WO2018088485A1

WO2018088485A1 - Co-modified silicone

Info

Publication number: WO2018088485A1
Application number: PCT/JP2017/040456
Authority: WO
Inventors: 岸本　典久; 谷口　佳範; 智浩飯村; 武吉沢; 堀　誠司; 岳史杉村
Original assignee: 東レ・ダウコーニング株式会社
Priority date: 2016-11-14
Filing date: 2017-11-09
Publication date: 2018-05-17
Also published as: JPWO2018088485A1; JP7208795B2

Abstract

Provided is: a co-modified silicone which has at least two kinds of units selected from among disiloxy units represented by formulae (I)-(III) in each molecule; or a co-modified silicone which has two or more disiloxy units represented by formula (I) in each molecule. (I) X¹R¹SiO_2/2 unit (In the formula, X¹ represents a protected amino group-containing organic group; and R¹ represents a monovalent hydrocarbon group, a silicon atom-bonded hydrogen atom or a hydroxyl group.) (II) X²R¹SiO_2/2 unit (In the formula, X² represents an alkoxysilyl group-containing organic group; and R¹ is as defined in formula (I).) (III) X³R¹SiO_2/2 unit (In the formula, X³ represents an epoxy group-containing organic group; and R¹ is as defined in formula (I).)

Description

Co-modified silicone

The present invention relates to a novel co-modified silicone, and more specifically to a co-modified silicone suitable as a polymer modifier.

Silicone compounds having an organopolysiloxane structure are widely used as polymer modifiers for modifying various polymers. For example, Patent Document 1 discloses a technique in which a silicone compound having an organopolysiloxane structure modified with an epoxy group-containing organic group is used as a modifier for modifying a conjugated diene polymer.

Patent Document 2 discloses a technique in which a specific hydrocarbyloxysilane compound having a polysiloxane group and a group capable of becoming onium is used as a modifier for modifying a conjugated diene polymer. In addition, in the technique of Patent Document 2, a compound represented by SiR ⁶ (OR ⁷ ) (OR ⁸ ) (R ⁹ X) is disclosed as a specific example of such a hydrocarbyloxysilane compound (R ⁶ , R ⁷ , R ⁸ , and R ⁹ are an alkyl group, an alkenyl group, and the like, and X is a group that can be onium.).

On the other hand, in recent years, in the various polymers such as the conjugated diene polymer, further improvement is demanded in the modifier used in such polymers from the viewpoint of satisfying various required characteristics. . For example, in conjugated diene polymers and the like, when used in tire applications, from the viewpoint of producing a fuel-efficient tire, it is required to have excellent fuel efficiency. In order to meet this demand, further improvements are required in the modifier.

JP 2004-231905 A JP 2012-193277 A

The present invention has been made in view of such a situation, and relates to a novel co-modified silicone, and more specifically, to provide a co-modified silicone suitable as a polymer modifier.

As a result of intensive studies to achieve the above object, the present inventors have at least two kinds selected from a protected amino group-containing organic group, an alkoxysilyl group-containing organic group, and an epoxy group-containing organic group in the same molecule. The inventors have found that a co-modified silicone or a co-modified silicone having two or more protected amino group-containing organic groups in the same molecule is suitable as a modifier for a polymer, and has completed the present invention.

That is, according to the present invention, a co-modified silicone having at least two or more kinds selected from disiloxy units represented by the following formulas (I) to (III) in the same molecule, or a disiloxy represented by the following formula (I): Co-modified silicones having two or more units in the same molecule are provided.
(I) X ¹ R ¹ SiO _2/2 unit (wherein X ¹ is a protected amino group-containing organic group, and R ¹ is a monovalent hydrocarbon group, a silicon atom-bonded hydrogen atom or a hydroxyl group)
(II) X ² R ¹ SiO _2/2 unit (wherein X ² is an alkoxysilyl group-containing organic group, and R ¹ is the same as in formula (I)).
(III) X ³ R ¹ SiO _2/2 unit (wherein X ³ is an epoxy group-containing organic group, and R ¹ is the same as in formula (I)).

The co-modified silicone of the present invention preferably has a linear, branched or cyclic polysiloxane structure.

In the co-modified silicone of the present invention, two or more disiloxy units represented by the formula (I) selected from the disiloxy units represented by the formulas (I) to (III) are represented by the following formula (A): It is preferable to have a structure in which a siloxane bond is formed in the molecule shown.
—X′R ¹ Si—O—SiX ″ R ¹ — (A)
(In the formula (A), X ′ and X ″ are different groups selected from X ¹ to X ³ in the formulas (I) to (III), or X ′ and X ″ are both X ¹ in the formula (I), and R ¹ is the same as in the above formulas (I) to (III).

The co-modified silicone of the present invention is preferably a compound represented by the following formula (1-1), (1-2), (2-1) or (2-2).

(In the formula (1-1), X ′ and X ″ are groups different from each other selected from X ¹ to X ³ in the formulas (I) to (III), and R ¹ represents the formula (I ) To (III), a is a positive integer, b is a positive integer, c is 0 or a positive integer, and a + b + c is 3 to 30.)

(In the above formula (1-2), X ¹ is the same as in the above formula (I), R ¹ is the same as in the above formula (I), a ′ is an integer of 2 or more, and c ′ is 0. Or a positive integer, and a ′ + c ′ is 3 to 30.)

(In the above formula (2-1), X ′ and X ″ are groups different from each other selected from X ¹ to X ³ in the formulas (I) to (III), and R ¹ represents the formula (I ) To (III), m is a positive integer, n is a positive integer, p is 0 or a positive integer, and m + n + p is 2 to 500.)

(In the above formula (2-2), X ¹ is the same as in the above formula (I), R ¹ is the same as in the above formula (I), m ′ is an integer of 2 or more, and p ′ is 0. Or a positive integer, and m ′ + p ′ is 2 to 500.)

In the co-modified silicone of the present invention, the protected amino group-containing organic group represented by X ¹ is preferably a group represented by the following formula (3), (4) or (5).

(In the above formula (3), R ¹¹ to R ¹⁴ are an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and these may be the same or different from each other. Is an integer from 1 to 12. f is an integer from 1 to 12.)

(In the above formula (4), R ¹⁵ to R ²⁰ are an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and these may be the same or different from each other. (It is an integer from 1 to 12.)

(In the above formula (5), R ²¹ and R ²² are alkyl groups having 1 to 6 carbon atoms, which may be the same or different from each other. H is an integer of 1 to 12) is there.)

Co-modified silicone of the present invention includes a disiloxy unit represented by the formula (I), and a disiloxy unit represented by the formula (II) and / or the formula (III), by X ¹ in the "molecular The number of groups shown / the sum of the number of groups represented by X ² and the group represented by X ³ in the molecule ”is preferably in the range of 0.2 to 10.

The co-modified silicone of the present invention is preferably a compound represented by the formula (1-1). In the formula (1-1), c is 0, a + b is 3 to 6, and X ′ Is a protected amino group-containing organic group represented by the formula (3) or (4), X ″ is an alkoxysilyl group-containing organic group represented by X ² , and an epoxy group-containing organic group represented by X ³ It is preferable that it is 1 or more types chosen from.

The co-modified silicone of the present invention is preferably a compound represented by the formula (2-1). In the formula (2-1), p is 0, m + n is 2 to 100, and X ′ Is a protected amino group-containing organic group represented by the formula (3) or (4), and X ″ is an alkoxysilyl group-containing organic group represented by X ² and an epoxy group-containing organic group represented by X ^3. One or more selected are preferable.

Further, according to the present invention, represented by an organopolysiloxane having silicon-bonded hydrogen atom, protected amino group-containing organic group represented by X ^1, alkoxysilyl-containing organic group represented by X ^2, and X ³ There is provided a method for producing any one of the above-mentioned co-modified silicones, which comprises a step of hydrosilylation reaction with one or more precursors selected from epoxy group-containing organic groups.

