaction system containing the sugar alcohol-modified silicone and stir using mechanical force. The acid treatment step can be carried out by selecting an arbitrary temperature and treatment time, and is performed at a temperature of 0 to 200 ° C., more preferably 50 to 100 ° C., for 0.1 to 24 hours, more preferably 0.5 to It can be carried out with a reaction time of about 10 hours. The amount of the acidic substance used can be appropriately selected according to the acid strength, the processing apparatus and the processing time, and the processing temperature. For example, sodium hydrogen sulfate, potassium hydrogen sulfate, ammonium hydrogen sulfate, citric acid, glycolic acid, phosphoric acid In the case of an acidic substance having an equivalent medium acid strength, the range of 10 to 500 ppm is preferable with respect to the sugar alcohol-modified silicone, and the range of 20 to 200 ppm is more preferable. In addition, in the case of an acidic substance having a higher acid strength such as hydrochloric acid or sulfuric acid, the range of 0.1 to 50 ppm is preferable with respect to the sugar alcohol-modified silicone, and a weak acidic substance having a low acid strength, activated clay, acidic clay, solid In the case of a solid acid typified by acidic zirconium oxide, strongly acidic cation exchange resin, fluorinated sulfonic acid resin, zeolite, etc., the range of 500 to 10,000 ppm is preferable with respect to sugar alcohol-modified silicone.

In the production method of the present invention, from the viewpoint of efficiently reducing odor, it is preferable to include a step of heating and / or decompressing (stripping step) after the acid treatment step. By the heating and / or depressurization, low boiling point components that are odor-causing substances can be removed (stripped). Further, more odor-causing substances can be removed by performing the acid treatment step again after stripping. At this time, when an acidic substance remains in the reaction system, there is an advantage that it is not necessary to add an additional acidic substance and only water is added. That is, the acid treatment step and the stripping step can be repeated twice or more for the purpose of increasing the degree of low bromide.

“Low boiling point components” distilled off in the stripping step include carbonyl compounds such as propionaldehyde, which is an odor-causing substance, and low molecular weight acetals, as well as reaction solvents used for the synthesis of sugar alcohol-modified silicones, etc. Contains volatile components.

The stripping step may be performed before the acid treatment step.

As the stripping method, known reaction conditions can be adopted, but stripping under normal pressure or reduced pressure is preferable, and it is preferably performed at 120 ° C. or lower. In order to perform stripping efficiently, it is preferable to carry out under reduced pressure or under an inert gas injection such as nitrogen gas. Specifically, an example of the operation for distilling off the low-boiling components is as follows: a sugar alcohol-modified silicone containing low boiling components or a composition thereof, or a hydrogenated product thereof is added to a reflux condenser, a nitrogen insertion port, etc. The prepared flask is charged, the inside is decompressed while supplying nitrogen gas, the temperature is raised, and the pressure and temperature are kept constant to distill off the light matter. In general, the decompression condition is 0.1 to 10.0 KPa, the heating temperature is 50 to 170 ° C., and the treatment time is 10 minutes to 24 hours.

In the present invention, the sugar alcohol-modified silicone may be neutralized with a basic substance after the acid treatment step. Examples of the basic substance include inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, aqueous ammonia and sodium hydrogen carbonate, and organic bases such as amine and pyridine. The amount of the basic substance is preferably an amount that neutralizes the reaction system containing the sugar alcohol-modified silicone, but the amount added can be adjusted so as to be weakly acidic or weakly alkaline as necessary.

In the present invention, hydrogenation treatment may be performed before and / or after the acid treatment step, or before and / or after the stripping step, and such forms are also included in the scope of the present invention. Although it is possible to obtain a further odor reduction effect by performing a non-bromide treatment by a hydrogenation reaction, the hydrogenation treatment is complicated and requires relatively expensive reagents and special equipment. It is. On the other hand, in the present invention, a sufficient odor reduction effect can be obtained by the acid treatment step. Therefore, it is necessary to perform such a hydrogenation treatment, and therefore the hydrogenation treatment can be omitted in the present invention.

(Synthesis process and acid treatment process of sugar alcohol-modified silicone)
The acid treatment step according to the present invention can be performed at any stage as long as it can be contacted with the sugar alcohol-modified silicone.

That is, in the production process of the sugar alcohol-modified silicone, it may be a process in which the sugar alcohol-modified silicone obtained by hydrosilylation reaction or the like is low-brominated in one step by coexisting an acidic substance. Moreover, you may perform an acid treatment process as another process after the synthetic | combination process of sugar alcohol modified silicone. Further, it may be a step of adding an acidic substance to sugar alcohol-modified silicone that has already been produced at a timing such as before shipment or use. In addition, it is preferable to attach the removal process (preferably stripping process) of an odor causative substance after these acid treatment processes, and you may perform an acid treatment process twice or more if desired.

More specifically, the method for producing a low odor sugar alcohol-modified silicone according to the present invention may be in any of the following forms (1) to (3).
(1) In the presence of at least one acidic substance,
A method for producing a low odor sugar alcohol-modified silicone comprising a step of hydrosilylating at least one sugar alcohol group-containing compound having a carbon-carbon double bond and at least one organohydrogenpolysiloxane.
(2) a step of obtaining a sugar alcohol-modified silicone by hydrosilylation of at least one sugar alcohol group-containing compound having a carbon-carbon double bond, and at least one organohydrogenpolysiloxane, and the sugar alcohol; A method for producing a low-odor sugar alcohol-modified silicone, comprising a step of treating a modified silicone with at least one acidic substance.
(3) In the presence of at least one reaction medium, at least one sugar alcohol group-containing compound having a carbon-carbon double bond and at least one organohydrogenpolysiloxane are subjected to a hydrosilylation reaction to produce sugar. A method for producing a low odor sugar alcohol-modified silicone, comprising a step of obtaining an alcohol-modified silicone, and a step of adding at least one acidic substance to the obtained sugar alcohol-modified silicone.

In particular, from the viewpoint of industrially obtaining a low bromide external preparation or cosmetic raw material (sugar alcohol-modified silicone), which reduces odor more effectively,
(A) a sugar alcohol group-containing compound having a carbon-carbon double bond;
(B) A step [A] of synthesizing a sugar alcohol-modified silicone by hydrosilylation reaction with an organohydrogenpolysiloxane; and the synthesis step [A], or after the synthesis step [A].
Process of treating sugar alcohol-modified silicone in the presence of at least one acidic substance [B]
It is preferable that it is a manufacturing method of the sugar alcohol modified silicone characterized by including this.

The types of the sugar alcohol group-containing compound are as described above. That is, as the sugar alcohol group-containing compound, a sugar alcohol group-containing compound having one carbon-carbon double bond per molecule can be used, but one carbon-carbon double bond is present per molecule. An unsaturated ether compound of a sugar alcohol can be suitably used. In particular, xylitol monoallyl ether is preferable.

The kind of the organohydrogenpolysiloxane is as described above. That is, the organohydrogenpolysiloxane is not particularly limited as long as it has a silicon atom-bonded hydrogen atom, but the organohydrogensiloxane represented by the general formula (1 ') is preferable.

The molecular structure of such an organohydrogenpolysiloxane is not limited, and examples thereof include straight-chain, partially-branched straight-chain, branched-chain, cyclic, and dendritic, and are preferably straight-chain. Moreover, the molecular weight is not specifically limited, From a low molecular weight body to a high molecular weight body can be used. Specifically, the number average molecular weight is preferably in the range of 1 to 1,000,000, more preferably in the range of 300 to 500,000.

Examples of such organohydrogenpolysiloxanes include organohydrogenpolysiloxanes represented by the following structural formula. These organohydrogenpolysiloxanes are: (i) a side chain only, (ii) one end of a side chain or molecular chain, and (iii) a linear organo group having silicon-bonded hydrogen atoms at both ends of the side chain or molecular chain. Hydrogen polysiloxane.

In the formula, R ¹ is as defined in the general formula (1 ′), v is 0 or a positive integer, w is a positive integer, and z is 0 or a positive integer.

Particularly, examples of the linear organohydrogenpolysiloxane that can be suitably used include polysiloxanes represented by the above formula (1-1) ′. Such organohydrogenpolysiloxanes may be used alone or in combination of two or more.

The hydrosilyl reaction can be carried out as described above. For example, the hydrosilylation reaction can be performed according to a known method in the presence or absence of a solvent. Reaction solvents include alcohol solvents such as ethanol and isopropyl alcohol; aromatic hydrocarbon solvents such as toluene and xylene; ether solvents such as dioxane and THF; n-hexane, cyclohexane, n-heptane, cycloheptane, methyl Examples include aliphatic hydrocarbon solvents such as cyclohexane; chlorinated hydrocarbon organic solvents such as carbon tetrachloride.

The hydrosilylation reaction may be performed in the absence of a catalyst, but is preferably performed in the presence of a catalyst because the reaction proceeds at a low temperature in a short time. The kind of hydrosilyl reaction catalyst, the method of use, etc. are as described above.

The reaction temperature of the hydrosilylation reaction is usually 20 to 120 ° C., and the reaction time is usually 10 minutes to 24 hours, preferably 1 to 10 hours.

When performing the above hydrosilylation reaction, [the amount of carbon-carbon double bonds in the sugar alcohol group-containing compound / the amount of carbon-carbon double bonds of the sugar alcohol group-containing compound in the organohydrogenpolysiloxane] The ratio of the amount of silicon-bonded hydrogen atoms to be added] is preferably in the range of 0.8 to 1.5, and more preferably in the range of 1.0 to 1.3. That is, when synthesizing the sugar alcohol-modified silicone or the sugar alcohol-modified silicone-containing composition according to the present invention, it is more preferable to use the sugar alcohol group-containing compound in a slight excess. Charges with the ratio above 1.5 are possible, but are uneconomical because the proportion of the remaining raw material increases. When the above ratio is 0.8 to 1.0, silicon-bonded hydrogen atoms consumed by the hydrosilylation reaction are in the range of 0.8 to 1.0, and silicon bonds are in a ratio of 0 to 0.2. Although it is calculated that a hydrogen atom remains, depending on the reaction conditions, a dehydrogenation reaction with a hydroxyl group contained in the sugar alcohol group or an alcoholic hydroxyl group of the reaction solvent may occur, and the remaining silicon-bonded hydrogen atom may be consumed. Is possible.

On the other hand, if the ratio is less than 0.8, unreacted organohydrogenpolysiloxane may remain. When such a sugar alcohol-modified silicone or a sugar alcohol-modified silicone-containing composition is used as an external preparation or a cosmetic raw material, the remaining organohydrogenpolysiloxane reacts with other raw materials to generate hydrogen gas. Thus, it may cause undesirable effects such as alteration of the external preparation or cosmetic preparation, the cause of fire, and the expansion of the container. In addition, when the above-mentioned ratio is less than 0.8 and an attempt is made to consume residual silicon-bonded hydrogen atoms due to the dehydrogenation reaction, the ratio of Si—O—C crosslinks increases, resulting in gelation during production. The danger increases. Therefore, it is preferable that the above ratio exceeds 0.8, that is, the sugar alcohol group-containing compound is reacted under more than 0.8 equivalents so that the organohydrogenpolysiloxane can be completely consumed safely.

In addition, the types of the acidic substances are as described above. Only one kind of acidic substance may be used, or two or more kinds of acidic substances may be used in combination. Further, the acid treatment step and the step of removing the odor-causing substance by heating and / or reducing the pressure (stripping step) may be repeated twice or more.

(Measurement method of carbonyl value)
Furthermore, the present invention provides a method for accurately and simply quantifying a carbonyl compound which is considered to be one of the causes of sugar alcohol-modified silicone odor. This method can quantify the degree of odor of a product by a simple and safe means. Therefore, the degree of low bromide can be safely and objectively quantified without the need for performing a sensory test, and the sugar alcohol-modified silicone according to the present invention, or an external preparation containing the same, or In cosmetic products, it is useful in that it makes it possible to indicate to the consumer that the product is low bromide.

More specifically, the method includes a sugar alcohol-modified silicone containing a carbonyl compound or a composition containing the sugar alcohol-modified silicone, and 2,4-dinitrophenylhydrazine (2,4-DNPH) at least one kind. In this method, the carbonyl value of the sugar alcohol-modified silicone or a composition containing the sugar alcohol-modified silicone is measured from the absorbance of a reaction solution obtained by reacting in a reaction medium containing a monovalent lower alcohol having 1 to 4 carbon atoms. The “carbonyl compound” is not a compound having a carbonyl group such as aldehydes and ketones, but also has no carbonyl group such as acetal or propenyl ether, but decomposes under certain conditions to generate a carbonyl group. Such potential carbonyl compounds are also included.

In the present invention, from the absorbance of a reaction solution obtained by reacting a sugar alcohol-modified silicone or a carbonyl compound in a composition containing the same with 2,4-DNPH, the carbonyl of the sugar alcohol-modified silicone or a composition containing the sugar alcohol is obtained. The total amount of carbonyl in terms of propanal in the sugar alcohol-modified silicone or the composition can be measured from the carbonyl value using a calibration curve measured in advance.

The “carbonyl value” is an index value of the carbonyl content, and is obtained by converting the absorbance (absorbance at 430 nm or 460 nm) of the reaction solution obtained by reacting 2,4-DNPH with the sample per 1 g of the sample. Value.

The carbonyl value is measured by utilizing the property that hydrazone produced by reacting carbonyls with 2,4-DNPH in the presence of an acid is basic and forms a quinoid ion. The carbonyl value is determined from the absorbance at 430 nm (maximum wavelength derived from saturated carbonyl in the vicinity) or 460 nm (maximum wavelength derived from unsaturated carbonyl in the vicinity) indicating the degree.

The “total amount of carbonyl” is the total amount of the carbonyl compound relative to the sugar alcohol-modified silicone or the composition containing the same. By measuring the carbonyl value of a standard sample having a known carbonyl compound concentration (propionaldehyde concentration) to obtain a calibration curve, various samples (sugar alcohol-modified silicone or a composition containing the same) are analyzed for carbonyl compounds. Concentration (total amount of carbonyl) can be measured.

In the measurement method of the present invention, at least a monovalent lower alcohol having 1 to 4 carbon atoms is used as a reaction solvent in the reaction between a carbonyl compound and 2,4-DNPH, but it is preferable to use water in combination.

By using water together with a monovalent lower alcohol having 1 to 4 carbon atoms as a reaction solvent, even a sample containing an aldehyde condensate (potential carbonyl compound) such as acetal can have its carbonyl value. It can be determined with high accuracy and it is possible to quantify the total amount of carbonyl in consideration of the odor compounds that cause odor. The reason for this is not clear, but it is presumed that the presence of water in the reaction system decomposes the aldehyde condensate and ensures the reaction with 2,4-DNPH. The mixing ratio of the monohydric lower alcohol having 1 to 4 carbon atoms and water in the reaction solvent is 99.9: 0. 1 monohydric lower alcohol: water (mass ratio) of 1 to 4 carbon atoms. 1 to 50:50 is preferable, and 99: 1 to 75:25 is more preferable.

In the present invention, the “reaction solvent” refers to a solvent present in the reaction system of the carbonyl compound in the sample and 2,4-DNPH, (a) In addition to the solvent used for preparing the sample solution, The reaction solvent is constituted by (b) the solvent used for preparing the acid solution to be added, (c) the solvent used for preparing the 2,4-DNPH solution, and the like.

(A) the alcohol constituting the sample solution, (b) the alcohol constituting the acid solution, and (c) the alcohol constituting the 2,4-DNPH solution are each a monovalent lower alcohol having 1 to 4 carbon atoms. The alcohol in the reaction solvent obtained by mixing them may contain a monovalent lower alcohol having 1 to 4 carbon atoms.

In the measurement method of the present invention, it is preferable to use alcohol as a solvent (hereinafter also referred to as “dilution solvent”) to be added in order to keep the volume of the reaction solution constant when measuring the absorbance of the reaction solution. It is preferable to use a monohydric lower alcohol having 1 to 4 atoms. It should be noted that all of the dilution solvent need not be alcohol, and water and / or an organic solvent (having no carbonyl group in its structure) as a part of the dilution solvent as long as the effects of the present invention are not impaired. And less harmful) may be used.

The monovalent lower alcohol having 1 to 4 carbon atoms is preferably a saturated alcohol, and examples thereof include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, and sec-butanol. These monovalent lower alcohols are preferably appropriately selected from those that can dissolve or uniformly disperse the sample according to the structure and composition of the sugar alcohol-modified silicone or the composition containing the sugar alcohol. For example, in the case of a sugar alcohol-modified silicone having a high modification rate with a sugar alcohol and high hydrophilicity or a composition containing the same, it is suitable to select methanol or ethanol. On the other hand, in the case of a sugar alcohol-modified silicone having a small modification rate with a sugar alcohol and not so hydrophilic, or a composition containing the same, it is often appropriate to select n-propanol or i-propanol. Further, in the case of a sugar alcohol-modified silicone co-modified with a strong organic oily group such as a long chain alkyl group or a composition containing the same, n-butanol, i-butanol, or sec-butanol may be selected. Is suitable. One monovalent lower alcohol having 1 to 4 carbon atoms may be used alone, or two or more kinds may be mixed and used.

These alcohols are not harmful like benzene and can dissolve various substances having different polarities and molecular weights. Therefore, by using these alcohols as a reaction solvent and a diluting solvent, each operation for obtaining a carbonyl value can be performed safely and easily.

As the monovalent lower alcohol having 1 to 4 carbon atoms, for example, any one having a purity of a reagent special grade can be used without any problem. However, when particularly precise analysis is required, the total amount of aldehydes and ketones contained therein is 3 ppm or less, preferably 2 ppm or less, more preferably 1 ppm or less (hereinafter also referred to as “ultra-high purity alcohol”). ) Is preferably used. By using ultra-high-purity alcohol with a total amount of aldehyde / ketone of 3 ppm or less as a reaction solvent, even for samples with low carbonyl content (for example, carbonyl value less than 2), the carbonyl value is accurate to 3 significant figures. Can be requested.

As a preparation method (purification method) of ultra-high purity alcohol, an appropriate amount of 2,4-DNPH and an acid having no oxidizing action (for example, hydrochloric acid or trichloroacetic acid) are added to the alcohol to be purified, and this system is taken for several hours. And a method of distilling alcohol under normal pressure or reduced pressure after heating and stirring. These purification treatments are preferably carried out within 24 hours before measuring the absorbance of the reaction solution.

Moreover, it is preferable to use the commercially available high purity reagent refine | purified as ultra high purity alcohol until the total amount of aldehydes and ketones will be 3 ppm or less. Commercially available high purity reagents that can be used as ultra high purity alcohol include ethanol (99.8%) Infinity Pure, ethanol (99.8%) for precision analysis, ethanol (99.5%) high performance liquid chromatograph For ethanol, 99.5% spectroscopic analysis, 2-propanol (99.9%) Infinity Pure, 2-propanol (99.9%) for precision analysis, 2-propanol (99.5%) high performance liquid chromatography For graph, 2-propanol (99.5%) for spectroscopic analysis, 1-propanol (99.8%) Infinity Pure, 1-propanol (99.5%) for high-performance liquid chromatograph, methanol (99.8%) Infinity Pure, methanol (99.8%) for precision analysis, methanol (99.5%) high performance liquid chromatograph , Methanol (99.5%) for spectroscopy, n- butyl alcohol high speed liquid chromatography, n- butyl alcohol spectroscopic analysis (Wako Pure Chemical Industries, Ltd.) can be exemplified, and the like.

Even in the case of the high-purity reagent as described above, the total amount of aldehyde / ketone may increase with time and the total amount of aldehyde / ketone may exceed 3 ppm. Further, after opening, the total amount exceeds 3 ppm in a relatively short time (for example, within 24 hours). Therefore, when particularly precise analysis is required, from the viewpoint of satisfying the essential requirements as an ultra-high purity alcohol (total amount of aldehyde / ketone is 3 ppm or less), the high-purity reagent is:
(A) manufactured within 6 months before use, and
(B) It is preferably opened within 24 hours before use.

In the measurement method of the present invention, the solvent used as the reaction solvent does not need to consist only of a monovalent lower alcohol having 1 to 4 carbon atoms or a mixed solvent of a monovalent lower alcohol having 1 to 4 carbon atoms and water. As long as the effects of the present invention are not impaired, an organic solvent that does not have a carbonyl group in its structure and is less harmful may be used as a part of the reaction solvent. However, when an organic solvent other than a monovalent lower alcohol having 1 to 4 carbon atoms is used as a part of the reaction solvent, the organic solvent (part) and a monovalent lower alcohol having 1 to 4 carbon atoms are used. The total amount of aldehydes and ketones contained in the reaction solvent (all except water) obtained by mixing alcohol (remainder) is preferably 3 ppm or less.

In the measurement method of the present invention, an acid and 2,4-DNPH are added to a sample solution obtained by dissolving a sample in a solvent, and the carbonyl compound and 2,4-DNPH in the sample are heated by treating this system. After the reaction, the reaction mixture is cooled, alkali is added to the system, and then the basic reaction solution (reaction solution used for measuring the absorbance) is prepared by adjusting to a certain volume with a diluting solvent. it can. Here, as a container for preparing the basic reaction solution, it is preferable to use a volumetric flask having a volume of 10 to 100 mL.

(1) Sample solution Since the solvent used to prepare the sample solution directly constitutes the reaction solvent, such a solvent is preferably a mixed solvent of ultrahigh purity alcohol and water. The mass of the sample solution (sample and solvent) used for measuring the absorbance is usually about 2 to 6 g, preferably about 5 g. The mass of the sample included in the sample solution varies depending on the amount of the reaction solution prepared for measuring the absorbance (volume of the volumetric flask used) and the carbonyl content (carbonyl value) in the sample. When a reaction solution (reaction solution used for measuring absorbance) is prepared using a volumetric flask, the pure content is preferably 5 to 250 mg, more preferably 10 to 150 mg.

(2) Acids added to the acid sample solution include mineral acids such as dilute sulfuric acid, hydrochloric acid, dilute nitric acid and phosphoric acid, organic acids such as trichloroacetic acid, trifluoroacetic acid, formic acid, acetic acid, sulfonic acid and phenolic acid, AlCl ₃ Lewis acids such as FeCl ₃ and TiCl ₄ can be used, and these can be used alone or in combination of two or more. Of these, trichloroacetic acid, dilute sulfuric acid (especially with a concentration of 20% or less) and hydrochloric acid (especially with a concentration) from the viewpoint that the total amount of carbonyl in a highly purified sugar alcohol-modified silicone or a composition containing the same can be accurately determined. 37% or less) is preferred. Moreover, it is preferable that the acid used in the present invention is as high a purity as possible (a reagent special grade or higher purity).

These acids may be added to the sample solution as they are, but it is preferable to add them in a solution state in which they are dissolved in an appropriate solvent from the viewpoint of accurate measurement. Since the solvent used for preparing the acid solution directly constitutes the reaction solvent, such a solvent includes a monovalent lower alcohol having 1 to 4 carbon atoms, or 1 to 4 carbon atoms. It is preferable to use a mixed solvent of monohydric lower alcohol and water. When preparing a reaction solution (reaction solution containing 5 to 250 mg of sample in a pure fraction) in a 50 mL volumetric flask, the amount of acid added is preferably 0.03 to 5.0 g in a pure fraction.

