WO2015162907A1

WO2015162907A1 - Method for producing liquid transparent or semi-transparent sugar derivative-modified silicone composition

Info

Publication number: WO2015162907A1
Application number: PCT/JP2015/002155
Authority: WO
Inventors: 田村　誠基; さゆり澤山; 達央早田
Original assignee: 東レ・ダウコーニング株式会社
Priority date: 2014-04-21
Filing date: 2015-04-20
Publication date: 2015-10-29
Also published as: JPWO2015162907A1

Abstract

Provided is a liquid sugar derivative-modified silicone composition having a transparent or semi-transparent external appearance. Also provided is a method for producing a liquid transparent or semi-transparent sugar derivative-modified silicone composition, said method including a water addition step in which water is added to a liquid sugar derivative-modified silicone or a composition thereof.

Description

Process for producing transparent or translucent liquid sugar derivative-modified silicone composition

The present invention relates to a method for producing a transparent or translucent liquid sugar derivative-modified silicone composition. Furthermore, the present invention relates to the use of the sugar derivative-modified silicone for external preparations, cosmetics, and various industrial materials. This application claims priority based on Japanese Patent Application No. 2014-087713 for which it applied to Japan on April 21, 2014, and uses the content here.

Examples of the saccharide-silicone compound include silicone-modified polysaccharides in which a polysaccharide is modified with silicone (the main skeleton of the molecule is a polysaccharide, see Patent Documents 1 to 6), a silicone chain or a silicone skeleton that is relatively short. A sugar derivative-modified silicone having a sugar or oligosaccharide chain (molecular main skeleton is silicone, see Patent Documents 7 to 28) is known.

The former is often a powdery solid and the latter is often a viscous liquid. In general, opacity in appearance does not matter for powdered products, but when a liquid product is cloudy, appearance and potential phase separation are often regarded as problems. As for the liquid sugar derivative-modified silicone, many studies have been made on the chemical structure and the production method as described above, but there are very few products that are commercialized due to the high manufacturing difficulty on a commercial scale. Moreover, the compound which consists of saccharide | sugar and a silicone had the subject that the freedom degree to a structural design was low and the utilization range did not spread.

As a method for producing a sugar derivative-modified silicone, a method in which a sugar derivative having a reactive unsaturated group is added to an organohydrogensiloxane is known (Patent Documents 8 to 10, 13, 17 to 19, and 23 to 28). When the molecular weight or weight ratio of the silicone part in the sugar derivative-modified silicone structure is small, the remaining sugar derivative and the sugar derivative-modified silicone are compatible with each other, so that a product with less turbidity can be easily obtained (Patent Documents 10, 18, 19, However, there is a problem that the range of use is limited because the structures that can be designed are limited. Normally, in many sugar derivative-modified silicones, the compatibility between the residual sugar derivative and the product sugar derivative-modified silicone is low, and the appearance of the product is non-uniform in white turbidity, often resulting in phase separation during storage after production. . For this reason, a purification treatment for removing the remaining sugar derivative is performed by techniques such as solvent extraction, column chromatography, dialysis, membrane separation, and reprecipitation (Patent Documents 9, 13, and 17). However, since these purification methods require a large amount of organic solvent and water, there are serious problems in terms of waste treatment and efficiency. In addition, there is a problem that the apparatus is limited to application on a laboratory scale and is not suitable for mass production on a commercial scale.

Patent Document 24 shows an example in which a hydroxyl-protected compound is used as a sugar derivative, but deprotection is required after the reaction with organohydrogensiloxane. The above problem of phase separation is inevitable. Moreover, the method of deprotecting after introducing the protected sugar derivative into the silicone chain is that the hydrolysis is performed in an environment where the hydrophobicity by the silicone is increased, which is very inefficient. Therefore, the acid treatment conditions have to be harsh for deprotection, and as a result of the cleavage of the silicone main chain, a new problem arises that the desired product cannot be obtained with good reproducibility.

As another method for producing a sugar derivative-modified silicone, a method is known in which amino-modified silicone is used as a starting material and a sugar derivative containing a sugar lactone or an α, β-unsaturated carbonyl group is reacted (Michael addition). (Patent Documents 7, 11, 12, 16, 22). However, the amide bond formed by the reaction between the amino group of the amino-modified silicone and the sugar lactone is unstable and has a problem that hydrolysis is likely to occur. In addition, in the reaction of amino-modified silicone with a sugar derivative containing an α, β-unsaturated carbonyl group, a secondary or tertiary amino group is formed. There are concerns such as skin irritation.

Patent Document 14 discloses a method of reacting a sugar derivative having an amino group with an epoxy-modified silicone as a starting material. Although the resulting sugar derivative-modified silicone has improved stability against hydrolysis, it is difficult to be incorporated into cosmetics and the like because it is highly colored and tends to generate a strong ammonia-like odor over time. Have a problem. Moreover, since it has a secondary or tertiary amino group, there is a concern such as compatibility with a prescription for blending it or skin irritation.

Patent Documents 15, 20, and 21 disclose a method for producing and purifying a special sugar derivative-modified silicone, but it is very complicated and difficult to mass-produce on a commercial scale.

For the reasons described above, there are few practical sugar derivative-modified silicones, and variations in chemical structure have been unavoidable. Accordingly, there has been a demand for the development of a stable sugar derivative-modified silicone having a low turbidity and a method for producing the same, which is easy to produce and hardly causes phase separation and sedimentation of unreacted raw materials after the production.

Japanese Patent Laid-Open No. 06-145201 Japanese Patent Laid-Open No. 08-283302 Japanese Patent Laid-Open No. 08-134103 Japanese Patent Laid-Open No. 08-283304 JP 11-349601 A JP 2001-240605 A JP-A-62-068820 Japanese Patent Laid-Open No. 62-037039 JP 05-186596 A Japanese Patent Laid-Open No. 06-316590 JP 07-133352 A Japanese Patent Laid-Open No. 08-269204 JP-A-10-259186 Japanese Patent Laid-Open No. 10-330489 JP-A-11-092490 JP 2000-186150 A Special table 2003-503520 gazette JP 2002-11840 A JP 2002-179798 A Japanese Patent Laid-Open No. 2003-147082 Japanese Patent Laid-Open No. 2003-146991 JP 2008-542474 A JP 2008-179578 A JP 2008-274241 A JP 2011-246705 A JP 2011-246706 A JP 2012-246445 A JP 2012-246446 A

An object of the present invention is to provide a liquid sugar derivative-modified silicone composition having a transparent or translucent appearance. In particular, the present invention provides a liquid sugar derivative-modified silicone composition having high transparency, transparency being stable with respect to temperature history, stable after long-term storage, and hardly causing separation or precipitation. The purpose is to do.

In addition, the present invention is easy to manufacture, has little waste, is excellent in yield and productivity, is less likely to cause phase separation and sedimentation of unreacted raw materials after manufacturing, is chemically stable and excellent in practicality It is an object of the present invention to provide a stable liquid sugar derivative-modified silicone composition having a transparent or translucent appearance and containing a sugar derivative-modified silicone.

Another object of the present invention is to use the transparent or translucent liquid sugar derivative-modified silicone produced by such a method for an external preparation, cosmetics, or various industrial materials.

The object of the present invention is achieved by a method for producing a transparent or translucent liquid sugar derivative-modified silicone composition comprising a water addition step of adding water to a liquid sugar derivative-modified silicone or a composition thereof.

In the water addition step, 0.1 to 10 parts by weight of water can be added to 100 parts by weight of the liquid sugar derivative-modified silicone or composition thereof.

In the water addition step, the liquid sugar derivative-modified silicone or composition thereof and the water are preferably mixed and homogenized.

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

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

Wherein R ¹¹ is independently 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 described above), L ¹ represents the following general formula (3) when i = 1;

(In the formula, each R ³ independently represents a substituted or unsubstituted, linear or branched monovalent hydrocarbon group having 1 to 30 carbon atoms, and each R ⁴ independently represents the number of carbon atoms. represents 1-6 alkyl group or a phenyl group, Z is a divalent organic radical, i is represented of a silylalkyl group represented by L ^i, the number of layers is a number of repetitions of the silylalkyl group is k When the number of layers is an integer of 1 to 10, L ^{i + 1} is the silylalkyl group when i is less than k, R ⁴ when i = k, h ⁱ represents a silylalkyl group having a siloxane dendron structure, and Q represents a sugar derivative 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. It may be a sugar derivative-modified silicone represented by

The sugar derivative group may be a group derived from monosaccharides, disaccharides or oligosaccharides (oligosaccharides).

The sugar derivative group may be a sugar alcohol group-containing organic group.

The sugar derivative-modified silicone has 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 0 or 1) and may be modified with a sugar alcohol group-containing organic group.

The sugar derivative-modified silicone may be a liquid sugar derivative-modified crosslinked silicone.

The production method of the present invention includes a liquid oil addition step of adding a liquid oil agent to the liquid sugar derivative-modified silicone or a composition thereof before and / or after the water addition step and / or simultaneously with the water addition step. Further, it can be included.

The liquid oil agent preferably has an affinity for the liquid sugar derivative-modified silicone.

In the liquid oil addition step, 5 to 1000 parts by mass of liquid oil can be added to 100 parts by mass of the liquid sugar derivative-modified silicone or composition thereof.

In the liquid oil addition step, it is preferable to mix and homogenize the liquid sugar derivative-modified silicone or a composition thereof and the liquid oil.

In the present invention, the sugar derivative-modified silicone or a composition thereof is treated with an acidic substance, and odorous substances and low-boiling components generated by the treatment of the acidic substance are removed by heating or decompressing. Is preferred.

The present invention also relates to a transparent or translucent liquid sugar derivative-modified silicone composition obtained by the production method of the present invention.

The object of the present invention is also achieved by an external preparation or cosmetic or an industrial material containing a transparent or translucent liquid sugar derivative-modified silicone composition obtained by the production method of the present invention. .

The production method of the present invention can provide a liquid sugar derivative-modified silicone composition having a transparent or translucent appearance. In particular, the liquid sugar derivative-modified silicone composition obtained by the present invention has high transparency, transparency is stable with respect to temperature history, and is stable even after long-term storage.

In addition, the present invention is easy to manufacture, has little waste, is excellent in yield and productivity, is less likely to cause phase separation and sedimentation of unreacted raw materials after manufacturing, is chemically stable and excellent in practicality In addition, a stable and liquid sugar derivative-modified silicone composition having a transparent or translucent appearance can be provided.

In addition, the transparent or translucent sugar derivative-modified silicone obtained by the production method of the present invention can be suitably used for external preparations or cosmetics, and can be widely used for various industrial materials. .

The first aspect of the present invention is a method for producing a liquid transparent or translucent sugar derivative-modified silicone composition comprising a water addition step of adding water to a liquid sugar derivative-modified silicone or a composition thereof.

Hereinafter, the first aspect of the present invention will be described in detail.

[Sugar derivative-modified silicone]
The sugar derivative-modified silicone to which the present invention can be applied is a silicone compound modified with a sugar derivative and is in a liquid state, preferably at least at 100 ° C. And if it satisfy | fills this condition, there will be no restriction | limiting in the chemical structure.

In the present invention, the term “liquid” or “liquid” means that the liquid level of the organopolysiloxane in a predetermined container is leveled, the container is tilted, and after 1 hour, preferably after 30 minutes, more preferably Means that after 10 minutes the liquid level can become horizontal again. Here, “horizontal” means forming a plane that intersects at right angles to the direction of action of gravity. The sugar derivative-modified silicone is preferably a liquid at least at 100 ° C., but more preferably exhibits a liquid state in the range of 100 ° C. or lower to room temperature. Specifically, it is preferably liquid at 80 ° C., more preferably liquid at 40 ° C., and even more preferably liquid at room temperature (25 ° C.). Naturally, it is liquid at 100 ° C. or higher, but it may be heated to 100 ° C., for example, even if it is a semi-gel or soft solid that does not exhibit fluidity at temperatures below room temperature (25 ° C.). For example, liquid sugar derivative-modified silicones are included within the range of liquid sugar derivative-modified silicones.

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

Here, when the sugar derivative-modified silicone represented by the general formula (1) has a long-chain type organic group or a chain-like organosiloxane group represented by R ² , b is a number greater than 0, 0.0001 ≦ b ≦ 1.5 is preferable, and 0.001 ≦ b ≦ 1.5 is more preferable. Similarly, when the sugar derivative-modified silicone represented by the general formula (1) has a silylalkyl group having a siloxane dendron structure represented by L ¹ above, c is a number greater than 0, and 0.0001 ≦ c ≦ 1.5 is preferable, and 0.001 ≦ c ≦ 1.5 is more preferable.