In the method for producing a co-modified silicone of the present invention, the organopolysiloxane having a silicon atom-bonded hydrogen atom is preferably a compound represented by the following formula (1 ′) or (2 ′).

(In the above formula (1 ′), R ¹ is the same as in the above formulas (I) to (III). A is a positive integer, b is a positive integer, c is 0 or a positive integer, and a + b + c Is 3 to 30.)

(In the above formula (2 ′), R ¹ is the same as in the above formulas (I) to (III). M is a positive integer, n is a positive integer, p is 0 or a positive integer, and m + n + p Is 2 to 500.)

Further, according to the present invention, a polymer modifier containing any one of the above-mentioned co-modified silicones is provided.

Furthermore, according to the present invention, there is provided a cosmetic raw material, a cosmetic, a surface treatment agent or a dispersant containing any one of the above-mentioned co-modified silicones.

According to the present invention, a co-modified silicone suitable as a polymer modifier can be provided. The co-modified silicone of the present invention can be suitably used as a polymer modifier.

The co-modified silicone of the present invention is a co-modified silicone having at least two or more kinds selected from disiloxy units represented by the following formulas (I) to (III) in the same molecule, or a disiloxy represented by the following formula (I). It is a co-modified silicone having two or more units in the same molecule.
(I) X ¹ R ¹ SiO _2/2 unit (wherein X ¹ is a protected amino group-containing organic group, and R ¹ is a monovalent hydrocarbon group, a silicon atom-bonded hydrogen atom or a hydroxyl group)
(II) X ² R ¹ SiO _2/2 unit (wherein X ² is an alkoxysilyl group-containing organic group, and R ¹ is the same as in formula (I)).
(III) X ³ R ¹ SiO _2/2 unit (wherein X ³ is an epoxy group-containing organic group, and R ¹ is the same as in formula (I)).

First, the co-modified silicone of the present invention has at least two or more types selected from the disiloxy units represented by the above formulas (I) to (III) in the same molecule (hereinafter referred to as “first embodiment” as appropriate). The co-modified silicone according to the present invention will be described.

The co-modified silicone according to the first aspect of the present invention only needs to have at least two kinds selected from the disiloxy units represented by the above formulas (I) to (III) in the same molecule. Those having a disiloxy unit represented by the formula (I) and a disiloxy unit represented by the above formula (II), those having a disiloxy unit represented by the above formula (I) and a disiloxy unit represented by the above formula (III), Those having a disiloxy unit represented by the formula (II) and a disiloxy unit represented by the above formula (III), a disiloxy unit represented by the above formula (I), a disiloxy unit represented by the above formula (II) and the above Examples thereof include those having a disiloxy unit represented by the formula (III). Further, the disiloxy unit represented by the above formula (I) may contain two or more types having different structures, and similarly, the disiloxy unit represented by the above formulas (II) and (III). However, it may contain two or more types having different structures.

The co-modified silicone according to the first aspect of the present invention may be any silicone having at least two kinds selected from the disiloxy units represented by the above formulas (I) to (III) in the same molecule. Effects as a modifier for coalescence, for example, when used as a modifier for polymers, the affinity between the polymer and a filler such as silica can be increased, thereby improving the various properties. From the viewpoint, those containing at least the disiloxy unit represented by the above formula (I) are preferable, and those having the disiloxy unit represented by the above formula (I) and the disiloxy unit represented by the above formula (II), More preferred are those having a disiloxy unit represented by (II) and a disiloxy unit represented by the above formula (III).

The disiloxy unit represented by the above formula (I) is a unit represented by the formula: X ¹ R ¹ SiO _2/2 , and in formula (I), X ¹ is a protected amino group-containing organic group, and R ¹ Is a monovalent hydrocarbon group, a silicon-bonded hydrogen atom or a hydroxyl group.

The protected amino group-containing organic group represented by X ¹ is not particularly limited as long as it has a structure in which a protective group is introduced into the amino group, and two hydrogen atoms of a primary amino group (ie, —NH ₂ ). A group containing a protected amino group having a structure in which an atom is substituted with a group that acts as a protecting group for an amino group is preferable. Such a protecting group is not particularly limited, and may be a group that can be deprotected by a method using an acid or a base, a hydrolysis reaction, and gives a primary amino group by deprotection. preferable. Specific examples of such a protecting group include a hydrocarbyl group and a silyl group. In addition, such a protective amino group-containing organic group contains a primary amino group or a secondary amino group by deprotection of the protective group, and thereby, mainly with a filler such as silica. It is thought to act to improve the affinity.

Examples of the protected amino group-containing organic group include those having a silyl group as a protecting group, such as a group represented by the following formula (3), a group represented by the following formula (4), or a formula (5) below. Preferred examples include a group.

In the above formula (3), R ¹¹ to R ¹⁴ are an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms. They may be the same or different. R ¹¹ to R ¹⁴ are preferably exemplified by a methyl group, an ethyl group, an n-butyl group, a tert-butyl group, and the like. Particularly, all of the groups represented by R ¹¹ to R ¹⁴ are methyl groups. Alternatively, one or more of the groups represented by R ¹¹ to R ¹⁴ may be an alkyl group other than a methyl group (for example, a tert-butyl group), and the rest may be a methyl group. E is an integer of 1 to 12, preferably an integer of 1 to 6, more preferably an integer of 1 to 4, and f is an integer of 1 to 12, preferably an integer of 1 to 6, Preferably, it is an integer of 1 to 4.

In the above formula (4), R ¹⁵ to R ²⁰ are an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, which are the same as each other. Or may be different. R ¹⁵ to R ²⁰ are preferably exemplified by a methyl group, an ethyl group, an n-butyl group, a tert-butyl group, and the like. Particularly, all of the groups represented by R ¹⁵ to R ²⁰ are methyl groups. Alternatively, one or more of the groups represented by R ¹⁵ to R ²⁰ may be an alkyl group other than a methyl group (for example, a tert-butyl group), and the rest may be a methyl group. G is an integer of 1 to 12, preferably an integer of 1 to 6, and more preferably an integer of 1 to 4.

In the above formula (5), R ²¹ and R ²² are each an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, which may be the same or different. R ²¹ and R ²² are preferably exemplified by a methyl group, an ethyl group, an n-butyl group, a tert-butyl group, and the like. In particular, both of the groups represented by R ²¹ and R ²² are methyl groups. Alternatively, one of the groups represented by R ²¹ and R ²² may be an alkyl group other than a methyl group (for example, a tert-butyl group), and the other may be a methyl group. H is an integer of 1 to 12, preferably an integer of 1 to 6, and more preferably an integer of 1 to 4.

In the group represented by the above formula (3), the group represented by —SiR ¹¹ R ¹² — (CH ₂ ) _f —SiR ¹³ R ¹⁴ — can be deprotected by a method using an acid or a base, or a hydrolysis reaction. Act as a protective group. Similarly, in the group represented by the above formula (4), the group represented by —SiR ¹⁵ R ¹⁶ R ¹⁷ and the group represented by —SiR ¹⁸ R ¹⁹ R ²⁰ are prepared by a method using an acid or a base, It acts as a protecting group that can be deprotected by a decomposition reaction.

As the protected amino group-containing organic group, those having a silyl group as the protecting group are preferred from the viewpoint that they function well as a protecting group and can also perform a deprotection reaction favorably, and the group represented by the above formula (3) And a group represented by the above formula (4) are preferred.