(3) 2,4-DNPH
As 2,4-DNPH added to the sample solution, it is preferable to use a reagent special grade containing equal amount of water or having a purity higher than that. Further, the purity may be further increased by a purification operation such as recrystallization. 2,4-DNPH may be added as it is to the sample solution, but it is preferable to add it in a solution state dissolved in an appropriate solvent from the viewpoint of accurate measurement. The solvent used for preparing the 2,4-DNPH solution directly constitutes the reaction solvent, and as such a solvent, the monovalent lower alcohol having 1 to 4 carbon atoms, or carbon It is preferable to use a mixed solvent of a monohydric lower alcohol having 1 to 4 atoms and water. When preparing a reaction solution (reaction solution containing 5 to 250 mg of pure sample) in a 50 mL volumetric flask, the amount of 2,4-DNPH added is preferably 0.5 to 100 mg of pure component. .

(4) The heat treatment conditions of the heat treatment sample, the mixed solution containing acid and 2,4-DNPH are 20 to 180 minutes at 30 to 120 ° C. (however, a temperature lower than the boiling point of the reaction solvent). . When the treatment temperature is less than 30 ° C., the reaction between the carbonyl compound in the sample and 2,4-DNPH requires a long time and is not efficient. On the other hand, when heated at a temperature higher than 120 ° C., the produced hydrazone may be decomposed. When the treatment time is less than 20 minutes, it is difficult to complete the reaction with 2,4-DNPH. On the other hand, when the treatment time exceeds 180 minutes, the produced hydrazone may be decomposed.

(5) As the alkali added to the reaction solution by the reaction of the carbonyl compound in the alkali sample with 2,4-DNPH, it is preferable to use an inorganic strong base such as potassium hydroxide or sodium hydroxide. These alkalis may be added to the sample solution as they are, but it is preferable to add them in a solution state in which they are dissolved in an appropriate solvent from the viewpoint of accurate measurement. As such a solvent, an alkali can be dissolved and the structure thereof does not have a carbonyl group, is compatible with the solvent used as a reaction solvent, and is one of the less harmful ones. Alternatively, two or more types can be selected and used, and specifically, monovalent saturated lower alcohols such as methanol, ethanol, 2-propanol, 1-propanol, or water and / or other organics. A mixed solvent formed by mixing a suitable amount of a solvent (having no carbonyl group in its structure and having little harmfulness) can be exemplified. Ultra high purity alcohol, or ultra high purity alcohol and water It is preferable to use a mixed solvent. When preparing a reaction solution (reaction solution containing 5 to 250 mg of sample in a pure fraction) in a 50 mL volumetric flask, the amount of alkali added is preferably 0.05 to 5.0 g in a pure fraction.

(6) The reaction solution to which the diluting solvent alkali is added is adjusted to a constant volume (for example, 50 mL) with a diluting solvent mainly composed of alcohol. As the alcohol constituting the diluting solvent, it is preferable to use an ultra-high purity alcohol.

(7) Specific preparation method An example of a method for preparing a reaction solution to be used for the measurement of absorbance is as follows: a 5-mL to 250-mL sample is added to a 50 mL volumetric flask, and a monovalent lower limit of 1 to 4 carbon atoms. 5 g of a sample solution dissolved in a mixed solvent of alcohol and water is charged, and then 0.03 to 5.0 g of an acid is dissolved in a monovalent lower alcohol having 1 to 4 carbon atoms; After adding 5 to 500 mg of 2,4-DNPH dissolved in a monohydric lower alcohol having 1 to 4 carbon atoms, the volumetric flask was stoppered, and 30 to 120 ° C. for 20 to 180 minutes. The carbonyl compound in the sample and 2,4-DNPH are reacted by heating, and after cooling to room temperature, 0.05 to 5.0 g of alkali is dissolved in alcohol in the volumetric flask. Added solution Followed by addition of diluted solvent consisting of an alcohol to adjust the volume to 50 mL.

In the measurement method of the present invention, the basic reaction solution obtained as described above is subjected to filtration treatment as necessary, and then the absorbance at 430 nm or 460 nm is measured. Here, when the carbonyl compound contained in the sample is presumed to be mainly a saturated carbonyl compound, the absorbance at 430 nm is measured for the reaction solution, and the carbonyl compound contained in the sample is mainly unsatisfactory. When it is estimated that the compound is a saturated carbonyl compound, the absorbance at 460 nm is measured for the reaction solution. In measuring the absorbance, it is preferable to use a quartz-made absorption cell for containing the reaction solution. The length (thickness) of the liquid layer defined by the absorption cell is preferably 1 cm.

The measurement of absorbance is preferably carried out 10 minutes to 20 minutes after the alkali is added to the reaction solution obtained by the reaction of the carbonyl compound and 2,4-DNPH in the sample. Absorbance measured before 10 minutes from the addition of alkali may lack stability, and after 20 minutes from addition of alkali, the reaction solution will fade and the absorbance will decrease. There is a tendency to decrease. Based on experience with various samples, the most reproducible value can be obtained by measuring the absorbance after 15 minutes from the addition of alkali.

In the measurement method of the present invention, the carbonyl value of a sample (sugar alcohol-modified silicone or a composition containing the same) is determined from the absorbance measured as described above. From this carbonyl value, the total amount of carbonyl in the sample can be measured using a calibration curve measured in advance. Here, the calibration curve is obtained by measuring the carbonyl value of a plurality of standard samples whose total carbonyl amount (propionaldehyde concentration) is known according to the above-described method (measurement method of carbonyl value).

For example, the absorbance (A ₁ ) and absorbance (A ₂ ) measured by the following steps (1) to (9) are expressed by the formula: CV = (A ₁ -A ₂ ) / B [where B is the sample solution The carbonyl value of a standard sample whose total carbonyl amount (propionaldehyde concentration) is known is measured by substituting it into the mass (g) of the sample contained in 5.000 g] and determining the carbonyl value (CV). Thus, a calibration curve is obtained, and the carbonyl value of a sample (sugar alcohol-modified silicone or a composition containing the same) whose total carbonyl amount is unknown is measured by the same method as that employed to obtain this calibration curve. From the carbonyl value and the calibration curve, the total amount of carbonyl in the sample can be measured. In addition, when a particularly precise analysis is required, the following solvent used in the following step (1) and step (9) contains ultra-high purity alcohol and water, and in the following step (7). It is preferable that the postscript solvent to be used contains an ultra high purity alcohol.

[Process]
(1) Step of preparing a sample solution by dissolving a sample in a solvent (2) Step of adding 3 mL of an alcohol solution of 4.3% (wt / vol) trichloroacetic acid to 5.000 g of the sample solution (3) Step (4) of adding 5 mL of 2,4-DNPH alcohol solution [0.025% (wt / vol)] to the mixed solution obtained in Step (2) in (4) Obtained in Step (3) above The mixed solution is heated at 60 ° C. for 30 minutes to react the carbonyl compound in the sample with 2,4-DNPH (5) The reaction solution obtained in the above step (4) is reacted at room temperature for 30 to 70 minutes. Step of leaving (6) Step of adding 10 mL of an alcohol solution of potassium hydroxide [4.0% (wt / vol)] to the reaction solution left in the step (5) (7) Step of the above From (6) to 5-10 After the lapse of time, a solvent is added to the reaction solution to prepare a reaction solution having a total amount of 50 mL, and if necessary, the reaction solution is filtered (8) 10 to 20 minutes from the above step (6) Thereafter, as a step (9) blank test for measuring the absorbance (A ₁ ) at 430 nm or 460 nm for the reaction solution obtained in the above step (7), using 5.000 g of solvent instead of the sample solution, A step of measuring absorbance (A ₂ ) at 430 nm or 460 nm for a solution obtained by performing the same operations as in the above steps (2) to (7).

Note that either the measurement of the calibration curve (measurement of the carbonyl value of the standard sample) or the measurement of the carbonyl value of the unknown sample may be performed first.

Hereinafter, each step will be described. The steps (2) to (7) relating to the preparation of the reaction solution are usually performed using a 50 mL volumetric flask.

Step (1) is a step of preparing a sample solution by dissolving a sample in a solvent containing a monovalent lower alcohol having 1 to 4 carbon atoms. The proportion of the sample in the sample solution is changed according to the predicted carbonyl value for the sample. For example, a sample whose carbonyl value is predicted to be less than 6 is 2 to 3% by weight (mass)% (100 to 150 mg per 5.000 g of the sample solution), and a sample whose carbonyl value is predicted to be in the range of 6 to 15. Is 0.8 to 2% by weight (mass)% (40 to 100 mg per 5.000 g of the sample solution), and 0.4 to 0.8% by weight (mass) for the sample whose carbonyl value is predicted to be in the range of 15 to 30. % (20 to 40 mg per 5.000 g of sample solution), 0.2 to 0.4% by weight (mass)% (10 to 10 per 5 000 g of sample solution) for a sample whose carbonyl value is expected to be in the range of 30 to 60 20 mg), and the sample whose carbonyl value is predicted to exceed 60 is preferably less than 0.2% by weight (mass)% (less than 10 mg per 5.000 g of the sample solution).

Moreover, when preparing a sample solution, it is preferable to dilute a sample in steps. For example, as a method for preparing 5.000 g of a sample solution of 2% by weight (mass), first, 2.00 g of a sample is dissolved in 23.00 g of a monohydric lower alcohol having 1 to 4 carbon atoms, and 8 wt. 25.00 g of a (mass)% solution is prepared. Next, a method in which 1.250 g of an 8% by weight (mass)% solution and 3.750 g of a monohydric lower alcohol having 1 to 4 carbon atoms is accurately added to a 50 mL volumetric flask and diluted 4-fold is given. be able to.

In the step (2), 5.000 g (sample: 0.100 g) of the 2 wt (mass)% sample solution obtained in the above step (1) was added to 4.3% (wt / vol) of trichloroacetic acid. In this step, 3 mL of an alcohol solution is added using a whole pipette or the like. The solvent of the alcohol solution (monovalent lower alcohol having 1 to 4 carbon atoms) is preferably an ultra-high purity alcohol particularly when precise analysis is required. In this case, the alcohol solution of trichloroacetic acid was opened by opening a bottle containing 100 mL of ultrahigh purity alcohol, and 4.3 g of trichloroacetic acid was directly added to the bottle, and the bottle was capped, and then shaken and mixed. It is preferable to prepare by homogenizing in the bottle. The alcohol solution of trichloroacetic acid is preferably prepared within 24 hours before measuring the absorbance of the reaction solution.

In step (3), 5 mL of 2,4-DNPH alcohol solution [0.025% (wt / vol)] is added to the mixed solution obtained in step (2) using a whole pipette or the like. It is a process. The solvent of the 2,4-DNPH alcohol solution (monohydric lower alcohol having 1 to 4 carbon atoms) is preferably an ultra-high purity alcohol particularly when precise analysis is required. In this case, the alcohol solution of 2,4-DNPH opens a bottle containing 100 mL of ultra-high purity alcohol, and 50 mg of 2,4-DNPH (a reagent-grade product containing an equal amount of water) is directly added to the bottle. After adding and capping the bottle, it is preferable to prepare it by completely dissolving 2,4-DNPH in the bottle by placing it in an ultrasonic cleaner for about 5 minutes. The alcohol solution of 2,4-DNPH is preferably prepared within 24 hours before measuring the absorbance of the reaction solution. It is preferable to further add water in order to hydrolyze the precursor of a carbonyl compound such as acetal present in the sample and detect it as a carbonyl compound.

Step (4) is a step of reacting the carbonyls in the sample with 2,4-DNPH by heating the mixed solution obtained in the above step (3) at 60 ° C. for 30 minutes. A reaction solution containing hydrazone is obtained.

Step (5) is a step in which the reaction solution obtained in step (4) is allowed to cool at room temperature for 30 to 70 minutes.

Step (6) is a step in which 10 mL of an alcohol solution of potassium hydroxide [4.0% (wt / vol)] is added and mixed with the reaction solution after being left standing using a whole pipette or the like. As a result, the reaction solution shows basicity, and the produced hydrazone becomes quinoid ions and develops color. The solvent of this potassium hydroxide alcohol solution (monohydric lower alcohol having 1 to 4 carbon atoms) is preferably an ultra-high purity alcohol particularly when precise analysis is required. In this case, the alcohol solution of potassium hydroxide is opened in a bottle containing 100 mL of ultra-high purity alcohol, and 4.0 g of potassium hydroxide (special grade reagent in pellet form) is directly added to this bottle, It is preferable to prepare the solution by completely dissolving potassium hydroxide in the bottle by capping and shaking until the pellet disappears, and then placing it in an ultrasonic cleaner for about 5 to 10 minutes. The alcohol solution of potassium hydroxide is preferably prepared within 24 hours before measuring the absorbance of the reaction solution.

In step (7), after 5 to 10 minutes have elapsed from step (6) above, a dilute solvent consisting of a monovalent lower alcohol having 1 to 4 carbon atoms (preferably ultrapure alcohol) is added to the reaction solution. In this step, a reaction solution (basic reaction solution) having a total amount of 50 mL is prepared. When this reaction solution is non-uniform due to the precipitation of neutralized salt, it can be further filtered to obtain a uniform solution.

In the step (8), the reaction solution obtained in the above step (7) is 430 nm (when it is estimated that the carbonyl contained in the sample is mainly saturated carbonyl) or (the carbonyl contained in the sample is This is a step of measuring the absorbance (A ₁ ) at 460 nm (when presumed to be mainly unsaturated carbonyl). The absorbance measurement is required to be performed 10 minutes to 20 minutes after the addition of the potassium hydroxide alcohol solution in the above step (6), and from the time of addition of the potassium hydroxide alcohol solution. Most preferably, the absorbance is measured after 15 minutes.

In the step (9), as a blank test, in place of the sample solution, 5.000 g of monohydric lower alcohol having 1 to 4 carbon atoms is used, and the same operation as in the above steps (2) to (7) ( Addition of an alcohol solution of trichloroacetic acid; addition of an alcohol solution of 2,4-DNPH and addition of water; heating and cooling of the resulting mixed solution; addition of an alcohol solution of potassium hydroxide; monovalent carbon number of 1 to 4 This is a step of measuring the absorbance (A ₂ ) at 430 nm or 460 nm for a solution obtained by adding a dilution solvent comprising a lower alcohol).

The absorbance (A ₁ ) obtained by the above steps (1) to (8) and the absorbance (A ₂ ) obtained by the above step (9) are respectively expressed by the formula: CV = (A ₁ -A ₂ ) / By substituting for B, the carbonyl value (CV) can be determined. In the above formula, B is the weight (mass) (g) of the sample contained in 5.000 g of the sample solution, and 0.1 (5.000 × 0) in the sample solution of 2 wt (mass)%. .02).

The sugar alcohol-modified silicone obtained by the production method of the present invention or a composition containing the same has low odor, and the carbonyl value measured by the above method is reduced to 2.5 Abs / g or less. Conversely, sugar alcohol-modified silicones with a reduced carbonyl value hardly feel odor even when blended in cosmetics, etc., and agree well with the results of sensory tests. Furthermore, the sugar alcohol-modified silicone obtained by the production method of the present invention or the composition containing the same preferably has a carbonyl value measured by the above method of 2.0 Abs / g or less, and 1.6 Abs / g or less. Even more preferably. When acid treatment is not performed, the carbonyl value of sugar alcohol-modified silicone or a composition containing the same is generally 9.0 Abs / g or more, and a unique odor is felt. Furthermore, in polyether-modified silicone and polyglycerin-modified silicone, it is difficult to achieve a carbonyl value of 2.5 Abs / g or less only by acid treatment.

Unlike the conventional low odor polyether-modified silicone, the low odor sugar alcohol-modified silicone of the present invention is essentially less likely to be oxidized and denatured by oxygen in the air. Therefore, in order to prevent oxidative degradation, it is not essential to add an antioxidant such as phenols, hydroquinones, benzoquinones, aromatic amines, or vitamins to increase oxidative stability. The addition of a suitable antioxidant such as BHT (2,6-di-t-butyl-p-cresol), vitamin C, vitamin E and the like further improves the stability. At this time, the addition amount of the antioxidant used is in the range of 10 to 1000 ppm, preferably 50 to 500 ppm, based on the weight (mass) of the sugar alcohol-modified silicone.

(External preparation or raw material for cosmetics)
The low odor sugar alcohol-modified silicone of the present invention is substantially odorless and has reduced odor generation over time. Moreover, the silicon-oxygen bond constituting the main chain of the sugar alcohol-modified silicone and the carbon-oxygen bond constituting the side chain are not cleaved, and the composition is uniform as a whole. Therefore, the low odor sugar alcohol-modified silicone of the present invention can be suitably used as an external preparation used for the human body and a raw material for cosmetics.

The proportion of the low odor sugar alcohol-modified silicone in the raw materials for external preparations and cosmetics is preferably 10 to 100% by weight (mass) based on the total weight (mass) of the raw material, and 20 to 100% by weight ( (Mass)% is more preferable, and 30 to 100% by weight (mass)% is even more preferable. This is because the low-odor sugar alcohol-modified silicone of the present invention can be diluted with an appropriate medium such as silicone oil, organic oil, alcohols, and used as a raw material for external preparations and cosmetics. The ratio of the raw material blended into the external preparation or cosmetic is not particularly limited, but for example, 0.1 to 40% by weight (mass)% based on the total weight (mass) of the external preparation or cosmetic. Preferably, it can be used in the range of 1 to 30% by weight, more preferably 2 to 20% by weight, and even more preferably 3 to 10% by weight.

(External preparations / cosmetics)
The low odor sugar alcohol-modified silicone of the present invention or the external preparation and the cosmetic raw material comprising the low odor sugar alcohol modified silicone of the present invention can be suitably blended in the external preparation or the cosmetic. The external preparation or cosmetic of the invention can be constituted. These include antiperspirant compositions whose active ingredients are acidic substances, weakly acidic external preparations or cleaning agents that are expected to have a peeling effect, cosmetics, etc. It is considered that the occurrence is particularly likely to occur), and exhibits its odorless true value.

An external preparation is applied to human skin, nails, hair, and the like. For example, a pharmaceutical active ingredient can be blended and used for treatment of various diseases. Cosmetics are also applied to human skin, nails, hair, etc., but are used for cosmetic purposes. As the external preparation or cosmetic, an antiperspirant, skin cleanser, skin external preparation or skin cosmetic, or a hair cleanser, hair external preparation or hair cosmetic is preferable.

The antiperspirant, skin cleanser, skin external preparation or skin cosmetic according to the present invention contains the low-odor sugar alcohol-modified silicone of the present invention, and the form thereof is not particularly limited, but is in the form of a solution or emulsion. , Cream, solid, semi-solid, paste, gel, powder, multilayer, mousse, spray, water-in-oil or oil-in-water emulsion composition (emulsion composition). May be. Specifically, as a skin external preparation or skin cosmetic according to the present invention, lotion, emulsion, cream, sunscreen emulsion, sunscreen cream, hand cream, cleansing, massage agent, cleaning agent, antiperspirant, deodorant Basic cosmetics such as agents; makeup cosmetics such as foundation, makeup base, blusher, lipstick, eye shadow, eyeliner, mascara, nail enamel, etc.

Similarly, the hair cleansing agent, hair external preparation or hair cosmetic according to the present invention contains the low odor sugar alcohol-modified silicone of the present invention and can be used in various forms. For example, they may be used by dissolving or dispersing them in alcohols, hydrocarbons, volatile cyclic silicones, etc., or by dispersing them in water using an emulsifier and using them in the form of an emulsion. Further, a propellant such as propane, butane, trichloromonofluoromethane, dichlorodifluoromethane, dichlorotetrafluoroethane, carbon dioxide gas or nitrogen gas can be used as a spray. Examples of other forms include emulsions, creams, solids, semi-solids, pastes, gels, powders, multilayers, mousses, and the like. These various forms can be used as a shampoo, rinse, conditioning, set lotion, hair spray, permanent wave, mousse, hair dye and the like.

The external preparation or cosmetic of the present invention is a component, water, powder or colorant, alcohol, water-soluble polymer, film formation, which is used in ordinary external preparations or cosmetics as long as the effects of the present invention are not hindered. Agent, oil agent, oil-soluble gelling agent, organically modified clay mineral, surfactant, resin, UV absorber, salt, moisturizer, preservative, antibacterial agent, fragrance, salt, antioxidant, pH adjuster, chelating agent , Refreshing agents, anti-inflammatory agents, skin beautifying agents (whitening agents, cell activators, rough skin improving agents, blood circulation promoters, skin astringents, antiseborrheic agents, etc.), vitamins, amino acids, nucleic acids, hormones, inclusions A compound or the like, a physiologically active substance, a pharmaceutically active ingredient, and a fragrance can be added, and these are not particularly limited.

Water does not contain components harmful to the human body and may be clean, and examples thereof include tap water, purified water, mineral water, and deep ocean water. When the external preparation or cosmetic of the present invention is water-based, a water-soluble additive component can be arbitrarily added to the aqueous phase as long as the effects of the present invention are not impaired. As components constituting the aqueous phase, vitamin B group described later, vitamin C and derivatives thereof, pantothenic acid and derivatives thereof, water-soluble active substances such as vitamins such as biotin, antiperspirant active ingredients, water-soluble ultraviolet absorbers, Various water-soluble pigments and the like can be blended, but are not limited thereto. In addition, for the purpose of improving the storage stability and the like of external preparations or cosmetics, known pH adjusters, preservatives, antibacterial agents, and antioxidants can be appropriately blended.

As a powder or a colorant, if it is used for normal external preparations or cosmetics, its shape (spherical, rod-like, needle-like, plate-like, irregular shape, spindle-like, etc.) and particle size (smoke-like) , Fine particles, pigment grades, etc.) and particle structures (porous, nonporous, etc.) can be used, but when these powders and / or colorants are blended as pigments, It is preferable to blend one or more selected from inorganic pigment powder, organic pigment powder, and resin powder having an average particle diameter in the range of 1 nm to 20 μm.