The sugar derivative-modified silicone has a long chain organic group represented by R ² or a chain organosiloxane group represented by R ² or a silylalkyl group having a siloxane dendron structure represented by L ¹ together with the sugar derivative group represented by Q. Is preferred.
At this time, preferable values of b and c are expressed as follows depending on the essential functional group.
(1) When having a group represented by R ² : 0.001 ≦ b ≦ 1.5 and 0 ≦ c ≦ 1.5
(2) when having the group represented by ^{L 1:} a 0 ≦ b ≦ 1.5, and 0.001 ≦ c ≦ 1.5
(3) In the case of having both a group represented by R ² and a group represented by L ¹ : 0.001 ≦ b ≦ 1.5 and 0.001 ≦ c ≦ 1.5

The monovalent organic group represented by R ¹ in the general formula (1) may be the same as or different from each other, and is not particularly limited as long as it is not a functional group corresponding to R ² , L ^{1, or} Q. A substituted or unsubstituted, linear or branched monovalent hydrocarbon group of the formula 1 to 8, —R ⁵ O (AO) _n R ⁶ (wherein AO is an oxyalkylene having 2 to 4 carbon atoms) R ⁵ represents a substituted or unsubstituted, linear or branched divalent hydrocarbon group having 3 to 5 carbon atoms, R ⁶ represents a hydrogen atom, 1 to 24 carbon atoms, A substituted or unsubstituted linear or branched monovalent hydrocarbon group or a substituted or unsubstituted linear or branched acyl group having 2 to 24 carbon atoms, n = 1 To 100) (poly) oxyalkylene group, alkoxy group, water Group, a hydrogen atom is preferably. However, R ¹ does not all become a hydroxyl group, a hydrogen atom, the alkoxy group or the (poly) oxyalkylene 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 derivative-modified silicone is introduced with a modified group other than the sugar derivative group (—Q), particularly a short chain or medium chain hydrocarbon-based group as R ¹ for the purpose of imparting further functionality, or is designed. 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 raw material for cosmetics or fiber treatment agents, amino groups, amide groups, aminoethylaminopropyl groups, carboxyl groups, etc. are monovalent hydrocarbon groups for the purpose of improving the feeling of use, feel and durability. Can be introduced as a substituent.

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 polysiloxane, so that it can be incorporated into an external preparation or cosmetic. The affinity to various components such as the body, emulsification and dispersibility, 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 both functional groups. In the sugar derivative-modified silicone, in particular, part or all of R ² is preferably a monovalent long chain hydrocarbon group, and by having such a monovalent long chain hydrocarbon group in the molecule, the sugar Derivative-modified silicones exhibit superior compatibility not only with silicone oils but also with non-silicone oils with a high alkyl group content, for example, emulsification with non-silicone oils with excellent thermal and temporal stability. 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 having 9 to 30 carbon atoms, preferably 9 to 30 carbon atoms, more preferably 10 to 24 carbon atoms, an aminoalkyl group, and an amidoalkyl. Group and ester 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 has the general formula: — (CH ₂ ) _v —CH ₃ (v is a number in the range of 8 to 29). The group represented by these is illustrated. An alkyl group having 10 to 24 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, or 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, an amino group, a methacryl group, a mercapto group, and the like. R ¹¹ is particularly preferably a methyl group, a phenyl group or a hydroxyl group, a form in which 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 derivative-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, butyl, pentyl, hexyl, heptyl and octyl; cycloalkyl such as cyclopentyl and cyclohexyl; alkenyl such as vinyl, allyl and butenyl; phenyl and tolyl Aryl groups such as aralkyl 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 the 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 addition reaction of a functional group having an unsaturated hydrocarbon group such as a methacryloxy group at the end. Depending on the method of introducing a silylalkyl group having a siloxane dendron structure, these may be used. 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 a ^{^{L 2 ~ L k L i,}} Z is an alkylene group or ^-R 7 ^{-COO-R 8} having 2 to 10 carbon atoms - in The divalent organic group is preferably a group selected from an ethylene group, a propylene group, a methylethylene group, a hexylene group, and —CH ₂ C (CH ₃ ) COO—C ₃ H ₆ —. Particularly preferred.

In the above 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 ⁸ 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 preferably a group selected from divalent organic groups represented by the following formula.

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

In the general formula (1), Q can be a group derived from monosaccharides, disaccharides or oligosaccharides (oligosaccharides). In this case, the sugar-derived modified silicone according to the present invention is modified with monosaccharides, disaccharides or oligosaccharides (oligosaccharides).

In general formula (1), Q is preferably a group derived from sugar alcohols. Therefore, Q is preferably a sugar alcohol group-containing organic group. In the sugar alcohol group-containing organic group, the sugar alcohol residue is preferably bonded to the silicon atom via a divalent organic group. In this case, the sugar-derived modified silicone according to the present invention is modified with sugar alcohols.

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

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

In the sugar derivative-modified silicone according to the present invention, at least one of the sugar alcohol-containing organic groups represented by the general formula (4-1) or (4-2) is preferably 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, a heptamethylene group, an octamethylene group, etc .; a carbon atom number 2 to 2 such as a vinylene group, an arylene group, a butenylene group, a hexenylene group, an octenylene 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 derivative group, preferably the sugar alcohol-containing organic group, may be either the side chain or the terminal of the polysiloxane main chain, and two or more sugar derivative groups in one molecule of the sugar derivative-modified silicone. It may be a structure having Furthermore, these two or more sugar derivative groups may be the same or different sugar derivative groups. These two or more sugar derivative 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 non-crosslinked sugar derivative-modified silicone has, for example, (a) a sugar derivative having one reactive unsaturated group in one molecule in the presence of a hydrosilylation reaction catalyst, and (b) a silicon atom-bonded hydrogen atom. An organopolysiloxane, and (c) an 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) can be obtained by reacting a long-chain hydrocarbon compound or a chain organopolysiloxane compound having one reactive unsaturated group in one molecule. 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 (c), -L ¹ is introduced by component (d), and -R ² is introduced by component (e).

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

The sugar derivative-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 derivative 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 derivative-modified silicone may be the unsaturated organic compound, the unsaturated ether compound of the sugar derivative, 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 organopolysiloxane. Thereby, an organic group and a sugar derivative group, and optionally a silylalkyl group having a siloxane dendron structure and / or a long-chain hydrocarbon group or a chain organopolysiloxane group can be introduced into the polysiloxane chain. it can. 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 derivative-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) (b1) an organohydrogenpolysiloxane and (a) a sugar derivative having one reactive unsaturated group in one molecule It can be obtained by reacting at least. (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 the chain organopolysiloxane having one in one molecule.

The sugar derivative-modified silicone includes (a) a sugar derivative having one reactive unsaturated group in one molecule, and optionally (d) a siloxane dendron compound having one reactive unsaturated group in one molecule. And / or (e) a hydrocarbon compound having one reactive unsaturated group in one molecule or a chain organopolysiloxane having one reactive unsaturated group in one molecule, The component (a), the component (d) and / or the component (e) and the component (b2) organohydrogenpolysiloxane are reacted together, or the component (b1) and the organohydrogenpolysiloxane are optional. The component (d) and / or the component (e) are sequentially subjected to an addition reaction, and then the component (a) is further subjected to an addition reaction.

Examples of (b) organopolysiloxane having a silicon atom-bonded hydrogen atom used for the synthesis of the sugar derivative-modified silicone 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) (b2) organohydrogenpolysiloxane is preferred.

The sugar derivative-modified silicone is preferably synthesized by hydrosilylation reaction of (a1) a sugar derivative having a carbon-carbon double bond at the end of the molecular chain and (b2) an organohydrogenpolysiloxane. In this case, the organohydrogenpolysiloxane as the component (b2) is obtained by reacting with the component (d) and / or the component (e) by a sequential addition reaction. Siloxane is preferred. In this case, the organohydrogensiloxane immediately before the reaction with the component (a) (after the sequential reaction with other components) is preferably represented by the following structural formula (1-1A).

(1-1A)
(Where
R ² and L ¹ are each independently as described above,
X is a group selected from the group consisting of a methyl group, R ² , L ¹ and a hydrogen atom (H);
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 a hydrogen atom. )

The sugar derivative having one reactive unsaturated group in one molecule used for the synthesis of the sugar derivative-modified silicone is preferably (a1) a sugar derivative having a carbon-carbon double bond at the end of the molecular chain. is there. As a sugar derivative having one reactive unsaturated group in one molecule, (B) a sugar derivative group having an unsaturated bond described later on condition that one reactive unsaturated group is present in one molecule. The same organic compound can be used.

As a siloxane dendron compound having one reactive unsaturated group in one molecule used for the synthesis of the sugar derivative-modified silicone, the following general formula (3 ′):

{Where
R ³ and R ⁴ are as described above, R ^D is a hydrogen atom or a methyl group,
Z ′ represents the same divalent organic group as Z,
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 ′.
h ^j is one carbon molecular chain terminal represented by} represents a silylalkyl group represented by a number ranging from 0 to 3) - preferably a compound having a siloxane dendron structure having a carbon-carbon double bond .

(E) a hydrocarbon compound having one reactive unsaturated group in one molecule or a chain-organopolysiloxane having one reactive unsaturated group in one molecule used for the synthesis of the sugar derivative-modified silicone according to the present invention As siloxane, the following general formula: (2 ′)

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

(Where
R ^D , Z ′, R ¹¹ and r are as described above).

(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 for synthesizing the sugar derivative-modified silicone or the composition containing the same can be performed according to a known method in the presence or absence of a solvent. Here, the reaction solvent includes 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, cyclohexane Examples thereof include aliphatic hydrocarbon solvents such as heptane and methylcyclohexane; 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 and in a short time. Examples of such a catalyst include platinum, ruthenium, rhodium, palladium, osmium, iridium and other compounds, and platinum compounds are particularly effective because of their 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. When a platinum catalyst is used, the amount of the catalyst used is about 0.0001 to 0.1% by mass as metal platinum, and is preferably in the range of 0.0005 to 0.05% by mass, but is not limited thereto. .

The reaction temperature of the hydrosilylation reaction is usually 30 to 120 ° C., and the reaction time is usually 10 minutes to 24 hours, preferably 1 to 10 hours.

The sugar derivative-modified silicone to which the present invention can be applied can be a liquid sugar derivative-modified crosslinked silicone. Liquid sugar-derived versus modified cross-linked silicone
(A) organohydrogenpolysiloxane,
(B) a sugar derivative group-containing organic compound having one or more reactive unsaturated groups in one molecule, and (C) (C1) an organic having an average number of reactive unsaturated groups greater than 1 in one molecule. It is obtained by reacting a compound and (C2) one or more organic compounds selected from the group consisting of organic compounds having one or more reactive unsaturated groups and one or more epoxy groups in one molecule { However, when the component (C) contains a sugar derivative group-containing organic group, the use of the component (B) is optional}, has a sugar derivative group-containing organic group bonded to a silicon atom, and An organically modified silicone having a cross-linked structure containing a Si—C bond in the cross-linked portion is preferred.

The (A) organohydrogenpolysiloxane is not particularly limited as long as it has a hydrogen atom bonded to a silicon atom, but on average more than 1, preferably 1.01 to 100, More preferably, those having silicon-bonded hydrogen atoms of 1.1 to 50, still more preferably 1.2 to 25, and particularly preferably 1.3 to 10, are preferably linear, branched or network organo Polysiloxanes can be used. There is no restriction | limiting also about the position of the silicon atom bond hydrogen atom on organohydrogenpolysiloxane, and it may be located either on the main chain or at the end. However, from the viewpoint of reducing the degree of crosslinking, it is preferably located at the end. As the component (A), one type of organohydrogenpolysiloxane may be used, or two or more types of organohydrogenpolysiloxane may be used.

Examples of the component (A) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, trimethylsiloxy group-blocked methylhydrogenpolysiloxane at both ends, and both ends. Trimethylsiloxy-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, dimethylhydrogensiloxy-blocked dimethylsiloxane at both ends, dimethylhydrogensiloxy-blocked dimethylpolysiloxane at both ends, dimethylhydrogensiloxy-blocked dimethylsiloxane / methyl at both ends Hydrogensiloxane copolymer, trimethylsiloxy group-capped methylhydrogensiloxane / diphenylsiloxane copolymer, both ends trimethylsiloxy group-capped methylhydrogensiloxane / diphenylsiloxane Hexane-dimethylsiloxane copolymer, (CH ₃₎ a copolymer consisting of ₂ HSiO _1/2 units and SiO _4/2 units, and (CH ₃₎ ₂ HSiO _1/2 units and SiO _4/2 units (C Examples are copolymers comprising ₆ H ₅ ) SiO _3/2 units.

(A) component is average composition formula (11):
R ¹ _a H _b SiO _{(4-ab) / 2} (11)

(In the average composition formula (11), R ¹ independently represents a monovalent organic group, and 1.0 ≦ a ≦ 3.0 and 0.001 ≦ b ≦ 1.5). Those represented are preferred.

(A) The molecular structure of the organohydrogenpolysiloxane is not limited, and examples thereof include linear, partially branched linear, branched, cyclic, and dendritic, and are preferably linear. 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.

As such an organohydrogenpolysiloxane, the following structural formula (i) R ¹ ₃ SiO (R ¹ ₂ SiO) _v (R ¹ SiHO) _w SiR ¹ ₃
(Ii) HR ¹ ₂ SiO (R ¹ ₂ SiO) _v (R ¹ SiHO) _z SiR ¹ ₃
(Iii) HR ¹ ₂ SiO (R ¹ ₂ SiO) _v (R ¹ SiHO) _z SiR ¹ ₂ H
(In structural formulas (i) to (iii), R ¹ is as described above, v is 0 or a positive integer, w is a positive integer, and z is 0 or a positive integer). Illustrative are organohydrogenpolysiloxanes. These organohydrogenpolysiloxanes are (i) a side chain only, (ii) one end of a side chain or molecular chain, and (iii) a straight chain having silicon-bonded hydrogen atoms at both ends of the side chain or molecular chain. Organohydrogenpolysiloxane.

