JP6907877B2 - Organosilicon compound, its production method and curable composition - Google Patents

Description

The present invention relates to an organosilicon compound, a method for producing the same, and a curable composition. More specifically, the present invention relates to an organosilicon compound having a polyphenylene ether structure, a hydrolyzable group, and a polymerizable reactive group in the molecule, and a method for producing the same. The present invention also relates to a curable composition containing the organosilicon compound.

A silane coupling agent is a compound having a part having reactivity with an inorganic substance (a hydrolyzable group bonded to a Si atom) and a part having a high reactivity and solubility with an organic substance in one molecule, and is an inorganic substance and an organic substance. Since it acts as an adhesion aid at the interface with, it is widely used as a composite resin modifier.

Further, the polyphenylene ether compound has high heat resistance and excellent dielectric properties such as dielectric constant and dielectric loss tangent, and particularly excellent dielectric properties in the high frequency band (high frequency region) from MHz band to GHz band, that is, high frequency characteristics. It has been known.
Therefore, as an application example of the polyphenylene ether compound, it is considered that it is suitable for use as a molding material for high frequency in recent years. Specific applications include a base material (copper-clad laminate) for printed wiring boards provided in electronic devices that use electrical signals in the high-frequency region, and its use as a component for constituting substrate materials is being considered. Has been done.

As a typical composition of the base material (copper-clad laminate) of the printed wiring board capable of supporting a high frequency region, a composition composed of an epoxy resin and a cyanate ester compound mixed with a polyphenylene ether compound can be mentioned.
However, in recent years, further improvement of high frequency characteristics has been required, and a polyphenylene ether compound having a polymerizable reactive group such as a (meth) acrylic group or an alkenyl group is used as a main agent, and a plurality of polymerizations such as triallyl isocyanurate are used. It has been studied to perform thermosetting with a peroxide or the like using a compound having a sex reactive group as a cross-linking agent.

In such an application, an electronic circuit board having good transmission characteristics is indispensable because an electric signal in a high frequency region tends to be attenuated in a wiring circuit.
In order to obtain an electronic circuit board with good transmission characteristics, an insulating resin material with a small dielectric loss tangent such as a polyphenylene ether compound is used, and at the same time, the surface of the conductor (metal wiring such as copper foil) is smoothed to reduce the roughness. It is effective to reduce the skin resistance by reducing the thickness.

However, in the conventional copper-clad laminate, the surface of the copper foil is uneven and the anchor effect is exhibited to ensure the adhesion between the resin material and the copper foil. Therefore, the transmission characteristics are the same as those of the high-frequency substrate material described above. When the surface of the copper foil is smoothed in order to obtain the above, there is a problem that the anchor effect is weakened and the adhesion between the resin material and the copper foil is deteriorated.
Therefore, the use of a general silane coupling agent has been studied in order to improve the adhesion, but at present, the adhesion cannot be sufficiently satisfied.

Further, Patent Document 1 discloses an alkoxysilyl group-containing silane-modified phenylene ether resin obtained by subjecting a bifunctional phenylene ether resin and an alkoxysilane partial condensation reaction to a dealcohol condensation reaction.
However, in the compound of Patent Document 1, the alkoxysilyl group, which has the highest reactivity and contributes to the improvement of adhesion, is consumed in the dealcohol condensation reaction due to the production method, so that the adhesion between the resin material and the copper foil is poor. It was enough.

Japanese Unexamined Patent Publication No. 2005-330324

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an organosilicon compound effective as a resin modifier for a high-frequency substrate material, a method for producing the same, and a curable composition containing the organosilicon compound. And.

As a result of diligent studies to solve the above problems, the present inventors have found a predetermined organic silicon compound having a polyphenylene ether structure, a hydrolyzable group and a polymerizable reactive group in the molecule, and a method for producing the same. Since the composition containing the organic silicon compound provides a cured product capable of exhibiting good copper foil adhesion and dielectric properties such as dielectric constant and dielectric loss tangent, it is suitable as a curable composition for forming a high frequency substrate material. The present invention was completed.