Examples of the powder or colorant include inorganic powders, organic powders, surfactant metal salt powders (metal soaps), colored pigments, pearl pigments, organically modified viscosity minerals, metal powder pigments, and the like. A composite of these pigments can also be used. Specifically, as the inorganic powder, 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, sodium silicate, sodium magnesium silicate, magnesium silicate, magnesium aluminum silicate, calcium silicate , Barium silicate, strontium silicate, metal tungstate, hydroxyapatite, vermiculite, hydrite, bentonite, montmorillonite, hectorite, zeolite, ceramic powder, dicalcium phosphate, alumina, hydroxylation Luminium, boron nitride, boron nitride, etc .; organic powders such as polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane powder, benzoguanamine powder, polymethylbenzoguanamine powder, polytetrafluoroethylene powder, polymethyl methacrylate Powder, cellulose, silk powder, nylon powder, 12 nylon, 6 nylon, silicone powder, silicone rubber spherical powder, silicone rubber spherical powder coated with polymethylsilsesquioxane, polymethylsilsesquioxane spherical powder Body, styrene / acrylic acid copolymer, divinylbenzene / styrene copolymer, vinyl resin, urea resin, phenol resin, fluororesin, Base resin, acrylic resin, melamine resin, epoxy resin, polycarbonate resin, microcrystalline fiber powder cake, starch powder, lauroyl lysine, etc .; surfactant metal salt powder cake includes zinc stearate, aluminum stearate, calcium stearate, stearin Magnesium oxide, zinc myristate, magnesium myristate, zinc palmitate, zinc laurate, zinc cetyl phosphate, calcium cetyl phosphate, sodium cetyl phosphate, etc .; Colored pigments ベン include bengara, iron oxide, iron hydroxide, iron titanate Inorganic red pigments such as inorganic red pigments such as γ-iron oxide, inorganic yellow pigments such as yellow iron oxide and ocher, inorganic black pigments such as black iron oxide and carbon black, inorganic purple pigments such as manganese violet and cobalt violet, Chromium hydroxide, black oxide Inorganic green pigments such as cobalt oxide, cobalt titanate and the like, inorganic blue pigments such as bitumen and ultramarine blue, red 3, red 104, red 106, red 201, red 202, red 204, red 205 No., Red No. 220, Red No. 226, Red No. 227, Red No. 228, Red No. 230, Red No. 401, Red No. 505, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Yellow No. 204, Yellow No. 401, Blue No. 1, Blue No. 2, Blue No. 201, Blue No. 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 No., orange 207 and other tar-type pigments raked, natural pigments such as carminic acid, laccaic acid, calsamine, braziline, crocin etc. , Titanium oxide coated mica, mica titanium, iron oxide-treated mica titanium, titanium oxide coated mica, bismuth oxychloride, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, fish scale foil, titanium oxide coated colored mica, etc .; Includes metal powders such as aluminum, gold, silver, copper, platinum, and stainless steel.

In particular, examples of the inorganic powder 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 a composite thereof. In more detail, the inorganic ultraviolet protection component may be formulated with the above-mentioned inorganic powder pigment, metal powder pigment or the like as an ultraviolet dispersant, such as titanium oxide, zinc oxide, cerium oxide, Examples thereof include metal oxides such as sub-titanium oxide and iron-doped titanium oxide, metal hydroxides such as iron hydroxide, plate-like iron oxide, metal flakes such as aluminum flakes, and ceramics such as silicon carbide. Of these, at least one selected from particulate metal oxide or particulate metal hydroxide having an average particle diameter in the range of 1 to 100 nm is particularly preferable.

Examples of the organically modified viscosity mineral include dimethylbenzyl dodecyl ammonium montmorillonite clay, dimethyl dioctadecyl ammonium montmorillonite clay, dimethyl alkyl ammonium hectorite, benzyl dimethyl stearyl ammonium hectorite, distearyl dimethyl ammonium chloride-treated aluminum magnesium silicate, and the like. . Examples of these commercially available products include Benton 27 (benzyldimethylstearylammonium chloride-treated hectorite: manufactured by Sakai National Red), Benton 38 (distearyldimethylammonium chloride-treated hectorite: manufactured by Sakai National Red), and the like.

As the silicone rubber spherical powder (sometimes referred to as silicone elastomer spherical powder), those having a primary particle diameter in the range of 0.1 to 50 μm are preferable. Examples of such commercially available silicone rubber spherical powders include Trefill E-506S, Trefill E-508, 9701, Cosmetic Powder, 9702 Powder, manufactured by Toray Dow Corning. Moreover, the silicone rubber spherical powder can be used in the external preparation or cosmetic of the present invention even in the form of an aqueous dispersion. Examples of such commercially available aqueous dispersions include BY 29-129 and PF-2001 PIF Emulsion manufactured by Toray Dow Corning.

Furthermore, it is particularly preferable that these powders or colorants have been subjected to water repellency treatment. In addition, surface treatment is performed with a composite of these powders and / or colorants, or a general oil, a silicone compound other than the sugar alcohol-modified silicone according to the present invention, a fluorine compound, a surfactant, or the like. What was used can also be used and can be used 1 type or 2 types or more as needed.

Examples of such a water repellent treatment include those obtained by treating the powder and / or colorant with various water repellent surface treatment agents, such as methyl hydrogen polysiloxane treatment, silicone resin treatment, Silicone gum treatment, acrylic silicone treatment, organosiloxane treatment such as fluorinated silicone treatment, metal soap treatment such as zinc stearate treatment, silane coupling agent treatment, silane treatment such as alkylsilane treatment, perfluoroalkylsilane, perfluoroalkyl Fluorine compound treatment such as phosphate ester salt, perfluoropolyether treatment, amino acid treatment such as N-lauroyl-L-lysine treatment, oil agent treatment such as squalane treatment, acrylic treatment such as alkyl acrylate treatment, etc. It is possible to use 1 type or more in combination.

As these powders or colorants, silicone resin powder, silicone rubber powder, organic resin powder (excluding silicone resin powder), organically modified viscosity mineral, titanium oxide, zinc oxide, titanium mica, metal soap, It is at least one powder or colorant selected from the group consisting of inorganic extender pigments and inorganic color pigments.

As the alcohols, one or more selected from lower alcohols, sugar alcohols and higher alcohols can be used. Specifically, lower alcohols such as ethanol and isopropanol; sugar alcohols such as sorbitol and maltose; lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol, hexyldodecanol , Higher alcohols such as octyldodecanol, cetostearyl alcohol, 2-decyltetradecinol, cholesterol, sitosterol, phytosterol, lanosterol, POE cholesterol ether, monostearyl glycerin ether (batyl alcohol), monooleyl glyceryl ether (ceracyl alcohol) Is mentioned.

The water-soluble polymer is formulated for the purpose of improving the feeling of use of external preparations or cosmetics, and is amphoteric, cationic, anionic, nonionic, as long as it is used for ordinary external preparations or cosmetics. Any water-swellable clay mineral can be used, and one or more water-soluble polymers can be used in combination. Since these water-soluble polymers have a thickening effect on the water-containing component, gel-like water-containing external preparations or cosmetics, water-in-oil emulsion external preparations or cosmetics, oil-in-water emulsion external preparations or cosmetics are particularly useful. Useful when obtaining.

Examples of amphoteric water-soluble polymers include amphoteric starch, dimethyldiallylammonium chloride derivatives (for example, acrylamide / acrylic acid / dimethyldiallylammonium chloride copolymer, acrylic acid / dimethyldiallylammonium chloride copolymer), and methacrylic acid derivatives (for example, And polymethacryloylethyldimethylbetaine, N-methacryloyloxyethyl N, N-dimethylammonium-α-methylcarboxybetaine / alkyl methacrylate copolymer, etc.).

Examples of cationic water-soluble polymers include quaternary nitrogen-modified polysaccharides (for example, cation-modified cellulose, cation-modified hydroxyethyl cellulose, cation-modified guar gum, cation-modified locust bean gum, cation-modified starch), dimethyldiallylammonium chloride derivatives ( For example, dimethyldiallylammonium chloride / acrylamide copolymer, polydimethylmethylenepiperidinium chloride, etc.), vinylpyrrolidone derivatives (for example, vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer salt, vinylpyrrolidone / methacrylamidepropyltrimethylammonium chloride) Copolymer, vinylpyrrolidone / methylvinylimidazolium chloride copolymer, etc.), methacrylic acid derivatives (for example, methacryloylethyldimethyl) Thanh chloride methacryloyloxyethyl trimethyl ammonium-2-hydroxyethyl methacrylate copolymer, methacryloyl ethyl dimethyl betaine chloride methacryloyloxyethyl trimethyl ammonium methacrylate methoxy polyethylene glycol copolymer) and the like.

Examples of the anionic water-soluble polymer include polyacrylic acid or an alkali metal salt thereof, polymethacrylic acid or an alkali metal salt thereof, hyaluronic acid or an alkali metal salt thereof, acetylated hyaluronic acid or an alkali metal salt thereof, methyl vinyl ether, anhydrous Water-soluble polymer of aliphatic carboxylic acid or its metal salt such as hydrolyzate of maleic acid copolymer, carboxymethyl cellulose or its alkali metal salt, methyl vinyl ether-maleic acid half ester copolymer, acrylic resin alkanolamine liquid, Carboxyvinyl polymers are exemplified.

Nonionic water-soluble polymers include polyvinylpyrrolidone, highly polymerized polyethylene glycol, vinylpyrrolidone / vinyl acetate copolymer, vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer, vinylcaprolactam / vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer Coalesce, cellulose or derivatives thereof (eg, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose), keratin and collagen or derivatives thereof, calcium alginate, pullulan, agar, gelatin, tamarind seed polysaccharide, xanthan gum, carrageenan, high Methoxyl pectin, low methoxyl pectin, guar gum, pectin, gum arabic, crystalline cellulose, Binogalactan, gum karaya, gum tragacanth, alginic acid, albumin, casein, curdlan, duran gum, dextran, quince seed gum, tragacanth gum, chitin / chitosan derivatives, starch (rice, corn, potato, wheat, etc.), keratin and collagen or derivatives thereof, etc. Natural polymer compounds are exemplified.

The water-swellable clay mineral is an inorganic water-soluble polymer and is a kind of colloid-containing aluminum silicate having a three-layer structure, and is generally exemplified by the following formula (A).
(X, Y) _2-3 (Si, Al) ₄ O ₁₀ (OH) ₂ Z _1/3 · nH ₂ O (A)
(However, X is Al, Fe (III), Mn (III), or Cr (III), Y is Mg, Fe (II), Ni, Zn, or Li, and Z is K, Na or Ca)
Specific examples of such inorganic water-soluble polymers include bentonite, montmorillonite, piderite, nontronite, saponite, hectorite, aluminum magnesium silicate, and silicic anhydride, which are natural products and synthetic products. Any of these may be used.

As the oil, any solid, semi-solid, pasty, or liquid can be used as long as it is used in ordinary external preparations or cosmetics. Specifically, one or two or more types selected from silicone oil, hydrocarbon oil, ester oil, vegetable oils and fats, animal fats and oils, fatty acids, higher alcohols, triglycerides, artificial sebum, and fluorine-based oils are exemplified. it can.

Specifically, the silicone oil includes a linear organopolysiloxane represented by the following general formula (5) or a cyclic organopolysiloxane represented by the general formula (6) and a branched organopolysiloxane represented by the general formula (7). Examples include siloxane.

In the above formulas (1) to (3), R ⁹ represents a hydrogen atom, a hydroxyl group or a monovalent unsubstituted or fluorine-substituted alkyl group having 2 to 30 carbon atoms, an aryl group, an amino-substituted alkyl group, an alkoxy group, and ( _{_{CH 3) 3 SiO {(CH}} 3) 2 SiO} u Si (CH 3) 2 CH 2 CH 2 - is a radical selected from the groups represented by, specifically, an ethyl group, a propyl group, a butyl group , Pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group and other saturated aliphatic hydrocarbon groups; vinyl group, allyl group, hexenyl group and other unsaturated aliphatic hydrocarbon groups; cyclopentyl group, cyclohexyl group Saturated alicyclic hydrocarbon groups such as: phenyl groups, tolyl groups, naphthyl groups and other aromatic hydrocarbon groups, and hydrogen atoms bonded to carbon atoms of these groups are partially halogen atoms, epoxy groups, carboxyl groups , Amino group, methacryl group, Examples thereof include a group substituted with a trimethylsiloxy group bonded through an organic group containing a mercapto group or the like or a divalent hydrocarbon group and / or a chain-like polydimethylsiloxane bond. m is an integer from 0 to 1000, n is an integer from 0 to 1000, m + n is an integer from 1 to 2000, x, y is 0, 1, 2, or 3, p and q are integers from 0 to 8, and 3 ≦ p + q ≦ 8, r is an integer of 1 to 4, and u is an integer of 0 to 500.

Specific examples of silicone oils having these structures include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane as cyclic organopolysiloxanes. (D6), 1,1-diethylhexamethylcyclotetrasiloxane, phenylheptamethylcyclotetrasiloxane, 1,1-diphenylhexamethylcyclotetrasiloxane, 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane, , 3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetracyclohexyltetramethylcyclotetrasiloxane, tris (3,3,3-trifluoropropyl) trimethylcyclotrisiloxa 1,3,5,7-tetra (3-methacryloxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (3-acryloxypropyl) tetramethylcyclotetrasiloxane, 1,3,5 , 7-Tetra (3-carboxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (3-vinyloxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (p- Vinylphenyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra [3- (p-vinylphenyl) propyl] tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (N-acryloyl-N) -Methyl-3-aminopropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (N, N-bis ( Examples include lauroyl) -3-aminopropyl) tetramethylcyclotetrasiloxane. Examples of the linear organopolysiloxane include trimethylsiloxy group-blocked dimethylpolysiloxane having a molecular chain at both ends (dimethylsilicone having a low viscosity such as 2 cst and 6 cst to a high viscosity such as 1 million cst), organohydrogenpolysiloxane, trimethyl at both ends of the molecular chain. Siloxy group-blocked methylphenylpolysiloxane, molecular chain both ends trimethylsiloxy group-blocked dimethylsiloxane / methylphenylsiloxane copolymer, molecular chain both ends trimethylsiloxy group-blocked diphenylpolysiloxane, molecular chain both ends trimethylsiloxy group-blocked dimethylsiloxane diphenyl Siloxane copolymer, trimethylpentaphenyltrisiloxane, phenyl (trimethylsiloxy) siloxane, trimethylsiloxy group-blocked methylalkylpolysiloxane, molecular chain Trimethylsiloxy group-blocked dimethylpolysiloxane / methylalkylsiloxane copolymer at both ends, trimethylsiloxy group-blocked dimethylsiloxane / methyl (3,3,3-trifluoropropyl) siloxane copolymer at both ends, α, ω-dihydroxy Polydimethylsiloxane, α, ω-diethoxypolydimethylsiloxane, 1,1,1,3,5,5,5-heptamethyl-3-octyltrisiloxane, 1,1,1,3,5,5,5- Heptamethyl-3-dodecyltrisiloxane, 1,1,1,3,5,5,5-heptamethyl-3-hexadecyltrisiloxane, tristrimethylsiloxymethylsilane, tristrimethylsiloxyalkylsilane, tetrakistrimethylsiloxysilane, tetramethyl 1,3-dihydroxydisiloxane, ok Methyl-1,7-dihydroxy-cyclotetrasiloxane, hexamethyl-1,5-diethoxy trisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, higher alkoxy-modified silicones, higher fatty acid-modified silicones and the like.

Hydrocarbon oils include liquid paraffin, light liquid isoparaffin, heavy liquid isoparaffin, petrolatum, n-paraffin, isoparaffin, isododecane, isohexadecane, polyisobutylene, hydrogenated polyisobutylene, polybutene, ozokerite, ceresin, microcrystalline wax, paraffin Examples include wax, polyethylene wax, polyethylene / polypropylene wax, squalane, squalene, pristane, polyisoprene and the like.

Ester oils include hexyldecyl octoate, cetyl octanoate, isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, oleyl oleate, decyl oleate, octyldodecyl myristate, dimethyloctanoic acid Hexyldecyl, cetyl lactate, myristyl lactate, diethyl phthalate, dibutyl phthalate, lanolin acetate, ethylene glycol monostearate, propylene glycol monostearate, propylene glycol dioleate, glyceryl monostearate, glyceryl monooleate, tri-2- Glyceryl ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, ditrimethylolpropane triethylhexanoate, (isostear Acid / sebacic acid) ditrimethylolpropane, trimethylolpropane trioctanoate, trimethylolpropane triisostearate, diisopropyl adipate, diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, malic acid Diisostearyl, hydrogenated castor oil monoisostearate, N-alkyl glycol monoisostearate, octyldodecyl isostearate, isopropyl isostearate, isocetyl isostearate, ethylene glycol di-2-ethylhexanoate, cetyl 2-ethylhexanoate, Tetra-2-ethylhexanoic acid pentaerythritol, octyldodecyl gum ester, ethyl oleate, octyldodecyl oleate, neopentyl dicaprate Cole, triethyl citrate, 2-ethylhexyl succinate, dioctyl succinate, isocetyl stearate, diisopropyl sebacate, di-2-ethylhexyl sebacate, diethyl sebacate, dioctyl sebacate, dibutyl octyl sebacate, cetyl palinate, palmitic Octyldodecyl acid, octyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptyl undecyl palmitate, cholesteryl 12-hydroxystearylate, dipentaerythritol fatty acid ester, 2-hexyldecyl myristate, laurin Ethyl acetate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, N-lauroyl-L-glutamic acid di (cholesteryl / behenyl / octy Dodecyl), N-lauroyl-L-glutamate di (cholesteryl / octyldodecyl), N-lauroyl-L-glutamate di (phytosteryl / behenyl / octyldodecyl), N-lauroyl-L-glutamate di (phytosteryl / octyldodecyl), N-lauroyl sarcosine isopropyl, diisostearyl malate, neopentyl glycol dioctanoate, isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate, isononyl isononanoate, isotridecyl isononanoate, octyl isononanoate, isotridecyl isononanoate, diethyl dineopentanoate Pentanediol, methylpentanediol dineopentanoate, octyldodecyl neodecanoate, 2-butyl-2-octanoate Cyl-1,3-propanediol, pentaerythrityl tetraoctanoate, hydrogenated rosin pentaerythrityl, pentaerythrityl triethylhexanoate, (hydroxystearic acid / stearic acid / rosinic acid) dipentaerythrityl, polyglyceryl tetraisostearate, nonaisostearin Polyglyceryl-10, deca (erucic acid / isostearic acid / ricinoleic acid) polyglyceryl-8, (hexyldecanoic acid / sebacic acid) diglyceryl oligoester, glycol distearate (ethylene glycol distearate), diisopropyl linoleate diisopropyl, dimer Diisostearyl linoleate, dimerdiolelic acid di (isostearyl / phytosteryl), dimerdilinoleic acid (phytosteryl / behenyl) , Dimer linoleic acid (phytosteryl / isostearyl / cetyl / stearyl / behenyl), dimer dilinoleic acid dimer dilinoleyl, diisostearic dimer dilinoleyl, dimer dilinoleyl hydrogenated rosin condensate, dimer dilinoleic acid cured castor Oil, hydroxyalkyl dimer dilinoleyl ether, glyceryl triisooctanoate, glyceryl triisostearate, glyceryl trimyristate, glyceryl triisopalmitate, glyceryl trioctanoate, glyceryl trioleate, glyceryl diisostearate, tri (caprylic acid / caprin Acid) glyceryl, tri (caprylic acid / capric acid / myristic acid / stearic acid) glyceryl, hydrogenated rosin triglyceride (hydrogenated ester gum), rosin Reglycerides (ester gums), glyceryl behenate, glyceryl di-2-heptylundecanoate, diglyceryl myristate, cholesteryl acetate, cholesteryl nonanoate, cholesteryl stearate, cholesteryl isostearate, cholesteryl oleate, 12- Cholesteryl hydroxystearate, macadamia nut oil fatty acid cholesteryl, macadamia nut oil fatty acid phytosteryl, phytosteryl isostearate, soft lanolin fatty acid cholesteryl, hard lanolin fatty acid cholesteryl, long chain branched fatty acid cholesteryl, long chain α-hydroxy fatty acid cholesteryl, octyldodecyl ricinoleate, lanolin fatty acid Octyldodecyl, octyldodecyl erucate, isostearic acid hydrogenated castor oil And avocado oil fatty acid ethyl, lanolin fatty acid isopropyl and the like.

Natural animal and vegetable oils and semi-synthetic oils include avocado oil, linseed oil, almond oil, ibotarou, eno oil, olive oil, cacao butter, kapok wax, kayak oil, carnauba wax, liver oil, candelilla wax, beef tallow, beef leg fat, beef bone Fat, hydrogenated beef tallow, Kyonin oil, whale wax, hydrogenated oil, wheat germ oil, sesame oil, rice germ oil, rice bran oil, sugarcane wax, sasanqua oil, saflower oil, shea butter, cinnamon oil, cinnamon oil, jojoballow, olive Squalane, 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, Jojoba ester, macadamia nut oil, beeswax, mink oil, cottonseed oil, cotton wax, owl, owl kernel oil, montan wax, coconut oil, hydrogenated coconut oil, tricoconut oil fatty acid glyceride, sheep fat, peanut oil, lanolin, liquid lanolin, reduced lanolin Lanolin alcohol, hard lanolin, lanolin acetate, lanolin fatty acid isopropyl, 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.

Examples of higher fatty acids include 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), Examples include isostearic acid and 12-hydroxystearic acid.

Examples of the higher alcohol include lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol, hexyl decanol, octyldodecanol, cetostearyl alcohol, 2-decyltetradecyl Nord, cholesterol, sitosterol, phytosterol, lanosterol, POE cholesterol ether, monostearyl glycerin ether (batyl alcohol), monooleyl glyceryl ether (ceralkyl alcohol) and the like.

Examples of the fluorinated oil agent include perfluoropolyether, perfluorodecalin, perfluorooctane, and the like, and these oil agents can be used singly or in combination of two or more.

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 palmitate, sucrose fatty acid ester such as sucrose palmitate, sucrose stearate, inulin stearate, fructooligosaccharide 2-ethylhexane Fructooligosaccharide fatty acid esters such as acid esters, benzylidene derivatives of sorbitol such as monobenzylidene sorbitol, dibenzylidene sorbitol, dimethylbenzyl dodecyl ammonio Montmorillonite clay, clay minerals modified with organic compounds such as dimethyl dioctadecyl ammonium montmorillonite clay and the like, which may be optionally used singly or two or more.

In the external preparation or cosmetic of the present invention, a surfactant other than the above components can be blended. Such surfactants include silicone surfactants other than the sugar alcohol-modified silicone according to the present invention, anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and semipolar surfactants. 1 type, or 2 or more types of surfactant chosen from the group which consists of can be used together.

The silicone-based surfactant is a silicone-based surfactant other than the low odor sugar alcohol-modified silicone according to the present invention. Such silicone surfactants are often used as components for emulsification and washing of oil agents, dispersion of powders and surface treatments. Typically, polyglyceryl-modified silicone, glyceryl-modified silicone, sugar-modified silicone, fluorine polyether Examples include modified silicone, polyether-modified silicone, carboxylic acid-modified silicone, sugar-modified silicone, linear silicone / polyether block copolymer, and long-chain alkyl / polyether co-modified silicone.