The monovalent organic group is not particularly limited, but the following (D1) to (D10)
(D1) a substituted or unsubstituted, linear or branched monovalent hydrocarbon group having 1 to 60 carbon atoms,
(D2) -R ²⁸ O (AO) _z1 R ²⁹ (wherein AO represents an oxyalkylene group having 2 to 4 carbon atoms, and R ²⁸ is a substituted or unsubstituted straight chain having 3 to 5 carbon atoms. Represents a chain or branched divalent hydrocarbon group, and R ²⁹ represents a hydrogen atom, a substituted or unsubstituted linear or branched monovalent hydrocarbon group having 1 to 24 carbon atoms, or carbon A substituted or unsubstituted, linear or branched acyl group having 2 to 24 atoms, wherein z1 = 1 to 100),
(D3) a substituted or unsubstituted, linear or branched alkoxy group having 1 to 30 carbon atoms,
(D4) hydroxyl group,
(D5) —R ³⁰ —COOR ³¹ (wherein R ³⁰ represents a substituted or unsubstituted, straight-chain or branched divalent hydrocarbon group having 2 to 20 carbon atoms, and R ³¹ represents a carbon atom) An ester group represented by the formula (1) represents a substituted or unsubstituted, linear or branched monovalent hydrocarbon group;
(D6) —R ¹⁷ —OCOR ¹⁸ (wherein R ¹⁷ represents a substituted or unsubstituted, linear or branched divalent hydrocarbon group having 2 to 20 carbon atoms, and R ¹⁸ represents a carbon atom) Ester group (D7) L ¹ represented by the formula 1-30, which represents a substituted or unsubstituted, linear or branched monovalent hydrocarbon group
Here, L ¹ is the following general formula (33) when i = 1:

(In general formula (33),
R ¹² represents a substituted or unsubstituted, linear or branched monovalent hydrocarbon group having 1 to 30 carbon atoms, and each R ¹³ independently represents an alkyl having 1 to 6 carbon atoms. group or a phenyl group, Z is a divalent organic radical, i is represented of a silylalkyl group represented by L ^i, the number of layers is a number of repetitions of the silylalkyl group is 1 ~ k when k The number of layers k is an integer of 1 to 10, L ^{i + 1} is the silylalkyl group when i is less than k, R ¹³ when i = k, and h ⁱ is 0 to 3 A silylalkyl group having a siloxane dendron structure represented by:
(D8) The following general formula (44):

(In the general formula (44), each R ¹⁴ independently represents a substituted or unsubstituted, linear or branched, monovalent hydrocarbon group having 1 to 30 carbon atoms, a hydroxyl group, or a hydrogen atom. , R ¹⁴ 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 100). An alkyl group substituted with a siloxane structure,
(D9) The following general formula (55):

(In the general formula (55), R ¹⁵ represents a substituted or unsubstituted, linear or branched divalent hydrocarbon group having 2 to 20 carbon atoms),
(D10) The following general formula (66):

(In the general formula (66), R ¹⁶ represents a substituted or unsubstituted, linear or branched divalent hydrocarbon group having 2 to 20 carbon atoms, and R ⁶ and R ⁷ are as defined above. It is preferable to be selected from alicyclic epoxy groups represented by:

Examples of the substituted or unsubstituted linear or branched monovalent hydrocarbon group in (D1), (D2) and (D5) to (D8) include, for example, methyl group, ethyl group, propyl group, butyl Group, pentyl group, hexyl group, heptyl group, octyl group and other alkyl groups; cyclopentyl group, cyclohexyl group and other cycloalkyl groups; vinyl group, allyl group, butenyl group and other alkenyl groups; phenyl group, tolyl group and other aryl groups An aralkyl group such as a benzyl group; and a hydrogen atom bonded to a carbon atom of these groups is at least partially a halogen atom such as fluorine, or an epoxy group, a glycidyl group, an acyl group, a carboxyl group, an amino group, And a group substituted with an organic group including a methacryl group and a mercapto group. 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 substituted or unsubstituted linear or branched divalent hydrocarbon group in (D2), (D5), (D6), (D9) and (D10) is as described above.

Examples of the substituted or unsubstituted, linear or branched alkoxy group in (D3) include lower alkoxy groups such as methoxy group, ethoxy group, isopropoxy group, butoxy group, lauryl alkoxy group, myristyl alkoxy group, pal Examples include higher alkoxy groups such as a mitylalkoxy group, an oleylalkoxy group, a stearylalkoxy group, and a behenylalkoxy group.

Of the alkyl group having 1 to 6 carbon atoms or phenyl group in (D7), the alkyl group having 1 to 6 carbon atoms includes methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl. , Linear, branched or cyclic alkyl groups such as s-butyl, pentyl, neopentyl, cyclopentyl and hexyl.

In general formula (33), 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 ¹² , R ¹³ 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 (33-1).

When the number of hierarchies is k = 2, L ¹ is represented by the following general formula (33-2).

When the number of hierarchies is k = 3, L ¹ is represented by the following general formula (33-3).

In the structure represented by the general formulas (33-1) to (33-3) 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 (33) and (33-1) to (33-3), 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 addition reaction of a functional group having an unsaturated hydrocarbon group such as a methacryloxy group at the end. Depending on the method of introducing a silylalkyl group having a siloxane dendron structure, these may be used. 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 ¹⁹ — 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 ¹⁹ —COO—R ²⁰ — 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 group selected from a methylethylene group or a hexylene group is particularly preferable, and an ethylene group is most preferable.

In the above general formula, each R ¹⁹ 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 ¹⁹ 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 ²⁰ is preferably a group selected from divalent organic groups represented by the following formula.

(B) The sugar derivative group-containing organic compound having a reactive unsaturated group is not particularly limited as long as it has at least one reactive unsaturated group and one sugar derivative group in each molecule. Although it may be derived from monosaccharides, disaccharides, oligosaccharides (oligosaccharides), or may be derived from sugar alcohols, the following general formula (4′-1):

(Where
R ′ represents an unsaturated organic group,
e is 1 or 2, and is 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 an allyl group, a methallyl group, and a 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.

As the component (C1), the organic compound having an average number of unsaturated bonds larger than 1 in one molecule is preferably more than 1.0, preferably 1.01 to 10, on average. More preferably 1.2 to 8, even more preferably 1.5 to 6, particularly preferably 2.0 to 4.5, as long as it has an unsaturated bond, preferably a carbon-carbon double bond. There is no limitation, and a linear, branched or network organic compound can be used. As the organic compound, organopolysiloxane or unsaturated aliphatic hydrocarbon is preferable. There is no limitation on the position of the unsaturated bond on the organic compound, preferably organopolysiloxane or unsaturated aliphatic hydrocarbon, and it may be located either on the main chain or at the end. However, from the viewpoint of easy control of the crosslinking density, it is preferable to use a high-purity compound having two unsaturated groups in one molecule, for example, those positioned at both ends.

The unsaturated bond is preferably present in the unsaturated aliphatic hydrocarbon group. The unsaturated aliphatic hydrocarbon group preferably has 2 to 30 carbon atoms, and more preferably has 2 to 20 carbon atoms. Examples of the monovalent unsaturated aliphatic hydrocarbon group having 2 to 30 carbon atoms include vinyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, pentenyl, and hexenyl. A linear or branched alkenyl group such as a group; a cycloalkenyl group such as a cyclopentenyl group or a cyclohexenyl group; a cycloalkenylalkyl group such as a cyclopentenylethyl group, a cyclohexenylethyl group or a cyclohexenylpropyl group; and an ethynyl group And alkynyl groups such as propargyl group. Alkenyl groups are preferred, with vinyl and hexenyl groups being particularly preferred.

When the component (C1) is an organopolysiloxane, the unsaturated aliphatic hydrocarbon group containing an unsaturated bond is preferably bonded to a silicon atom. When the component (C1) is an organopolysiloxane, the group bonded to the silicon atom other than the unsaturated aliphatic hydrocarbon has a substituted or unsubstituted monovalent hydrocarbon group or a reactive functional group. It can be a monovalent organic group.

The substituted or unsubstituted monovalent hydrocarbon group is typically a substituted or unsubstituted, linear or branched, 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, more preferably A monovalent saturated hydrocarbon group having 1 to 4 carbon atoms and a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably 6 to 12 carbon atoms. The component (C1) may have a C 1-12 alkoxy group such as a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group as a monovalent organic group.

Examples of the monovalent saturated hydrocarbon group having 1 to 30 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. A linear or branched alkyl group such as a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group, and a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Can be mentioned.

Examples of the monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms include aryl groups such as phenyl, tolyl, xylyl, and mesityl groups. A phenyl group is preferred. In addition, in this specification, the aromatic hydrocarbon group includes a group in which an aromatic hydrocarbon and an aliphatic saturated hydrocarbon are combined in addition to a group consisting of only an aromatic hydrocarbon. Examples of the group in which an aromatic hydrocarbon and a saturated hydrocarbon are combined include an aralkyl group such as a benzyl group or a phenethyl group.

The hydrogen atom on the monovalent hydrocarbon group may be substituted with one or more substituents, and examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), a hydroxyl group , An amide group, an ester group, a carboxyl group, and an isocyanate group. A monovalent saturated or aromatic hydrocarbon group having at least one substituent is preferred. Specifically, 3,3,3-trifluoropropyl group, 3-chloropropyl group, 3-hydroxypropyl group, 3- (2-hydroxyethoxy) propyl group, 3-carboxypropyl group, 10-carboxydecyl group And 3-isocyanatopropyl group.

Examples of the monovalent organic group having a reactive functional group include a reactive functional group selected from the group consisting of a hydroxyl group, a mercapto group, an epoxy group, an amino group, an amide group, an ester group, a carboxyl group, and an isocyanate group. And monovalent saturated or aromatic hydrocarbon groups. There may be one or more reactive functional groups present in the monovalent organic group. Preferred R ¹ is a monovalent saturated or aromatic hydrocarbon group having at least one reactive functional group as described above. Specific examples of the reactive functional group include a 3-hydroxypropyl group, a 3- (2-hydroxyethoxy) propyl group, a 3-mercaptopropyl group, a 2,3-epoxypropyl group, and a 3,4-epoxybutyl group. 4,5-epoxypentyl group, 2-glycidoxyethyl group, 3-glycidoxypropyl group, 4-glycidoxybutyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3 , 4-epoxycyclohexyl) propyl group, aminopropyl group, N-methylaminopropyl group, N-butylaminopropyl group, N, N-dibutylaminopropyl group, 3- (2-aminoethoxy) propyl group, 3- ( 2-aminoethylamino) propyl group, 3-carboxypropyl group, 10-carboxydecyl group, 3-isocyanatopropyl group, etc. Door can be.

As the component (C1), a linear, cyclic or branched polysiloxane is preferable. The linear component (C1) is preferably a polymer containing a diorganosiloxane unit and a triorganosiloxy unit. For example, dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain, dimethyl at both ends of the molecular chain. Vinylsiloxy group-blocked dimethylsiloxane / methylphenylsiloxane copolymer, molecular chain both ends dimethylvinylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, molecular chain both ends trimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer Dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer blocked with trimethylsiloxy group at both ends of molecular chain, dimethylsiloxane / methylvinylsiloxane copolymer blocked with silanol group at both ends of molecular chain, A polymer in which part of the methyl group is substituted with an alkyl group other than a methyl group such as an ethyl group or a propyl group, or a halogenated alkyl group such as a 3,3,3-trifluoropropyl group, and A mixture of two or more kinds of coals is exemplified, and in particular, a linear diorganopolysiloxane having an unsaturated aliphatic hydrocarbon group, particularly an alkenyl group only at both ends of the molecular chain is preferable.

The branched (C1) component is particularly preferably a polymer containing a diorganosiloxane unit, an organosilsesquioxane unit, and a triorganosiloxy unit. Examples of silicon-bonded organic groups in these units include alkyl groups such as methyl, ethyl, and propyl; alkenyl groups such as vinyl, allyl, butenyl, and hexenyl; and aryls such as phenyl and tolyl. A monovalent hydrocarbon group such as a halogenated alkyl group such as a 3,3,3-trifluoropropyl group, and may have a very small amount of a hydroxyl group, and further an alkoxy group such as a methoxy group, The at least two silicon-bonded organic groups in the polymer must be unsaturated aliphatic hydrocarbon groups, especially alkenyl groups. The ratio of these units is not limited, but in this polymer, the amount of diorganosiloxane units is in the range of 80.00 to 99.65 mol%, and the organosilsesquioxane units are 0.10 to Preferably the amount is in the range of 10.00 mol% and the remaining mol% is triorganosiloxy units.

Examples of the component (C1) that is a cyclic polysiloxane include methylvinylcyclosiloxane and methylhexenylcyclosiloxane.

As the component (C1), for example, the average composition formula (22):
R ³² _p R ³³ _q SiO _{(4-pq) / 2} (22)
(In the formula (22), R ³² may be independent of each other but represents a monovalent organic group different from R ^33, and R ³³ is independently of each other a monovalent group having 2 to 30 carbon atoms. (C1-5) an unsaturated group-containing silicone compound represented by a saturated aliphatic hydrocarbon group and 1.0 ≦ p ≦ 2.5 and 0.001 ≦ q ≦ 1.5. It is done. The monovalent unsaturated aliphatic hydrocarbon group having 2 to 30 carbon atoms is as described above.