（式中、Ｘは、ポリフェニレンエーテル構造を有するｎ価の有機基を表し、Ｒ¹は、互いに独立して、非置換もしくは置換の炭素原子数１〜１０のアルキル基、または非置換もしくは置換の炭素原子数６〜１０のアリール基を表し、Ｒ²は、互いに独立して、非置換もしくは置換の炭素原子数１〜１０のアルキル基、または非置換もしくは置換の炭素原子数６〜１０のアリール基を表し、Ｒ⁷は、互いに独立して、重合性反応基を含有する一価炭化水素基を表し、Ａ¹は、互いに独立して、単結合、またはヘテロ原子を含有する二価の連結基を表し、Ａ²は、互いに独立して、単結合、またはヘテロ原子を含まない、非置換もしくは置換の炭素原子数１〜２０の二価炭化水素基を表し、ｍは、１〜３の数であり、ｐは、１〜１０の数であり、ｑは、１〜１０の数であり、ｎ＝ｐ＋ｑであり、ｎは、２〜２０の数である。）
２． 平均構造式（２）で表される１の有機ケイ素化合物、

｛式中、Ｒ¹、Ｒ²、Ｒ⁷、Ａ¹、Ａ²およびｍは、前記と同じ意味を表し、Ｒ³は、互いに独立して、ハロゲン原子、非置換もしくは置換の炭素原子数１〜１２のアルキル基、非置換もしくは置換の炭素原子数１〜１２のアルコキシ基、非置換もしくは置換の炭素原子数１〜１２のアルキルチオ基、または非置換もしくは置換の炭素原子数１〜１２のハロアルコキシ基を表し、Ｒ⁴は、互いに独立して、水素原子、ハロゲン原子、非置換もしくは置換の炭素原子数１〜１２のアルキル基、非置換もしくは置換の炭素原子数１〜１２のアルコキシ基、非置換もしくは置換の炭素原子数１〜１２のアルキルチオ基、または非置換もしくは置換の炭素原子数１〜１２のハロアルコキシ基を表し、ｂは、互いに独立して、１〜１００の数であり、ｃは、０より大きく２未満の数であり、Ｚは、下記式（３）で表される連結基を表す。

〔（式中、Ｒ⁴は、前記と同じ意味を表し、Ｌは、単結合、または下記式（４）〜（１１）から選ばれる連結基を表す。）

（式中、Ｒ⁵は、互いに独立して、水素原子または炭素原子数１〜１２のアルキル基を表し、Ｒ⁶は、互いに独立して炭素原子数１〜１２のアルキル基を表し、ｋは、１〜１２の整数を表し、ｊは、１〜１，０００の数を表す。）〕｝
３． 前記Ａ¹−Ａ²が、単結合、式（１２）で表される連結基または式（１３）で表される連結基である１または２の有機ケイ素化合物、

（式中、ａは、互いに独立して１〜２０の数であり、Ｙは、互いに独立して、酸素原子または硫黄原子であり、＊は、Ｘまたはフェニレン基との結合部位を表す。）
４． 前記Ｒ⁷の重合性反応基が、アクリロイルオキシ基、メタクリロイルオキシ基、スチリル基、ビニル基またはエポキシ基である１〜３のいずれかの有機ケイ素化合物、
５． 前記Ｒ⁷の重合性反応基が、アクリロイルオキシ基またはメタクリロイルオキシ基である１〜４のいずれかの有機ケイ素化合物、
６． 平均構造式（１４）

（式中、Ｒ³、Ｒ⁴、ｂおよびＺは、前記と同じ意味を表す。）
で表される、水酸基を有するポリフェニレンエーテル化合物と、前記水酸基と反応し得る官能基および重合性反応基を有する化合物と、式（１５）

（式中、Ｒ¹、Ｒ²、Ａ²およびｍは、前記と同じ意味を表す。）
で表される、イソシアネート基およびアルコキシシリル基を有する化合物とを、反応させることを特徴とする１〜５のいずれかの有機ケイ素化合物の製造方法。
７． 前記水酸基と反応し得る官能基および重合性反応基を有する化合物が、式（１６）

（式中、Ｒ⁷およびＡ²は、前記と同じ意味を表す。）
で表される、イソシアネート基および重合性反応基を有する化合物である６の有機ケイ素化合物の製造方法、
８． １〜５のいずれかの有機ケイ素化合物を含有する硬化性組成物、
９． ８の硬化性組成物が硬化してなる物品
を提供する。 That is, the present invention
1. 1. Organosilicon compound represented by the average structural formula (1),