Anionic surfactants include saturated or unsaturated fatty acid salts (for example, sodium laurate, sodium stearate, sodium oleate, sodium linolenate, etc.), alkyl sulfates, alkyl benzene sulfonic acids (for example, hexyl benzene sulfonic acid, toctil) Benzenesulfonic acid, dodecylbenzenesulfonic acid, etc.) and salts thereof, polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkenyl ether sulfate, polyoxyethylene alkyl sulfate ester, sulfosuccinic acid alkyl ester salt, polyoxyalkylene sulfosuccinic acid alkyl Ester salt, polyoxyalkylene alkyl phenyl ether sulfate, alkane sulfonate, octyltrimethylammonium hydroxide, dodecyltrimethylammo Um hydroxide, alkyl sulfonate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyalkylene alkyl ether acetate, alkyl phosphate, polyoxyalkylene alkyl ether phosphate, acyl glutamate, α-acyl sulfonate, alkyl Sulfonate, alkyl allyl sulfonate, α-olefin sulfonate, alkyl naphthalene sulfonate, alkane sulfonate, alkyl or alkenyl sulfate, alkyl amide sulfate, alkyl or alkenyl phosphate, alkyl amide phosphate Salt, alkyloylalkyl taurine salt, N-acyl amino acid salt, sulfosuccinate, alkyl ether carboxylate, amide ether carboxylate, α-sulfo fatty acid ester salt, alanine derivative, glycine Conductor, arginine derivatives and the like. Examples of the salt include alkali metal salts such as sodium salts, alkaline earth metal salts such as magnesium salts, alkanolamine salts such as triethanolamine salts, and ammonium salts.

As cationic surfactants, alkyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, tallow alkyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, stearyl trimethyl ammonium bromide, behenyl trimethyl ammonium bromide, Distearyldimethylammonium chloride, dicocoyldimethylammonium chloride, dioctyldimethylammonium chloride, di (POE) oleylmethylammonium chloride (2EO), benzalkonium chloride, alkylbenzalkonium chloride, alkyldimethylbenzalkonium chloride, benzethonium chloride, Stearyldimethylbenzylammonium chloride, lanolin-derived quaternary ammonium Salt, diethylaminoethylamide stearate, dimethylaminopropylamide stearate, amidopropyldimethylhydroxypropylammonium chloride, stearoylcholaminoformylmethylpyridinium chloride, cetylpyridinium chloride, tall oil alkylbenzylhydroxyethylimidazolinium chloride, benzylammonium Salts are exemplified.

Nonionic surfactants include polyglyceryl diisostearate, diglyceryl polyhydroxystearate, isostearyl glyceryl ether, polyoxyalkylene ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene fatty acid esters, polyoxyalkylene fatty acid diesters, Polyoxyalkylene resin acid esters, polyoxyalkylene (cured) castor oils, polyoxyalkylene alkylphenols, polyoxyalkylene alkyl phenyl ethers, polyoxyalkylene phenyl phenyl ethers, polyoxyalkylene alkyl esters, polyoxyalkylene Alkyl esters, sorbitan fatty acid esters, polyoxyalkylene sorbitan alkyl esters, polyoxy Alkylene sorbitan fatty acid esters, polyoxyalkylene sorbite fatty acid esters, polyoxyalkylene glycerin fatty acid esters, polyglycerin alkyl ethers, polyglycerin fatty acid esters, sucrose fatty acid esters, fatty acid alkanolamides, alkyl glucosides, polyoxy Examples include alkylene fatty acid bisphenyl ethers, polypropylene glycol, diethylene glycol, polyoxyethylene / polyoxypropylene block polymers, alkyl polyoxyethylene / polyoxypropylene block polymer ethers, and fluorosurfactants.

Amphoteric surfactants such as imidazoline type, amide betaine type, alkyl betaine type, alkyl amide betaine type, alkyl sulfobetaine type, amide sulfobetaine type, hydroxysulfobetaine type, carbobetaine type, phosphobetaine type, aminocarboxylic acid type, amide Amino acid type amphoteric surfactants are exemplified. Specifically, 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt, etc. Imidazoline-type amphoteric surfactants; alkylbetaine-type amphoteric surfactants such as lauryldimethylaminoacetic acid betaine and myristylbetaine; palm oil fatty acid amidopropyldimethylaminoacetic acid betaine lees, palm kernel fatty acid amidopropyldimethylaminoacetic acid betaine lees, beef tallow fatty acid amidopropyl Dimethylaminoacetic acid betaine koji, hardened tallow fatty acid amidopropyl dimethylaminoacetic acid betaine koji, lauric acid amidopropyl dimethylaminoacetic acid betaine koji, myristic acid amidopropyl dimethylaminoacetic acid betaine koji, palmitic acid Amidobetaine-type amphoteric surfactants such as amidopropyldimethylaminoacetic acid betaine, stearic acid amidopropyldimethylaminoacetic acid betaine, oleic acid amidopropyldimethylaminoacetic acid betaine; alkylsulfobetaine-type amphoteric surfactants such as coconut oil fatty acid dimethylsulfopropylbetaine Agents; alkylhydroxysulfobetaine-type amphoteric surfactants such as lauryldimethylaminohydroxysulfobetaine; phosphobetaine-type amphoteric surfactants such as laurylhydroxyphosphobetaine; N-lauroyl-N′-hydroxyethyl- N′-carboxymethylethylenediamine Sodium, N-oleoyl-N′-hydroxyethyl- N′-carboxymethylethylenediamine sodium, N-cocoyl-N′-hydroxyethyl-N′-ca Ruboxymethyl ethylenediamine sodium, N-lauroyl-N′-hydroxyethyl- N′-carboxymethylethylenediamine potassium, N-oleoyl-N′-hydroxyethyl- N′-carboxymethylethylenediamine potassium, N-lauroyl-N-hydroxy Ethyl- N'-carboxymethylethylenediamine sodium, N-oleoyl-N-hydroxyethyl- N'-carboxymethylethylenediamine sodium, N-cocoyl-N-hydroxyethyl- N'-carboxymethylethylenediamine sodium, N-lauroyl-N -Hydroxyethyl- エチル N ', N'-dicarboxymethylethylenediamine monosodium, N-oleoyl-N-hydroxyethyl- N', N'-dicarboxymethylethylene Amine monosodium, N-cocoyl-N-hydroxyethyl-N ′, N′-dicarboxymethylethylenediamine monosodium, N-lauroyl-N-hydroxyethyl- N ′, N′-dicarboxymethylethylenediamine disodium, N— Amidoamino acid type amphoteric interfaces such as oleoyl-N-hydroxyethyl- N ', N'-dicarboxymethylethylenediamine disodium, N-cocoyl-N-hydroxyethyl- N', N'-dicarboxymethylethylenediamine disodium An activator is exemplified.

Examples of the semipolar surfactant include alkylamine oxide type surfactants, alkylamine oxides, alkylamidoamine oxides, alkylhydroxyamine oxides, and the like. Alkyldimethylamine oxide having 10 to 18 carbon atoms and 8 to 18 carbon atoms are exemplified. Alkoxyethyldihydroxyethylamine oxide and the like are preferably used. Specifically, dodecyldimethylamine oxide, dimethyloctylamine oxide, diethyldecylamine oxide, bis- (2-hydroxyethyl) dodecylamine oxide, dipropyltetradecylamine oxide, methylethylhexadecylamine oxide, dodecylamidopropyl Dimethylamine oxide, cetyldimethylamine oxide, stearyl dimethylamine oxide, tallow dimethylamine oxide, dimethyl-2-hydroxyoctadecylamine oxide, lauryl dimethylamine oxide, myristyl dimethylamine oxide, stearyl dimethylamine oxide, isostearyl dimethylamine oxide, palm Fatty acid alkyldimethylamine oxide, caprylic amidopropyldimethyla Oxide, capric acid amidopropyl dimethylamine oxide, lauric acid amidopropyl dimethylamine oxide, myristic acid amidopropyl dimethylamine oxide, palmitic acid amidopropyl dimethylamine oxide, stearic acid amidopropyl dimethylamine oxide, isostearic acid amidopropyl dimethylamine oxide, Oleic acid amidopropyl dimethylamine oxide, ricinoleic acid amidopropyl dimethylamine oxide, 12-hydroxystearic acid amidopropyl dimethylamine oxide, palm fatty acid amidopropyl dimethylamine oxide, palm kernel oil fatty acid amidopropyl dimethylamine oxide, castor oil fatty acid amidopropyl Dimethylamine oxide, lauric acid amidoethyldimethyla Oxide, myristate amidoethyl dimethylamine oxide, palm fatty acid amidoethyl dimethylamine oxide, lauric acid amidoethyl diethylamine oxide, myristic amidoethyl diethylamine oxide, palm fatty acid amidoethyl diethylamine oxide, lauric acid amidoethyl dihydroxyethylamine oxide, myristic acid amide Examples include ethyl dihydroxyethylamine oxide and coconut fatty acid amidoethyl dihydroxyethylamine oxide.

The ultraviolet protective agent includes an inorganic ultraviolet protective agent and an organic ultraviolet protective agent. If the external preparation or cosmetic of the present invention is used for sunscreen, it preferably contains at least one organic ultraviolet protective agent, and an ultraviolet protective component corresponding to UV-A and an ultraviolet light corresponding to UV-B. More preferably, a protective component is used in combination.

The inorganic ultraviolet protective agent may be an inorganic powder pigment, metal powder pigment or the like blended as an ultraviolet dispersant, such as titanium oxide, zinc oxide, cerium oxide, low-order titanium oxide, iron-doped titanium oxide, etc. And metal hydroxides such as iron hydroxide, plate-like iron oxide, metal flakes such as aluminum flakes, and ceramics such as silicon carbide.

As organic UV protection agents, benzoic acid UV absorbers such as paraaminobenzoic acid, anthranilic acid UV absorbers such as methyl anthranilate, salicylic acid UV absorbers such as methyl salicylate, and cinnamon such as octyl paramethoxycinnamate Acid ultraviolet absorbers, benzophenone ultraviolet absorbers such as 2,4-dihydroxybenzophenone, urocanic acid ultraviolet absorbers such as ethyl urocanate, and dibenzoyl such as 4-t-butyl-4'-methoxy-dibenzoylmethane Examples include methane-based ultraviolet absorbers, 2- [4- (diethylamino) -2-hydroxybenzoyl] benzoic acid hexyl ester (Ubinal A plus), and the like.

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, and zinc salts 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 and stearic acid; amine salts and amino acid salts include, for example, salts of amines such as triethanolamine, and amino acids such as glutamic acid And the like. In addition, a salt such as hyaluronic acid and chondroitin sulfate, an aluminum zirconium glycine complex, and the like, and an acid-alkali neutralized salt used in cosmetic formulations can also be used.

Examples of moisturizers include polyhydric alcohols such as glycerin, sorbitol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, glucose, xylitol, maltitol, and polyethylene glycol; hyaluronic acid, chondroitin sulfate, pyrrolidone carboxylate, There are polyoxyethylene methyl glucoside, polyoxypropylene methyl glucoside, PEG / PPG dimethyl ether and the like.

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, triclosan, photosensitizer, phenoxyethanol, and the like, but in the case of lipstick, it is preferable not to mix them.

Examples of the antioxidant include tocopherol, butylhydroxyanisole, dibutylhydroxytoluene, phytic acid and the like.

Examples of the pH adjuster include lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, dl-malic acid, potassium carbonate, sodium hydrogen carbonate, ammonium hydrogen carbonate and the like.

Examples of the chelating agent include alanine, edetic acid sodium salt, sodium polyphosphate, sodium metaphosphate, phosphoric acid and the like.

Examples of the refreshing agent include L-menthol and camphor, and examples of the anti-inflammatory agent include allantoin, glycyrrhetinic acid, glycyrrhizic acid, tranexamic acid, and azulene.

Skin cleansing ingredients include placenta extract, whitening agent such as arbutin, glutathione, and yukinoshita extract, cell activators such as royal jelly, skin roughening agent, nonyl acid wallenylamide, nicotinic acid benzyl ester, nicotinic acid β-butoxyethyl ester , Capsaicin, gingerone, cantalis tincture, ictamol, caffeine, tannic acid, α-borneol, tocopherol nicotinate, inositol hexanicotinate, cyclandrate, cinnarizine, trazoline, acetylcholine, verapamil, cephalanthin, γ-oryzanol Accelerators, skin astringents such as zinc oxide and tannic acid, antiseborrheic agents such as sulfur and thianthol, etc., vitamins include vitamin A oil, retinol, retinol acetate, retinol palmitate, etc. Vitamin A2 such as vitamin A, riboflavin, riboflavin butyrate, flavin adenine nucleotide, vitamin B6 such as pyridoxine hydrochloride, pyridoxine dioctanoate, pyridoxine tripalmitate, vitamin B12 and its derivatives, vitamin B15 and its derivatives, etc. Vitamin C such as L-ascorbic acid, L-ascorbic acid dipalmitate, L-ascorbic acid-2-sodium sulfate, L-ascorbic acid diester dipotassium, ergocalciferol, cholecalciferol Vitamin D such as α-tocophenol, β-tocopherol, γ-tocopherol, dl-α-tocopherol acetate, dl-α-tocopherol nicotinate, dl-α-tocopherol succinate, etc. Vitamin H, vitamin P, nicotinic acid, nicotinic acid benzyl nicotinate and the like, calcium pantothenate, D- pantothenyl alcohol, pantothenyl ethyl ether, and the like pantothenic acids such as acetyl pantothenyl ethyl ether.

Examples of amino acids include glycine, valine, leucine, isoleucine, serine, threonine, phenylalanine, arginine, lysine, aspartic acid, glutamic acid, cystine, cysteine, methionine, tryptophan and the like and / or salts thereof.

Examples of nucleic acids include deoxyribonucleic acid, and examples of hormones include estradiol and etenyl estradiol.

The physiologically active ingredient is a substance that imparts some physiological activity to the skin or hair when applied to the skin or hair and is lipophilic. For example, anti-inflammatory agent, anti-aging agent, squeeze agent, hair growth agent, hair restorer, moisturizer, blood circulation promoter, desiccant, warming sensation, vitamins, wound healing promoter, stimulation relieving agent, analgesic agent, cell An activator, an enzyme component, etc. are mentioned. Similarly, natural plant extract components, seaweed extract components and herbal medicine components can be preferably blended.

An active pharmaceutical ingredient is a substance having a disease therapeutic effect, and examples thereof include proteins, peptides, and low molecular compounds.

The fragrance is not particularly limited as long as it is a lipophilic fragrance. The fragrance is extracted from flowers, seeds, leaves, roots, etc. of various plants, the fragrance is extracted from seaweed, and each part or secretion of the animal. Examples include extracted fragrances (e.g., pepper, sperm) and artificially synthesized fragrances (e.g., menthol, musk, acetate ester, vanilla). A fragrance | flavor is mix | blended in order to provide a fragrance and fragrance to an external preparation or cosmetics. Examples of the pigment include oil-soluble dyes, extender pigments, inorganic pigments, organic pigments, and lipophilic fluorescent whitening agents.

[Combination with other silicone cosmetic ingredients]
The external preparation or cosmetic according to the present invention further includes a solid silicone resin or a crosslinkable organopolysiloxane, an acrylic silicone dendrimer copolymer, a silicone raw rubber (silicone gum), a polyamide-modified silicone, depending on the dosage form and formulation. An alkyl-modified silicone wax and an alkyl-modified silicone resin wax can be blended. The low odor sugar alcohol-modified silicone obtained by the present invention has a main chain composed of a polysiloxane chain, and has a hydrophilic sugar alcohol-modified group as a modifying group. Therefore, the compounding stability with these silicone-based compounds is improved. And has the advantage of being able to design cosmetics that take advantage of the characteristic feel of these silicone-based cosmetic raw materials.

[Solid silicone resin or crosslinkable organopolysiloxane]
The external preparation or cosmetic of the present invention of the present invention can further contain a solid silicone resin or a crosslinkable organopolysiloxane. The solid silicone resin or the crosslinkable organopolysiloxane is preferably hydrophobic so that it does not dissolve at all in water at room temperature or the solubility of the component in 100 g of water is less than 1% by weight (mass).

The solid silicone resin is an organopolysiloxane having a highly branched structure, network structure or cage structure, and is solid at room temperature. As long as the object of the present invention is not violated, any silicone resin that is usually used in cosmetics can be used. Solid silicone resin is particles such as spherical powder, flake powder, needle powder, flat flake powder (including plate powder having an appearance generally understood as plate and particle aspect ratio). In particular, a silicone resin powder containing a monoorganosiloxy unit (T unit) and / or a siloxy unit (Q unit) described later is preferably used.

When a solid silicone resin is blended with the low odor sugar alcohol-modified silicone obtained by the present invention, the compatibility with the oil agent and the uniform dispersibility are improved, and the application to the application part accompanying the blending of the solid silicone resin is improved. It is useful in that it provides an effect of improving the feeling of use such as uniform adhesion and an effect of improving the durability of the makeup such as water resistance and sebum resistance.

Examples of solid silicone resins include triorganosiloxy units (M units) (organo groups are only methyl groups, methyl groups and vinyl groups or phenyl groups), diorganosiloxy units (D units) (organo groups are methyl groups). Group only, methyl group and vinyl group or phenyl group), monoorganosiloxy unit (T unit) (organo group is methyl group, vinyl group or phenyl group) and any combination of siloxy unit (Q unit) There are MQ resin, MDQ resin, MTQ resin, MDTQ resin, TD resin, TQ resin, and TDQ resin. Furthermore, trimethylsiloxysilicic acid, polyalkylsiloxysilicic acid, dimethylsiloxy unit-containing trimethylsiloxysilicic acid, and alkyl (perfluoroalkyl) siloxysilicic acid are exemplified. These silicone resins are oil-soluble, and those that are soluble in volatile silicone are particularly preferred.

In particular, a high refractive index phenyl silicone resin having a high phenyl group content (for example, 217 Flakes resin manufactured by Toray Dow Corning Co., Ltd.) can be easily made into a flaky silicone resin powder. When blended into the composition, the skin and hair can be given a lustrous transparency.

The crosslinkable organopolysiloxane has a structure in which the organopolysiloxane chain is three-dimensionally cross-linked by reaction with a crosslinkable component comprising a polyether unit, an alkylene unit having 4 to 20 carbon atoms, or an organopolysiloxane unit. Is preferred.

Specifically, the crosslinkable organopolysiloxane includes an organohydrogenpolysiloxane having a silicon-bonded hydrogen atom, a polyether compound having an unsaturated bond at both ends of the molecular chain, and more than one double bond in the molecule. It can be obtained by addition reaction of an unsaturated hydrocarbon having an organic polysiloxane having more than one double bond in the molecule.
Here, the crosslinkable organopolysiloxane is an unreacted silicon-bonded hydrogen atom, an aromatic hydrocarbon group such as a phenyl group, a long chain alkyl group having 6 to 30 carbon atoms such as an octyl group, a polyether group, or a carboxyl group. It may or may not have a modifying functional group such as, and can be used without limitation regardless of the physical form such as dilution and properties, the production method, and the like.

As an example, such a crosslinkable organopolysiloxane includes an SiO unit, an HSiO unit, an R ^b SiO unit, an R ^b HSiO unit, an R ^b SiO unit, an R ^b SiO unit, and an R ^b HSiO unit (where R ^b is an aliphatic group). Selected from the group consisting of a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, excluding unsaturated groups, and part of R ^b being a monovalent hydrocarbon group having 8 to 30 carbon atoms. And an organohydrogenpolysiloxane containing 1.5 or more hydrogen atoms bonded to silicon atoms in the molecule on average, and a polysiloxane having unsaturated hydrocarbon groups at both ends of the molecular chain. Polyether compounds such as oxyalkylene compounds, polyglycerin compounds or polyglycidyl ether compounds, general formula: CH═CH—C _r H—CH═CH ₂ (wherein r is 0 to An unsaturated hydrocarbon which is an α, ω-diene represented by the following formula: or an SiO ₂ unit, (CH═CH) SiO unit, R ^c SiO unit, R ^c (CH═CH) SiO unit, R ^c SiO unit, R ^c SiO unit and R ^c (CH═CH) SiO unit, wherein R ^c is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms excluding an aliphatic unsaturated group. An addition reaction with a crosslinkable component selected from organopolysiloxanes composed of structural units selected from the group consisting of 1.5 and more than 1.5 vinyl groups bonded to silicon atoms in the molecule. Can be obtained. The modifying functional group can be introduced by an addition reaction to unreacted silicon-bonded hydrogen atoms. For example, 1-hexene is reacted with a crosslinkable organopolysiloxane having an unreacted silicon-bonded hydrogen atom to introduce a hexyl group that is a C6 alkyl group.

Such a crosslinkable organopolysiloxane can be used without limitation regardless of the physical form such as dilution and properties, the production method, and the like. Particularly preferred are α, described in US Pat. No. 5,654,362. ω-diene cross-linked silicone elastomer (commercially available is DC 9040 Silicone Elastomer Blend, DC 9041 Silicone Elastomer Blend, DC 9045 Silicone Elastomer Blend, DC 9046 Silicone Elaston, USA) Similarly, as a partially crosslinked organopolysiloxane polymer, the INCI name (International Nomenclature C
osmetic Ingredient labeling names) (dimethicone / vinyl dimethicone) crosspolymer, (dimethicone / phenylvinyldimethicone) crosspolymer, (PEG-8-30 / C6-C30 alkyl dimethicone) crosspolymer, (vinyl dimethicone / C6-C30 alkyl dimethicone) ) Crosspolymer, (dimethicone / polyglycerin) crosspolymer, and the like.

When an emulsifiable cross-linkable organopolysiloxane that is cross-linked with a polyether compound is blended as a component in an external preparation or cosmetic, the low-odor sugar alcohol-modified silicone obtained by the present invention functions as a dispersant. There is an advantage that a uniform emulsification system (dosage form) can be formed.

On the other hand, when a non-emulsifiable crosslinkable organopolysiloxane that is crosslinked with an unsaturated hydrocarbon group such as organopolysiloxane or diene is blended in an external preparation or cosmetic as a component, the skin and hair are smooth and smooth. The effect of concealing a wrinkle and a wrinkle of a mat | matte external appearance and skin is acquired. Furthermore, since the effect of thickening by holding various oil agents is high, there is an advantage that the feeling of adhesion of the cosmetic to the skin is improved and the longevity of the makeup is also improved.

The solid silicone resin or the crosslinkable organopolysiloxane can be blended in one or more types depending on the purpose. It is preferably blended within the range of 05 to 25% by weight (mass)%, and more preferably within the range of 0.1 to 15% by weight (mass)%.

[Acrylic silicone dendrimer copolymer]
The external preparation or cosmetic of the present invention can further contain an acrylic silicone dendrimer copolymer. The acrylic silicone dendrimer copolymer is a vinyl polymer having a carbosiloxane dendrimer structure in the side chain. For example, the vinyl polymer described in Japanese Patent No. 4009382 (Japanese Patent Laid-Open No. 2000-063225) includes: Particularly preferred examples are illustrated. Examples of commercially available products include FA 4001CM Silicone Acrylate manufactured by Toray Dow Corning Co., Ltd., FA 4002 ID Silicone Acrylate, etc., and the side chain thereof has 8 to 30 carbon atoms, preferably 14 to 22 carbon atoms. It may be an acrylic silicone dendrimer copolymer having a long chain alkyl group. When such an acrylic silicone dendrimer copolymer is blended alone, it has excellent film-forming properties, so by blending in the external preparation or cosmetic according to the present invention, it is possible to form a strong coating film on the coated part, Sustainability such as sebum resistance and friction resistance is greatly improved.