In the average composition formula (22), the monovalent organic group as R ³² is not particularly limited, but the following (E1) to (E6):
(E1) A substituted or unsubstituted, straight-chain or branched monovalent hydrocarbon group having 1 to 60 carbon atoms (however, a monovalent hydrocarbon having 2 to 20 carbon atoms having an aliphatic unsaturated group) (Excluding groups)
(E2) hydroxyl ^(E3) -R 30 -COOR ³¹ ^{^(wherein, R 30} and ^{R 31} being as described above) ester group ^(E4) -R 17 -OCOR ¹⁸ ^(wherein represented ^{by, R 17} And R ¹⁸ is as described above) (E5) —R ²¹ —NR ²² COR ²³ (wherein R ²¹ is a substituted or unsubstituted, straight chain having 2 to 20 carbon atoms) Represents a linear or branched divalent hydrocarbon group, R ²² represents a hydrogen atom or a substituted or unsubstituted, linear or branched monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ²³ represents An amide group (E6) -R ²⁴ -CONR ²⁵ R ²⁶ (representing a substituted or unsubstituted, straight-chain or branched monovalent hydrocarbon group having 1 to 30 carbon atoms) ²⁴ is a substituted or non-substituted group having 2 to 20 carbon atoms. Represents a substituted linear or branched divalent hydrocarbon group, and R ²⁵ and R ²⁶ each independently represents a hydrogen atom or a substituted or unsubstituted linear or branched group having 1 to 20 carbon atoms. A monovalent hydrocarbon group in the form of an amide group). The definition, type, etc. of the substituted or unsubstituted linear or branched monovalent hydrocarbon group or divalent hydrocarbon group are as described above.

On the other hand, the component (C1) may be an unsaturated aliphatic hydrocarbon. Examples of the unsaturated aliphatic hydrocarbon include those having two or more unsaturated bonds such as diene, diyne, and enyne. Diene, diyne, and enyne are preferable in terms of crosslinking. Diene, diyne, and enyne are a group of compounds having a structure in which at least two unsaturated bonds are separated by one or more, preferably two or more single bonds in the molecule. These unsaturated aliphatic hydrocarbon groups may exist at the end of the molecular chain or may exist as a pendant group in the middle of the molecular chain.

Examples of the unsaturated aliphatic hydrocarbon as the component (C1) include α, ω-unsaturated alkenes and alkynes having 2 to 30 carbon atoms. Examples of the component (C1) include the general formula (22-1):
CH ₂ = CH (CH ₂ ) _x CH = CH ₂ (22-1)

(C1-1) α, ω-diene represented by (in formula (22-1), 1 ≦ x ≦ 20), formula (22-2):
CH≡C (CH ₂ ) _x C≡CH (22-2)

Α, ω-diyne (C1-2) represented by (in formula (22-2), 1 ≦ x ≦ 20), formula (22-3):
CH ₂ = CH (CH ₂ ) _x C≡CH (22-3)

(C1-3) α, ω-en-in represented by (in general formula (22-3), 1 ≦ x ≦ 20), general formula (22-4):
C _m H _2m-1 O (C _n H _2n O) _y C _m H _2m-1 (22-4)

(In general formula (22-4), 2 ≦ m ≦ 20, 2 ≦ n ≦ 4, y is the total number of repeating oxyethylene units, oxypropylene units, and oxybutylene units, and 1 ≦ y ≦ 180 (C1-4) bisalkenyl polyether compounds represented by

Specific examples of the unsaturated aliphatic hydrocarbon as the component (C1) include 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, Examples include 1,9-decadiene, 1,11-dodecadiene, 1,13-tetradecadiene, 1,19-eicosadiene, 1,3-butadiene, 1,5-hexadiyne, 1-hexene-5-in and the like.

The component (C1) can be used alone, or two or more components having different structures can be used in combination. That is, the component (C1) may be a mixture of one or more types of organopolysiloxane and one or more types of unsaturated aliphatic hydrocarbons. Therefore, “having an average number of unsaturated bonds greater than 1” here means that when two or more organopolysiloxanes and / or unsaturated aliphatic hydrocarbons are used, the average is 1 It means having more than one unsaturated bond per molecule.

(C2) Component (C2) As an organic compound having one or more unsaturated bonds and one or more epoxy groups in one molecule, a total of two or more, preferably 2 to 10, more preferably in one molecule There is no structural limitation as long as it has 2 to 7, more preferably 2 to 5, particularly preferably 2 to 4 unsaturated bonds and an epoxy group, and a linear, branched or network-like organic compound is used. Can be used. As the organic compound, organopolysiloxane or unsaturated aliphatic hydrocarbon is preferable. There is no limitation on the position of the unsaturated bond on the organic compound, preferably organopolysiloxane or unsaturated aliphatic hydrocarbon, and it may be located either on the main chain or at the end. However, from the viewpoint of easy crosslink density control, it is preferable to use a high-purity compound in which the total of unsaturated groups and epoxy groups in one molecule is 2.

The unsaturated bond is preferably present in the unsaturated aliphatic hydrocarbon group. Examples of the unsaturated aliphatic hydrocarbon group include those described above.

When component (C2) is an organopolysiloxane, the unsaturated aliphatic hydrocarbon group and / or epoxy group containing an unsaturated bond are preferably bonded to a silicon atom. When the component (C2) is an organopolysiloxane, the group bonded to the silicon atom other than the unsaturated aliphatic hydrocarbon or epoxy group is the above-described substituted or unsubstituted monovalent hydrocarbon group, or , A monovalent organic group having a reactive functional group.

As the component (C2), an epoxy group-containing unsaturated aliphatic hydrocarbon having at least one epoxy group is preferable. Examples of the unsaturated aliphatic hydrocarbon include the compounds having an unsaturated aliphatic hydrocarbon group described above. A compound having a monounsaturated aliphatic hydrocarbon group is preferred.

As the component (C2), for example, the general formula (22-6):

(In the general formula (22-6), R ⁴ has one unsaturated bond, and is a substituted or unsubstituted, linear or branched monovalent hydrocarbon having 2 to 20 carbon atoms. (C2-1) unsaturated epoxy compound represented by the general formula (22-7):

(In the general formula (22-7), R ⁵ has one unsaturated bond, and is a substituted or unsubstituted, linear or branched monovalent hydrocarbon having 2 to 20 carbon atoms. represents a group, R ⁶ represents a hydrogen atom or a methyl group, R ⁷ is represented by a hydrogen atom or a methyl group) include (C2-2) unsaturated group-containing alicyclic epoxy compound. The definitions, types, and the like of the unsaturated bond and the substituted or unsubstituted linear or branched monovalent hydrocarbon group in the above general formula are as described above.

Specific examples of the epoxy group-containing unsaturated aliphatic hydrocarbon as the component (C2) include allyl glycidyl ether, methallyl glycidyl ether, 1-methyl-4-isopropenyl cyclohexene oxide, and 1,4-dimethylcyclohexene oxide. 4-vinylcyclohexene oxide, vinyl norbornene monoxide, dicyclopentadiene monooxide, butadiene monoxide, 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene, 2,6-dimethyl-2, 3-epoxy-7-octene is exemplified. Among these, 4-vinylcyclohexene oxide is preferable. Examples of the unsaturated aliphatic hydrocarbon having a cyclic structure include dicyclopentadiene, divinylbenzene, cyclohexadiene, cyclooctadiene, and cyclopentadiene.

The component (C2) can be used alone, or two or more components having different structures can be used in combination.

The reaction for producing the sugar derivative-modified crosslinked silicone can be performed according to a known method in the presence or absence of a reaction solvent. The reaction between the unsaturated group and the Si—H group is a hydrosilylation reaction. (C2) When crosslinking is performed using an organic compound epoxide having one or more reactive unsaturated groups and one or more epoxy groups in one molecule, the reaction between the unsaturated group and the Si—H group. And the formation of an ether bond by self-ring-opening polymerization between epoxy groups (cationic polymerization reaction that occurs in the presence of a Si—H group and a platinum catalyst) occurs to form a bridge. In order to accelerate this reaction, irradiation with high energy rays such as ultraviolet rays or a general catalyst for cationic polymerization can be further added.

The reaction solvent is not particularly limited as long as it is non-reactive, but alcohol solvents such as ethanol and isopropyl alcohol; aromatic hydrocarbon solvents such as toluene and xylene; ether solvents such as dioxane and THF An aliphatic hydrocarbon solvent such as n-hexane, cyclohexane, n-heptane, cycloheptane, and methylcyclohexane; and a chlorinated hydrocarbon organic solvent such as carbon tetrachloride. You may use the oil agent mentioned later as a reaction solvent. When an oil agent is used as the reaction solvent, a liquid sugar derivative-modified silicone having a sugar derivative group-containing organic group bonded to a silicon atom after the crosslinking reaction and having a crosslinked structure containing a carbon-silicon bond in the crosslinked portion; A composition comprising an oil agent can be obtained directly.

The hydrosilylation reaction can be performed as described above.

By the hydrosilylation reaction or the cationic polymerization reaction of the epoxy group, the (A) component is crosslinked by the (C) component, and the polysiloxane chain derived from the (A) component includes a carbon-silicon bond derived from the (C) component. Connected by Moreover, (A) component is equipped with the sugar derivative group containing organic group derived from (B) component. In this way, a sugar derivative-modified crosslinked silicone having a crosslinked structure can be obtained.

The sugar derivative-modified cross-linked silicone having a cross-linked structure essentially has a structure in which it is connected by a cross-linked portion containing a carbon-silicon bond derived from the component (C). It may have a cross-linked part by —C bond. This structure can be formed between polysiloxane chains when the components (A) to (C) have functional groups capable of condensation reaction such as silanol groups and alkoxy groups, and when the crosslinking conditions are severe, This is because the hydroxyl group in the sugar derivative group derived from the component (B) can be partially formed by partially reacting with the Si—H group in (A).

In the production of the sugar derivative-modified crosslinked silicone having the crosslinked structure, the component (C) may be further reacted with the component (A) after the reaction between the component (A) and the component (B). And (B) component may be further reacted with (A) component after the reaction of (C) component.

When the (C) component is further reacted with the (A) component after the reaction between the (A) component and the (B) component, it reacts with the reactive unsaturated group of the (C) component per molecule of the (A) component. The average value of the number of silicon atom-bonded hydrogen atoms is preferably 1.0 or more. That is, the number of silicon atom-bonded hydrogen atoms per molecule in the component (A) that constitutes a crosslinked part and reacts with the reactive unsaturated group in the component (C) is 1.0 or more on average. It is preferably in the range of 0.2 to 1.5, particularly preferably in the range of 0.6 to 1.3.

In producing the sugar derivative-modified crosslinked silicone having the crosslinked structure, in addition to the components (A), (B) and (C), (Q) an organic compound having one reactive unsaturated group in one molecule. The compound (excluding the component (C2)) may be further reacted. One type of (Q) component may be used, or two or more types of (Q) component may be used. The reaction can be carried out sequentially, preferably in the presence of a hydrosilylation reaction catalyst. In addition, the definition, kind, etc. of the reactive unsaturated group in the component (Q) are as described above.

For example, when the (C) component is further reacted with the (A) component after the reaction between the (A) component and the (B) component, the (Q) component is added before the reaction between the (A) component and the (B) component. (A) It reacts with component, (A) component reacts with (B) component after (A) component reacts with (A) component, or (C) after further reaction with (Q) component You may make it react with (A) component.

For example, when the component (B) is further reacted with the component (A) after the reaction between the component (A) and the component (C), the component (Q) is added before the reaction between the component (A) and the component (C). (A) the component is reacted, the component (A) is reacted with the component (C), the component (Q) is reacted with the component (A), or the component (Q) is further reacted with the component (B). You may make it react with (A) component.

As the component (Q), for example, (Q1) a siloxane dendron compound having one reactive unsaturated group in one molecule, (Q2) a hydrocarbon compound having one reactive unsaturated group in one molecule, or a reaction Chain organopolysiloxane having one unsaturated group per molecule.

(Q1) As the siloxane dendron compound having one reactive unsaturated group in one molecule, the compound of the above general formula (3 ') is preferable.

(Q2) As the hydrocarbon compound having one reactive unsaturated group in one molecule or the chain organopolysiloxane having one reactive unsaturated group in one molecule, the above general formula (2-1) and The compound of the above general formula (2 ′) having the group (2-2) is preferable.

(Q2) Examples of the hydrocarbon compound having one reactive unsaturated group in one molecule include those similar to the above-mentioned (e) hydrocarbon compound having one reactive unsaturated group in one molecule. .

[Water addition process]
The method for producing a transparent or translucent liquid sugar derivative-modified silicone composition according to the present invention includes a water addition step of adding water to the liquid sugar derivative-modified silicone or composition thereof.

The amount of water added in the water addition step is not particularly limited, but is 0.1 to 10 parts by weight, preferably 0.2 to 10 parts by weight with respect to 100 parts by weight of the liquid sugar derivative-modified silicone or composition thereof. 5 parts by weight, more preferably 0.5 to 3 parts by weight of water can be added. An amount in which the light transmittance of the composition after mixing and homogenization described later exhibits a maximum value (peak value) is preferable. In the vicinity of the optimum amount of water added, the appearance of the composition becomes a transparent or translucent uniform liquid at a temperature at which the composition exhibits a liquid state, and the stability of the composition is also optimal.