(In the formula, X represents an n-valent organic group having a polyphenylene ether structure, and R ¹ is an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted alkyl group. Represents an aryl group having 6 to 10 carbon atoms, and R ² is an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aryl group having 6 to 10 carbon atoms independently of each other. Representing a group, R ⁷ represents a monovalent hydrocarbon group containing a polymerizable reactive group ^{independently of each other, and A 1} represents a divalent linkage containing a single bond or a hetero atom independently of each other. Representing a group, A ² represents an unsubstituted or substituted divalent hydrocarbon group having 1 to 20 carbon atoms, which is independent of each other and does not contain a single bond or a hetero atom, and m represents a divalent hydrocarbon group having 1 to 20 carbon atoms. A number, p is a number from 1 to 10, q is a number from 1 to 10, n = p + q, and n is a number from 2 to 20.)
2. 1 organosilicon compound represented by the average structural formula (2),

{In the formula, R ¹ , R ² , R ⁷ , A ¹ , A ² and m have the same meanings as described above, and R ³ is independent of each other and has 1 halogen atom, unsubstituted or substituted carbon atom number 1. Alkyl groups of ~ 12, unsubstituted or substituted alkoxy groups with 1 to 12 carbon atoms, unsubstituted or substituted alkylthio groups with 1 to 12 carbon atoms, or unsubstituted or substituted halos with 1 to 12 carbon atoms Representing an alkoxy group, R ⁴ is a hydrogen atom, a halogen atom, an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms, an unsubstituted or substituted alkoxy group having 1 to 12 carbon atoms, and the like. Represents an unsubstituted or substituted alkylthio group having 1 to 12 carbon atoms or an unsubstituted or substituted haloalkoxy group having 1 to 12 carbon atoms, and b is a number of 1 to 100 independently of each other. c is a number greater than 0 and less than 2, and Z represents a linking group represented by the following formula (3).

[(In the formula, R ⁴ represents the same meaning as described above, and L represents a single bond or a linking group selected from the following formulas (4) to (11).)

(In the formula, R ⁵ represents an alkyl group having a hydrogen atom or 1 to 12 carbon atoms ^{independently of each other, R 6} represents an alkyl group having 1 to 12 carbon atoms independently of each other, and k represents an alkyl group having 1 to 12 carbon atoms. , 1-12, where j represents a number from 1 to 1,000.)]}
3. 3. 1 or 2 organosilicon compounds, wherein A ^1- A ² is a single bond, a linking group represented by the formula (12) or a linking group represented by the formula (13).

(In the formula, a is a number of 1 to 20 independently of each other, Y is an oxygen atom or a sulfur atom independently of each other, and * represents a binding site with X or a phenylene group.)
4. The ^{organosilicon compound according to any one of 1 to 3, wherein the polymerizable reactive group of R 7} is an acryloyloxy group, a methacryloyloxy group, a styryl group, a vinyl group or an epoxy group.
5. The organosilicon compound according to any one of 1 to 4, ^{wherein the polymerizable reactive group of R 7 is an acryloyloxy group or a methacryloyloxy group.}
6. Average structural formula (14)

(In the formula, R ³ , R ⁴ , b and Z have the same meanings as described above.)
A polyphenylene ether compound having a hydroxyl group represented by the above, a compound having a functional group capable of reacting with the hydroxyl group and a polymerizable reactive group, and the formula (15).

(In the formula, R ¹ , R ² , A ² and m have the same meanings as described above.)
The method for producing an organosilicon compound according to any one of 1 to 5, which comprises reacting a compound having an isocyanate group and an alkoxysilyl group represented by.
7. The compound having a functional group capable of reacting with the hydroxyl group and a polymerizable reactive group is represented by the formula (16).

(In the formula, R ⁷ and A ² have the same meanings as described above.)
A method for producing an organosilicon compound (6), which is a compound having an isocyanate group and a polymerizable reactive group, represented by.
8. A curable composition containing any of the organosilicon compounds 1 to 5.
9. Provided is an article in which the curable composition of No. 8 is cured.