The combined use of the low odor sugar alcohol-modified silicone and acrylic silicone dendrimer copolymer obtained by the present invention improves the surface protection characteristics such as sebum resistance and the like due to strong water repellency due to the carbosiloxane dendrimer structure, and pores There is an advantage that unevenness such as can be effectively inconspicuous. In addition, the sugar alcohol-modified silicone has an advantage that, for example, the cosmetic silicone dendrimer copolymer can be suitably adapted to other oil agents, so that, for example, cosmetic durability can be improved and deterioration of the skin surface and hair can be suppressed over a long period of time.

The blending amount of the acrylic silicone dendrimer copolymer is appropriately selected according to the purpose and the intention of blending, but is preferably in the range of 1 to 99% by weight (mass)% of the external preparation or the whole cosmetic, and 30 to More preferably within the range of 70% by weight (mass).

[Silicone raw rubber (silicone gum)]
In the external preparation or cosmetic of the present invention, a silicone raw rubber (silicone gum) having a viscosity at room temperature of 1,000,000 mm ² / s or more, which has an extremely high viscosity but has fluidity, is also silicone. It can be suitably used as an oil. Silicone gum is a linear diorganopolysiloxane having a very high degree of polymerization, and is also referred to as silicone raw rubber or organopolysiloxane gum. Silicone gum is distinguished from the above oily silicones in that it has a high degree of polymerization and thus has a measurable plasticity. These silicone gums are used as they are or as liquid gum dispersions (silicone gum oil dispersions) dispersed in oily silicone, for use in external preparations or cosmetics according to the present invention, especially for the purpose of imparting feel. Can be blended.

Examples of such silicone raw rubber include substituted or unsubstituted organopolysiloxane having a dialkylsiloxy unit (D unit), such as dimethylpolysiloxane, methylphenylpolysiloxane, aminopolysiloxane, methylfluoroalkylpolysiloxane, or the like. As a typical example, a general formula: R ¹⁰ (CH ₃ ) ₂ SiO {(CH ₃ ) ₂ SiO} _s {(CH ₃ ) R ¹² SiO} _t Si (CH ₃ ) ₂ R ¹⁰ (wherein R ¹² is a vinyl group, a phenyl group, an alkyl group having 6 to 20 carbon atoms, an aminoalkyl group having 3 to 15 carbon atoms, a perfluoroalkyl group having 3 to 15 carbon atoms, carbon A group selected from alkyl groups containing a quaternary ammonium base having a number of 3 to 15, and the terminal group R ¹⁰ is a group having 1 to 8 carbon atoms. A group selected from an alkyl group, a phenyl group, a vinyl group, an aminoalkyl group having 3 to 15 carbon atoms, a hydroxyl group and an alkoxy group having 1 to 8 carbon atoms, and s = 2,000 to 6,000, t = 0 to 1,000, s + t = 2,000 to 6,000). Among them, dimethylpolysiloxane raw rubber having a polymerization degree of 3000 to 20000 is preferable. Further, an amino-modified methylpolysiloxane raw rubber having a 3-aminopropyl group, N- (2-aminoethyl) 3-aminopropyl group or the like in the side chain or terminal of the molecule is preferable. Moreover, in this invention, a silicone gum can be used 1 type or in combination of 2 or more types as needed.

Since the silicone gum has an ultra-high degree of polymerization, it forms a protective film with excellent persistence to hair and excellent breathability. For this reason, it is a component which can give gloss and luster especially to hair, and can give a firm and firm texture to the entire hair during and after use. Silicone gum having a high degree of polymerization can also be blended in external preparations and cosmetics in a form that is diluted with silicone oil to lower the viscosity.

The blending amount of the silicone gum is, for example, in the range of 0.05 to 30% by weight (mass)%, preferably in the range of 1 to 15% by weight (mass)% of the external preparation or cosmetic. Silicone gum can be easily blended if it is used as an emulsified composition prepared in advance through an emulsification step (including emulsion polymerization), and can be stably blended in the hair cosmetic composition of the present invention. When the blending amount of the silicone gum is less than the lower limit, there is a possibility that the specific touch and the gloss imparting effect on the hair are insufficient.

[Polyamide-modified silicone]
Polyamide-modified silicones that can be suitably blended in the external preparation or cosmetics of the present invention include, for example, Shirosan described in US Pat. No. 5,981,680 (Japanese Patent Laid-Open No. 2000-038450) and Japanese Translation of PCT International Publication No. 2001-512164. Examples of the base polyamide compound include 2-8178 Gelrant, 2-8179 Gelrant, etc. (manufactured by Dow Corning, USA). Such a polyamide-modified silicone also functions as a thickening / gelling agent for oily raw materials, particularly silicone oil.

When the polyamide-modified silicone is used in combination with the low odor sugar alcohol-modified silicone obtained according to the present invention, the external preparation or cosmetic of the present invention has good elongation and comfort when applied to the skin, hair, etc. The adhesiveness is further improved. In addition, it gives a glossy transparency and excellent gloss, and it is possible to adjust the viscosity and hardness (flexibility) of the entire cosmetic including oily raw materials as appropriate. There is an advantage in quality that a sticky feel) can be suppressed. Furthermore, the use of low-odor sugar alcohol-modified silicone improves the dispersion stability of fragrances, powders, and the like, so that, for example, there is a feature that a uniform and fine makeup feel lasts for a long time.

[Silicone wax]
Silicone waxes that can be suitably blended in the external preparation or cosmetic of the present invention are higher alkyl-modified silicones and alkyl-modified silicone resins. The higher alkyl-modified silicone is waxy at room temperature and is a useful component as a part of the base material of solid cosmetics (for example, oily solid skin cosmetics and solid hair cosmetics). Therefore, it can be suitably used in the external preparation or cosmetic of the present invention. Examples of such higher alkyl-modified silicone waxes include molecular long-chain trimethylsiloxy group-capped methyl long-chain alkyl polysiloxane, molecular chain both-end trimethylsiloxy group-capped dimethylpolysiloxane / methyl long-chain alkylsiloxane copolymer, molecule Examples include long-chain alkyl-modified dimethylpolysiloxane at both chain ends. Examples of these commercially available products include AMS-C30 Cosmetic Wax, 2503 Cosmetic Wax, etc. (manufactured by Dow Corning, USA).

The low odor sugar alcohol-modified silicone obtained by the present invention has good compatibility with higher alkyl-modified silicone waxes and excellent dispersion characteristics in the wax, so that an external preparation or cosmetic excellent in long-term storage stability can be obtained. Can do. Further, the moldability of external preparations or cosmetics, particularly solid cosmetics is also excellent. In particular, in a system containing powder, there is an effect of uniformly dispersing the powder uniformly in the base material containing the higher alkyl-modified silicone wax, and after molding, moderately relieving the hardness of the base material, It is possible to provide an external preparation or a cosmetic material that extends smoothly and uniformly.

In the external preparation or cosmetic of the present invention, the higher alkyl-modified silicone wax preferably has a melting point of 60 ° C. or higher from the viewpoint of cosmetic durability and high temperature stability.

The alkyl-modified silicone resin is a component that imparts sebum durability, moisture retention, and a fine texture to external preparations or cosmetics, and a wax-like one can be suitably used at room temperature. For example, a silsesquioxane resin wax described in JP-T-2007-532754 is preferred. Examples of these commercially available products include SW-8005 C30 RESIN WAX (made by Dow Corning, USA).

The low odor sugar alcohol-modified silicone obtained by the present invention is excellent in long-term storage stability because of its good compatibility with the alkyl-modified silicone resin wax as well as the higher alkyl-modified silicone wax, and excellent dispersion characteristics in the wax. An external preparation or cosmetic can be obtained. Furthermore, the oil phase containing such an alkyl-modified silicone resin wax can be stably emulsified, optionally together with other surfactants, providing a moist feel and moisturizing effect on the skin and hair, as well as water resistance and resistance. An effect of improving the longevity represented by sebum can also be imparted.

Moreover, when the external preparation or cosmetics which concern on this invention are antiperspirants, or according to the objective, an antiperspirant active ingredient and a deodorant agent can be mix | blended.

Antiperspirant active ingredients can be exemplified by astringent salts such as aluminum chlorohydrate or aluminum-zirconium tetrachlorohydrex glycine (ZAG), such as aluminum, hafnium, zinc and zirconium salts such as aluminum halide, aluminum hydroxyhalide, Zirconium halide, zirconium oxyhalide, zirconium hydroxyhalide, zirconium hydroxide hydroxide, zirconium zirconium chloride, zirconium lactate-aluminum, basic aluminum halide, such as Al ₂ (OH) ₅ Cl, aluminum bromide, buffered aluminum sulfate, alum, baked Alum and their various water, alcohol or glycine complexes (eg aluminum including aluminum, zirconium and glycine) -Zirconium chlorohydrate and glycine complex (ZAG complex)) can also be used. These antiperspirant active ingredients may be used alone or in combination of two or more. When the antiperspirant composition according to the present invention is a water-in-oil emulsion antiperspirant composition, these antiperspirant active ingredients are one of the water phase ingredients. On the other hand, soybean extracts and isoflavones are also known to have an antiperspirant effect. Since these are low in water solubility, they are preferably used by dissolving in an oil phase.

In the present invention, it is suitable for the personal care composition that the blended amount of the antiperspirant active ingredient is an amount sufficient to reduce sweating and the content thereof is suppressed to a small amount. sell. Specifically, it is preferable that the antiperspirant composition contains 5 to 25% by weight (mass) of antiperspirant active ingredient in terms of the antiperspirant effect and feel. In the case of a water-soluble antiperspirant active ingredient, for economic reasons, it is preferable to maximize the proportion of water in the composition while maintaining the antiperspirant effect, but the antiperspirant active ingredient is saturated with respect to the aqueous phase. It can also be added up to the amount.

In the external preparation or cosmetics of the present invention, particularly an antiperspirant composition, a deodorant agent can be blended together with the antiperspirant active ingredient or in place of the antiperspirant active ingredient. Deodorant agents can include deodorants, fragrances, and substances that prevent or remove odors from sweat. Such deodorant agents are antibacterial agents (bactericides or fungicides), bacteriostatic agents, odor adsorbents, deodorants, fragrances, etc., for the purpose of preventing body odor such as foul odor, sweat odor and foot odor. Blended. In addition, it goes without saying that these deodorant agents are useful in cosmetics and external preparations other than antiperspirants, and can be suitably blended in the external preparations or cosmetics of the present invention.

Antibacterial agents include, for example, alkyltrimethylammonium bromide, cetylpyridinium chloride, benzethonium chloride, benzalkonium chloride, chlorhexidine hydrochloride, chlorhexidine gluconate, diisobutylphenoxyethoxyethyldimethylbenzylammonium chloride, N-lauroyl sarcosine sodium, N-palmitoyl sarcosine Sodium, N-myristoylglycine, N-lauroylsarcosine potassium, trimethylammonium chloride, aluminum chlorohydroxy sodium lactate, triethyl citrate, tricetylmethylammonium chloride, 1,5-pentanediol, 1,6-hexanediol, 2,4 , 4′-trichloro-2′-hydroxydiphenyl ether (triclosan), , 4,4'-trichlorocarbanilide (triclocarban); diaminoalkylamides such as L-lysine hexadecylamide; heavy metal salts such as citric acid, salicylic acid, pyroctose, preferably zinc salts, and their acids, Heavy metal salts, preferably zinc pyrithione, zinc zinc sulfate, ethyl paraben, butyl paraben, hinokitiol, farnesol, phenoxyethanol, isopropylmethylphenol, propolis, lysozyme, lysozyme chloride, lysozyme and vitamin E or a derivative thereof, lysozyme and Examples include combinations of organic acids such as α-hydroxy acids.

As the bacteriostatic agent, for example, glyceryl monoalkyl ethers such as 1-heptyl glyceryl ether, 1- (2-ethylhexyl) glyceryl ether, 1-octyl glyceryl ether, 1-decyl glyceryl ether and 1-dodecyl glyceryl ether are used. I can do it.

The odor adsorbing substance can be used without particular limitation as long as it is a substance that adsorbs odor-causing substances and reduces odor, and these are part of the already described inorganic powders and organic polymers. Includes those that exhibit properties.

For example, zinc oxide, magnesium oxide, zeolite, metasilicate aluminate, silicic anhydride, colloidal silica, talc, mica, hydroxyapatite, cellulose, corn starch, silk, nylon powder, crosslinkable organopolysiloxane powder, organopolysiloxane Elastomer spherical powder or the like can be used as an odor adsorbing substance. Similarly, carbonates and hydrogen carbonates such as alkali metal carbonates and alkali metal hydrogen carbonates, ammonium salts, tetraalkylammonium salts and the like can be used, and sodium and potassium salts of these odor adsorbents are more preferable. Also, organic or inorganic porous particles (for example, silver ion-carrying zeolite, silver ion / zinc ion / ammonium ion-carrying zeolite) carrying metal ions such as silver, copper, zinc, and cerium, and silver cancrinite are included. An aggregate of acicular crystals can also be used. These can be suitably used as deodorant agents in that they act both as antibacterial agents and odor adsorbing substances.

Furthermore, hydroxyalkylated cyclodextrin, liquor extract and brown algae extract containing rice fermentation broth, keihi, clove, fennel, pepper, peppermint, yuzu, gentian, apricot, eucalyptus, clara, mulberry, aloe, sage, roman chamomile, Various extracts derived from animals, plants, microorganisms, and fungi such as urgon, gobishi, gardenia, hamamelis, and herbs can also be suitably used as deodorant agents. Some of these components overlap with the above-mentioned physiologically active components, but it is useful and preferable for cosmetic composition design to select these extracts for the purpose of acting as a deodorant agent. .

The odor adsorbing substance is preferably contained in the total composition in an amount of 0.001 to 60% by weight (mass)%, 0.01 to 30% by weight (mass)%, and more preferably 0.01 to 3% by weight (mass)%. More preferred. If the content of the odor adsorbing substance is within this range, it is useful in that the deodorizing performance can be improved without deteriorating the strength and feel of the preparation.

Suitable perfumes include any topical material that provides a composition that is known or otherwise effective in masking malodors associated with sweating or otherwise has the desired fragrance. These include any perfume or perfume chemicals, such as perfume precursors and deodorant fragrances, suitable for topical application to the skin, and may be perfume ingredients that are scented as needed.

[Antiperspirant composition]
As described above, the low-odor sugar alcohol-modified silicone according to the present invention is a widely used external preparation or cosmetic raw material, and can be widely used as a composition applied to the human body as a cosmetic or pharmaceutical. Is. Therefore, more specifically, the antiperspirant composition will be described as an example. The antiperspirant composition according to the present invention can be selected from any of water-in-oil emulsions (water-based preparations), stick-form preparations, and aerosol preparations such as sprays. As the blending component, the above cosmetic ingredients can be appropriately selected and used according to the type of preparation. In particular, the antiperspirant active ingredient blended in the water phase or oil phase is as described above, and it is preferable to blend the deodorant ingredient as desired.

[Water-in-oil emulsion antiperspirant composition]
In the anti-perspirant composition of the water-in-oil emulsion type which is one embodiment of the present invention, an oil phase component containing the low odor sugar alcohol-modified silicone of the present invention (low odor sugar alcohol-modified silicone, volatile oil agent) , Non-volatile oil agent, solubilizer, etc.) and the aqueous phase component are mixed by any method. At this time, in order to ensure transparency, the aqueous phase and the oil phase are mixed independently, and then the emulsification is performed by adjusting the difference in refractive index between the two phases at 25 ° C. to be 0.0020 unit or less. Therefore, it is preferable to improve the transparency and stability of the water-in-oil emulsion antiperspirant composition.

Furthermore, the emulsion composition containing the low odor sugar alcohol-modified silicone of the present invention is obtained by independently mixing an aqueous phase and an oil phase containing at least the low odor sugar alcohol-modified silicone and an oil agent. By adjusting the difference in refractive index at room temperature to 0.0020 unit or less and emulsifying, the transparency can be adjusted. More specifically, the method for adjusting transparency of an emulsion composition according to the present invention includes the following procedures (i) to (iv).
(I) (A) Oil phase components such as low odor sugar alcohol-modified silicone, volatile oil, non-volatile oil, solubilizer and the like are mixed by any method known in the art. Similarly, the aqueous phase component is also mixed in a separate container.
(Ii) The refractive index (RI) of each phase is measured separately at room temperature (25 ° C.).
(Iii) The refractive index of each phase is adjusted so that the difference in refractive index between these two phases is at least within 0.0020 units, thereby ensuring the optical transparency of the final mixture.
(Iv) These two phases are emulsified. The emulsification can be carried out by a desired emulsification means. In general, these two phases are gradually poured into the oil phase while stirring using a mechanical means such as a shear mixer. The phases are combined as an emulsion.

The method for adjusting the transparency of the emulsion according to the present invention can be suitably used particularly in the preparation of a water-in-oil emulsion composition, and the obtained emulsion composition is subjected to high shear conditions with a homogenizer or other suitable apparatus. Processing below can further improve its transparency and stability. In the above procedure (iii), when a translucent to highly transparent emulsion is prepared, the difference in refractive index between these two phases is within the refractive index (RI) unit of at least about 0.0020. It is preferably within a unit of about 0.00010, and most preferably there is no difference in refractive index between the two.

On the other hand, when it is necessary to prepare a white emulsion, in applications where the transparency of the emulsion is not particularly required, an opaque emulsion composition can be obtained by performing an emulsification treatment without adjusting the refractive index of each phase. .

The adjustment of the refractive index can be easily performed by diluting the aqueous phase with an additional amount of water. Furthermore, the emulsion composition containing the low-odor sugar alcohol-modified silicone of the present invention has its water content. A refractive index (RI) adjuster may be blended in the phase or oil phase to adjust the difference in refractive index between the oil phase and the water phase, thereby ensuring optical transparency of the emulsion composition. That is, when the difference in refractive index between the two phases is 0 or very small, the emulsion composition as a whole becomes transparent or translucent.

The type and amount of the refractive index adjusting agent vary depending on the refractive index of the water phase and the oil phase, and are generally present in an amount sufficient to adjust the refractive index of the water phase and the oil phase so as to obtain optical transparency. .

The refractive index adjusting agent can be used without particular limitation as long as it is a compound having an action of increasing the refractive index value of the aqueous phase of the composition or a component that decreases the refractive index value of the oil phase of the composition. . The addition of the refractive index adjusting agent may be performed at any of the steps (i) to (iv) described above, but practically, each phase is adjusted using the refractive index adjusting agent in the procedure (iii). It is preferable to adjust the refractive index.

Components used as a refractive index adjuster for the aqueous phase include lower monohydric alcohols, polyhydric alcohols and derivatives thereof, sugar alcohols and derivatives thereof, polyoxyalkylene group-containing alcohols, polyoxyalkylene group-containing ethers, silicones -Silicone surfactants such as polyether copolymers (excluding the low-odor sugar alcohol-modified silicone of the present invention), water-soluble polymers, any water-soluble polar substance, water-soluble inorganic salt, organic Examples thereof include acid salts and amino acids. One or more of these water phase refractive index modifiers may be used in combination.

More specifically, the refractive index adjusting agent for the aqueous phase is propylene glycol, dipropylene glycol, glycerin, sorbitol, mannitol, xylitol, pentaerythritol, trimethylolpropane, hexylene glycol, octylene glycol, 1,2-butane. Diol, 1,2-pentanediol, 4-methyl-1,2-pentanediol, 2-methyl-1,2-pentanediol, 3,3-methyl-1,2-butanediol, 4-methyl-1, 2-hexanediol, 1,2-heptanediol, 3-phenyl-1,2-propanediol, glycerol isopropyl ether, glycerol propyl ether, glycerol ethyl ether, glycerol methyl ether, glycerol butyl ether, glycerol isopen Ether, diglycerol isopropyl ether, diglycerol isobutyl ether, triglycerol isopropyl ether, alkylxylitol ether, alkyl sorbitol ether, 1,2,6-hexanetriol, 1,2-hexanediol, 1,2,4-butane Triol, 1,2-butylene glycol, 1,3-butylene glycol, diglycerin, triglycerin, tetraglycerin, polyglycerin, polyethylene glycol, glycerin monoalkyl ether (eg, xyl alcohol, ceralkyl alcohol, batyl alcohol, etc.) Sugar alcohols (eg, maltitol, maltotriose, sucrose, erythritol, glucose, fructose, amylolytic sugar, maltose, xylitol, Pung-degraded sugar-reducing alcohol, etc.); Glysolid; Tetrahydrofurfuryl alcohol; POE-tetrahydrofurfuryl alcohol; POP-butyl ether; Phosphoric acid; POP / POE-pentaneerythritol ether, silicone-polyether copolymer, silicone- (poly) glycerin copolymer, sugar-modified silicone, or any water-soluble polar material, water-soluble such as sodium chloride Inorganic salts, organic acid salts, amino acids and the like can also be used.

The components used as the refractive index adjusting agent for the oil phase are selected from those exemplified above as “oil agents”, oils and fats usually used in cosmetics, higher alcohols, higher fatty acids, organic lipophilic surfactants, etc. The thing can be illustrated. However, since it is used for adjusting the refractive index of the oil phase, the oil agent is different from the oil agent used as the base oil of the oil phase of the emulsion. One or more of these water phase refractive index modifiers may be used in combination. Further, for the purpose of adjusting the refractive index of the oil phase, a mixture of two kinds of base oils may be used.

Specific examples of the oil phase refractive index modifier include silicone oils, ester oils such as lauryl myristate, diisopropyl sebacate, diisopropyl adipate, and C8-C18 alkyl benzoates, mineral oil, polydecene, hydrogenated polyisobutene, and the like. Long chain alcohols such as hydrocarbon oil, oleyl alcohol, batyl alcohol, lanolin alcohol, cholesterol, phytosterol, octyldodecanol, PPG-3 myristyl ether, PPG-14 butyl ether, POE (20) glyceryl triisostearate or other mixtures Illustrated.

By blending the low odor sugar alcohol-modified silicone of the present invention into a water-in-oil emulsion antiperspirant composition, it can provide a smooth and smooth and natural coating feeling without any discomfort. The low-odor sugar alcohol-modified silicone of the present invention can also act as an emulsifier for stably emulsifying and dispersing an aqueous phase containing an antiperspirant active ingredient in oil. The amount used is 0.1 to 10 parts, preferably 0.5 to 5 parts, based on 100 parts by weight (mass) of the entire composition. Furthermore, in the antiperspirant of the present invention, there is an advantage that a water-in-oil emulsion type transparent antiperspirant composition having excellent transparency can be obtained by using the above-described method for adjusting the transparency of the emulsion. In addition, the low odor sugar alcohol-modified silicone of the present invention is essentially odorless compared to conventional polyether-modified silicone low bromide-treated products, so that an acidic antiperspirant active component and water coexist. It is stable even in the formulation of a water-in-oil emulsion type antiperspirant composition, and has an excellent feature that it is difficult to generate off-flavors over time.