Specific examples of the protected amino group constituting the protected amino group-containing organic group include bis (trihydrocarbylsilyl) amino group, bis (dihydrocarbylhydrosilyl) amino group, 1-aza-disila-1-cyclohydrocarbyl group, (tri Hydrocarbylsilyl) (hydrocarbyl) amino group, (dihydrocarbylhydrosilyl) (hydrocarbyl) amino group, 1-aza-2-sila-1-cyclohydrocarbyl group, dihydrocarbylamino group, 1-aza-1-cyclohydrocarbyl group, etc. Can be mentioned.

Further, constituting the disiloxy unit ^X 1 ^R 1 _{SiO 2/2} represented by the above formula (I), ^{R 1} is a monovalent hydrocarbon group, a silicon-bonded hydrogen atom or a hydroxyl group, preferably a monovalent hydrocarbon radical It is. The monovalent hydrocarbon group is preferably an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and further preferably a methyl group. It is.

The disiloxy unit represented by the above formula (II) is a unit represented by the formula: X ² R ¹ SiO _2/2 , and in formula (II), X ² is an alkoxysilyl group-containing organic group, and R ¹ Is a monovalent hydrocarbon group, a silicon-bonded hydrogen atom or a hydroxyl group.

The alkoxysilyl group-containing organic group represented by X ^2, may be a group containing an alkoxysilyl group is not particularly limited, as alkoxysilyl group, mono alkoxysilyl group, dialkoxy silyl group, trialkoxysilyl group Any of these may be included, and examples thereof include a group represented by the following formula (6).

In the above formula (6), each R ²³ is independently an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, and R ²⁴ is a silicon atom-bonded hydrogen atom, An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an allyloxy group having 6 to 20 carbon atoms, or a halogen atom. j is an integer of 1 to 20, preferably an integer of 3 to 10, more preferably an integer of 4 to 8, and k is an integer of 1 to 3. Incidentally, when k is 2 or 3, R ²³ is a presence of a plurality, the plurality of R ²³ may be different be the same as each other. Similarly, when k is 1, R ²⁴ is a presence of a plurality, the plurality of R ²⁴ may be different be the same as each other.

Specific examples of the alkoxysilyl group contained in the alkoxysilyl group-containing organic group include trialkoxysilyl groups such as trimethoxysilyl group and triethoxysilyl group; dimethoxymethyl group, diethoxymethyl group, dimethoxyethyl group, diethoxyethyl Dialkoxyalkylsilyl groups such as a group; monoalkoxydialkyl groups such as a methoxydimethyl group, an ethoxydimethyl group, a methoxydiethyl group, and an ethoxydiethyl group; Among these, when used as a polymer modifier, for example, when used as a polymer modifier, it is possible to increase the affinity between the polymer and a filler such as silica. The trialkoxysilyl group is preferable and the trimethoxysilyl group is more preferable from the viewpoint that the effect of improving the resistance is high.

Further, R ¹ constituting the disiloxy unit X ² R ¹ SiO _{2/2 represented} by the above formula (II) is a monovalent hydrocarbon group, a silicon atom-bonded hydrogen atom or a hydroxyl group, preferably a monovalent hydrocarbon group. It is. The monovalent hydrocarbon group is preferably an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and further preferably a methyl group. It is.

The disiloxy unit represented by the above formula (III) is a unit represented by the formula: X ³ R ¹ SiO _2/2 , and in formula (III), X ³ is an epoxy group-containing organic group, and R ¹ is A monovalent hydrocarbon group, a silicon-bonded hydrogen atom or a hydroxyl group;

The epoxy group-containing organic group represented by X ³ is not particularly limited as long as it is an organic group containing an epoxy group, and includes 2-glycidoxyethyl group, 3-glycidoxypropyl group, 4-glycidide. Glycidoxyalkyl group such as xylbutyl; 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) propyl group, 2- (3,4-epoxynorbornyl) ethyl Groups, epoxycycloalkylalkyl groups such as 2- (3,4-epoxy-3-methylcyclohexyl) -2-methylethyl group; oxiranyl such as 4-oxiranylbutyl group and 8-oxiranyloctyl group Alkyl group; and the like. Among these, a glycidoxyalkyl group is preferable, and a 3-glycidoxypropyl group is particularly preferable.

Further, R ¹ constituting the disiloxy unit X ³ R ¹ SiO _{2/2 represented} by the above formula (III) is a monovalent hydrocarbon group, a silicon atom-bonded hydrogen atom or a hydroxyl group, preferably a monovalent hydrocarbon group. It is. The monovalent hydrocarbon group is preferably an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and further preferably a methyl group. It is.

In the co-modified silicone according to the first aspect of the present invention, inclusion of a disiloxy unit represented by the above formula (I), a disiloxy unit represented by the above formula (II), and a disiloxy unit represented by the above formula (III) The ratio is not particularly limited. For example, the co-modified silicone according to the first aspect of the present invention is represented by the above-mentioned formula (I) and the above formula (II) or the above formula (III). In the case of having a disiloxy unit, “the number of groups represented by X ¹ in the molecule / the sum of the number of groups represented by X ² and the group represented by X ³ in the molecule” is 0. It may be in the range of 1-20 and is preferably in the range of 0.2-10.

Alternatively, when the co-modified silicone according to the first aspect of the present invention has a disiloxy unit represented by the above formula (II) and a disiloxy unit represented by the above formula (III), The number of groups represented by X ² in the group / the number of groups represented by X ³ in the molecule ”is preferably in the range of 0.1 to 10, more preferably in the range of 0.5 to 9, and more preferably in the range of 1 to A range of 6 is more preferred.

In the case where the co-modified silicone according to the first aspect of the present invention has a disiloxy unit represented by the above formula (II) and a disiloxy unit represented by the above formula (III), a modified polymer is used. from the viewpoint of being able to enhance the effect of the agent, contained in disiloxy unit represented by above-mentioned formula (II), as alkoxysilyl group-containing organic group represented by X ^2, j in the above formula (6) Is preferably an integer of 3 to 10 and does not contain a silicon-bonded hydrogen atom in the molecule, and the alkoxysilyl group-containing organic group represented by X ² is represented by the formula (6) j is more preferable to contain what is an integer of 4-8, as alkoxysilyl group-containing organic group represented by X ^2, j in the formula (6) in is an integer from 4-8 Containing the, and, what is particularly preferably contains no silicon-bonded hydrogen atoms in the molecule. In addition, in the case of having a disiloxy unit represented by the above formula (II) and a disiloxy unit represented by the above formula (III), the phrase “does not contain a silicon-bonded hydrogen atom in the molecule” It means that none of R ¹ , X ² and X ³ contained contains a silicon-bonded hydrogen atom. Specifically, all R ¹ contained in the molecule is a monovalent hydrocarbon group or a hydroxyl group, and the alkoxysilyl group-containing organic group represented by X ² is a group represented by the above formula (6). In this case, all R ²⁴ contained in the molecule is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an allyloxy group having 6 to 20 carbon atoms, or a halogen atom. Means.

The structure of the co-modified silicone according to the first aspect of the present invention is not particularly limited, and may have any linear, branched, or cyclic polysiloxane structure.

In the co-modified silicone according to the first aspect of the present invention, two types selected from the disiloxy units represented by the above formulas (I) to (III) have a siloxane bond in the molecule represented by the following formula (A). It is preferable that the compound has a structure in which is formed, and a compound represented by the following formula (1-1) or the following formula (2-1) is more preferable.
—X′R ¹ Si—O—SiX ″ R ¹ — (A)
In the above formula (A), X ′ and X ″ are different groups selected from X ¹ to X ³ in the above formulas (I) to (III), and R ¹ represents the above formulas (I) to (I). It is the same as III).

In the above formula (1-1), X ′ and X ″ are different groups selected from X ¹ to X ³ in the above formulas (I) to (III), and R ¹ represents the above formula (I) The same as in (III). a is a positive integer, b is a positive integer, c is 0 or a positive integer, and a + b + c is 3 to 30.