The organosilicon compound of the present invention has a polyphenylene ether structure and highly reactive hydrolyzable groups and polymerizable reactive groups in the molecule, and has copper foil adhesion and dielectric constant as compared with conventional silane coupling agents. It has excellent dielectric properties such as reactivity and dielectric tangent.
The composition containing the organosilicon compound of the present invention having such properties can be suitably used as a curable composition, particularly as a curable composition for forming a high-frequency substrate material.

Hereinafter, the present invention will be specifically described.
The organosilicon compound according to the present invention is represented by the average structural formula (1).

Here, X represents an n-valent organic group containing a polyphenylene ether structure, and R ¹ is an alkyl group having 1 to 10 unsubstituted or substituted carbon atoms independently of each other, or an unsubstituted or substituted carbon. Representing an aryl group having 6 to 10 atoms, R ² is an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aryl group having 6 to 10 carbon atoms independently of each other. R ⁷ represents a monovalent hydrocarbon group containing a polymerizable reactive group ^{independently of each other, and A 1} represents a divalent linking group containing a single bond or a hetero atom independently of each other. A ² represents an unsubstituted or substituted divalent hydrocarbon group having 1 to 20 carbon atoms, which is independent of each other and does not contain a single bond or a hetero atom, and m is a number of 1 to 3. , P is a number from 1 to 10, q is a number from 1 to 10, n = p + q, and n is a number from 2 to 20.

The alkyl group having 1 to 10 carbon atoms of R ¹ and R ² may be linear, cyclic or branched, and specific examples thereof include methyl, ethyl, n-propyl and i-propyl. Linear or branched alkyl groups such as n-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl groups; cyclopropyl, cyclobutyl , Cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl groups and the like.
Specific examples of the aryl group having 6 to 10 carbon atoms of R ¹ and R ² include phenyl, α-naphthyl, β-naphthyl group and the like.
Further, a part or all of the hydrogen atoms of each of these groups may be substituted with an alkyl group having 1 to 10 carbon atoms, a halogen atom such as F, Cl, Br, a cyano group, or the like, and such a group. Specific examples of the above include 3-chloropropyl, 3,3,3-trifluoropropyl, 2-cyanoethyl, trill, xsilyl group and the like.

Among these, ^{as R 1} , from the viewpoint of hydrolyzability, a linear alkyl group having 1 to 5 carbon atoms is preferable, a methyl or ethyl group is more preferable, and a methyl group is even more preferable.
On the other hand, as R ² , a linear alkyl group is preferable, a methyl or ethyl group is more preferable, and a methyl group is even more preferable.
Further, m is an integer of 1 to 3, preferably 2 to 3 from the viewpoint of reactivity, and more preferably 3.

Specific examples of the divalent linking group containing the heteroatom of A ¹ include an ether bond (-O-), a thioether bond (-S-), an amino bond (-NH-), and a sulfonyl bond (-S (-S ()). = O) _2- ), phosphinyl bond (-P (= O) OH-), oxo bond (-C (= O)-), thiooxo bond (-C (= S)-), ester bond (-C (= S)-) = O) O-), thioester bond (-C (= O) S-), thionoester bond (-C (= S) O-), dithioester bond (-C (= S) S-), carbonate ester bond (-OC (= O) O-), thiocarbonate ester bond (-OC (= S) O-), amide bond (-C (= O) NH-), thioamide bond (-C (= S) NH-) ), Urethane bond (-OC (= O) NH-), thiourethane bond (-SC (= O) NH-), thionourethane bond (-OC (= S) NH-), dithiourethane bond (-SC (=)) S) NH-), urea bond (-NHC (= O) NH-), thiourea bond (-NHC (= S) NH-) and the like can be mentioned.
Among these, ^{as A 1} , a single bond, an ether bond (-O-), or a urethane bond (-OC (= O) NH-) is preferable.

On the other hand, specific examples of the unsubstituted or substituted divalent hydrocarbon group having 1 to 20 carbon atoms which does not contain the hetero atom of ^{A 2 include methylene, ethylene, trimethylene, propylene, isopropylene, tetramethylene, isobutylene, and the like.} Pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene, heptadecamethylene, octadecamethylene, nonadeca Alkylene groups such as methylene and eikosadecilene groups; cycloalkylene groups such as cyclopentylene and cyclohexylene groups; arylene groups such as phenylene and α- and β-naphthylene groups can be mentioned.
Among these, a single bond, methylene, ethylene, trimethylene and octamethylene groups are preferable, a single bond, methylene, ethylene and trimethylene groups are more preferable, and ethylene and trimethylene groups are even more preferable.