The amount of volatile oil used as the base oil of the water-in-oil emulsion antiperspirant composition is 5 to 40 parts, preferably 10 to 30 parts when the entire composition is 100 parts by weight (mass). More preferably, it is 15 to 20 parts. As the volatile oil, oils whose vapor pressure is measured at 25 ° C. among those exemplified as the “oil agent” component in the present invention can be used. That is, the volatile oil has a vapor pressure at 25 ° C. of 0.01 to 8 hPa, preferably 0.02 to 2.0 hPa, and a boiling point at 1 atm of less than 250 ° C.

In the water-in-oil emulsion antiperspirant composition, the types and amounts of the antiperspirant active component and the deodorant component are as described above, and can be appropriately adjusted as desired.

As the non-volatile oil agent, among those exemplified as the “oil agent” in the present invention, those not corresponding to the above “volatile oil”, silicone surfactants (however, excluding the low odor sugar alcohol-modified silicone of the present invention) And ether oils such as dioctyl ether, carbonate ester oils such as dioctyl carbonate and dioctadecyl carbonate, ester oils such as neopentyl glycol dicaprate, polyalkylene glycol and derivatives thereof. These have emollient effects and effects of adjusting the feel and form of the water-in-oil emulsion antiperspirant composition. The amount of the non-volatile oil used is 1 to 10 parts by weight (mass), preferably 2 to 8 parts by weight (mass) as described above.

In the water-in-oil emulsion type transparent antiperspirant composition according to the present invention, a solubilizer can also be used. These solubilizers are those exemplified as the “oil agent” in the present invention, oils and fats usually used in cosmetics, higher alcohols, higher fatty acids, organic lipophilic surfactants, etc. The oil agent used as the base oil, the oil agent used as the refractive index adjusting agent, or an oil agent different from the non-volatile oil is selected. However, there are cases where the refractive index adjusting agent, base oil, and non-volatile oil serve as a solubilizer. The amount of solubilizer used is about 0.1 to about 20 parts by weight (mass) of the total composition, preferably 1.0 to 10.0 parts by weight (mass).

Another component that may be present in the water-in-oil emulsion antiperspirant composition of the present invention may be a powder or a colorant. Specific examples include those exemplified above as “powder or colorant”. In addition, crosslinkable organopolysiloxanes, organopolysiloxane elastomer spherical powders, silicone resins, acrylic silicone dendrimer copolymers, silicone raw rubber, polyamide-modified silicones, alkyl-modified silicone waxes, alkyl-modified silicone resin waxes, and the like are also water-in-oil according to the present invention. It may preferably be present in an emulsion type antiperspirant composition. The proportion of these components is generally 0 to 8 parts by weight (mass) when the total composition is 100 parts by weight (mass), but is not limited.

A surfactant may also be added to the water-in-oil emulsion antiperspirant composition according to the present invention. Specifically, any hydrophilic emulsifier represented by what was previously exemplified as “surfactant” and having an HLB of more than 8 is included. The blending amount is generally 0 to 2 parts by weight (mass) based on 100 parts by weight (mass) of the total composition. However, it will be appreciated by those skilled in the art that this ratio is adjusted based on the required HLB of the system. Examples of hydrophilic nonionic surfactants preferred as surfactants include POE-sorbitan fatty acid esters; POE sorbit fatty acid esters; POE-glycerin fatty acid esters; POE-fatty acid esters; POE-alkyl ethers; Types: POE / POP-alkyl ethers; Tetra POE / Tetra POP-ethylenediamine condensates; POE-castor oil hardened castor oil derivatives; POE-honey beeswax / lanolin derivatives; alkanolamides; Alkylamines; POE-fatty acid amides; sucrose fatty acid esters; alkylethoxydimethylamine oxides; trioleyl phosphates and the like.

In addition to the above components, the external preparation of the present invention (as an example of an antiperspirant composition) includes a thickener, an oil-soluble gelling agent, an organically modified clay mineral, a physiologically active component, a skin beautifying component, and pH adjustment. Various components such as an agent, an antioxidant, a solvent, a chelating agent, a moisturizing component, and a drug can be used as long as the object of the present invention is not impaired.

The antiperspirant composition according to the present invention is used by applying an amount sufficient to suppress sweat and / or wrinkles or odors to the armpits and other parts. About 0.1 to 10 g is preferably applied to the target site on the skin, more preferably 0.1 to 5 g, and even more preferably 0.1 to 1 g.

[Non-water stick antiperspirant composition]
Next, the stick-like antiperspirant composition which is one embodiment of the present invention will be described. The stick-like antiperspirant composition is one form of a solid antiperspirant composition, and may be a form containing water, such as a solid W / O emulsion, or an external preparation composition substantially free of water. It can also be. Here, a system that does not substantially contain water will be described as an example. The non-aqueous stick-like antiperspirant composition is excellent in stability and advantageous when it is desired to obtain a dry feeling.

In the non-aqueous stick-like antiperspirant composition according to one embodiment of the present invention, the oil phase components such as the low odor sugar alcohol-modified silicone, volatile oil, higher alcohol, wax, and nonvolatile oil of the present invention are used. The mixture is mixed and heated and stirred at a temperature at which solid components such as higher alcohol and wax melt (for example, about 80 ° C.) to form a single liquid phase. While maintaining the temperature slightly higher than the freezing point of the system (for example, about 65 ° C.), the remaining components other than the antiperspirant active component are added while stirring, and the active component is further added. After stirring well, it can be produced by pouring into a container and solidifying at room temperature. In addition, stirring operation can be performed by stirring means using well-known mechanical force, such as a mixer.

By blending the low odor sugar alcohol-modified silicone of the present invention into a non-aqueous stick-like antiperspirant composition, it can provide a smooth smoothness, an appropriate moisturizing feeling, and a natural feeling without any discomfort. Therefore, when a dry feeling is too strong, it can be relieved and a natural feeling of use can be brought about. In addition, the low odor sugar alcohol-modified silicone of the present invention effectively adsorbs to the surface of the powder or solid fine particles to suppress particle aggregation, and stably and uniformly disperse the powder or solid fine particles in the oil. Have As a result, the non-aqueous stick-like antiperspirant composition containing the low-odor sugar alcohol-modified silicone of the present invention has the advantage that there is little white residue after application and drying. Furthermore, since the low odor sugar alcohol-modified silicone of the present invention has good compatibility with solid oils such as higher alcohols and waxes, the stick hardness can be controlled, and after coating and drying, white deposits derived from solid oils can be controlled. Has the effect of mitigating the occurrence. In addition, the low odor sugar alcohol-modified silicone of the present invention is essentially non-odorous compared to conventional polyether-modified silicone low bromide-treated products, etc. The stick-like antiperspirant composition formulation is also excellent in stability and has the advantage that there is almost no off-flavor generation over time. The amount to be used is 0.1 to 10 parts by weight (mass), preferably 0.5 to 5 parts by weight (mass) when the entire composition is 100 parts by weight (mass).

In the non-aqueous stick-type antiperspirant composition according to the present invention, one or more volatile oils can be used, and the total composition is 5 to 70 wt. %) Is preferable because a good feel can be obtained.

In the non-aqueous stick-type antiperspirant composition according to the present invention, as the antiperspirant active component, the components exemplified above can be used without particular limitation. However, since it is non-aqueous, a water-soluble salt or the like is preferably used as it is as a solid and is dispersed as fine particles in the composition. The average particle size of the fine particles of the antiperspirant active ingredient is preferably about 0.1 to 100 μm, more preferably 0.1 to 20 μm, and even more preferably 0.1 to 10 μm. On the other hand, for example, by using a combination of relatively small particles having an average particle diameter in the range of 0.5 to 8 μm and relatively large particles having an average particle diameter in the range of 12 to 50 μm, It is also possible to improve touch characteristics such as a slip feeling when the agent composition is applied.

In the non-aqueous stick-like antiperspirant composition, one or more antiperspirant active ingredients can be used, and the total composition preferably contains 10 to 70% by weight (mass)%, preferably 15 to 50% by weight ( (Mass)%, and more preferably 15 to 25% by weight (mass)% is more preferable because the effect of suppressing sweat and odor can be sufficiently obtained and the feel is good. Moreover, the same deodorant agent as described above can be blended together with / or in place of the antiperspirant active ingredient, and the type, amount used, etc. are as described above.

The higher alcohols that can be used in the non-aqueous stick-like antiperspirant composition according to the present invention are those having 12 to 50 carbon atoms, preferably 16 to 30 carbon atoms, and more preferably 18 to 24 carbon atoms. If it is in this range, a good feel can be obtained. Specific examples include cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol and the like. One or more types of higher alcohols can be used, and the total composition contains 1 to 50% by weight, preferably 5 to 35% by weight, more preferably 10 to 25% by weight. The If it is in this range, it is possible to obtain a good feel as well as moderate shaping.

The non-volatile oil agent that can be used in the non-aqueous stick-like antiperspirant composition according to the present invention includes those that are not included in the above “volatile oil” among those exemplified as the “oil agent” in the present invention, and various silicone oils. , Hydrocarbon oils such as mineral oil, polydecene, hydrogenated polyisobutene, silicone surfactants (excluding the low-odor sugar alcohol-modified silicone of the present invention), ether oils such as dioctyl ether, dioctyl carbonate, dioctadecyl carbonate, etc. Carbonate oil, isopropyl palmitate, isopropyl myristate, lauryl myristate, diisopropyl sebacate, diisopropyl adipate, C8-C18 alkyl benzoates, etc., poly (eg PPG-3 myristyl ether, PPG-14 butyl ether) Alkylene Call and derivatives thereof, isostearyl alcohol or oleyl alcohol, 2-ethylhexyl alcohol, lipophilic surfactant and an organic solvent and the like. In addition to the emollient effect, these have an effect of adjusting the feel and form, and may function as a compatibilizer for the oil phase. One or more kinds of these non-volatile oils can be used, and are contained in the total composition in an amount of 1 to 30% by weight, preferably 5 to 15% by weight.

The non-aqueous stick-like antiperspirant composition according to the present invention can further contain a wax and is preferable because the high-temperature stability is improved. Examples of the wax include those described above as “oil agents”, oils and fats, higher fatty acids and the like that are solid at room temperature. Further, among the aforementioned crosslinkable organopolysiloxane, organopolysiloxane elastomer spherical powder, silicone resin, acrylic silicone dendrimer copolymer, silicone raw rubber, polyamide-modified silicone, alkyl-modified silicone wax, and alkyl-modified silicone resin wax, they are solid at room temperature. Some are illustrated.
Preferably, hydrogenated castor oil, fatty acid, waxy modified silicone, glycerol monostearate, 2-8178 Gelrant, 2-8179 Gelrant, etc. (manufactured by Dow Corning, USA), AMS-C30 Cosmetic Wax, 2503 Cosmetic Wax, etc. US Dow Corning Co., Ltd.), alkyl-modified silicone resin wax, etc. can be exemplified, and the resulting stick-like antiperspirant composition is imparted with appropriate hardness and stability.

One or more kinds of the above-mentioned waxes can be used, and 1 to 10% by weight (mass)%, and further 2 to 8% by weight (mass)% in the total composition has excellent stability and good touch. Is preferable.

Furthermore, in the non-aqueous stick-like antiperspirant composition according to the present invention, the total weight (mass) “X” of the oil phase components excluding volatile oil and solid oil, and the antiperspirant active ingredient and the deodorant The ratio of the total weight (mass) “Y” is X / Y = 1/7 to 5/6, and further 1/6 to 2/3, while maintaining high feel and antiperspirant deodorant ability. This is preferable because white residue can be suppressed.

Other components that may be present in the non-aqueous stick-like antiperspirant composition according to the present invention include those exemplified above as “powder or colorant”, the aforementioned crosslinkable organopolysiloxane, organopoly Siloxane elastomer spherical powder, silicone resin, acrylic silicone dendrimer copolymer, silicone raw rubber, polyamide-modified silicone, alkyl-modified silicone wax, alkyl-modified silicone resin wax, and the proportion of these components is usually about 0 based on the total amount of the composition Parts to about 8 parts, but not limited. In addition to the above components, thickeners, oil-soluble gelling agents, organically modified clay minerals, bioactive ingredients, skin-beautifying ingredients, pH adjusters, antioxidants, solvents, chelating agents, moisturizing ingredients, chemicals Etc. can be used as long as the object of the present invention is not impaired.

The antiperspirant composition according to the present invention is used by applying an amount sufficient to suppress sweat and / or wrinkles or odors to the armpits and other parts. About 0.1 to 10 g is preferably applied to the target site on the skin, more preferably 0.1 to 5 g, and even more preferably 0.1 to 1 g. The stick composition of the present invention is preferably applied once or twice a day in order to effectively suppress sweat and / or wrinkles or odors.

[Aerosol antiperspirant composition]
Next, an aerosol antiperspirant composition which is one of the external preparations containing the low odor sugar alcohol-modified silicone according to the present invention and is one embodiment of the present invention will be described. The aerosol antiperspirant composition may be in a form containing water, or may be a preparation for external use which does not substantially contain water. Non-aqueous aerosol antiperspirant composition is advantageous for obtaining a dry and smooth use feeling, while water-containing aerosol antiperspirant composition is effective in antiperspirant action and provides a refreshing feeling. There is an advantage that it is easy.

The aerosol antiperspirant composition according to the present invention includes a propellant, powder components dispersed therein (antiperspirant active ingredients, deodorant agents, usability improving ingredients, etc.), and low odor properties according to the present invention. Sugar alcohol-modified silicone, liquid oil, and the like can be blended.

In the aerosol antiperspirant composition according to the present invention, the antiperspirant active component may be a powder or a solution. In the case of a powder, it is preferably dispersed as fine particles in the composition. The average particle size of the fine particles is preferably about 0.1 to 100 μm, more preferably 0.1 to 20 μm, and even more preferably 0.1 to 10 μm. In the case of a solution form, an aqueous solution can also be used. However, in order to further improve the storage stability of the composition, the AP active component is propylene glycol, polyethylene glycol, alkyl glycerol ether, alkyl etherified saccharide, alkyl etherified sugar alcohol, etc. It is more preferable to use a material complexed or dissolved with the polyols. Examples of the antiperspirant active component that can be used in the aerosol antiperspirant composition according to the present invention include the same components as described above.

One or more antiperspirant active ingredients can be used, preferably 0.001 to 20.0% by weight (mass)%, more preferably 0.1 to 10% of the total weight (mass) of the aerosol antiperspirant composition. 0.0% by weight (mass).

In the aerosol antiperspirant composition according to the present invention, the deodorant agent that can be blended together with or in place of the antiperspirant active ingredient includes an antibacterial agent (bactericide or antifungal agent), bacteriostatic agent, odor adsorbing substance, deodorant Agents, fragrances and the like. Specific examples of these components are as described above, and the preferable blending amount is 0.01 to 10.0% by weight (mass) in the total weight (mass) of the aerosol antiperspirant composition, and more preferably 0.1 to 3.%. 0% by weight (mass).

The low odor sugar alcohol-modified silicone of the present invention is incorporated into an aerosol antiperspirant composition, thereby effectively adsorbing on the surface of the powder or solid fine particles, thereby suppressing particle aggregation, and the powder or solid It has the effect of dispersing fine particles stably and uniformly in the system. As a result, the aerosol antiperspirant composition formulated with the low odor sugar alcohol-modified silicone of the present invention reduces aerosol valve clogging, and the whiteness after use is inconspicuous, and also has uniform adhesion to the skin. Expected to have improved benefits. In addition, the AP active ingredient and the deodorant may sense dryness or tension on the skin after use, which may cause dry skin or reduced skin elasticity and unnatural skin sensation. These disadvantages are expected to be alleviated by using odorous sugar alcohol-modified silicone. Further, since the low odor sugar alcohol-modified silicone of the present invention is essentially odorless compared to conventional polyether-modified silicone low bromide-treated products, etc., an aerosol antiperspirant composition containing an acidic antiperspirant active ingredient It is also stable in product formulations and has the advantage that there is almost no change over time in the scent of the aerosol antiperspirant composition. The amount used is about 0.1 to about 10 parts by weight (mass), preferably about 0.5 to about 5 parts by weight (mass).

The particle diameter of the powder is preferably 1 to 20 μm, and more preferably 5 to 15 μm, in order to give a smooth feel to the skin. When the particle diameter is larger than 20 μm, roughness is felt, and when the particle diameter is 1 μm or less, a problem of particle scattering may occur.

Examples of the propellant used in the present invention include gaseous solvents such as propane, n-butane, isobutane, isopentane, pentane, dimethyl ether, liquefied petroleum gas (LPG), and liquefied natural gas. In particular, LPG, dimethyl ether, and isopentane are preferable. These may be used alone or in combination of two or more. Alternative chlorofluorocarbons and chlorofluorocarbons such as 1,1-difluoroethane can also be blended, but are not preferable due to environmental problems. Carbon dioxide and nitrogen gas can also be used from the environmental and safety aspects. The filling amount of the propellant is not particularly limited and is appropriately determined according to a conventional method.

Typical powder components other than the AP active component and the deodorant agent to be blended in the aerosol antiperspirant composition according to the present invention include usability improving components. The usability improving component has an action of imparting a smooth feeling to the skin, and is an inorganic powder such as silica gel, talc, bentonite, kaolinite, true spherical silica, smectite, or a material subjected to surface treatment on these, Composites such as polyethylene powder, nylon powder, polystyrene powder, crosslinkable organopolysiloxane powder, organopolysiloxane elastomer spherical powder, silicone resin powder and other organic powders, and inorganic powders containing metal oxides Examples thereof include powders. That is, the usability improving component here is the one exemplified above as “powder or colorant”, the aforementioned crosslinkable organopolysiloxane, organopolysiloxane elastomer spherical powder, silicone resin, acrylic silicone dendrimer copolymer, silicone raw rubber Polyamide-modified silicone, alkyl-modified silicone wax, and alkyl-modified silicone resin wax. These usability improving components may be used in combination of one or more.

Examples of the liquid oil agent blended in the aerosol antiperspirant composition according to the present invention include those that are liquid at room temperature among those exemplified above as the “oil agent” in the invention. The liquid oil agent has the effect of uniformly adhering the powder onto the skin and improving the feeling of use, and can be used alone or in combination of two or more. From the viewpoint of not only feel but also emollient effect and formulation flexibility, the liquid oil agent preferably contains silicone oil. The silicone oil preferably has a viscosity range of 100,000 cst (25 ° C.) or less, more preferably 100 cst (25 ° C.) or less, in order to obtain a smooth feel without stickiness. The blending amount of the liquid oil is preferably 0.1 to 50% by weight (mass)%, more preferably 0.5 to 25% by weight (mass)% in the total amount of the aerosol antiperspirant composition. When the blending amount is less than 0.1% by weight (mass)%, the oily feel is not smooth, and the skin fit does not improve. It may also adversely affect the stability of the formulation.

In addition, when mix | blending a liquid oil agent in the aerosol antiperspirant composition which concerns on this invention, what made the form of the O / W emulsion by emulsifying a liquid oil agent previously can also be mix | blended. This is effective when it is difficult to stably and uniformly disperse in an aerosol antiperspirant composition as it is because the viscosity of the liquid oil is high. At this time, it is desirable to use an O / W emulsion formulation having resistance to alcohols described later, and it is preferable to use a phosphate surfactant or a nonionic surfactant having an oleyl group as the surfactant. It is effective in obtaining an O / W emulsion having good blending stability. Also, an O / W emulsion having good blending stability can be obtained by using a phosphoric acid surfactant and a general nonionic surfactant in combination.

In the aerosol antiperspirant composition according to the present invention, water, ethanol, IPA, polyhydric alcohol, surface activity is further used for the purpose of more effectively expressing the antiperspirant action by dissolving the antiperspirant active component in the system. You may mix | blend an agent etc. However, some monohydric alcohols such as ethanol and IPA, and some polyhydric alcohols such as propylene glycol and 1,3-butylene glycol are inflamed or inflamed in the sensitive axillary part of the skin during and after application when the compounding amount is large. Tend to cause irritation. Therefore, the amount of the lower monohydric alcohol is desirably 50% by weight or less based on the total amount of the aerosol antiperspirant composition. In addition, it is desirable that the amount of polyhydric alcohol that tends to cause irritation or the like in sensitive parts of the skin be 20% by weight or less of the total amount of the aerosol antiperspirant composition. Preferred polyhydric alcohols are the components exemplified above as the “aqueous phase refractive index modifier”. Regarding water, the weight (mass) ratio (antiperspirant active ingredient / water) with the antiperspirant active ingredient is preferably in the range of 1 / 0.5 to 1/2. Within this range, it can be expected that the antiperspirant action is further improved and the onset thereof is accelerated without causing a sticky feeling.

The incorporation of the surfactant is effective for improving the stability of the aerosol antiperspirant composition containing water. That is, a non-aqueous aerosol antiperspirant composition is prepared by first mixing a component excluding a propellant and powder to prepare a stock solution, and uniformly dispersing the powder in this stock solution and then filling the propellant. Since it is usually manufactured, stability problems are unlikely to occur. On the other hand, when an aerosol antiperspirant composition containing water is produced by the same method, the stability of the system decreases when a propellant such as liquefied petroleum gas (LPG) is mixed, and components such as an antiperspirant component Has a problem that it is likely to precipitate as starch. For this reason, the types and amounts of liquid oils that can be blended are limited, and countermeasures such as lowering the concentration of the antiperspirant active ingredient and increasing the amount of alcohol used are necessary, and the degree of freedom of formulation is low. However, these problems can be alleviated by blending an appropriate surfactant.

Suitable surfactants include one or more nonionic or weakly acidic surfactants from the viewpoint of the antiperspirant active component being acidic and the effect of stabilizing the dispersion of the aerosol antiperspirant composition system. Agents are preferred. Among these, polyoxyethylene polyoxypropylene cetyl ether phosphoric acid and polyoxyethylene oleyl ether phosphoric acid are preferable.

The amount of the surfactant blended is preferably from 0.1 to 25% by weight (mass)%, more preferably from 0.1 to 10% by weight (mass)%, based on the total amount of the aerosol antiperspirant composition. When the blending amount is less than 0.1% by weight (mass)%, the effect of improving the stability of the preparation is poor.

Other components that may be present in the aerosol antiperspirant composition according to the present invention include inorganic salts or organic acid salts, silicone surfactants (except the low-odor sugar alcohol-modified silicone of the present invention), Crosslinkable organopolysiloxane, organopolysiloxane elastomer spherical powder, silicone resin, acrylic silicone dendrimer copolymer, silicone raw rubber, polyamide-modified silicone, alkyl-modified silicone wax, alkyl-modified silicone resin wax, and interfaces other than silicone surfactants It is an activator, and specific component names are as described above. The proportion of these components is usually from about 0 to about 8 parts based on the total amount of the composition, but is not limited. In addition to the above components, thickeners, oil-soluble gelling agents, organically modified clay minerals, bioactive ingredients, skin-beautifying ingredients, pH adjusters, antioxidants, solvents, chelating agents, moisturizing ingredients, chemicals Etc. can be used as long as the object of the present invention is not impaired.

The aerosol antiperspirant composition according to the present invention can be sprayed using an ordinary aerosol container or an aerosol container having a resin-coated inner surface for the purpose of rust prevention or the like. It is also possible to spray using a double container using an inner bag.