In the above formula (2-1), X ′ and X ″ are different groups selected from X ¹ to X ³ in the above formulas (I) to (III), and R ¹ represents the above formula (I) The same as in (III). m is a positive integer, n is a positive integer, p is 0 or a positive integer, and m + n + p is 2 to 500.

In the above formula (1-1), X ′ and X ″ may be different groups selected from X ¹ to X ³ in the above formulas (I) to (III), but X ′ is X ¹ in a protected amino group-containing organic group represented, X '' is, alkoxysilyl group-containing organic group represented by X ^2, and it is an epoxy group-containing one or more selected from organic groups represented by X ³ Preferably, X ′ is a protected amino group-containing organic group represented by the above formula (3) or (4), X ″ is an alkoxysilyl group-containing organic group represented by X ² , and X ³ More preferably, it is at least one selected from epoxy group-containing organic groups.

In the above formula (1-1), a is a positive integer, b is a positive integer, c is 0 or a positive integer, and a + b + c may be 3 to 30, but c is 0, a + b is preferably 3 to 30, c is 0, a + b is more preferably 3 to 6, c is 0, and a + b is particularly preferably 4 to 6. A mixture of cyclic siloxanes having different degrees of polymerization may be used.

In the formula (2-1), X ′ and X ″ may be different groups selected from X ¹ to X ³ in the formulas (I) to (III). A protected amino group-containing organic group represented by X ¹ , wherein X ″ is one or more selected from an alkoxysilyl group-containing organic group represented by X ² and an epoxy group-containing organic group represented by X ³ X ′ is a protected amino group-containing organic group represented by the above formula (3) or (4), X ″ is an alkoxysilyl group-containing organic group represented by X ² , and X ³ It is more preferable that it is 1 or more types chosen from the epoxy group containing organic group shown.

In the above formula (2-1), m is a positive integer, n is a positive integer, p is 0 or a positive integer, m + n + p may be 2 to 500, and p is 0. m + n is preferably 2 to 500, p is 0, more preferably m + n is 2 to 100, p is 0, and m + n may be a number in the range 2 to 50. It is particularly preferred that the number is. Further, it may be a mixture of two or more types of chain siloxanes having different degrees of polymerization.

Next, the co-modified silicone of the present invention is a co-modified silicone having two or more disiloxy units represented by the above formula (I) in the same molecule (hereinafter referred to as “co-modified silicone according to the second embodiment” as appropriate). ) Will be described.

The co-modified silicone according to the second aspect of the present invention is not limited as long as it has two or more disiloxy units represented by the above formula (I) in the same molecule, and is the same as the disiloxy unit represented by the above formula (I). May have two or more, or may have two or more types having different structures as the disiloxy unit represented by the above formula (I).

The disiloxy unit represented by the above formula (I) is a unit represented by the formula: X ¹ R ¹ SiO _2/2 , and in formula (I), X ¹ is a protected amino group-containing organic group, and R ¹ Is a monovalent hydrocarbon group, a silicon-bonded hydrogen atom or a hydroxyl group. X ¹ and R ¹ can be the same as those of the co-modified silicone according to the first aspect described above, and the preferred aspects are also the same as those of the co-modified silicone according to the first aspect described above. .

The structure of the co-modified silicone according to the second aspect of the present invention is not particularly limited, and may have any of a linear, branched, or cyclic polysiloxane structure.

The co-modified silicone according to the second aspect of the present invention has a structure in which two or more disiloxy units represented by the above formula (I) form a siloxane bond in the molecule represented by the following formula (A). The compound represented by the following formula (1-2) or the following formula (2-2) is more preferable.
—X′R ¹ Si—O—SiX ″ R ¹ — (A)
In the above formula (A), X ′ and X ″ are both X ¹ in the above formula (I), R ¹ is the same as R ¹ in the above formula (I).

In the above formula (1-2), X ¹ is the same as in the above formula (I), and R ¹ is the same as in the above formula (I). a ′ is an integer of 2 or more, c ′ is 0 or a positive integer, and a ′ + c ′ is 3 to 30.

In the above formula (2-2), X ¹ is the same as in the above formula (I), and R ¹ is the same as in the above formula (I). m ′ is an integer of 2 or more, p ′ is 0 or a positive integer, and m ′ + p ′ is 2 to 500.

In the above formula (1-2), X ¹ is the same as in the above formula (I), but X ¹ is a protected amino group-containing organic group represented by the above formula (3) or (4). preferable. In the above formula (1-2), a ′ is an integer of 2 or more, c ′ is 0 or a positive integer, and a ′ + c ′ may be 3 to 30, but c ′ is 0. A ′ is preferably 3 to 30, c ′ is 0, more preferably a ′ is 3 to 6, c ′ is 0, and a ′ is 4 to 6. Particularly preferred. It may be a mixture of two or more types of cyclic siloxanes having different degrees of polymerization.

In the formula (2-2), X ¹ is the same as in the formula (I), but X ¹ is a protected amino group-containing organic group represented by the formula (3) or (4). It is preferable. In the above formula (2-2), m ′ is an integer of 2 or more, p ′ is 0 or a positive integer, m ′ + p ′ may be 2 to 500, and p ′ is 0. M ′ is preferably 2 to 500, p ′ is 0, more preferably m ′ is 2 to 100, p ′ is 0, and m ′ is a number in the range of 3 to 50. 3 to 30 is particularly preferable. It may be a mixture of two or more types of chain siloxanes having different degrees of polymerization.

The method for producing the co-modified silicone according to the first and second aspects of the present invention is not particularly limited. For example, an organopolysiloxane having a silicon-bonded hydrogen atom and a protected amino group represented by X ¹ containing organic group, alkoxysilyl group-containing organic group represented by X ^2, and X ³ in a method of reacting a hydrosilylation 1 or more and a precursor selected from an epoxy group-containing organic group represented is preferred.

As the organopolysiloxane having a silicon atom-bonded hydrogen atom, one corresponding to the target compound may be used, but a compound represented by the following (1 ′) or (2 ′) can be preferably used.

In the above formula (1 ′), R ¹ is the same as in the above formulas (I) to (III). a is a positive integer, b is a positive integer, c is 0 or a positive integer, a + b + c is 3 to 30, c is preferably 0, a + b is preferably 3 to 30, and c is 0 More preferably, a + b is 3 to 6, particularly preferably c is 0, and a + b is 4 to 6.

In the above formula (2 ′), R ¹ is the same as in the above formulas (I) to (III). m is a positive integer, n is a positive integer, p is 0 or a positive integer, m + n + p is 2 to 500, p is preferably 0, m + n is preferably 2 to 500, and p is 0 M + n is more preferably 2 to 100, p is 0, m + n may be a number in the range of 3 to 50, and 3 to 30 is particularly preferable.

Selected and organopolysiloxane having silicon-bonded hydrogen atom, protected amino group-containing organic group represented by X ^1, alkoxysilyl-containing organic group represented by X ^2, and an epoxy group-containing organic group represented by X ³ The ratio of these used when reacting with one or more precursors (hereinafter referred to as “precursor” as appropriate) is the protected amino group represented by X ¹ contained in the target co-modified silicone. group-containing organic group may be appropriately selected depending on the ratio of the epoxy group-containing organic group represented by the alkoxysilyl group-containing organic group, and X ³ represented by X ^2. Also, protected amino group-containing organic group represented by X ^1, the case of introducing two or more groups of the epoxy group-containing organic group represented by the alkoxysilyl group-containing organic group, and X ³ represented by X ² is The order in which the precursors corresponding to these groups are reacted is not particularly limited. The precursor comprises protected amino group-containing organic group represented by X ^1, alkoxysilyl-containing organic group represented by X ^2, and one or more groups selected from epoxy-containing organic group represented by X ³ It is a precursor.