The water used in the water addition step 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. Water added in the range of 0.09 to 9% by weight, preferably 0.1 to 5% by weight, more preferably 0.4 to 3% by weight of the total composition after the addition of water can be used.

Mixing and homogenization is preferably performed by mixing using mechanical force, and can be performed, for example, in a paddle mixer, a propeller stirrer, a reactor or a container equipped with stirring blades, and an emulsifier or kneader as necessary. Etc. can also be used. The mixing and homogenization is not necessarily performed at room temperature, and the temperature can be adjusted according to the composition, fluidity, and the like. Usually, it is preferably carried out within the range from 0 to around 70 ° C. The same applies to the mixing and homogenization of the sugar derivative-modified silicone or the composition thereof and the liquid oil described later to obtain the sugar derivative-modified silicone composition according to the present invention.

The transparent or translucent liquid sugar derivative-modified silicone composition after the water addition step preferably has a visible light transmittance of 50% or more, more preferably 70% or more, and even more preferably 80% or more. The visible light transmittance of the liquid sugar derivative-modified silicone composition before the water addition step is often less than 50%, more often less than 25%, and usually less than 5%. . As visible light, light having a wavelength of 360 to 830 nm is preferable, but light having a wavelength of 400 to 760 nm is more preferable. For example, 750 nm wavelength light can be used. Further, the transmittance measurement is preferably an optical path length of 1 to 30 mm, more preferably an optical path length of 5 to 20 mm. For example, it can be performed with an optical path length of 10 mm. The transparent or translucent liquid sugar derivative-modified silicone composition obtained by the present invention after the water addition step has a light transmittance of 50 measured in particular with an optical path length of 10 mm using light having a wavelength of 750 nm. % Or more, more preferably 70% or more, and still more preferably 80% or more. Such a sugar derivative-modified silicone composition is visually transparent or translucent and exhibits a substantially transparent appearance.

The content of the sugar derivative-modified silicone in the transparent or translucent liquid sugar derivative-modified silicone composition after the water addition step (and before the addition of the liquid oil described later) is not particularly limited. From 50 to 99.99% by weight, preferably from 70 to 99.9% by weight, and more preferably from 90 to 99% by weight, based on the total weight.

[Liquid oil addition process]
In the production method of the present invention, a liquid oil addition step of adding a liquid oil agent to the liquid sugar derivative-modified silicone or a composition thereof before and / or after the water addition step and / or simultaneously with the water addition step is further performed. Can be included. Here, “liquid” means as described above.

The liquid oil agent preferably has an affinity for the liquid sugar derivative-modified silicone. Preferably, the oil is one or more oils selected from silicone oil, nonpolar organic compound or low to high polarity organic compound that is liquid at 5 to 100 ° C., and nonpolar organic compound and low to high polarity organic compound As hydrocarbon oil, fatty acid ester oil and liquid fatty acid triglyceride are preferable. These are components that are widely used especially as base materials for cosmetics, but these oils include known vegetable oils, animal fats, higher alcohols, fatty acid triglycerides, artificial sebum, fluorine-based oils. You may use together 1 type selected from oil, or 2 or more types. A composition containing a sugar derivative-modified silicone modified with the sugar derivative exhibits excellent compatibility and dispersibility even with non-silicone oils when the sugar derivative-modified silicone has a long-chain alkyl group. Further, hydrocarbon oils, fatty acid ester oils, and the like can be stably blended in cosmetics, and the moisturizing characteristics of these non-silicone oils can also be utilized. Therefore, a composition containing a sugar derivative-modified silicone modified with the sugar derivative can improve the blending stability of these non-silicone oils in cosmetics.

Also, by using hydrocarbon oil and / or fatty acid ester oil together with silicone oil, in addition to the refreshing feel unique to silicone oil, it retains moisture on the skin and moisturizes skin and hair in cosmetics. A moisturizing feeling (also referred to as “moist feeling”) and a smooth feel can be imparted, and there is an advantage that the temporal stability of the cosmetic is not impaired. Furthermore, cosmetics containing hydrocarbon oils and / or fatty acid ester oils and silicone oils apply these moisturizing ingredients (hydrocarbon oils and / or fatty acid ester oils) on the skin or hair in a more stable and uniform state. Therefore, the moisturizing effect of the moisturizing component on the skin is improved. Therefore, compared with cosmetics containing only non-silicone oils (hydrocarbon oil, fatty acid ester oil, etc.), cosmetics containing silicone oil together with non-silicone oils can give a smoother and moist feel. There is an advantage that you can.

These oil agents are the same as those disclosed by the applicants in paragraphs 0141 to 0150 of the above-mentioned Patent Document 28 (Japanese Patent Laid-Open No. 2012-246446).

The addition amount of the liquid oil agent in the liquid oil agent addition step is not particularly limited, but is 5 to 1000 parts by weight, preferably 10 to 500 parts by weight with respect to 100 parts by weight of the liquid sugar derivative-modified silicone or composition thereof. Parts, more preferably 50 to 200 parts by weight of a liquid oil agent can be added.

In the liquid oil agent addition step, the liquid sugar derivative-modified silicone or composition thereof (or the transparent or translucent liquid sugar derivative-modified silicone composition after the water addition step) and the liquid oil agent are as described above. It is preferable to mix and homogenize.

Unlike conventional polyether-modified silicones and the like, the sugar derivative-modified silicone composition according to the present invention is essentially stable with little tendency to be oxidized and deteriorated by oxygen in the air. Therefore, it is not essential to add an antioxidant such as phenols, hydroquinones, benzoquinones, aromatic amines, or vitamins to increase oxidative stability in order to prevent oxidative degradation. However, the addition of such antioxidants such as BHT (2,6-di-t-butyl-p-cresol), 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 derivative-modified silicone.

The transparent or translucent liquid sugar derivative-modified silicone composition after the liquid oil addition step preferably has a visible light transmittance of 50% or more, more preferably 70% or more, and even more preferably 80% or more. . As visible light, light having a wavelength of 360 to 830 nm is preferable, but light having a wavelength of 400 to 760 nm is more preferable. For example, 750 nm wavelength light can be used. Further, the transmittance measurement is preferably an optical path length of 1 to 30 mm, more preferably an optical path length of 5 to 20 mm. For example, it can be performed with an optical path length of 10 mm. In particular, the light transmittance measured at an optical path length of 10 mm using light having a wavelength of 750 nm is 50% or more, more preferably 70% or more, and even more preferably 80% or more.

The content of the sugar derivative-modified silicone in the transparent or translucent liquid sugar derivative-modified silicone composition after the liquid oil addition step is not particularly limited, but is 10 based on the total weight of the composition. ˜99 wt% is preferred, 40˜95 wt% is preferred, and 80˜90 wt% is more preferred.

(Acid treatment and odor reduction of sugar derivative-modified silicone or composition thereof)
In the production method of the present invention, the sugar derivative-modified silicone or its composition (mixture) is treated with an acidic substance, and odorous substances and low-boiling components generated by the treatment of the acidic substance are removed by heating or decompression. If so, a higher quality sugar derivative-modified silicone or a composition thereof can be obtained. The treatment can be carried out in the presence of a nonpolar solvent and / or a polar solvent and / or water, but the acidic substance is preferably used by being dissolved or dispersed in a polar solvent such as water. More preferably, the treatment is performed in a form containing an aqueous solution.

The acidic substance contained in the acidic aqueous solution can be arbitrarily selected, but it is solid at 25 ° C. and water-soluble, and the pH at 25 ° C. of the aqueous solution when 50 g is dissolved in 1 L of ion-exchanged water. It is optimal to use one or more acidic inorganic salts characterized in that is 4 or less.

The treatment with the acidic aqueous solution can be most preferably carried out when the liquid sugar derivative-modified silicone is synthesized by a hydrosilylation reaction, and the liquid sugar derivative-modified silicone is the liquid sugar derivative-modified crosslinked. Even if it is silicone, it can implement suitably. Here, for the sake of simplicity, as an example of the acid treatment and odor reduction method for a sugar derivative-modified silicone or a mixture containing the same, a case of a sugar derivative-modified silicone synthesized by a hydrosilylation reaction and containing no crosslinked structure will be described as an example. To do.

Preferably, the acid treatment is
(Ax) a sugar derivative having a carbon-carbon double bond at the end of a molecular chain, and (bx) a sugar derivative-modified silicone or a reaction mixture containing it as a main component by hydrosilylation reaction of an organohydrogenpolysiloxane. Or after the synthesis step [V], or after the synthesis step [V]
A sugar derivative-modified silicone or a reaction mixture containing it as a main component,
(Cx) Presence of one or more kinds of acidic inorganic salts that are solid at 25 ° C., water-soluble, and have 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. Process to process below [W]
including. In addition, since the treatment step using the acidic inorganic salt involves generation of an odor-causing substance, it may include a step of removing the odor-causing substance by heating or decompressing after the step [W]. More preferable from the viewpoint of effectiveness.

As an example, in step [V], (ax) a sugar derivative such as (poly) sugar monoallyl ether, (bx) a linear organohydrogenpolysiloxane represented by the structural formula (1-1A) is used. When the above hydrosilylation reaction is performed on the silicon-bonded hydrogen atom in the component (bx) in an amount that makes the amount of the component (ax) excessive, the sugar derivative represented by the structural formula (1-1) A modified silicone is synthesized, and a crude product of the reaction mixture containing the sugar derivative-modified silicone as a main component and containing the sugar derivative-modified silicone and an unreacted component (ax) is obtained.

In the step (W), the crude product is hydrolyzed using a specific acidic inorganic salt, so that the silicon-oxygen bond constituting the main chain of the polysiloxane and the carbon-oxygen bond in the side chain portion can be cleaved. This is a process for causing the sugar derivative-modified silicone or its composition to be low bromide at a high level and effectively suppressing the generation of odor over time.

Specifically, the step (W) is a step of removing odor-causing substances from a crude product of a reaction mixture containing a sugar derivative-modified silicone as a main component by hydrolysis, and (cx) a solid at 25 ° C. Yes, in the presence of one or more kinds of acidic inorganic salts, characterized in that the aqueous solution when dissolved in 1 L of ion-exchanged water has a pH at 25 ° C. of 4 or less when dissolved in 1 L of ion-exchanged water. It is characterized by performing. The pH value of the sample aqueous solution can be measured at room temperature (25 ° C.) using a pH meter using a glass electrode. Specifically, “HM-10P” manufactured by Toa Denpa Kogyo Co., Ltd. Can be used.

The acidic inorganic salt as the component (cx) is solid at 25 ° C., water-soluble, and the pH of the aqueous solution when 50 g is dissolved in 1 L of ion-exchanged water needs to be 4 or less. More preferably, the pH is preferably 3.5 or less, and particularly preferably 2.0 or less. By hydrolyzing the sugar derivative-modified silicone or a composition thereof using such a water-soluble acidic inorganic salt, the sugar derivative-modified silicone or a mixture thereof can be obtained without almost cutting the C—O bond or the Si—O bond. The composition can be low bromide at a high level to effectively suppress odor formation over time.

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 component (cx) is at least one acidic inorganic salt 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. Moreover, these acidic inorganic salts may be used individually by 1 type, and may be used in combination of 2 or more types. Furthermore, since these acidic inorganic salts are solid at room temperature (25 ° C.), they can be easily removed by filtration after the treatment. Moreover, since it is water-soluble, it can be easily washed away with water even in a washing step after production.

On the other hand, in the hydrolysis treatment with an acetate or a phosphate that does not satisfy the condition of the component (cx), the sugar derivative-modified silicone or the composition after hydrolysis cannot be sufficiently low-brominated. On the other hand, the hydrolysis treatment with a strong acid such as hydrochloric acid or the hydrolysis treatment with a known solid acid such as zirconia sulfate can achieve a certain degree of low bromination, but at the time of hydrolysis, the CO bond or Si— O-bond breakage is likely to occur.

Specific examples of the acidic inorganic salt as the component (cx) include lithium hydrogen sulfate, sodium hydrogen sulfate, potassium hydrogen sulfate, rubidium hydrogen sulfate, cesium hydrogen sulfate, ammonium hydrogen sulfate, sodium hydrogen sulfite, and hydrates thereof. Illustrated. The pH of the aqueous solution when 50 g of the acidic inorganic salt is dissolved in 1 L of ion-exchanged water is as shown 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.

The treatment in the presence of the acidic inorganic salt is carried out, for example, in (1) a reaction system of a reaction mixture (for example, a reaction vessel such as a flask) containing a sugar derivative-modified silicone synthesized by a hydrosilylation reaction as a main component. (2) An acidic inorganic salt and water or an acidic inorganic salt and water and a hydrophilic solvent are added and stirred, and the like. It is preferable to perform the process using an acidic inorganic salt in the presence of water and / or a hydrophilic medium.