The antiperspirant composition according to the present invention is used by spraying it on the armpits or other sites and applying an amount sufficient to suppress sweat and / or wrinkles or odors. About 0.1 to 5 g is preferably applied to the target site on the skin, more preferably 0.1 to 3 g, and even more preferably 0.1 to 1 g. The aerosol antiperspirant composition according to the present invention is preferably applied by spraying once or twice a day in order to effectively suppress sweat and / or wrinkles or odor.

The sugar alcohol-modified silicone produced by the method for producing a sugar alcohol-modified silicone of the present invention has a reduced odor and can be suitably used as an external preparation or a raw material for cosmetics.

In addition, since the carbonyl value measuring method of the present invention can accurately and easily determine the carbonyl compound, an external preparation or cosmetic raw material containing a sugar alcohol-modified silicone obtained by the production method of the present invention, It can be suitably used for odor evaluation of products for external use and cosmetics.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto. In the following composition formula, Me ₃ SiO group (or Me ₃ Si group) is “M”, Me ₂ SiO group is “D”, and Me ₂ HSiO group (or Me ₂ HSi group) is “M ^H ”. , The MeHSiO group is expressed as “D ^H ”, and the unit in which the methyl group (Me) in M and D is modified with any substituent is expressed as “M ^R ” and “D ^R ”.

[Example 1]
In the reactor, 131.5 g of methyl hydrogen polysiloxane represented by an average composition formula: MD ₃₁ ^DH ₁₅ M and vinyltristrimethyl represented by an average composition formula: CH ₂ ═CH—Si (OSiMe ₃ ) ₃ While charging 37.9 g of siloxysilane and stirring at room temperature under nitrogen flow, an isopropyl alcohol solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt concentration 0.45 wt%) ) 0.31 g was added. Thereafter, the reactor was heated in an oil bath at 60 ° C., and after 30 minutes, the temperature of the reaction solution in the reactor rose to 72 ° C. Here, 1 g of the reaction solution was sampled, and the reaction rate was targeted by the alkali decomposition gas generation method (the remaining Si—H groups were decomposed with KOH ethanol / water solution and the reaction rate was calculated from the volume of the generated hydrogen gas). Confirmed that it has reached. After allowing the reactor to cool, 33.0 g of 1-dodecene was added to the reaction solution at 32 ° C., immediately generating heat and rising to 64 ° C. after 10 minutes. When the temperature was kept in a 70 ° C. oil bath and confirmed by the same method after another 50 minutes, the reaction rate reached the target. Next, 8.3 g of xylitol monoallyl ether, 175 g of isopropyl alcohol (IPA), and 0.025 g of vitamin E were charged, and 0.31 g of the platinum catalyst was added. After confirming that the reaction rate reached the target after 1 hour, 46.7 g of 1-dodecene and 0.31 g of the platinum catalyst were added. When the reaction solution was collected and confirmed after 3 hours, the hydrosilylation reaction was completed and the sugar alcohol modification represented by the average composition formula: MD ₃₁ D ^{R * 1} ₃ D ^{R * 21} ₁₁ D ^{R * 3} ₁ M It was found that silicone was formed. Here, R ^{* 1} , R ^{* 21} and R ^{* 3} are as follows.
R ^{* 1} = -C ₂ H ₄ Si (OSiMe ₃ ) ₃
R ^{* 21} = -C ₁₂ H ₂₅
R ^{* 3} = xylitol residue

Next, after distilling off the low boiling point under reduced pressure, an aqueous solution consisting of 0.013 g of sodium hydrogen sulfate / 4.5 g of ion-exchanged water was added, followed by treatment at 60-70 ° C. for 30 minutes, and further up to 20 Torr. The odor component and water generated under reduced pressure were distilled off. Thereafter, 4.5 g of ion-exchanged water was added again, and the operation of reducing the pressure in the same manner and distilling off the odorous component and water was repeated twice (in the final pressure-reducing operation, 1 to 60-60 ° C. and 20 Torr). Time maintaining), average composition formula: MD ₃₁ D ^{R * 1} ₃ D ^{R * 21} ₁₁ D ^{R * 3} ₁ M Obtained as a liquid. Here, R ^{* 1} , R ^{* 21} and R ^{* 3} are as described above. In this composition, generation of off-flavor was not observed even after 1 week from the production.

Incidentally, the xylitol monoallyl ether, the structural _{_{formula: CH 2 = CH-CH 2}} -OCH 2 [CH (OH)] 3 CH 2 OH, and the structural _{_{formula: CH 2 = CH-CH 2}} -OCH {CH ( OH) CH ₂ OH} ₂ is a raw material containing xylitol monoallyl ether represented by a mass ratio of about 9: 1. In Example 1, —C ₃ H ₆ — OCH ₂ [CH (OH)] ₃ CH ₂ OH or —C ₃ H ₆ —OCH {CH (OH) CH ₂ OH} ₂ was introduced as a xylitol residue at a similar mass ratio.

[Comparative Example 1]
In the reactor, 128.0 g of methyl hydrogen polysiloxane represented by an average composition formula: MD ₃₁ ^DH ₁₅ M and vinyl tristrimethyl represented by an average composition formula: CH ₂ ═CH—Si (OSiMe ₃ ) ₃ While charging 36.8 g of siloxysilane and stirring at room temperature under nitrogen flow, an isopropyl alcohol solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt concentration 0.45 wt%) ) 0.31 g was added. Thereafter, the reactor was heated in an oil bath at 65 ° C., and the temperature of the reaction solution in the reactor rose to 84 ° C. after 25 minutes. After 45 minutes, when the liquid temperature dropped to 70 ° C., 1 g of the reaction liquid was sampled, and it was confirmed that the reaction rate reached the target by the alkali decomposition gas generation method. Thereafter, 32.0 g of 1-dodecene was added to the reaction solution at 40 ° C., and heat was immediately generated. After 2 minutes, the temperature rose to 73 ° C. When the temperature was kept in a 70 ° C. oil bath and confirmed by the same method after another 30 minutes, the reaction rate reached the target. Subsequently, 14.9 g of polyglycerol monoallyl ether, 175 g of isopropyl alcohol (IPA), and 0.03 g of vitamin E were charged, and 0.31 g of the platinum catalyst was added. After confirming that the reaction rate reached the target after 1 hour, 45.5 g of 1-dodecene and 0.31 g of the platinum catalyst were added. After 4.5 hours, the reaction solution was collected and confirmed, and a slight generation of hydrogen gas was observed. By calculating the reaction rate, a polyglycerin-modified silicone represented by an average composition formula: MD ₃₁ DR ^{* 1} ₃ _DR ^{* 21} _{10.9 DR} ^{* 41} ₁ ^DH _0.1 M is generated. I understood. Here, R ^{* 1} , R ^{* 21} and R ^{* 41} are as follows.
R ^{* 1} = -C ₂ H ₄ Si (OSiMe ₃ ) ₃
R ^{* 21} = -C ₁₂ H ₂₅
R ^{* 41} = -C ₃ H ₆ OX (X is a polyglycerin moiety)

Next, after distilling off the low boiling point under reduced pressure, an aqueous solution consisting of 0.013 g of sodium hydrogen sulfate / 4.5 g of ion-exchanged water was added, followed by treatment at 60-70 ° C. for 30 minutes, and further up to 10 Torr. The odor component and water generated under reduced pressure were distilled off. Thereafter, 4.5 g of ion-exchanged water was added again, and the operation of reducing the pressure in the same manner and distilling off the odor component and water was repeated twice (in the final pressure-reducing operation, 1.-70 at 60-70 ° C. and 10 Torr). 5 hours)), average composition formula: MD ₃₁ D ^{R * 1} ₃ D ^{R * 21} _10.9 D ^{R * 41} ₁ ^DH _0.1 M Of an opaque uniform viscous liquid. Here, R ^{* 1} , R ^{* 21} and R ^{* 41} are as described above. The composition was slightly odorous after one week after production.

The polyglycerin monoallyl ether is synthesized by ring-opening polymerization of 3 moles of glycidol with respect to 1 mole of glycerin monoallyl ether. Since glycerin monoallyl ether has two hydroxyl groups and glycidol can react with either of them, the polyglycerin moiety includes not only a chain structure but also a branched structure.

[Comparative Example 2] <Synthesis of polyether-modified silicone 2 (low odor treated product)>
In the reactor, 189.7 g of methyl hydrogen polysiloxane represented by average composition formula: MD ₃₁ ^DH ₁₅ M and vinyl tristrimethyl represented by average composition formula: CH ₂ ═CH—Si (OSiMe ₃ ) ₃ An isopropyl alcohol solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt concentration: 0.45 wt.) Is charged with 54.7 g of siloxysilane and stirred at 30 ° C. under nitrogen flow. %) 0.50 g was added. Thereafter, when the reactor was heated in an oil bath at 80 ° C., the temperature of the reaction solution in the reactor rose to 70 ° C. after 1 hour. Three hours later, 1 g of the reaction solution was sampled, and it was confirmed that the reaction rate reached the target by the alkali decomposition gas generation method. Thereafter, when 47.5 g of 1-dodecene was added at 70 ° C., heat was immediately generated, and the temperature rose to 101 ° C. after 1 minute. When the temperature was kept in a 70 ° C. oil bath and further confirmed by the same method after 1 hour, the reaction rate reached the target. Next, 61.9 g of polyoxyethylene (10) monoallyl ether, 120 g of isopropyl alcohol (IPA), and 0.04 g of vitamin E were charged, and 0.50 g of the platinum catalyst was added. After confirming that the reaction rate reached the target after 2 hours, 66.4 g of 1-dodecene and 1.50 g of the platinum catalyst were added. After 5.5 hours, the reaction solution was collected and confirmed, and the hydrosilylation reaction was completed. The polyether represented by the average composition formula: MD ₃₁ D ^{R * 1} ₃ D ^{R * 21} ₁₀ D ^{R * 42} ₂ M It was found that modified silicone was produced. Here, R ^{* 1} , R ^{* 21} and R ^{* 42} are as follows.
R ^{* 1} = -C ₂ H ₄ Si (OSiMe ₃ ) ₃
R ^{* 21} = -C ₁₂ H ₂₅
^{_{_{R * 42 = -C 3 H 6}}} O (C 2 H 4 O) 10 H

Next, after distilling off the low boiling point under reduced pressure, an aqueous solution consisting of 0.02 g of sodium bisulfate / 6.0 g of ion-exchanged water was added, followed by treatment at 60-70 ° C. for 5 minutes, and further up to 30 Torr. The odor component and water generated under reduced pressure were distilled off. Thereafter, 6.0 g of ion-exchanged water is added again, and the operation of reducing pressure in the same manner and distilling off the odorous component and water is repeated twice (in the final pressure reducing operation, 70 to 80 ° C., 3 Torr for 1 hour). Maintenance), and further subjected to microfiltration, 340 g of a composition containing a polyether-modified silicone represented by an average composition formula: MD ₃₁ D ^{R * 1} ₃ D ^{R * 21} ₁₀ D ^{R * 42} ₂ M Obtained as a homogeneous liquid. Here, R ^{* 1} , R ^{* 21} and R ^{* 42} are as described above. The composition was slightly odorous after one week after production.

[Comparative Example 3]
One-end vinyl-modified dimethyl represented by the structural formula CH ₂ = CHSiMe ₂ (OSiMe ₂ ) ₆ OSiMe ₃ was charged in a reactor with 111.6 g of methyl hydrogen polysiloxane represented by the average composition formula MD ₆₁ ^DH ₁₅ M. A mixture of 30.9 g of polysiloxane and 0.10 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt concentration 0.5 wt%) was added dropwise at room temperature. Stirring under nitrogen flow gave a linear siloxane branched polysiloxane intermediate.

In another reactor, 7.0 g of triglyceryl monoallyl ether, 50.4 g of 1-dodecene, 100 g of isopropyl alcohol, and platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex 0.40 g of an isopropyl alcohol solution (Pt concentration 0.5 wt%) was added, and the previously synthesized linear siloxane branched polysiloxane was added dropwise under reflux of the solvent while stirring under a nitrogen flow. Heating was continued stirring after the completion of dropping to 3 hours, was confirmed by alkaline decomposition gas generation method The reaction 1g was collected, the hydrosilylation reaction has been completed the average composition _{^{_{formula: MD 61 D R * 21 12}}} D R It was found that a triglycerin-modified silicone represented by ^{* 22} ₂ DR ^{* 43} ₁ M was produced. Here, R ^{* 21} , R ^{* 22} and R ^{* 43} are as follows.
R ^{* 21} = -C ₁₂ H ₂₅
^{_{_{R * 22 = -C 2 H 4}}} SiMe 2 (OSiMe 2) 6 OSiMe 3
R ^{* 43} = -C ₃ H ₆ OX (X is triglycerin moiety)

Next, the reaction solution was transferred to an autoclave, and after adding 4.0 g of sponge nickel catalyst, 2.0 g of water and 2.0 g of isopropyl alcohol, hydrogen gas was introduced and the conditions were 110 ° C. and 0.9 MPa for 6 hours. Hydrogenation treatment was performed. Next, the treated reaction mixture was cooled to 60 ° C. and blown with hydrogen gas, and then replaced with nitrogen gas three times. Next, the sponge nickel catalyst was removed by microfiltration to obtain 204 g of a colorless and transparent filtrate.

This filtrate was charged into another reactor and maintained under conditions of 100 ° C. and 20 Torr for 1 hour under a nitrogen flow to distill off the low boiling point, and the average composition formula: MD ₆₁ D ^{R * 21} ₁₂ D ^{R * 22} ₂ 138 g of a bromide-free composition containing a triglycerin-modified silicone represented by DR ^{* 43} ₁ M was obtained as an almost colorless translucent uniform liquid. Here, R ^{* 21} , R ^{* 22} and R ^{* 43} are as described above. In this composition, generation of off-flavor was not observed even after 1 week from the production.

[Comparative Example 4]
A reactor was charged with 114.8 g of methylhydrogenpolysiloxane represented by the average composition formula MD ₇₁ ^DH ₁₄ M and 27.1 g of 1-hexadecene, and stirred at a room temperature under a nitrogen stream with platinum-1, When 0.25 g of an isopropyl alcohol solution of 3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt concentration 0.45 wt%) was added, the reaction solution in the reactor was heated to 45 ° C. after 2 minutes. The temperature rose. Thereafter, the reactor was continuously heated in an oil bath at 60 ° C. After 1 hour, 1 g of the reaction solution was sampled and the reaction rate was confirmed by an alkali decomposition gas generation method, and it was found that the target was reached. Thereafter, 40.2 g of polyoxyethylene (10) monoallyl ether, 60 g of isopropyl alcohol (IPA), and 0.02 g of vitamin E were added, and 0.25 g of the platinum catalyst was added. After confirming that the reaction rate reached the target after 1.5 hours, 18.1 g of 1-hexadecene was added. When the reaction solution was collected and confirmed after 2.5 hours at 55-75 ° C., some generation of hydrogen gas was observed. By calculating the reaction rate, it was found that a polyether-modified silicone represented by an average composition formula: MD ₇₁ D ^{R * 23} _9.9 D ^{R * 42} ₄ ^DH _0.1 M was generated. Here, R ^{* 23} and R ^{* 42} are as follows.
R ^{* 23} = -C ₁₆ H ₃₃
^{_{_{R * 42 = -C 3 H 6}}} O (C 2 H 4 O) 10 H

Next, an aqueous solution consisting of 0.01 g of sodium hydrogensulfate / 3.0 g of ion-exchanged water was added to carry out a treatment at 70-75 ° C. for 30 minutes, and further, the flow rate of nitrogen gas was increased at normal pressure to thereby increase the isopropyl alcohol. The generated odor component, water and the like were distilled off. Thereafter, 3.0 g of ion-exchanged water was added again, and the operation of reducing the pressure to 70 to 75 ° C. to 10 Torr and distilling off the odorous component and water was repeated twice (in the final decompression operation, 65 to 75 ° C., The composition containing polyether-modified silicone represented by an average composition formula: MD ₇₁ D ^{R * 23} _9.9 D ^{R * 42} ₄ ^DH _0.1 M is maintained for 1 hour at 10 Torr). 156 g was obtained as a light brown transparent homogeneous liquid. Here, R ^{* 23} and R ^{* 42} are as described above. The composition was slightly odorous after one week after production.

[Comparative Example 5]
In the reactor, 89.9 g of methyl hydrogen polysiloxane represented by the average composition formula MD ₆₃ ^DH ₂₂ M, 36.4 g of polyoxyethylene (10) monoallyl ether, 73.7 g of 1-hexadecene, and 60 g of toluene were added. The mixture was charged and heated to 40 ° C. with stirring under a nitrogen stream. Add 0.06g of isopropyl alcohol solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt concentration 4.5wt%) and react at 80-110 ° C for 2.5 hours Was done. When 1 g of the reaction solution in the reactor was sampled and confirmed by an alkali decomposition gas generation method, the hydrosilylation reaction was complete. A composition containing a polyether-modified silicone represented by an average composition formula: MD ₆₃ D ^{R * 23} ₁₈ D ^{R * 42} ₄ M is obtained by heating the reaction liquid under reduced pressure to distill off the low boiling point. Obtained as a light brown translucent homogeneous liquid. Here, R ^{* 23} and R ^{* 42} are as follows.
R ^{* 23} = -C ₁₆ H ₃₃
^{_{_{R * 42 = -C 3 H 6}}} O (C 2 H 4 O) 10 H

Next, the above composition was transferred to an autoclave, 4.0 g of sponge nickel catalyst, 2.0 g of water, and 60 g of isopropyl alcohol were added, and hydrogen gas was introduced for 6 hours under conditions of 110 ° C./0.9 MPa. Hydrogenation treatment was performed. Next, the treated reaction mixture was cooled to 60 ° C. and blown with hydrogen gas, and then replaced with nitrogen gas three times. Next, the sponge nickel catalyst was removed by pressure filtration to obtain 210 g of a colorless and transparent filtrate.

This filtrate was charged into another reactor and maintained under conditions of 100 ° C. and 20 Torr for 1 hour under a nitrogen flow to distill off the low boiling point, and the average composition formula: MD ₆₃ D ^{R * 23} ₁₈ D ^{R * 42} ₄ 160 g of a bromide-free composition containing a polyether-modified silicone represented by M was obtained as a colorless transparent uniform liquid. Here, R ^{* 23} and R ^{* 42} are as described above. In this composition, generation of off-flavor was not observed even after 1 week from the production.

[Comparative Example 6]
In the reactor, 159.5 g of methyl hydrogen polysiloxane represented by average composition formula: MD ₇₂ ^DH ₁₂ M, vinyltristrimethylsiloxysilane represented by average composition formula: CH ₂ ═CH—Si (OSiMe ₃ ) ₃ 81.9 g, 19.8 g of xylitol monoallyl ether, 75 g of isopropyl alcohol (IPA), and 0.52 g of a methanol solution of 2.3% sodium acetate were charged and heated to 80 ° C. with stirring under a nitrogen stream. Thereafter, 0.20 g of an isopropyl alcohol solution of 10% chloroplatinic acid was added and reacted at 80 ° C. for 5 hours. When 1 g of the reaction solution in the reactor was sampled and the reaction rate was confirmed by an alkali decomposition gas generation method, the hydrosilylation reaction was completed. Then, the reaction solution is heated under reduced pressure to distill off the low-boiling components, whereby non-odorless containing a sugar alcohol-modified silicone represented by an average composition formula: MD ₇₂ D ^{R * 1} ₉ D ^{R * 3} ₃ M 222 g of a liquefied composition was obtained as a pale yellow opaque homogeneous viscous liquid. Here, R ^{* 1} and R ^{* 3} indicate the following. In this composition, generation of a strange odor was observed after one week from the production.
R ^{* 1} = -C ₂ H ₄ Si (OSiMe ₃ ) ₃
R ^{* 3} = xylitol residue

Incidentally, the xylitol monoallyl ether, the structural _{_{formula: CH 2 = CH-CH 2}} -OCH 2 [CH (OH)] 3 CH 2 OH, and the structural _{_{formula: CH 2 = CH-CH 2}} -OCH {CH ( OH) CH ₂ OH} ₂ is a raw material containing xylitol monoallyl ether represented by a mass ratio of approximately 9: 1. In Comparative Example 6, —C ₃ H ₆ — OCH ₂ [CH (OH)] ₃ CH ₂ OH or —C ₃ H ₆ —OCH {CH (OH) CH ₂ OH} ₂ was introduced as a xylitol residue at a similar mass ratio.

[Evaluation]
Using the various modified silicone-containing compositions obtained in Example 1 and Comparative Examples 1 to 6, W / O emulsions having the compositions shown in Table 2 below were prepared.

Specifically, a W / O emulsion having the above composition was prepared as follows.
1) The above oil phase components were charged into a 200 mL glass container.
2) The oil phase was homogenized by shaking in a timely manner while heating in a 60 ° C constant temperature bath.
3) The whole stirring was started at 1000 rpm using a homodisper mixer.
4) The aqueous phase component that had been mixed and homogenized in advance was gradually poured into the oil phase over 45 seconds.
5) The whole was stirred at 3000 rpm for 5 minutes.

The W / O emulsions obtained in this way (Example 1 and Comparative Examples 1 to 6) were stored at 40 ° C. for 2 weeks and stored at 40 ° C. for 1 month. It was evaluated by. Further, the total amount of carbonyl (COV) of the modified silicone was measured by a predetermined method shown below. The results are shown in Table 3.

In the table, the structures of functional groups and their classification are as follows.
<Group having siloxane dendron structure: R ^{* 1} >
R ^{* 1} = —C ₂ H ₄ Si (OSiMe ₃ ) ₃
<Sugar alcohol group-containing organic group: R ^{* 3} >
R ^{* 3} = —C ₃ H ₆ —OCH ₂ [CH (OH)] ₃ CH ₂ OH or —C ₃ H ₆ —OCH {CH (OH) CH ₂ OH} ₂
<Other hydrophilic group: R ^{* 4} >
^{_{_{R * 41 = -C 3 H 6}}} O-X (X is polyglycerin moiety)
R ^{* 42} = —C ₃ H ₆ O (C ₂ H ₄ O) ₁₀ H
R ^{* 43} = —C ₃ H ₆ O—X (X is a triglycerin moiety)
<Other organic groups: R ^{* 2} >
R ^{* 21} = -C ₁₂ H ₂₅
^{_{_{R * 22 = -C 2 H 4}}} SiMe 2 (OSiMe 2) 6 OSiMe 3
R ^{* 23} = -C ₁₆ H ₃₃

[Odor test]
28 g of each of the W / O emulsions of Example 1 and Comparative Examples 1 to 6 were weighed into a 35 ml glass bottle, sealed, and placed in a constant temperature bath at 40 ° C. The emulsion was taken out after 2 weeks and 1 month, the emulsion was returned to room temperature, and the degree of odor when opened was evaluated according to the following criteria.