Specific examples of the polymerizable reactive group of R ⁷ include an acryloyloxy group, a methacryloyloxy group, a styryl group, a vinyl group, an alkenyl group having 3 or more carbon atoms, an epoxy group, a maleimide group and the like.
Among these, an acryloyloxy group, a methacryloyloxy group, a styryl group, a vinyl group, and an epoxy group are preferable, and an acryloyloxy group and a methacryloyloxy group are more preferable.

X in the formula (1) represents an n-valent linking group containing a polyphenylene ether structure, and may have a linear structure, a branched structure, or a crosslinked structure therein.
The average of n per molecule is 2 to 20, but 2 to 10 is preferable, 2 to 5 is more preferable, and 2 is even more preferable. If n is less than 2, the reactivity is inferior due to the lack of hydrolyzable groups and polymerizable reactive groups. On the other hand, when n exceeds 20, the number of reaction sites becomes too large, so that the storage stability of the compound may be deteriorated or cracks may easily occur in the cured product.

In the formula (1), p ^{represents the number of monovalent hydrocarbon groups containing the polymerizable reactive group of R 7} , q represents the number of hydrolyzable groups, and n = p + q.
The average of p per molecule is 1 to 10, but 1 to 5 is preferable, 1 to 2 is more preferable, and 1 is even more preferable. If p is less than 1, the reactivity is inferior due to the lack of polymerizable reactive groups. On the other hand, when p exceeds 10, the number of reaction sites becomes too large, so that the storage stability of the compound may be deteriorated or cracks may easily occur in the cured product.
The average of q per molecule is 1 to 10, but 1 to 5 is preferable, 1 to 2 is more preferable, and 1 is even more preferable. If q is less than 1, the reactivity is inferior due to the lack of hydrolyzable groups. On the other hand, when q exceeds 10, the number of reaction sites becomes too large, so that the storage stability of the compound may be deteriorated or cracks may easily occur in the cured product.

The X is not particularly limited as long as it is an n-valent linking group containing a polyphenylene ether structure, but in consideration of enhancing copper foil adhesion and dielectric properties, in the present invention, the following formula is particularly used. The group represented is suitable.

Therefore, the organosilicon compound of the present invention preferably has an average structural formula represented by the formula (2), and by using these compounds, better copper foil adhesion and dielectric properties can be exhibited.

In these equations, R ¹ , R ² , R ⁷ , A ¹ , A ² and m have the same meanings as above, and R ³ is independent of each other and has 1 halogen atom, unsubstituted or substituted carbon atom number 1. ~ 12 alkyl groups, unsubstituted or substituted alkoxy groups with 1-12 carbon atoms, unsubstituted or substituted alkylthio groups with 1-12 carbon atoms, or unsubstituted or substituted halos with 1-12 carbon atoms Representing an alkoxy group, R ⁴ represents a hydrogen atom, a halogen atom, an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms, an unsubstituted or substituted alkoxy group having 1 to 12 carbon atoms, and the like. Represents an unsubstituted or substituted alkylthio group having 1 to 12 carbon atoms or an unsubstituted or substituted haloalkoxy group having 1 to 12 carbon atoms, and b is a number of 1 to 100 independently of each other. c is a number greater than 0 and less than 2, and Z represents a linking group represented by the following formula (3).

R ⁴ has the same meaning as above, and L represents a single bond or a linking group selected from the following formulas (4) to (11).

R ⁵ represents an alkyl group having a hydrogen atom or 1 to 12 carbon atoms ^{independently of each other, R 6} represents an alkyl group having 1 to 12 carbon atoms independently of each other, and k represents 1 to 1 It represents an integer of 12, and j represents a number from 1 to 1,000.