In particular, after the step [V], at least an acidic inorganic salt and water are added to a reaction system containing a crude product of a reaction mixture containing a sugar derivative-modified silicone as a main component to improve compatibility in some cases. Hydrolysis treatment in which another hydrophilic solvent is further added for the purpose of increasing treatment efficiency and stirring is further performed using mechanical force is preferable. The hydrolysis treatment can be carried out by selecting an arbitrary temperature and treatment time. The temperature is 0 to 200 ° C., more preferably 50 to 100 ° C., and 0.1 to 24 hours, more preferably 0.5 to The reaction time is preferably about 10 hours. The amount of the acidic inorganic salt used can be appropriately selected according to the treatment apparatus and treatment time, but is preferably in the range of 50 to 10,000 ppm, preferably 100 to 5 with respect to the reaction mixture containing the sugar derivative-modified silicone as a main component. A range of 1,000 ppm is more preferred.

After the acid treatment, it is preferable to include a stripping step for removing a low boiling point component (propionaldehyde or the like) which is a substance causing odor. Further, after stripping, the treatment in the presence of an acidic inorganic salt can be performed again to hydrolyze more propenyl ether group-containing sugar derivatives and the like, and to remove odor-causing substances such as propionaldehyde. . At this time, since the acidic inorganic salt remains, there is no need to newly add an acidic inorganic salt, and there is an advantage that only a hydrophilic solvent represented by water needs to be added. That is, the above step [W] and the stripping step can be repeated twice or more for the purpose of increasing the degree of low bromide.

The “low boiling point” distilled off in the stripping process includes propionaldehyde, which is the cause of odor, as well as the reaction solvent used in the hydrosilylation reaction (process [V]) and the low bromide treatment process. Used water and other hydrophilic solvents are included.

The stripping step (distillation of low-boiling substances) may be carried out on the crude product of the reaction mixture containing the sugar derivative-modified silicone as a main component as the previous step of the step [W], or the step [W]. As a subsequent step, the reaction mixture containing a sugar derivative-modified silicone as a main component may be carried out. Moreover, it can also implement as a pre-process and a post-process of process [W], respectively. Preferably, the step [W] is preferably carried out for the purpose of removing propionaldehyde which is an odor-causing substance generated by the hydrolysis reaction.

As a removal method, stripping under normal pressure or reduced pressure is preferable, and it is preferable to carry out 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 of distilling off low-boiling substances is as follows. A crude product of a reaction mixture containing a sugar derivative-modified silicone containing low-boiling substances as a main component is equipped with a reflux condenser, a nitrogen insertion port, etc. The flask is charged, the inside is depressurized while supplying nitrogen gas, the temperature is raised, and the light matter is distilled off by maintaining the pressure and temperature constant. In general, the decompression condition is 0.1 to 10.0 KPa, the heating temperature is 40 to 120 ° C., and the treatment time is 10 minutes to 24 hours.

Further, after the acid treatment step, the reaction mixture containing a sugar derivative-modified silicone as a main component may be neutralized with a basic substance. Examples of basic substances include inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, aqueous ammonia and sodium hydrogen carbonate, various amines, and organic bases such as basic amino acids. . The amount of the basic substance is preferably an amount that neutralizes the reaction system containing the reaction mixture containing the sugar derivative-modified silicone as a main component, but the amount added may be adjusted so as to be weakly acidic or weakly alkaline as necessary. it can.

Note that an alkaline buffering agent in an amount corresponding to 100 ppm to 50000 ppm may be further added to the reaction mixture containing the sugar derivative-modified silicone obtained as a main component after the acid treatment step. In the reaction mixture containing the sugar derivative-modified silicone as a main component, a trace amount of acid may be locally dissolved even after neutralization or filtration. By adding an alkaline buffer, the liquidity of cosmetics and the like containing the sugar derivative-modified silicone is maintained on the alkali side, thus reducing the risk of odor generation due to impurities of the sugar derivative-modified silicone. be able to. The useful alkaline buffer is not particularly limited as long as it is an alkaline buffer composed of a combination of a strong base and a weak acid, but alkaline such as trisodium phosphate, tripotassium phosphate, trisodium citrate, and sodium acetate. Buffering agents are exemplified. These alkaline buffering agents may be added to sugar derivative-modified silicone or a cosmetic raw material comprising a mixture containing the same as a main component, and other sugar raw materials modified with other cosmetic raw materials and water. Or may be added to the preparation stage of the cosmetic or the composition after blending. Thereby, the odor in the prescription over time can be suppressed further effectively.

The sugar derivative-modified silicone or a mixture containing it as a main component can be subjected to a hydrogenation treatment as a pre-process or a post-process of the treatment in the presence of an acidic inorganic salt in the step [W]. In the non-bromide treatment by the hydrogenation reaction, the treatment by the hydrogenation reaction may be performed after the treatment in the presence of the acidic inorganic salt according to the step [W], while the treatment by the hydrogenation reaction is performed. You may process in presence of the acidic inorganic salt concerning said process [W]. However, the hydrogenation treatment may generally lead to an increase in cost during product manufacture.

The second aspect of the present invention is an external preparation, cosmetic or industrial material containing the sugar derivative-modified silicone composition obtained by the production method of the present invention.

Since the sugar derivative-modified silicone composition obtained by the production method of the present invention is a transparent or translucent liquid, it can be suitably blended in an external preparation or cosmetic, and constitutes the external preparation or cosmetic of the present invention. can do. Moreover, the raw material for external preparations and cosmetics containing the sugar derivative modified silicone composition obtained by the manufacturing method of this invention can be manufactured, and it can also mix | blend with external preparations or cosmetics.

In particular, the sugar derivative-modified silicone composition obtained by the production method of the present invention has high transparency, and since the transparency is stable with respect to temperature history and after long-term storage, it has a transparent or translucent appearance. Can be suitably blended in external preparations or cosmetics for which is required. In addition, the sugar derivative-modified silicone composition obtained by the production method of the present invention has low odor, and there is almost no odor during formulation or over time. Moreover, there is an advantage that the silicon-oxygen bond that can constitute the main chain of the sugar derivative-modified silicone and the carbon-oxygen bond that can constitute the side chain are hardly broken. Therefore, the sugar derivative-modified silicone composition obtained by the production method of the present invention can be suitably used as a raw material for external preparations and cosmetics used in the human body.

The proportion of the sugar derivative-modified silicone composition in the raw material for external preparations or cosmetics is preferably 10 to 100% by weight (mass) based on the total weight (mass) of the raw material, preferably 20 to 100% by weight. (Mass)% is more preferred, and 30 to 100 weight (mass)% is even more preferred. 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 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.

The sugar derivative-modified silicone composition obtained by the production method of the present invention has a patent document 25 (Japanese Patent Laid-Open No. 2011-246705) and a patent document 26 (Japanese Patent Laid-Open No. 2011-2011), depending on its structure and the type of functional group possessed. Novel organopolysiloxane described in JP-A-246706), low-odor sugar alcohol-modified silicone described in JP-A-2012-246445, or JP-A-2012-246446 It is possible to apply to a common use with the novel liquid organopolysiloxane described in Japanese Patent Publication No. In addition, the sugar derivative-modified silicone composition obtained by the production method of the present invention can be used in combination with arbitrary cosmetic raw material components, external preparations, especially cosmetic dosage forms, types and formulation examples. It can be used in the same manner as the novel organopolysiloxane described in Document 26, the low odor sugar alcohol-modified silicone described in Patent Document 27, or the novel organopolysiloxane described in Patent Document 28. Etc. can be blended.

If the external preparation composition which concerns on this invention is a composition applied to a human body as cosmetics or a pharmaceutical, there will be no restriction | limiting in particular. The cosmetics of the present invention include skin products such as skin cleanser products, skin care products, makeup products, antiperspirant products, UV protection products; hair cleanser products, hair styling products, Hair coloring products, hair nourishing products, hair rinse products, hair conditioner products, hair treatment products, etc .; Examples of the medicament of the present invention include, but are not limited to, hair growth agents, hair growth agents, analgesics, bactericides, anti-inflammatory agents, refreshing agents, and skin antiaging agents.

The above skin cosmetics can be used for any part of the scalp, face (including lips, eyebrows, cheeks), fingers, nails, and whole body. Specifically, cleansing gel, cleansing cream, cleansing foam, cleansing milk, cleansing lotion, facial cleansing cream, eye makeup remover, facial cleansing foam, liquid soap (body soap), hand soap, gel soap, solid soap, facial rinse, Skin cleansing products such as body rinses, shaving creams, light-removing agents, acne-preventive cosmetics; skin creams, scalp treatments, skin milk, milk lotion, milky lotion, moisturizing liquid, beauty liquid, facial pack, body Skin care products such as powders, essences, shaving lotions, massages; foundations, liquid foundations, oily foundations, makeup bases, white powders, face powders, lipsticks Lip balm, cream, lip gloss, eye shadow, eyeliner, eye cream, eyebrow, eyelash cosmetics, eyebrow pencil, eyebrow brush, mascara, blusher, cheek cosmetic (blusher, cheek color), nail polish, pedicure, nail color Examples include makeup products such as nail lacquer, enamel remover and nail polish; antiperspirants such as deodorants; and UV protection products such as sunscreen agents and sunscreen agents (suntan agents).

The above-mentioned cosmetics for hair include detergents for hair such as shampoo and rinse-in shampoo; hair-styling products such as hair oil, hair wax, hair curl retention agent, set agent, hair cream, hair spray, hair liquid, etc .; Hair coloring products such as hair color sprays, hair color rinses and hair color sticks; hair tonic products such as hair tonics, hair treatment essences and hair packs; oil rinses, cream rinses, treatment rinses, hair conditioners, hair treatments, etc. Examples are hair rinses or hair conditioning products. The bath cosmetics are exemplified by bath oil, bath salt, and foam bath.

The form of the external preparation composition according to the present invention, particularly the cosmetic, is not particularly limited, and is liquid, W / O emulsion, O / W emulsion, W / O cream, O / W cream, solid It can be preferably applied to a shape (stick shape, etc.), paste shape, gel shape, powder shape, multilayer shape, mousse shape, mist shape, granule shape, flake shape, aragonite shape and the like. Particularly preferred forms are W / O emulsion, W / O cream, solid, paste, gel, and powder.

The external preparation composition according to the present invention, in particular, a cosmetic container is not particularly limited, but a jar, a pump, a tube, a bottle, a pressure can discharge container, a pressure-resistant aerosol container, a light shielding container, a compact container, a metal plate, An arbitrary container such as a stick container, a feeding container, a spray container, or a container with a partition provided with a mixed solution discharge port can be filled. Tubes tend to be separated in ordinary silicone-based preparations, but the external preparation composition according to the present invention, especially cosmetics, is excellent in stability, and should be stored stably even when filled in such tube containers. There is a merit that it is possible.

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.

The water that can be used in the cosmetics or external preparations according to the present invention 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 sea water. .

(Oil)
The oil agent that can be used in the cosmetic or external preparation according to the present invention is preferably one or more selected from silicone oil, nonpolar organic compound, or low polarity to high polarity organic compound that is liquid at 5 to 100 ° C. As non-polar organic compounds and low to high polar organic compounds, hydrocarbon oils, fatty acid ester oils and liquid fatty acid triglycerides are preferable. These are components that are widely used especially as base materials for cosmetics, but these oils include known vegetable oils, animal fats, higher alcohols, fatty acid triglycerides, artificial sebum, fluorine-based oils. You may use together 1 type selected from oil, or 2 or more types.

(Powder or colorant)
The powder or colorant that can be used in the cosmetic or external preparation according to the present invention is generally used as a component of cosmetics, and includes white and colored pigments and extender pigments. White and colored pigments are used for coloring cosmetics, while extender pigments are used for improving the feel of cosmetics. As the “powder” in the present invention, white and colored pigments usually used in cosmetics, and extender pigments can be used without particular limitation. In this invention, it is preferable to mix | blend 1 type or 2 or more types of powder. Powder shape (spherical, rod-like, needle-like, plate-like, irregular shape, spindle-like, bowl-like, etc.), particle size (fog-like, fine particles, pigment grade, etc.), and particle structure (porous, nonporous) Etc.) is not limited at all, but the average primary particle diameter is preferably in the range of 1 nm to 100 μm. In particular, when these powders or colorants are blended as pigments, one or more kinds selected from inorganic pigment powders, organic pigment powders, and resin powders having an average particle diameter in the range of 1 nm to 20 μm. Is preferably blended.

Examples of the powder include inorganic powders, organic powders, surfactant metal salt powders (metal soaps), colored pigments, pearl pigments, metal powder pigments, and the like, which are combined. be able to. Furthermore, what gave the water repellency process to these surfaces can be mentioned.

These specific examples are common to the powder or colorant disclosed in paragraphs 0219 to 0226 of Patent Document 28.

Among the exemplified powders, the silicone elastomer powder will be specifically described. The silicone elastomer powder is a crosslinked product of a linear diorganopolysiloxane mainly composed of diorganosiloxy units (D units), and an organohydrogenpolysiloxane having a silicon-bonded hydrogen atom at the side chain or terminal and a side chain or A diorganopolysiloxane having an unsaturated hydrocarbon group such as an alkenyl group at the terminal can be suitably obtained by a crosslinking reaction under a hydrosilylation reaction catalyst. Silicone elastomer powder is softer and more resilient than silicone resin powder consisting of T units and Q units, and also has excellent oil absorption, so that it absorbs fats and oils on the skin and prevents breakup of makeup. it can. And, when the surface treatment is performed with the sugar derivative-modified silicone composition obtained by the production method of the present invention, it is possible to perform a homogeneous treatment with high treatment efficiency, without reducing the suede feel of the silicone elastomer powder, It is possible to impart a unique effect and feel according to the type of the sugar derivative-modified silicone. Furthermore, when the sugar derivative-modified silicone composition is blended with a silicone elastomer powder in a cosmetic, the dispersion stability of the powder in the entire cosmetic is improved, and a stable cosmetic can be obtained over time. .