Odor test evaluation criteria:
◎: Odor is not felt at all ○: Slightly odor is felt △: Slight odor is felt ×: Solvent odor is clearly recognized XX: Strong solvent odor is observed and uncomfortable

[Measurement of total amount of carbonyl]
According to the following procedure, the total amount of carbonyls of the modified silicone compositions (samples) obtained in Example 1 and Comparative Examples 1 to 6 were measured as “carbonyl value (COV)”. Were quantitatively evaluated.

[Preparation Example 1A]
Weigh reagent special grade n-butanol (A) in a 100 mL brown glass bottle, add 4.3 g of special reagent grade trichloroacetic acid, cover the bottle, shake and homogenize, and alcohol of trichloroacetic acid A solution [4.3% acid concentration (wt / vol)] was prepared. Hereinafter, this solution is referred to as “trichloroacetic acid solution (1A)”. This preparation operation was performed within 3 hours before measuring the absorbance.

[Preparation Example 2A]
Reagent special grade n-butanol (A) is weighed into a 100 mL brown glass bottle, and 2,4-dinitrophenylhydrazine (reagent special grade containing an equal amount of water, hereinafter abbreviated as “2,4-DNPH”) 50 mg Then, the bottle is capped and then subjected to an ultrasonic cleaner for 10 minutes to completely dissolve 2,4-DNPH with alcohol (A), and 0.025% (wt / vol) An alcohol solution of 2,4-DNPH was prepared. Hereinafter, this solution is referred to as “2,4-DNPH solution (2A)”. This preparation operation was performed within 3 hours before measuring the absorbance.

[Preparation Example 3B]
Reagent grade ethanol (B) is weighed into a 100 mL brown glass bottle, and 4.0 g of potassium hydroxide (special grade reagent grade pellet) is added directly, the bottle is capped, and an ultrasonic washer with occasional shaking. For 20 minutes to completely dissolve potassium hydroxide with alcohol (B) to prepare a 4.0% (wt / vol) potassium hydroxide alcohol solution. Hereinafter, this solution is referred to as “potassium hydroxide solution (3B)”. This preparation operation was performed within 3 hours before measuring the absorbance.

[Measurement of carbonyl value]
2.00 g of a sample and 23.00 g of reagent-grade n-butanol (A) were charged into a 50 mL screw tube with a lid, and these were mixed to obtain 25.00 g of a sample solution (Sa) having a sample concentration of 8% by mass. Prepared.

1.250 g of the obtained sample solution (Sa) and 3.750 g of reagent-grade n-butanol (A) were charged into a 50 mL volumetric flask, and both were mixed to obtain a sample solution (Sb ) 5.000 g was prepared.

In the volumetric flask containing 5.000 g of the sample solution (Sb), 3 mL of the trichloroacetic acid solution (1A) obtained in Preparation Example 1A and the 2, 4-DNPH solution (2A) obtained in Preparation Example 2A 5 mL was added with a whole pipette. Furthermore, 1.050 g of purified water was added and mixed. This is because a precursor of a carbonyl compound such as acetal that may exist in the sample is also hydrolyzed and detected as carbonyl.

Next, after plugging the volumetric flask and winding a Teflon (registered trademark) seal around it to ensure airtightness, the volumetric flask is placed in a constant temperature bath at 60 ° C. and heated for 30 minutes. Was reacted with 2, に 4-DNPH. Subsequently, the said volumetric flask was taken out from the thermostat and left to stand at room temperature for 30 minutes.

Next, the stopper of the volumetric flask was opened, 10 mL of the potassium hydroxide solution (3B) obtained in Preparation Example 3B was added with a whole pipette, and the volumetric flask was shaken and mixed. 8 minutes after adding 10 mL of potassium hydroxide solution (3B), reagent grade n-butanol (A) was added as a diluent solvent, and this system was shaken to mix the reaction solution with a total volume of 50 mL (basic reaction). Solution) was prepared. Next, 15 minutes after the addition of 10 mL of potassium hydroxide solution (3B), the above reaction solution was placed in an absorption cell (liquid layer length = 1 cm), and the absorbance (A ₁ ) of 430 nm was measured by an absorptiometer. ) Was measured.

On the other hand, in the blank test, 5.000 g of reagent special grade n-butanol (A) was used in place of the sample solution (Sb), and the same operation as above [addition of trichloroacetic acid solution (1A), 2, 4- A solution obtained by adding a DNPH solution (2A), heating and cooling the obtained mixed solution, adding a potassium hydroxide solution (3B), and adding a diluting solvent comprising reagent-grade n-butanol (A). Was placed in an absorption cell (liquid layer length = 1 cm), and the absorbance (A ₂ ) at 430 nm was measured in the same manner as described above.

The carbonyl value (COV) was determined by substituting the absorbance (A ₁ ) and absorbance (A ₂ ) thus obtained into the formula: CV = (A ₁ -A ₂ ) /0.1.

As shown in Table 3, the odor and carbonyl value (COV) of the sugar alcohol-modified silicone (xylitol-modified silicone) obtained in Example 1 were significantly reduced by acid treatment. On the other hand, the polyether-modified silicone and polyglycerin-modified silicone obtained in Comparative Examples 1 to 6 are insufficient in odor and COV reduction effects only by the same acid treatment, and only after hydrogenation is carried out, Example 1 and The same odor reduction was achieved.

Furthermore, the low bromide sugar alcohol-modified silicone (xylitol-modified silicone) obtained in Example 1 has not only a bad odor in the modified silicone composition itself, but even an emulsion containing the same does not deteriorate over time. Therefore, it has been demonstrated that it is extremely useful as a raw material for external preparation compositions such as cosmetics.

In addition, the composition containing the low-brominated sugar alcohol-modified silicone obtained in Example 1 contained an acidic substance because it was not filtered, and was under acidic conditions. In the emulsification system containing, the generation of off-flavor due to aging or high temperature was extremely small. Therefore, the composition obtained in Example 1 is not only useful for general external preparations and cosmetics, but also an antiperspirant composition in which the active ingredient is an acidic substance, and is expected to have a peeling effect. In acidic external preparations or cleaning agents, cosmetics and the like (these formulations are acidic, it is considered that the generation of a different odor derived from modified silicone is particularly likely to occur), and the odorless true value is exhibited.

Hereinafter, the cosmetics and external preparations according to the present invention will be described with reference to their formulation examples, but the cosmetics and external preparations according to the present invention are not limited to the types and compositions described in these formulation examples. Needless to say. In addition, the numerical value has shown weight (mass)% in the formulation example, and all the raw materials which showed the product number are the product names marketed from Toray Dow Corning Co., Ltd.

[Prescription Example 1] Antiperspirant aerosol cosmetic (component) (Wt%)
1. Aluminum hydroxychloride 3.0
2. Zinc oxide 2.0
3. Silica 3.0
4). Silver ion, zinc ion, ammonium ion supported zeolite 1.0
5. Calcium stearate 0.1
6). Dimethylpolysiloxane 2.0
7. Cetyl octanoate 1.0
8). Liquid paraffin 1.0
9. Composition of Example 1 10.0
10. Sorbitan oleate 1.0
11. Antioxidant appropriate amount 12. Perfume appropriate amount13. Liquefied petroleum gas

(Production method)
A: Components 6 to 11 (oil phase part) and component 12 are mixed to form a uniform liquid.
B: Components 1 to 5 (powder part) are mixed in the above liquid and uniformly dispersed to obtain a dispersion.
C: The container is filled with the dispersion and component 13 (propellant) to obtain an antiperspirant aerosol cosmetic.

(effect)
The adhesion of the powder is good, the whiteness after use is inconspicuous, and the safety is high. There is no stickiness after application, it has a moderate level of lie, and a smooth and natural skin sensation can be obtained. Also, there is almost no change in scent over time.

[Formulation Example 2] Non-water pressure antiperspirant product (component) (Wt%)
1. Aluminum chlorohydrate 15wt% 1,2-hexanediol solution 12.0
2. Dimethylpolysiloxane (10 cst) 3.0
3. Decamethylcyclopentasiloxane 3.0
4). Composition of Example 1 3.0
5. Fragrance 1.0
6). Butane 25.0
7. Isobutane 30.0
8). Propane 3.0
9. Dimethyl ether 20.0

(Production method)
A: Components 1 to 5 are mixed to form a uniform liquid.
B: Fill the container with the liquid and components 6 to 8 (propellant).
C: Finally, component 9 (propellant) is filled to obtain a non-water pressurized antiperspirant product.

(effect)
Since a transparent and uniform pressurized liquid is obtained, there is no separation of antiperspirant active ingredients and the product life is long. The antiperspirant effect is immediate and the whiteness after use is inconspicuous. After application, a natural skin sensation with a moisturizing feeling can be obtained. Also, there is almost no change in scent over time.

[Formulation Example 3] Antiperspirant lotion composition (component) (Wt%)
1. Aluminum hydroxychloride 5.0
2. POE (15) POP (5) Cetyl ether phosphoric acid 5.0
3. Purified water 5.0
4). Talc 0.4
5. Spherical silica 0.4
6). Smectite 0.4
7. Nylon powder 0.4
8). Polyethylene powder 0.4
9. Decamethylcyclopentasiloxane 1.0
10. SH 556 FLUID * 1) 1.0
11. Polyether-modified silicone having a siloxane dendron structure 1.0
12 Composition of Example 1 0.5
13. Triclosan 0.1
14 Birch extract 0.1
15. Rosemary extract 0.1
16. Fragrance 1.0
17. Ethanol remainder
Note * 1) Phenyl trimethicone

(Production method)
A: Components 9 to 17 are mixed and dissolved to obtain a uniform liquid.
B: Components 1 to 3 are mixed and dissolved in the liquid.
C: Further, components 4 to 8 are mixed well and dispersed uniformly.

(effect)
Since a transparent and uniform liquid agent is obtained, the antiperspirant active ingredient and the like are not separated, and the stability over time is good. Antiperspirant action immediately appears on the skin immediately after application. After application, it suppresses the tension caused by the evaporation of ethanol, resulting in a natural skin sensation that is not sticky and smooth. Also, there is almost no change in scent over time.

[Prescription Example 4] Non-water sweat deodorant stick composition (component) (Wt%)
1. Stearyl alcohol 25.0
2. Behenyl alcohol 0.5
3. Hardened castor oil 4.0
4). Polypropylene glycol (average molecular weight 1000) 7.0
5. PPG-14 Butyl ether 1.0
6). Decamethylcyclopentasiloxane 30.0
7. Alkyl-polyether co-modified silicone having a siloxane dendron structure 3.0
8). Composition of Example 1 4.5
9. Aluminum, zirconium, tetrachlorohydrate, glycine 25.0

(Production method)
A: Components 1 to 3 and components 6 to 8 are dissolved by heating and stirring at 80 ° C.
B: Keep the resulting melt at 65 ° C., and add ingredients 4 to 5 while stirring to further dissolve.
C: Keep the resulting melt at 65 ° C., add component 9, stir well and disperse uniformly.
D: Pour into a container and solidify at room temperature.

(effect)
Since it can be smoothly applied to the skin without resistance, and the film is not sticky and has an appropriate moisturizing feeling, a comfortable and natural feeling of use can be obtained. The white residue after drying is almost invisible, and the antiperspirant effect is good. Moreover, there is almost no odor of a formulation over time.

[Prescription Example 5] Aerosol antiperspirant composition (component) (Wt%)
1. Aluminum hydroxychloride * 2) 5.0
2. Aluminum hydroxychloride * 3) 1.5
3. Purified water 10.0
4). POE (10) POP (5) Cetyl ether phosphoric acid 1.5
5. Magnesia silica 1.0
6). Porous silica 0.5
7. Polymethylsilsesquioxane powder 1.0
8). Decamethylcyclopentasiloxane 2.0
9. Composition of Example 1 0.5
10. Isopropyl methylphenol 0.05
11. Eucalyptus extract 0.5
12 Soy extract 0.1
13. Melissa extract 0.1
14 Apple extract 0.1
15. Fragrance * 4) 0.15
16. Ethanol 26.0
17. LPG (0.15 MPa / 20 ° C.) 50.0

* 2) REACH 101 MICRO-DRY (trade name, manufactured by Rehis)
* 3) REACH 501 MICRO-DRY (trade name, manufactured by Rehis)
* 4) Prepare according to the fragrance composition examples shown in Table 4.

(Production method)
A: Components 1 to 4 are mixed and dissolved to form a uniform liquid. (Water phase)
B: Separately, components 8 to 16 are mixed and dissolved to obtain a uniform liquid. (Ethanol phase)
C: The aqueous phase is mixed well with the ethanol phase to make a uniform liquid. (Stock solution)
D: Components 5 to 7 are mixed in the stock solution and dispersed uniformly.
E: Finally, component 17 is filled to obtain an aerosol type antiperspirant composition.

(effect)
Since a transparent and uniform pressurized liquid is obtained, there is no separation of antiperspirant active ingredients and the product life is long. Antiperspirant action immediately appears on the skin immediately after application. After application, a natural skin sensation with a moisturizing feeling without stickiness is obtained. Also, there is almost no change in scent over time.

[Formulation Example 6] W / O solid antiperspirant stick composition (component) (Wt%)
1. Dimethylpolysiloxane (2cst) 17.5
2. Benzoic acid C _12-15 alkyl 12.5
3. Polydecene 11.3
4). Composition of Example 1 6.9
5. β-sitosterol 2.4
6). γ-Oryzanol 2.4
7. Aluminum, zirconium, pentachlorohydrate 18.8
8). Purified water 18.8
9. Glycerin 9.4

(Production method)
A: Components 1 to 4 are dissolved by heating and stirring at 80 ° C.
B: The obtained dissolved material is kept at 80 ° C., and components 5 to 6 are sequentially added while stirring and further dissolved.
C: Separately, components 7 to 9 are mixed and dissolved, and then heated to 65 ° C.
D: The melt obtained in B is kept at 65 ° C., and the melt obtained in C is gradually added and emulsified while stirring.
E: Allow to stand and deaerate, then pour into a container and solidify at room temperature.

(effect)
It has a semi-transparent elegant appearance and moderate stick hardness. Moreover, it is excellent in a smooth and moist application feeling and has a good antiperspirant effect. Furthermore, there is almost no white residue after application and no odor of the preparation over time.

[Prescription Example 7] W / O emulsion type antiperspirant cream composition (component) (Wt%)
1. Mineral oil 4.0
2. Cetearyl alcohol 4.7
3. Glyceryl stearate 2.0
4). PEG-20 stearate 1.2
5. Composition of Example 1 1.5
6). Phenoxyethanol 0.4
7. Titanium oxide 0.2
8). Glycerin 6.0
9. Aluminum-Sirconium Tetrachlor-Hydrex Glycine 15.0
10. Purified water 65.0

(Production method)
A: Components 1 to 6 are dissolved by heating and stirring at 80 ° C.
B: The obtained melt is kept at 80 ° C., and component 7 is added and uniformly dispersed while stirring.
C: Separately, components 8 to 10 are mixed and dissolved, and then heated to 65 ° C.
D: The dispersion obtained in B is kept at 65 ° C., and the solution obtained in C is gradually added and emulsified while stirring.

(effect)
It is a cream that is smooth and has a natural application feeling without a sense of incongruity, and has a good balance between the immediate effect and the durability of the antiperspirant and moisturizing effects. Moisturizes skin and restores elasticity. There is almost no white residue after application and odor of the preparation over time.

[Prescription already disclosed in previous application]
The sugar alcohol-modified silicone according to the present invention can be used for external preparations other than antiperspirants and cosmetics. Specific examples of the prescription include the co-modified organopolyesters in the prescription examples shown in Japanese Patent Application Nos. 2010-105888, 2010-105888 and 2010-105896, and priority claims based thereon. In a formulation in which siloxane is replaced by a non-brominated sugar alcohol-modified silicone obtained by the production method of the present invention, Japanese Patent Application No. 2009-244975, Japanese Patent Application No. 2009-244977, Japanese Patent Application No. 2010-173094, and priority application based thereon The formulation etc. which replaced the sugar alcohol modified silicone of the Example in the shown formulation example with the non-brominated sugar alcohol modified silicone of this invention etc. are mentioned. By using the composition containing the non-brominated sugar alcohol-modified silicone of the present invention, in addition to the original effects of the formulation, there is a great advantage that almost no odor or scent change with time of the preparation is eliminated.

Claims

A method for producing a sugar alcohol-modified silicone, comprising a step of treating the sugar alcohol-modified silicone with at least one acidic substance.
A method for producing a sugar alcohol-modified silicone according to claim 1,
(A) a sugar alcohol group-containing compound having a carbon-carbon double bond;
(B) A step [A] of synthesizing a sugar alcohol-modified silicone by hydrosilylation reaction with an organohydrogenpolysiloxane; and the synthesis step [A], or after the synthesis step [A].
Process of treating sugar alcohol-modified silicone in the presence of at least one acidic substance [B]
A process for producing a sugar alcohol-modified silicone, comprising:
The sugar alcohol-modified silicone is represented by the following general formula (1):

{Where,
R 1 represents a monovalent organic group (excluding L and Q), a hydrogen atom or a hydroxyl group,
R 2 is a substituted or unsubstituted, linear or branched monovalent hydrocarbon group having 9 to 60 carbon atoms, or the following general formula (2-1);

(Wherein R 11 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, a hydroxyl group, or a hydrogen atom, and at least one of R 11 is the monovalent hydrocarbon group. T Is a number in the range of 2 to 10, and r is a number in the range of 1 to 500) or the following general formula (2-2);

(Wherein R 11 and r are as defined above), and represents a chain organosiloxane group,
L 1 is the following general formula (3) when i = 1;

(Where
R 3 represents a substituted or unsubstituted, linear or branched monovalent hydrocarbon group having 1 to 30 carbon atoms,
Each R 4 independently represents an alkyl group having 1 to 6 carbon atoms or a phenyl group;
Z represents a divalent organic group,
i represents the generation of a silylalkyl group represented by L i, an integer from 1 to k when the generation number is the number of repetitions of the silylalkyl group is k, the number of layers k is an integer from 1 to 10, L i + 1 is the silylalkyl group when i is less than k, R 4 when i = k, and h i is a number in the range of 0 to 3). Represents a silylalkyl group having
Q represents a sugar alcohol group-containing organic group,
a, b, c, and d are in the ranges of 1.0 ≦ a ≦ 2.5, 0 ≦ b ≦ 1.5, 0 ≦ c ≦ 1.5, and 0.0001 ≦ d ≦ 1.5, respectively. The method for producing a sugar alcohol-modified silicone according to claim 1 or 2, which is a sugar alcohol-modified silicone represented by
In the general formula (1), the monovalent organic group represented by R 1 is a substituted or unsubstituted, straight-chain or branched monovalent hydrocarbon group having 1 to 8 carbon atoms, —R 5 O ( AO) n R 6 (wherein AO represents an oxyalkylene group having 2 to 4 carbon atoms, and R 5 is a substituted or unsubstituted, linear or branched divalent group having 3 to 5 carbon atoms) R 6 represents a hydrocarbon group, R 6 is a hydrogen atom, a substituted or unsubstituted, straight-chain or branched monovalent hydrocarbon group having 1 to 24 carbon atoms, or a substituted group having 2 to 24 carbon atoms Or a polyoxyalkylene group, an alkoxy group, a hydroxyl group, or a hydrogen atom represented by an unsubstituted, linear or branched acyl group, where n = 1 to 100 (provided that R 1 is all a hydroxyl group, A hydrogen atom, the alkoxy group or the polyoxyalkylene group; The method for producing a sugar alcohol-modified silicone according to any one of claims 1 to 3, wherein
In the general formula (1), Q is the following general formula (4-1):

(Where
R represents a divalent organic group,
e is 1 or 2, or the following general formula (4-2):

(Where
R is as described above,
5. The method for producing a sugar alcohol-modified silicone according to claim 1, wherein e ′ is a sugar alcohol group-containing organic group represented by:
In the general formula (4-1) or (4-2), the divalent organic group as R is a substituted or unsubstituted, straight or branched divalent hydrocarbon group having 3 to 5 carbon atoms. The method for producing a sugar alcohol-modified silicone according to claim 5, wherein
In the general formula (1), a silylalkyl group having a siloxane dendron structure represented by L 1 is represented by the following general formula (3-1):

Or the following general formula (3-2):

(Where
R 3 , R 4 and Z are as described above,
7. The method for producing a sugar alcohol-modified silicone according to claim 1, wherein h 1 and h 2 are each independently a functional group represented by a number in the range of 0 to 3.
The sugar alcohol-modified silicone has the following structural formula (1-1):

(Where
R 2 , L 1 and Q are as described above,
X is a group selected from the group consisting of a methyl group, R 2 , L 1 and Q;
n1, n2, n3 and n4 are each independently a number in the range of 0 to 2,000, and n1 + n2 + n3 + n4 is a number in the range of 1 to 2,000. However, when n4 = 0, at least one of X is Q). The method for producing a sugar alcohol-modified silicone according to any one of claims 1 to 7.
The sugar alcohol-modified silicone has the following structural formula (1-1-1):

Or the following structural formula (1-1-2):

(Where
R 2 , Q, X, Z, n1, n2, n3 and n4 are as described above)
The manufacturing method of the sugar alcohol modified silicone in any one of Claims 1 thru | or 8 represented by these.
In the structural formula (1-1-1) or the structural formula (1-1-2), each Z independently represents the following general formula:

(Where
R 7 each independently represents a substituted or unsubstituted, linear or branched alkylene group or alkenylene group having 2 to 22 carbon atoms, or an arylene group having 6 to 22 carbon atoms. ,
R 8 is

The method for producing a sugar alcohol-modified silicone, which is a group selected from divalent organic groups represented by: a group selected from the group consisting of:
The method for producing a sugar alcohol-modified silicone according to any one of claims 1 to 10, wherein the acidic substance is selected from the group consisting of an inorganic acid, an organic acid, an acidic inorganic salt, a solid acid, and an acidic platinum catalyst.
The acidic substance is a water-soluble acidic inorganic salt that is solid at 25 ° C and has a pH of 4 or less at 25 ° C of an aqueous solution when 50 g is dissolved in 1 L of ion-exchanged water. 11. A process for producing a sugar alcohol-modified silicone according to any one of 11 above.
The method for producing a sugar alcohol-modified silicone according to any one of claims 1 to 12, comprising a step of removing an odor-causing substance by heating and / or reducing pressure after the acid treatment step.
An external preparation or a cosmetic raw material containing the sugar alcohol-modified silicone obtained by the production method according to claim 1.
An external preparation or cosmetic containing a sugar alcohol-modified silicone obtained by the production method according to claim 1.
The external preparation or cosmetic according to claim 15, which is an antiperspirant.
14. A monohydric lower alcohol having 1 to 4 carbon atoms and at least one carbonyl in the sugar alcohol-modified silicone obtained by the production method according to claim 1 and 2,4-dinitrophenylhydrazine. A method for measuring the carbonyl value of the sugar alcohol-modified silicone from the absorbance of a reaction solution obtained by reacting in a reaction medium containing
A sugar alcohol-modified silicone obtained by the production method according to any one of claims 1 to 13, wherein the carbonyl value measured by the carbonyl value measurement method according to claim 17 is 2.5 Abs / g or less. A sugar alcohol-modified silicone.