Any method can be used for introducing the organopolysiloxane having silicon-bonded hydrogen atoms and the precursor into the reaction apparatus, but the mixing molar ratio of these compounds does not deviate from the above range. It is preferable to make it. Furthermore, under heating conditions, silicon-bonded hydrogen atom may be introduced precursor in the organopolysiloxane having, or may but vice versa, protected amino group-containing organic group represented by X ^1, X ² in alkoxysilyl group-containing organic group represented, and in case of introducing two or more groups of the epoxy group-containing organic group represented by X ³ is in the organopolysiloxane having silicon-bonded hydrogen atom, each group It is preferred to add the corresponding precursors in order and react separately. Moreover, it is preferable that the temperature when this reaction is performed by heating is within a range of a suitable reaction temperature described later.

The reaction temperature between the organopolysiloxane having a silicon atom-bonded hydrogen atom and the precursor is not particularly limited as long as the intended reaction proceeds, and this reaction can be carried out at any temperature. You may go. When the reaction is carried out under heating, the reaction temperature is preferably in the range of 30 ° C to 100 ° C.

In addition, the above reaction can be performed at an arbitrary pressure, and there is no particular limitation on the pressure, but depending on the relationship with the boiling point of the raw material used, when the target temperature is not reached when heated at normal pressure, In the reaction at normal pressure, when the time required for completion of the reaction is remarkably long, the reaction may be performed under pressure.

The above reaction is preferably performed under an inert gas, for example, in an atmosphere of an inert gas selected from nitrogen and argon. It is also preferable to reduce the amount of water contained in the organopolysiloxane having silicon-bonded hydrogen atoms, which is a raw material, and the precursor as much as possible.

In addition, the above reaction may be performed using an organic solvent that does not contain active hydrogen, as selected as an organic solvent such as toluene, xylene, benzene, hexane, ethylene chloride, chloroform, trichloroethylene, and cyclohexane, as necessary. May be used.

Examples of the catalyst used in the hydrosilylation reaction between the organopolysiloxane having a silicon atom-bonded hydrogen atom and a precursor include Group VIII transition metal catalysts in the long-period periodic table, preferably platinum. System catalyst. Examples of such platinum-based catalysts include chloroplatinic acid, alcohol solutions of chloroplatinic acid, platinum olefin complexes, platinum alkenylsiloxane complexes, and platinum carbonyl complexes. The amount of catalyst used is not particularly limited as long as the target reaction proceeds.

The co-modified silicone according to the first and second aspects of the present invention can be produced as described above. The co-modified silicone according to the first and second aspects of the present invention is suitable as a polymer modifier, and more specifically, when used as a polymer modifier, a polymer In addition, it is possible to improve the affinity with a filler such as silica and thereby improve various characteristics, and therefore, it can be suitably used as a modifier for various polymers. In particular, a polymer composition obtained by blending a filler such as silica with a polymer modified with the co-modified silicone according to the first and second aspects of the present invention as a modifier, Since the dispersibility between the polymer and a filler such as silica can be improved, the effect of improving various characteristics by blending a filler such as silica can be more appropriately enhanced. As an example, fuel efficiency can be improved by using the co-modified silicone according to the first and second aspects of the present invention as a modifier for a conjugated diene polymer.

When used as a polymer modifier, the co-modified silicone of the present invention may be used alone or as a mixture of two or more. Specifically, the following mixture of co-modified silicones can be used as a polymer modifier.
(I) A mixture of co-modified silicones according to the first and second aspects (II) A co-modified silicone according to the first or second aspect, wherein the degree of siloxane polymerization, the modifying group or the modification rate Mixture of different co-modified silicones (III) Co-modified silicone according to the first aspect or second aspect, wherein the siloxane structure of the main chain is linear or cyclic (IV) Co-modified silicone mixtures according to combinations I) to (III)

The above-mentioned co-modified silicone or a mixture thereof may be used in combination with other modified silicones for use as a polymer modifier. For example, it may be used for a polymer modifier as a mixture with an epoxy-modified silicone or a known silicone modified with an alkoxysilyl group-containing organic group.

When the above-mentioned co-modified silicone or a mixture thereof is used for a polymer modifier, that is, when used as a polymer modifier, examples of the polymer to be modified include conjugated diene rubber. It is done. Examples of the conjugated diene rubber include a homopolymer of conjugated diene and a copolymer of conjugated diene and styrene.

When the above-mentioned co-modified silicone or a mixture thereof is used for a polymer modifier, that is, when used as a polymer modifier, the amount used is not particularly limited, but polymerization used for the production of a conjugated diene rubber The amount is preferably about 0.15 to 20 moles per mole of the initiator.

The co-modified silicone of the present invention can be used without limitation for uses other than the polymer modifier. For example, cosmetic raw materials, cosmetics, external preparations, surface treatment agents, and dispersants can be exemplified, and in particular, surface treatment agents for powder components such as silica, cosmetic raw materials containing powder components, powders such as silica, etc. It can be used as a component dispersant, and can form a slurry of a powder component, a dispersion composition containing powder and co-modified silicone, an optional oil agent, and the like.

Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, “part” means part by mass. In addition, this invention is not limited by these Examples.

[Example 1]
(Production of co-modified silicone 1)
The reactor was charged with 31.8 g of methylhydrogencyclosiloxane represented by the following formula (7) and heated to 40 ° C. with stirring under a nitrogen stream.

Next, 1.3 g of a toluene solution of platinum-1,3-divinyl-1,3-dimethyldisiloxane complex (Pt concentration 0.17 wt%) was added, and N-allyl-N, N-bis (trimethylsilyl) amine 53 was added. .3 g was added dropwise so as to keep the reaction temperature at 40 to 75 ° C. After completion of the dropping, stirring was continued at 70 to 75 ° C. for 1 hour, and then 0.5 g of the reaction solution was sampled, and an alkali decomposition gas generation method (remaining Si—H group was decomposed with KOH ethanol / water solution to generate hydrogen generated). The reaction rate was confirmed to be about 50% by calculating the reaction rate from the gas volume). Next, 74.8 g of 5-hexenyltrimethoxysilane was added dropwise so as to keep the reaction temperature at 70 to 80 ° C. After completion of dropping, 0.4 g of a toluene solution of platinum-1,3-divinyl-1,3-dimethyldisiloxane complex (Pt concentration 0.17 wt%) was added, and stirring was continued at 80 ° C. for 1 hour. 0.5 g of the reaction solution was sampled and it was confirmed that the reaction was completed by an alkali decomposition gas generation method. The reaction solution was heated to 155 ° C. under reduced pressure to distill off the low-boiling components for 3 hours, and 134.3 g of co-modified silicone 1 represented by the following formula (8) was obtained. The structure represented by the following formula (8) was also confirmed by ¹ H-NMR. The viscosity of the obtained co-modified silicone 1 was measured according to JIS-Z-8803 using an Ubbelohde type viscosity tube at 25 ° C. and found to be 300 mm ² / s.

(Production of modified conjugated diene rubber 1)
In a nitrogen atmosphere, charge 800 parts of cyclohexane, 94.8 parts of 1,3-butadiene, 25.2 parts of styrene, and 0.187 parts of tetramethylethylenediamine, and then add 0.045 part of n-butyllithium to the autoclave. Then, polymerization was started at 60 ° C. The polymerization reaction was continued for 60 minutes, and after confirming that the polymerization conversion was in the range of 95% to 100%, 1.35 parts of the co-modified silicone obtained above (use of n-butyllithium) After adding 1.50 times mole) and reacting for 30 minutes, 0.064 parts of methanol was added as a polymerization terminator to obtain a solution containing a conjugated diene polymer. Then, 100 parts of the obtained polymer component was treated with 2,4-bis [(octylthio) methyl] -o-cresol (trade name “Irganox 1520” manufactured by Ciba Specialty Chemicals) as an anti-aging agent. After adding 15 parts to the solution, the solvent was removed by steam stripping, followed by vacuum drying at 60 ° C. for 24 hours to obtain a solid modified conjugated diene rubber 1. The resulting modified conjugated diene rubber 1 had a weight average molecular weight (Mw) of 528,000.