The silicone elastomer powder can take various shapes such as a spherical shape, a flat shape, and an indefinite shape. The silicone elastomer powder may be in the form of an oil dispersion. The cosmetic of the present invention is a silicone elastomer powder having a particle shape, and has an average primary particle diameter measured by observation using an electron microscope and / or laser diffraction / scattering method of 0.1. Silicone elastomer powder that falls within a range of ˜50 μm and has a spherical primary particle shape can be suitably blended. The silicone elastomer constituting the silicone elastomer powder preferably has a hardness of 80 or less, more preferably 65 or less according to the type A durometer of JIS K 6253 “Testing method for hardness of vulcanized rubber and thermoplastic rubber”. .

Among these silicone elastomer powders, the specific example of the silicone elastomer spherical powder is the same as that disclosed in paragraph 0223 of Patent Document 28. As exemplified in the paragraphs 0224 to 0225, water repellency is achieved. Silicone elastomer powder that has been subjected to various surface treatments such as the above may be used.

The cosmetic or external preparation of the present invention can further contain other surfactants. These surfactants are components that function as a skin or hair washing component or an oil emulsifier, and a desired one can be selected according to the type and function of the cosmetic. More specifically, the other surfactant is selected from the group consisting of an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and a semipolar surfactant. In particular, it is preferable to use a silicone-based nonionic surfactant in combination.

These surfactants are the same as those disclosed in paragraphs 0237 to 0242 of Patent Document 28. Since the sugar derivative-modified silicone according to the present invention has a polar group and a nonpolar group in the molecule, it has a function as a dispersant. For this reason, when used in combination with a nonionic surfactant, it may function as an auxiliary to improve the stability of the nonionic surfactant, and may improve the stability of the entire preparation. In particular, since the sugar derivative-modified silicone composition obtained by the production method of the present invention has improved compatibility and affinity with various modified silicones, polyoxyalkylene-modified silicone (polyether-modified silicone), (poly) glycerin These silicone-based nonionic surfactants can be used in combination with derivative-modified silicones, etc., where alkyl branching, linear silicone branching, siloxane dendrimer branching, etc. are applied simultaneously with hydrophilic groups as needed. A thing can also be used suitably.

In the cosmetic or external preparation of the present invention, one or more polyhydric alcohols and / or lower monohydric alcohols can be used depending on the purpose. These alcohols are the same as those disclosed in paragraph 0227 of Patent Document 28.

In the cosmetic or external preparation of the present invention, one or more inorganic salts and / or organic acid salts can be used depending on the purpose. These salts are the same as those disclosed by the applicants in paragraph 0248 of Patent Document 28.

The cosmetic or external preparation of the present invention includes a crosslinkable organopolysiloxane, organopolysiloxane elastomer spherical powder, silicone resin, acrylic silicone dendrimer copolymer, silicone raw rubber, polyamide-modified silicone, alkyl-modified silicone wax depending on the purpose. In addition, at least one selected from the group consisting of alkyl-modified silicone resin waxes can be used. These silicone components are the same as those disclosed in paragraphs 0262 to 0287 of Patent Document 28.

In the cosmetic or external preparation of the present invention, one or more water-soluble polymers can be used depending on the purpose. These water-soluble polymers are the same as those disclosed in paragraphs 0228 to 0232 of Patent Document 28.

In the cosmetic or external preparation of the present invention, one or more ultraviolet protection components can be used depending on the purpose. These UV protection components are common with the organic and inorganic UV protection agents disclosed in paragraphs 0243 to 0247 of Patent Document 28. Particularly, UV protection components that can be suitably used include fine-particle titanium oxide, Fine zinc oxide, 2-ethylhexyl paramethoxycinnamate, 4-tert-butyl-4'-methoxydibenzoylmethane, hexyl diethylaminohydroxybenzoylbenzoate, benzotriazole UV absorber and 2,4,6-tris [4 -(2-Ethylhexyloxycarbonyl) anilino] 1,3,5-triazine "{INCI: octyltriazone}, 2,4-bis {[4- (2-ethyl-hexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine {INCI: bis-ethylhexene It is at least one selected from the group consisting of triazine-based ultraviolet absorbers such as siloxyphenol methoxyphenyl triazine and trade name: Tinosolve S}. These UV protection components are widely used, are easily available, and have a high UV protection effect, so that they can be suitably used. In particular, it is preferable to use inorganic and organic UV protection components in combination, and it is more preferable to use UV protection components corresponding to UV-A and UV protection components in combination.

In the cosmetic or external preparation of the present invention, by using the sugar derivative-modified silicone composition and the UV protection component in combination, the UV protection component is stabilized in the cosmetic while improving the overall feel and storage stability of the cosmetic. Therefore, it is possible to impart an excellent UV protection function to cosmetics.

The cosmetics or external preparations of the present invention include oil-soluble gelling agents, organically modified clay minerals, water-swelling clay minerals, antibacterial and preservatives, physiologically active ingredients, skin-beautifying ingredients, pH, in addition to the above-described components. Various components such as a regulator, an antioxidant, a solvent, a chelating agent, a moisturizing component, and a fragrance can be used as long as the object of the present invention is not impaired. These cosmetic optional ingredients are the same as those disclosed in Patent Document 28, paragraphs 0235, 0233, 0249 to 0260 and the like.

Moreover, when the cosmetics or external preparation which concerns on this invention is an antiperspirant, or according to the objective, an antiperspirant active ingredient and a deodorant agent can be mix | blended. These antiperspirant components and deodorant components are the same as those disclosed in paragraphs 0254 to 0263 of Patent Document 27. Similarly, when the cosmetic or external preparation according to the present invention is an antiperspirant composition, the preparation and usage of various antiperspirant compositions are disclosed in paragraphs 0264 to 0315 of Patent Document 27, etc. And in common.

The method for producing a sugar derivative-modified silicone composition of the present invention is inexpensive and simple, has little waste, is excellent in yield or productivity, and can be easily handled for production on a commercial scale. In addition, the sugar derivative-modified silicone composition obtained by the production method of the present invention has a very low risk of phase separation after production, sedimentation of unreacted raw materials, and the like. In particular, the liquid sugar derivative-modified silicone composition obtained by the production method of the present invention is stable against temperature history and maintains a stable and highly transparent appearance even after long-term storage. There is no inconvenience derived from it, and it is also easy to handle because it can be diluted with a liquid oil while maintaining transparency. Therefore, the present invention solves the fundamental problem that the conventional sugar-modified silicone has.

Therefore, the sugar derivative-modified silicone composition according to the present invention can be widely used not only for external preparations such as pharmaceuticals or cosmetics, but also for general industrial applications. Emulsification / dispersion effect, surface treatment effect, adsorption effect, coating effect, moisture retention / moisture retention effect, softening effect, friction reduction effect, lubrication effect, penetration ability, solubilization / compatibility, protection effect, adhesive effect, thickening The viscosity adjustment effect or the sustainability of these effects can be enjoyed in the various applications described above.

Specifically, the sugar derivative-modified silicone composition obtained according to the present invention can be suitably used as a raw material for external preparations, pharmaceuticals or cosmetics, and is excellent in, for example, fiber treatment agents, heat resistance / warm resistance / electrical properties. Varnishes, paint additives, coating agents, primers, pressure-sensitive adhesives, various polyols, foam stabilizers and modifiers for urethane and foaming agents, release agents, release agents, antifoaming agents, greases and oil compounds, insulation / Glossing / Water repellent / Heat medium / Refrigerant / Lubricating oils, Rubber / resin modifiers / additives / surface treatment agents, Silane coupling agent formulations / modifiers / precursors, It can also be suitably used as a raw material for general industrial materials such as coating / sealing materials for construction / lining, protective agents for optical fibers / electric wires, lubricants, buffer agents, electronic / electric parts, and the like.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to the following Example.

In the following examples and comparative examples, it is conveniently described as “production of sugar derivative-modified silicone No. X” and the like, but the obtained product is a small amount of unreacted raw material in addition to the main component. It is in the form of a mixture that also contains etc.

In the following composition formula, Me represents a methyl (—CH ₃ ) group, Me ₃ SiO group (or Me ₃ Si group) is “M”, Me ₂ SiO group is “D”, and MeHSiO group is “D ^H ”. is denoted as the units modified by any substituent methyl group in M and D is denoted as "M ^R" and "D ^R". Moreover, IPA shows isopropyl alcohol in a manufacture example.

Further, the following xylitol monoallyl ether and xylitol residues are raw materials and functional groups as shown in the present specification. More particularly, 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 { A raw material containing xylitol monoallyl ether represented by CH (OH) CH ₂ OH} ₂ in a substance amount ratio of about 9: 1. The sugar derivative-modified silicone according to the present invention is compatible with these. -C ₃ H ₆ —OCH ₂ [CH (OH)] ₃ CH ₂ OH or —C ₃ H ₆ —OCH {CH (OH) CH ₂ OH} ₂ has a similar mass ratio. Introduced.

[Production Example 1]
<Sugar derivative-modified silicone No. Synthesis of 1>
Methylhydrogenpolysiloxane 197.2g represented by the average composition formula ^{^M H} _D 400 ^M H to the reactor, xylitol monoallyl ether 2.8 g, were charged isopropyl alcohol (IPA) 200 g, while stirring under a nitrogen stream 70 Warmed to ° C. 0.060 g of an IPA solution (Pt concentration: 4.5 wt%) of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added, and the reaction was carried out at 80 ° C. for 5 hours. Next, 2 g of the reaction solution was sampled, and the reaction was completed by the alkali decomposition gas generation method (the remaining Si—H group was decomposed with an ethanol / water solution of KOH, and the reaction rate was calculated from the volume of the generated hydrogen gas). confirmed. Here, 200.0 g of dimethylpolysiloxane (2 cst, 25 ° C.) was added to the reaction solution, mixed and diluted. Furthermore, by heating this under reduced pressure and distilling off low-boiling components other than the diluent, the sugar derivative-modified silicone No. 1 represented by the average structural formula M ^{R * 21} D ₄₀₀ M ^{R * 21} is obtained. A mixture consisting of 1 and dimethylpolysiloxane (2 cst) was obtained. The silicone: diluent weight (mass) ratio is 1: 1. In the formula, R ^{* 21} represents the following.
R ^{* 21} = Xylitol residue This product was a homogeneous viscous liquid (opaque) with an off-white and slightly brownish taste.

[Production Example 2]
<Sugar derivative-modified silicone No. Synthesis of 2>
A reactor was charged with 191.8 g of methyl hydrogen polysiloxane represented by an average composition formula: MD ₇₄ ^DH ₁ M, 9.0 g of xylitol monoallyl ether, and 100 g of IPA, and the mixture was heated to 60 ° C. while stirring under a nitrogen stream. Warm up. An IPA solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt concentration 0.45 wt%) was added, and the reaction was carried out at 70 ° C. for 6 hours. Next, 2 g of the reaction solution was sampled, and it was confirmed that the reaction was completed by an alkali decomposition gas generation method. Furthermore, by heating this under reduced pressure and distilling off IPA at 100 to 110 ° C., the sugar derivative-modified silicone No. ₁ represented by the average structural formula MD ₇₄ DR ^{* 21} ₁ M 2 was obtained. Here, in the formula, R ^{* 21} is as described above.
The product was a dark brown opaque liquid.

[Production Example 3]
<Sugar derivative-modified silicone No. Synthesis of 3>
Average composition formula: 42.4 g of methyl hydrogen polysiloxane represented by MD _42.9 ^DH _6.7 M in the reactor, the following average composition formula:

4.6 g of 3-methacryloxypropyl (tris (trimethylsiloxy) silylethyldimethylsiloxy) silane represented by the formula: platinum-1,3-divinyl-1,1 at 75 to 80 ° C. with stirring under a nitrogen stream , 3,3-tetramethyldisiloxane complex IPA solution (Pt concentration 0.45 wt%) 0.06 ml was added, and the reaction was carried out for 1.5 hours. Next, 12.2 g of hexadecene (α-olefin purity 91.7%) and 0.05 ml of the above platinum catalyst were added, and the reaction was carried out for 5 hours. Next, 3.1 g of xylitol monoallyl ether (purity 91.2%) and 60 g of IPA were added to the reaction mixture, and 0.15 ml of the platinum catalyst was added. Sampling was performed after reacting at 80 ° C. for 4.5 hours, and the reaction rate was calculated.
It was found that a modified silicone intermediate represented by MD _42.9 DR ^{* 11} _4.4 DR ^* ²¹ _1.35 DR ^* ³¹ _0.3 ^DH _0.65 M was produced. Here, R ^{* 11,} R ^{* 21} and R ^{* 31} are as follows.
R ^{* 11} = -C ₁₆ H ₃₃
R ^{* 21} = xylitol residue

Next, 37.8 g of methyl vinyl polysiloxane represented by the average composition formula: ^Vi MD ₁₃₀ D ^Vi ₂ M ^Vi was added, heated under reduced pressure to distill off IPA, and then 60 g of toluene as a solvent for the crosslinking reaction. Added. Here, 0.26 ml of the above platinum catalyst was added, and the reaction was carried out at 80 to 110 ° C. for 7 hours. When confirmed by sampling, the reaction was complete. Thereafter, toluene was distilled off under reduced pressure at 110 to 120 ° C. As a result, 95 g of sugar derivative-modified crosslinked silicone (sugar derivative-modified silicone No. 3) was obtained as an opaque grayish brown oily uniform viscous liquid.