The alkyl group having 1 to 12 carbon atoms of R ³ and R ⁴ may be linear, cyclic or branched, and specific examples thereof include methyl, ethyl, n-propyl and i-propyl. Linear or branched n-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, etc. Alkyl groups: Cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl groups and the like can be mentioned.
The alkoxy group having 1 to 12 carbon atoms of R ³ and R ⁴ may be linear, cyclic or branched, and specific examples thereof include methoxy, ethoxy, propoxy, i-propoxy and n-. Butoxy, s-butoxy, t-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy groups, etc. Linear or branched alkoxy groups; cycloalkyloxy groups such as cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy groups and the like.
Further, a part or all of the hydrogen atoms of each of these groups may be substituted with halogen atoms such as F, Cl and Br, a mercapto group, a cyano group and the like, and specific examples of such groups include 3. -Chloropropyl, 3,3,3-trifluoropropyl, 3-mercaptopropyl, 2-cyanoethyl group and the like can be mentioned.
Examples of the halogen atoms of R ³ and R ⁴ include F, Cl, Br and the like.

Among these, ^{as R 3} , from the viewpoint of ease of production, a methyl group and a methoxy group are preferable, and a methyl group is more preferable.
On the other hand, as R ⁴ , a hydrogen atom, a methyl group, and a methoxy group are preferable, and a hydrogen atom is more preferable.

In addition, b is a number of 1 to 100 independently of each other, but is preferably 3 to 50, more preferably 5 to 20 from the viewpoint of copper foil adhesion and dielectric properties of the organosilicon compound. If b is smaller than 1, good copper foil adhesion and dielectric properties may not be obtained, and if b is larger than 100, the compatibility of the organosilicon compound with the organic resin may deteriorate. ..

Although c is a number larger than 0 and less than 2, it is preferably 0.1 to 1.9, more preferably 0.5 to 1.5, and 0.7, from the viewpoint of copper foil adhesion of the organosilicon compound. ~ 1.3 is even more preferable. When c is 0, it does not contain a polymerizable reactive group, so it does not react with the organic resin, and there is a risk that good copper foil adhesion cannot be obtained. When c is 2, it is hydrolyzable. Since it does not contain a group, it does not react with the copper foil, and there is a risk that good copper foil adhesion cannot be obtained.

Further, in the present invention, as the −A ¹ −A ² − group, a single bond, a group represented by the formula (12) or the formula (13) is preferable, and the group represented by the formula (12) is particularly preferable. Suitable.

The above a represents a number of 1 to 20 independently of each other, Y represents an oxygen atom or a sulfur atom independently of each other, and * represents an X of the formula (1) or a phenylene group of the formula (2). Represents the binding site of.
The number of a is 1 to 20 independently of each other, but from the viewpoint of ease of production, 1 to 10 is preferable, and 1 to 5 is more preferable.
Y is an oxygen atom or a sulfur atom independently of each other, but an oxygen atom is preferable from the viewpoint of ease of production.

The weight average molecular weight of the organosilicon compound of the present invention is not particularly limited, but the workability can be improved by setting the viscosity of the curable composition containing the compound in an appropriate range, and the obtained cured product can be obtained. Considering that sufficient copper foil adhesion and dielectric properties are imparted, a weight average molecular weight of 500 to 50,000 is preferable, 1,000 to 20,000 is more preferable, and 4,000 to 10,000 is even more preferable. The weight average molecular weight in the present invention is a polystyrene-equivalent value obtained by gel permeation chromatography (GPC).

The organosilicon compound of the present invention may be used in a state of containing a solvent.
The solvent is not particularly limited as long as it has a dissolving ability of the organic silicon compound represented by the formula (1), but from the viewpoint of solubility, volatileness and the like, aromatics such as toluene and xylene are used. Solvents: Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ether solvents such as tetrahydrofuran are preferable, and toluene and xylene are more preferable.
The amount of the solvent added is preferably 100 to 20,000 parts by mass, more preferably 200 to 10,000 parts by mass, based on 100 parts by mass of the organosilicon compound represented by the formula (1).

The organic silicon compound represented by the above formula (1) includes a compound having a group containing a plurality of hydroxyl groups and a polyphenylene ether structure in one molecule, and a compound having a functional group capable of reacting with the hydroxyl group and a polymerizable reactive group. , Can be obtained by reacting with a compound having an isocyanate group and an alkoxysilyl group (hereinafter referred to as isocyanate silane).
More specifically, the hydroxyl group of the polyphenylene ether compound having a hydroxyl group represented by the average structural formula (14) and the compound having a functional group capable of reacting with the hydroxyl group and a polymerizable reactive group are obtained by using the average structural formula (14). ) Is reacted in such an amount that the hydroxyl group of the compound represented by) remains, and then a reaction of forming a urethane bond is carried out between the excess hydroxyl group and the isocyanate group of the isocyanate silane represented by the formula (15). ..