In addition, the weight average molecular weight (Mw) was calculated | required as a polystyrene conversion molecular weight by the gel permeation chromatography. Specific measurement conditions were as follows.
Measuring instrument: High-performance liquid chromatograph (trade name “HLC-8220” manufactured by Tosoh Corporation)
Column: manufactured by Tosoh Corporation, two product names “GMH-HR-H” were connected in series.
Detector: differential refractometer (trade name “RI-8220” manufactured by Tosoh Corporation)
Eluent: Tetrahydrofuran Column temperature: 40 ° C

(Production of rubber composition and rubber cross-linked product)
In a Brabender type mixer with a capacity of 250 ml, 100 parts of the modified conjugated diene rubber 1 obtained above was masticated for 30 seconds, then 50 parts of silica (trade name “Zeosil 1165MP”, manufactured by Rhodia), and process oil ( 20 parts by Nippon Oil Corporation, trade name “Aromax T-DAE”), and silane coupling agent: bis (3- (triethoxysilyl) propyl) tetrasulfide (trade name “Si69”, manufactured by Degussa) 6 0.0 part was added and kneaded for 1.5 minutes starting at 110 ° C., then 25 parts of silica (trade name “Zeosil 1165MP”, manufactured by Rhodia), 3 parts of zinc oxide, 2 parts of stearic acid, and an antioxidant: N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine (manufactured by Ouchi Shinsei Chemical Co., Ltd., trade name “NOKU” Tsu added click 6C ") 2 parts, was further kneaded for 2.5 minutes, discharging a kneaded product from the mixer. The temperature of the kneaded product at the end of kneading was 150 ° C. And after cooling the obtained kneaded material to room temperature, it knead | mixed again for 2 minutes in 110 degreeC start temperature in a Brabender type mixer, Then, the kneaded material was discharged | emitted from the mixer. Next, with an open roll at 50 ° C., the obtained kneaded product was mixed with 1.40 parts of sulfur, a crosslinking accelerator: N-tert-butyl-2-benzothiazolylsulfenamide (trade name “Noxeller NS-P”, After adding 1.2 parts of Ouchi Shinsei Chemical Co., Ltd.) and 1.2 parts of diphenylguanidine (trade name “Noxeller D”, Ouchi Shinsei Chemical Co., Ltd.) and kneading them, a sheet-like rubber composition The thing was taken out.
Next, the obtained rubber composition was press-crosslinked at 160 ° C. for 20 minutes to prepare a test piece of a rubber cross-linked product having a length of 50 mm, a width of 12.7 mm, and a thickness of 2 mm. The wet grip properties and fuel economy were evaluated according to the above. The results are shown in Table 1.

(Wet grip)
About the test piece obtained above, tan δ at 0 ° C. was measured using a viscoelasticity measuring apparatus (manufactured by Rheometrics, product name “ARES”) under conditions of dynamic strain of 0.5% and 10 Hz. The value of tan δ is indicated by an index with the measured value of Comparative Example 1 being 100. The larger this index, the better the wet grip.

(Low fuel consumption performance)
About the test piece obtained above, tanδ at 60 ° C. was measured using a viscoelasticity measuring apparatus (manufactured by Rheometrics, product name “ARES”) under conditions of dynamic strain of 2.5% and 10 Hz. The value of tan δ is indicated by an index with the measured value of Comparative Example 1 being 100. The larger this index, the better the low heat buildup.

[Example 2]
(Production of co-modified silicone 2)
In Example 1, instead of N-allyl-N, N-bis (trimethylsilyl) amine, 1-allyl-2,2 ′, 5,5′-tetramethyl- (1-aza-2,5-disila Synthesis was performed in the same manner as in Example 1 except that 52.8 g of (cyclopentane) was used, and thus a co-modified silicone 2 represented by the following formula (9) was obtained. The structure represented by the following formula (9) was also confirmed by ¹ H-NMR. The viscosity of the obtained co-modified silicone 2 was measured according to JIS-Z-8803 at 25 ° C. using an Ubbelohde viscosity tube, and it was 230 mm ² / s.

(Production of modified conjugated diene rubber 2, rubber composition, and rubber cross-linked product)
A modified conjugated diene rubber 2 was obtained in the same manner as in Example 1 except that 1.35 parts of the co-modified silicone 2 obtained above was used in place of the co-modified silicone 1. The resulting modified conjugated diene rubber 2 had a weight average molecular weight (Mw) of 478,000.
Then, instead of the modified conjugated diene rubber 1, a rubber composition and a rubber cross-linked product were obtained in the same manner as in Example 1 except that the obtained modified conjugated diene rubber 2 was used. went. The results are shown in Table 1.

[Example 3]
(Production of co-modified silicone 3)
A reactor was charged with 38.0 g of methyl hydrogen polysiloxane represented by the following formula (10) and heated to 40 ° C. with stirring under a nitrogen stream.

Next, 0.9 g of a toluene solution of platinum-1,3-divinyl-1,3-dimethyldisiloxane complex (Pt concentration 0.17 wt%) was added, and N-allyl-N, N-bis (trimethylsilyl) amine 79 was added. 0.7 g was added dropwise so as to keep the reaction temperature at 40 to 80 ° C. After completion of the dropping, stirring was continued at 80 ° C. for 1.5 hours, and then 0.5 g of the reaction solution was collected, and an alkali decomposition gas generation method (remaining Si—H group was decomposed with KOH ethanol / water solution to generate hydrogen The reaction rate was confirmed to be about 70% by calculating the reaction rate from the gas volume). Next, 45.0 g of 5-hexenyltrimethoxysilane was added dropwise so as to keep the reaction temperature at 80 to 90 ° C. After completion of the dropping, 0.9 g of a toluene solution of platinum-1,3-divinyl-1,3-dimethyldisiloxane complex (Pt concentration 0.17 wt%) was added, and stirring was continued at 90-100 ° C. for 12 hours. 0.5 g of the reaction solution was sampled and it was confirmed that the reaction was completed by an alkali decomposition gas generation method. The reaction solution was heated to 150 ° C. under reduced pressure to distill off the low-boiling components for 3.5 hours, and 138.6 g of co-modified silicone 3 represented by the following formula (11) was obtained. The structure represented by the following formula (11) was also confirmed by ¹ H-NMR. The viscosity of the obtained co-modified silicone 3 was measured according to JIS-Z-8803 using an Ubbelohde viscosity tube at 25 ° C., and it was 1040 mm ² / s.

(Production of modified conjugated diene rubber 3)
In a nitrogen atmosphere, charge 800 parts of cyclohexane, 94.8 parts of 1,3-butadiene, 25.2 parts of styrene, and 0.187 parts of tetramethylethylenediamine, and then add 0.042 part of n-butyllithium to the autoclave. Then, polymerization was started at 60 ° C. The polymerization reaction was continued for 60 minutes, and after confirming that the polymerization conversion was in the range of 95% to 100%, 1.963 parts of the co-modified silicone obtained above (use of n-butyllithium) 1.00 times mol) was added and reacted for 30 minutes, and then 0.064 parts of methanol was added as a polymerization terminator to obtain a solution containing a conjugated diene polymer. Then, 100 parts of the obtained polymer component was treated with 2,4-bis [(octylthio) methyl] -o-cresol (trade name “Irganox 1520” manufactured by Ciba Specialty Chemicals) as an anti-aging agent. After adding 15 parts to the solution, the solvent was removed by steam stripping, followed by vacuum drying at 60 ° C. for 24 hours to obtain a solid modified conjugated diene rubber 3. The resulting modified conjugated diene rubber 3 had a weight average molecular weight (Mw) of 444,000.