[Comparative Example 1]
<Sugar derivative-modified silicone No. Comparative composition RE-1 containing 1>
The grayish white and slightly brownish opaque uniform viscous liquid (composition containing sugar derivative-modified silicone and dimethylpolysiloxane 2cs as main components) obtained in Production Example 1 was directly used as a sample.

[Comparative Example 2]
<Sugar derivative-modified silicone No. Preparation of Comparative Composition RE-2 Containing 2>
The dark brown opaque liquid (reaction mixture containing sugar derivative-modified silicone as a main component) obtained in Production Example 2 was used as a sample as it was.

[Comparative Example 3]
<Sugar derivative-modified silicone No. Preparation of Comparative Composition RE-3 Containing 3>
The opaque grayish brown oily uniform viscous liquid (reaction mixture containing sugar derivative-modified crosslinked silicone as a main component) obtained in Production Example 3 was used as a sample as it was.

[Example 1]
<Sugar derivative-modified silicone No. Preparation of Example Composition 1 Containing 1>
24.0888 g of an opaque white viscous liquid (composition containing sugar derivative-modified silicone and dimethylpolysiloxane 2cs as main components) obtained in Production Example 1 was collected in a 35 ml glass bottle and purified water 0 1958 g (equivalent to 1.63% by weight with respect to the reaction mixture) was added. The whole was thoroughly stirred with a stainless steel spatula for about 3 minutes, then left in a constant temperature bath at 40 ° C. to eliminate bubbles, and this operation was repeated 4 times until the whole became homogeneous. As a result, it was found that a transparent uniform fine brown viscous liquid was generated.

[Example 2]
<Sugar derivative-modified silicone No. Preparation of Example Composition 2 Containing 2>
24.0774 g of the dark brown opaque liquid (reaction mixture containing sugar derivative-modified silicone as a main component) obtained in Production Example 2 was collected in a 35 ml glass bottle, and 0.3203 g of purified water (1.33 wt.% With respect to the reaction mixture) % Equivalent) was added. The whole was thoroughly stirred with a stainless steel spatula for about 3 minutes, then left in a constant temperature bath at 40 ° C. to eliminate bubbles, and this operation was repeated three times until the whole became homogeneous. As a result, it was surprisingly found that a light brown transparent uniform liquid was produced.

[Example 3]
<Sugar derivative-modified silicone No. Preparation of Example Composition 3 Containing 3>
An opaque grayish brown oily uniform viscous liquid (reaction mixture containing sugar derivative-modified cross-linked silicone as a main component) obtained in Production Example 3 was collected in a 35 ml glass bottle, and 0.2502 g of purified water (the reaction mixture) 1.04% by weight). The whole was thoroughly stirred with a stainless steel spatula for about 3 minutes, then left in a constant temperature bath at 40 ° C. to eliminate bubbles, and this operation was repeated 4 times until the whole became homogeneous. As a result, it was surprisingly found that a light brown translucent almost uniform viscous liquid was produced.

“Example compositions 1 to 3 containing sugar derivative-modified silicone Nos. 1 to 3”, which are stabilized compositions containing the sugar derivative-modified silicone according to the present invention prepared by the above method, The contents of “compositions for comparison RE-1 to RE-3 containing sugar derivative-modified silicones No. 1 to 3” are shown in Table 2 below.

Note ^{* 1)} The chemical structure of the sugar derivative-modified silicone, which is the main component, is shown by an average composition formula.
^{* 2)} Dimethylpolysiloxane (2cs)

In the table, the structures of functional groups and their classification are as follows.
<Group having siloxane dendron structure: R ^{* 3} >

<Sugar derivative group: R ^{* 2} >
R ^{* 21} = xylitol residue <other organic group: R ^{* 1} >
R ^{* 11} = -C ₁₆ H ₃₃

[Stability test 1]
The samples of Example 2, Example 3, Comparative Example 2 and Comparative Example 3 were placed in a 50 ° C. constant temperature bath and allowed to stand for 1 month. On the other hand, the samples of Example 1 and Comparative Example 1 were placed in a 0 ° C. refrigerator and allowed to stand for 1 month. Then, these samples were taken out from the thermostat or refrigerator, returned to room temperature, and the external appearance of each sample was observed. The results are shown in Table 3.

[Stability test 2]
The sample after finishing the stability test 1 was allowed to stand at room temperature for another year, and then the appearance of each sample was observed. The results are shown in Table 4.

From the above results, the sample of the example is far superior to the sample of the comparative example in terms of transparency and homogeneity in appearance, and the superiority does not change even at high temperature, low temperature or long-term storage. confirmed.

Hereinafter, although the prescription example is shown and demonstrated about the cosmetics and external preparation which concern on this invention, the cosmetics and external preparation which concern on this invention are not limited to the kind and composition as described in these prescription examples.

Since the sugar derivative-modified silicone composition obtained by the present invention has high transparency, it is suitable as a component of products with an emphasis on appearance such as cosmetics and external preparations such as dermatological drugs, particularly liquid products. The sugar derivative-modified silicone composition obtained by the present invention is used in place of the conventional sugar derivative-modified silicone composition in cosmetics and external preparations using the conventional sugar derivative-modified silicone composition as a raw material or component. can do. As a result, white turbidity of cosmetics and external preparations can be prevented or reduced over a long period of time even in an environment with a large temperature change. Therefore, cosmetics and external preparations containing the sugar derivative-modified silicone composition obtained by the present invention are commercially advantageous.

The stabilized composition containing the sugar derivative-modified silicone according to the present invention can be used for various external preparations and cosmetics. Specific examples of the formulation include, for example, “co-modified silicones 1 to 2” in Examples 12 to 14 of various cosmetics and external preparations described in Patent Document 25 (Japanese Patent Laid-Open No. 2011-246705). Examples in which the corresponding component is replaced with a stabilized composition containing the sugar derivative-modified silicone according to the present invention (Example compositions 1 to 3 containing sugar derivative-modified silicones No. 1 to No. 3) can be mentioned.

In addition, components corresponding to “silicone compounds No. 1 to No. 5” in Examples 21 to 32 of various cosmetics and external preparations disclosed in Patent Document 26 (Japanese Patent Application Laid-Open No. 2011-246706) Examples include those that have been replaced with a stabilized composition containing the sugar derivative-modified silicone according to the invention (Example compositions 1 to 3 containing sugar derivative-modified silicone Nos. 1 to 3).

In addition, the “composition of Example 1” included in Formulation Examples 1 to 7 of various cosmetics and external preparations disclosed in Patent Document 27 (Japanese Patent Application Laid-Open No. 2012-246445) is a sugar derivative according to the present invention. Examples include those that have been replaced with stabilized compositions containing modified silicones (Example compositions 1 to 3 containing sugar derivative-modified silicones Nos. 1 to 3).

Further, “silicone compounds No. 1 to No. 6” or “Example 3” included in Formulation Examples 1 to 62 of various cosmetics and external preparations disclosed in Patent Document 28 (Japanese Patent Laid-Open No. 2012-246446). Or the component corresponding to “composition of 6” is replaced with a stabilized composition containing sugar derivative-modified silicone according to the present invention (Example compositions 1 to 3 containing sugar derivative-modified silicone No. 1 to 3). Can be mentioned.

In addition, for example, the sugar derivative-modified silicone no. The following composition based on a hydrocarbon-based cosmetic base material is also possible using Example Composition 3 containing 3. If the total amount of the following polyether-modified silicone is replaced with Example Composition 3, a PEG-FREE formulation is also possible. In the following, “part” means (weight) mass part.

[Prescription example: Liquid foundation (W / O)]
(component)
1. Isododecane 20 parts2. Isohexadecane 10 parts3. 3. Isotridecyl isononanoate 3 parts 4. Capric glyceryl tricaprylate 2 parts 5. 5. Polyether-modified silicone (Note 1) 1.0 part Sugar derivative-modified silicone No. Example Composition 3 Comprising 3 1.0 part7. Organic modified clay mineral (Benton 38V) 1.5 parts8. 8. Octyl methoxycinnamate 5 parts 9. Octylsilane-treated titanium oxide 8.5 parts10. Octylsilane-treated red iron oxide 0.4 parts11. Octylsilane-treated yellow iron oxide 1 part 12. Octylsilane-treated black iron oxide 0.1 part13. Dimethicone, dimethicone crosspolymer (Note 2) 2 parts14. Isododecane / (acrylates / polytrimethylsiloxy methacrylate) copolymer (Note 3) 1 part 15. 16. Trimethylsiloxysilicic acid 1 part 16.1,3-butylene glycol 5 parts Glycerin 3 parts18. Sodium chloride 0.5 part 19. Preservative appropriate amount20. Purified water remaining amount 21. Perfume

Note 1) ES-5300 manufactured by Toray Dow Corning
Note 2) DC9045 manufactured by Dow Corning
Note 3) FA-4002ID manufactured by Toray Dow Corning

(Production method)
Step 1: Components 1, 2, 5 to 8, and 13 to 15 are mixed with stirring.
Step 2: Components 3, 4, and 9 to 12 are kneaded and mixed using a three roll.
Step 3: The mixture of Step 2 is added to the mixture obtained in Step 1 under stirring, and the mixture is further stirred and mixed.
Step 4: An aqueous phase in which components 16 to 21 are uniformly dissolved is added to the mixture obtained in Step 3 and emulsified, and filled into a container to obtain a product.

The obtained W / O type liquid foundation has no unpleasant odor, is excellent in emulsification stability, has excellent water resistance and makeup persistence, has little texture and wrinkles, and has a light touch and adhesion. Is excellent.

Claims

A method for producing a transparent or translucent liquid sugar derivative-modified silicone composition, comprising a water addition step of adding water to a liquid sugar derivative-modified silicone or a composition thereof.
In the water addition step,
The production method according to claim 1, wherein 0.1 to 10 parts by mass of water is added to 100 parts by mass of the liquid sugar derivative-modified silicone or a composition thereof.
In the water addition step,
The production method according to claim 1 or 2, wherein the liquid sugar derivative-modified silicone or a composition thereof and the water are mixed and homogenized.
The sugar derivative-modified silicone is represented by the following general formula (1):

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

Wherein R 11 is independently 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 described above), L 1 represents the following general formula (3) when i = 1;

(In the formula, each R 3 independently represents a substituted or unsubstituted, linear or branched monovalent hydrocarbon group having 1 to 30 carbon atoms, and each R 4 independently represents the number of carbon atoms. represents 1-6 alkyl group or a phenyl group, Z is a divalent organic radical, i is represented of a silylalkyl group represented by L i, the number of layers is a number of repetitions of the silylalkyl group is k When the number of layers is an integer of 1 to 10, L i + 1 is the silylalkyl group when i is less than k, R 4 when i = k, h i represents a silylalkyl group having a siloxane dendron structure, and Q represents a sugar derivative 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 production method according to any one of claims 1 to 3, which is a sugar derivative-modified silicone represented by
The production method according to claim 4, wherein the sugar derivative group is a group derived from monosaccharides, disaccharides or oligosaccharides (oligosaccharides).
The production method according to claim 4 or 5, wherein the sugar derivative group is a sugar alcohol group-containing organic group.
The sugar derivative-modified silicone is represented by 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,
The method for producing a sugar derivative-modified silicone according to any one of claims 1 to 6, which is modified with a sugar alcohol group-containing organic group represented by: e 'is 0 or 1.
The production method according to claim 1, wherein the sugar derivative-modified silicone is a liquid sugar derivative-modified crosslinked silicone.
Before and / or after the water addition step and / or simultaneously with the water addition step,
The production method according to any one of claims 1 to 8, further comprising a liquid oil agent addition step of adding a liquid oil agent to the liquid sugar derivative-modified silicone or a composition thereof.
The manufacturing method of Claim 9 with which the said liquid oil agent has affinity with the said liquid sugar derivative modified silicone.
In the liquid oil addition step,
The production method according to claim 9 or 10, wherein 5 to 1000 parts by mass of a liquid oil agent is added to 100 parts by mass of the liquid sugar derivative-modified silicone or a composition thereof.
In the liquid oil addition step,
The manufacturing method according to any one of claims 9 to 11, wherein the liquid sugar derivative-modified silicone or a composition thereof and the liquid oil agent are mixed and homogenized.
The liquid sugar derivative-modified silicone or a composition thereof is treated with an acidic substance, and odorous substances and low-boiling components generated by the treatment of the acidic substance are removed by heating or decompressing. The manufacturing method in any one of thru | or 12.
A transparent or translucent liquid sugar derivative-modified silicone composition obtained by the production method according to claim 1.
An external preparation, a cosmetic, or an industrial material comprising the transparent or translucent liquid sugar derivative-modified silicone composition according to claim 14.