(Production of rubber composition and rubber cross-linked product)
In a Brabender type mixer with a capacity of 250 ml, 100 parts of the modified conjugated diene rubber 3 obtained above was masticated for 30 seconds, and then 53 parts of silica (trade name “Zeosil 1165MP” manufactured by Rhodia), process oil ( 30 parts by Nippon Oil Corporation, trade name “Aromax T-DAE”), and silane coupling agent: bis (3- (triethoxysilyl) propyl) tetrasulfide (trade name “Si69”, manufactured by Degussa) 6 .4 parts was added and kneaded for 1.5 minutes at 110 ° C. as the starting temperature, followed by 27 parts of silica (trade name “Zeosil 1165MP” manufactured by Rhodia), 3 parts of zinc oxide, 2 parts of stearic acid, and an antioxidant: N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine (manufactured by Ouchi Shinsei Chemical Co., Ltd., trade name “NOKU” Tsu added click 6C ") 2 parts, was further kneaded for 2.5 minutes, discharging a kneaded product from the mixer. The temperature of the kneaded product at the end of kneading was 150 ° C. After the kneaded product was cooled to room temperature, it was kneaded again in a Brabender type mixer at 110 ° C. for 2 minutes, and then the kneaded product was discharged from the mixer. Next, with an open roll at 50 ° C., the obtained kneaded product was mixed with 1.50 parts of sulfur, a crosslinking accelerator: N-cyclohexyl-2-benzothiazolylsulfenamide (trade name “Noxeller CZ-G”, Ouchi 1.8 parts of Shinsei Chemical Industry Co., Ltd.) and 1.5 parts of crosslinking accelerator: diphenylguanidine (trade name “Noxeller D”, produced by Ouchi Shinsei Chemical Industry Co., Ltd.) were added and kneaded. The rubber composition was taken out.
Next, the obtained rubber composition was press-crosslinked at 160 ° C. for 20 minutes to produce a test piece of rubber cross-linked product having a length of 50 mm, a width of 12.7 mm, and a thickness of 2 mm. The fuel efficiency was evaluated in the same manner as in 1. The results are shown in Table 2.

[Example 4]
(Production of co-modified silicone 4)
In Example 3, 45.3 g of allyl glycidyl ether was used in place of 5-hexenyltrimethoxysilane, and the amount of N-allyl-N, N-bis (trimethylsilyl) amine used was changed to N-allyl-N, N A co-modified silicone 4 represented by the following formula (12) was synthesized in the same manner as in Example 3 except that the molar ratio of bis (trimethylsilyl) amine to allyl glycidyl ether was changed to 1: 1. Obtained. The structure represented by the following formula (12) was also confirmed by ¹ H-NMR. The viscosity of the obtained co-modified silicone 4 was measured according to JIS-Z-8803 using an Ubbelohde type viscosity tube at 25 ° C. and found to be 890 mm ² / s.

(Production of modified conjugated diene rubber 4, rubber composition, and rubber cross-linked product)
A modified conjugated diene rubber 4 was obtained in the same manner as in Example 3, except that 1.665 parts of the co-modified silicone 4 obtained above was used instead of the co-modified silicone 3. The resulting modified conjugated diene rubber 4 had a weight average molecular weight (Mw) of 552,000.
Then, a rubber composition and a rubber cross-linked product were obtained in the same manner as in Example 3 except that the obtained modified conjugated diene rubber 4 was used instead of the modified conjugated diene rubber 3, and evaluation was performed in the same manner. went. The results are shown in Table 2.

[Example 5]
(Production of co-modified silicone 5)
Example 3 is the same as Example 3 except that the amount of N-allyl-N, N-bis (trimethylsilyl) amine and 5-hexenyltrimethoxysilane used is changed to a molar ratio of 6: 1. To obtain a co-modified silicone 5 represented by the following formula (13). The structure represented by the following formula (13) was also confirmed by ¹ H-NMR. The viscosity of the obtained co-modified silicone 5 was measured according to JIS-Z-8803 using an Ubbelohde type viscosity tube at 25 ° C. and found to be 1940 mm ² / s.

(Production of modified conjugated diene rubber 5, rubber composition, and rubber cross-linked product)
A modified conjugated diene rubber 5 was obtained in the same manner as in Example 3 except that 2.556 parts of the co-modified silicone 5 obtained above was used in place of the co-modified silicone 3. The resulting modified conjugated diene rubber 5 had a weight average molecular weight (Mw) of 395,000.
Then, a rubber composition and a rubber cross-linked product were obtained in the same manner as in Example 3 except that the obtained modified conjugated diene rubber 5 was used instead of the modified conjugated diene rubber 3, and evaluation was performed in the same manner. went. The results are shown in Table 2.

[Example 6]
(Production of co-modified silicone 6)
Example 3 is the same as Example 3 except that the amount of N-allyl-N, N-bis (trimethylsilyl) amine and 5-hexenyltrimethoxysilane used is changed to a molar ratio of 1: 4. To obtain a co-modified silicone 6 represented by the following formula (14). The structure represented by the following formula (14) was also confirmed by ¹ H-NMR. The viscosity of the obtained co-modified silicone 6 was measured according to JIS-Z-8803 using an Ubbelohde type viscosity tube at 25 ° C. and found to be 250 mm ² / s.

(Production of modified conjugated diene rubber 6, rubber composition, and rubber cross-linked product)
A modified conjugated diene rubber 6 was obtained in the same manner as in Example 3 except that 2.574 parts of the co-modified silicone 6 obtained above was used in place of the co-modified silicone 3. The resulting modified conjugated diene rubber 6 had a weight average molecular weight (Mw) of 611,000.
Then, a rubber composition and a rubber cross-linked product were obtained in the same manner as in Example 3 except that the obtained modified conjugated diene rubber 6 was used in place of the modified conjugated diene rubber 3, and evaluation was performed in the same manner. went. The results are shown in Table 2.

[Example 7]
(Production of co-modified silicone 7)
Example 3 was synthesized in the same manner as in Example 3 except that 5-hexenyltrimethoxysilane was not used and the amount of N-allyl-N, N-bis (trimethylsilyl) amine used was 117.1 g. Co-modified silicone 7 represented by the following formula (15) was obtained. The structure represented by the following formula (15) was also confirmed by ¹ H-NMR. The viscosity of the obtained co-modified silicone 7 was measured according to JIS-Z-8803 using an Ubbelohde type viscosity tube at 25 ° C. and found to be 4410 mm ² / s.

(Production of modified conjugated diene rubber 7, rubber composition, and rubber cross-linked product)
A modified conjugated diene rubber 7 was obtained in the same manner as in Example 3 except that 2.547 parts of the co-modified silicone 7 obtained above was used in place of the co-modified silicone 3. The resulting modified conjugated diene rubber 7 had a weight average molecular weight (Mw) of 292,000.
Then, a rubber composition and a rubber cross-linked product were obtained in the same manner as in Example 3 except that the obtained modified conjugated diene rubber 7 was used in place of the modified conjugated diene rubber 3, and evaluation was performed in the same manner. went. The results are shown in Table 2.

[Example 8]
(Production of co-modified silicone 8)
In Example 3, instead of the methyl hydrogen polysiloxane represented by the above formula (11), 44.0 g of methyl hydrogen polysiloxane represented by the following formula (16) was used, and N-allyl-N , N-bis (trimethylsilyl) amine was used in an amount of 75.4 g, 5-hexenyltrimethoxysilane was used in an amount of 25.5 g, and these ratios were changed to a molar ratio of 3: 1. Synthesis was performed in the same manner as in Example 3 to obtain a co-modified silicone 8 represented by the following formula (17). The structure represented by the following formula (17) was also confirmed by ¹ H-NMR. The viscosity of the obtained co-modified silicone 8 was measured according to JIS-Z-8803 using an Ubbelohde type viscosity tube at 25 ° C., and it was 230 mm ² / s.

(Production of modified conjugated diene rubber 8, rubber composition, and rubber cross-linked product)
A modified conjugated diene rubber 8 was obtained in the same manner as in Example 3 except that 1.809 parts of the co-modified silicone 8 obtained above was used instead of the co-modified silicone 3. The resulting modified conjugated diene rubber 8 had a weight average molecular weight (Mw) of 420,000.
Then, a rubber composition and a rubber cross-linked product were obtained in the same manner as in Example 3 except that the obtained modified conjugated diene rubber 8 was used instead of the modified conjugated diene rubber 3, and evaluation was performed in the same manner. went. The results are shown in Table 2.

[Comparative Example 1]
(Production of co-modified silicone 9)
In Example 3, 75.2 g of methylhydrogensiloxane represented by the following formula (18) was used instead of methylhydrogenpolysiloxane represented by the above formula (11), and 5-hexenyltrimethoxysilane was used. Was used in the same manner as in Example 3 except that the amount of N-allyl-N, N-bis (trimethylsilyl) amine used was changed to 74.9 g. Modified silicone 9 was obtained. The structure represented by the following formula (19) was also confirmed by ¹ H-NMR. The viscosity of the obtained co-modified silicone 9 was measured according to JIS-Z-8803 using an Ubbelohde type viscosity tube at 25 ° C. and found to be 6 mm ² / s.

(Production of modified conjugated diene rubber 9, rubber composition, and rubber cross-linked product)
A modified conjugated diene rubber 9 was obtained in the same manner as in Example 3, except that 0.284 part of the co-modified silicone 9 obtained above was used instead of the co-modified silicone 3. The resulting modified conjugated diene rubber 9 had a weight average molecular weight (Mw) of 229,000.
Then, instead of the modified conjugated diene rubber 3, the rubber composition and the crosslinked rubber were obtained in the same manner as in Example 3 except that the obtained modified conjugated diene rubber 9 was used. went. The results are shown in Table 2.

As shown in Tables 1 and 2, it can be confirmed that the co-modified silicone of the present invention can appropriately improve the properties of the polymer when used as a polymer modifier. It can be confirmed that the fuel efficiency can be improved when used as a modifier of a conjugated diene rubber as a specific example as in this example.

Claims

A co-modified silicone having at least two or more kinds selected from the disiloxy units represented by the following formulas (I) to (III) in the same molecule, or two or more disiloxy units represented by the following formula (I) in the same molecule A co-modified silicone.
(I) X 1 R 1 SiO 2/2 unit (wherein X 1 is a protected amino group-containing organic group, and R 1 is a monovalent hydrocarbon group, a silicon atom-bonded hydrogen atom or a hydroxyl group)
(II) X 2 R 1 SiO 2/2 unit (wherein X 2 is an alkoxysilyl group-containing organic group, and R 1 is the same as in formula (I)).
(III) X 3 R 1 SiO 2/2 unit (wherein X 3 is an epoxy group-containing organic group, and R 1 is the same as in formula (I)).
The co-modified silicone according to claim 1, comprising a linear, branched, or cyclic polysiloxane structure.
Two or more kinds of disiloxy units selected from the disiloxy units represented by the above formulas (I) to (III) have a siloxane bond in the molecule represented by the following formula (A). The co-modified silicone according to claim 1 or 2, comprising the formed structure.
—X′R 1 Si—O—SiX ″ R 1 — (A)
(In the formula (A), X ′ and X ″ are different groups selected from X 1 to X 3 in the formulas (I) to (III), or X ′ and X ″ are both X 1 in the formula (I), and R 1 is the same as in the above formulas (I) to (III).
The co-modified silicone according to any one of claims 1 to 3, which is a compound represented by the following formula (1-1), (1-2), (2-1) or (2-2).

(In the formula (1-1), X ′ and X ″ are groups different from each other selected from X 1 to X 3 in the formulas (I) to (III), and R 1 represents the formula (I ) To (III), a is a positive integer, b is a positive integer, c is 0 or a positive integer, and a + b + c is 3 to 30.)

(In the above formula (1-2), X 1 is the same as in the above formula (I), R 1 is the same as in the above formula (I), a ′ is an integer of 2 or more, and c ′ is 0. Or a positive integer, and a ′ + c ′ is 3 to 30.)

(In the above formula (2-1), X ′ and X ″ are groups different from each other selected from X 1 to X 3 in the formulas (I) to (III), and R 1 represents the formula (I ) To (III), m is a positive integer, n is a positive integer, p is 0 or a positive integer, and m + n + p is 2 to 500.)

(In the above formula (2-2), X 1 is the same as in the above formula (I), R 1 is the same as in the above formula (I), m ′ is an integer of 2 or more, and p ′ is 0. Or a positive integer, and m ′ + p ′ is 2 to 500.)
The protected amino group-containing organic group represented by X 1 is represented by the following formula (3), (4) or (5) co-modified silicone according to any one of claims 1 to 4 is a group represented by.

(In the above formula (3), R 11 to R 14 are an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and these may be the same or different from each other. Is an integer from 1 to 12. f is an integer from 1 to 12.)

(In the above formula (4), R 15 to R 20 are an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and these may be the same or different from each other. (It is an integer from 1 to 12.)

(In the above formula (5), R 21 and R 22 are alkyl groups having 1 to 6 carbon atoms, which may be the same or different from each other. H is an integer of 1 to 12) is there.)
It has the disiloxy unit represented by the formula (I) and the disiloxy unit represented by the formula (II) and / or the formula (III), and “the number of groups represented by X 1 in the molecule / intramolecular 6. The co-modified silicone according to claim 1, wherein the “sum of the number of the group represented by X 2 and the group represented by X 3 ” in the range of 0.2 to 10.
A compound represented by the formula (1-1),
In the formula (1-1), c is 0, a + b is 3 to 6, X ′ is a protected amino group-containing organic group represented by the formula (3) or (4), and X ″ but co-modified silicone according to the alkoxysilyl group-containing organic group, and X 3 according to claim 5 is at least one selected from an epoxy group-containing organic group represented by represented by X 2.
A compound represented by the formula (2-1),
In the formula (2-1), p is 0, m + n is 2 to 100, X ′ is a protected amino group-containing organic group represented by the formula (3) or (4), and X ″ but co-modified silicone according to the alkoxysilyl group-containing organic group and X 3 according to claim 5 is at least one selected from an epoxy group-containing organic group represented by represented by X 2.
Selected and organopolysiloxane having silicon-bonded hydrogen atom, protected amino group-containing organic group represented by X 1, alkoxysilyl-containing organic group represented by X 2, and an epoxy group-containing organic group represented by X 3 The method for producing a co-modified silicone according to any one of claims 1 to 8, further comprising a hydrosilylation reaction with one or more precursors.
The method for producing a co-modified silicone according to claim 9, wherein the organopolysiloxane having a silicon atom-bonded hydrogen atom is a compound represented by the following formula (1 ') or (2').

(In the above formula (1 ′), R 1 is the same as in the above formulas (I) to (III). A is a positive integer, b is a positive integer, c is 0 or a positive integer, and a + b + c Is 3 to 30.)

(In the above formula (2 ′), R 1 is the same as in the above formulas (I) to (III). M is a positive integer, n is a positive integer, p is 0 or a positive integer, and m + n + p Is 2 to 500.)
A polymer modifier containing the co-modified silicone according to any one of claims 1 to 8.
A cosmetic raw material, cosmetic, surface treatment agent or dispersant comprising the co-modified silicone according to any one of claims 1 to 8.