（式中、Ｒ³、Ｒ⁴、ｂおよびＺは、上記と同じ。）

(In the formula, R ³ , R ⁴ , b and Z are the same as above.)

（式中、Ｒ¹、Ｒ²、Ａ²およびｍは、上記と同じ。）

(In the formula, R ¹ , R ² , A ² and m are the same as above.)

The polyphenylene ether compound having a hydroxyl group represented by the formula (14) is available as a commercially available product, and as such a commercially available product, for example, PPO (trademark) SA90-100 manufactured by SABIC Innovative Plastics Co., Ltd. , PPO ™ resin powder, noyl ™ 640-111, and polyphenylene ether compounds distributed and rearranged by their partition rearrangement treatment.

On the other hand, specific examples of the isocyanate silane represented by the formula (15) include 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropylmethyldimethoxysilane, 3-isocyanatepropyldimethylmethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like. Examples thereof include 3-isocyanatepropylmethyldiethoxysilane and 3-isocyanatepropyldimethylethoxysilane.
Among these, 3-isocyanatepropyltriethoxysilane and 3-isocyanatepropyltrimethoxysilane are preferable, and 3-isocyanatepropyltrimethoxysilane is more preferable, from the viewpoint of hydrolyzability.

The functional group contained in the functional group capable of reacting with the hydroxyl group and the compound having a polymerizable reactive group is not particularly limited as long as it is a functional group that selectively reacts with the hydroxyl group, and is, for example, a carboxylic acid or a carboxylic acid. Examples thereof include esters, carboxylic acid anhydrides, carboxylic acid halides, halogen atoms (chlorine atom, bromine atom, iodine atom), methanesulfonate group, trifluoromethanesulfonate group, p-toluenesulfonate group, isocyanate group, isothiocyanate group and the like. However, a carboxylic acid halide, a halogen atom, an isocyanate group, and an isothiocyanate group are preferable, and an isocyanate group is more preferable.

The compound having a functional group capable of reacting with a hydroxyl group and a polymerizable reactive group is not particularly limited, and specific examples thereof include methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and methacrylic acid-. Methacrylic group-containing compounds such as 2-ethylhexyl, methacrylic acid anhydride, and methacryloyl chloride; acrylic acids such as acrylate, methyl acrylate, ethyl acrylate, butyl acrylate, -2-ethylhexyl acrylate, acrylate anhydride, and acryloyl chloride. Group-containing compounds; Styryl group-containing compounds such as p-chloromethylstyrene and m-chloromethylstyrene; alkenyl chloride compounds such as allyl chloride, methacrylic chloride, butenyl chloride, pentenyl chloride, hexenyl chloride, heptenyl chloride, octenyl chloride and nonenyl chloride. Alkenyl bromide compounds such as allyl bromide, methacrylic bromide, butenyl bromide, pentenyl bromide, hexenyl bromide, heptenyl bromide, octenyl bromide, nonenyl bromide; allyl iodide, methacrylic iodide, butenyl iodide. , Pentenyl iodide, hexenyl iodide, heptenyl iodide, octenyl iodide, nonenyl iodide and other alkenyl iodide compounds; alkyl halides and epoxy group-containing compounds such as epichlorohydrin; Compounds having an isocyanate group and a polymerizable reactive group; examples thereof include isothiocyanate compounds such as allyl isothiocyanate.

（式中、Ｒ⁷およびＡ²は、上記と同じ。）

(In the formula, R ⁷ and A ² are the same as above.)

Specific examples of the isocyanate compound represented by the formula (16) include 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 1,1- (bisacryloyloxymethyl) ethyl isocyanate, and allyl isocyanate.

Among these, from the viewpoint of reactivity and availability, methacryloyl chloride, acryloyl chloride, p-chloromethylstyrene, m-chloromethylstyrene, allyl chloride, octenyl chloride, allyl bromide, epichlorohydrin, 2-isocyanate. Natoethyl acrylate, 2-isocyanatoethyl methacrylate, 1,1- (bisacryloyloxymethyl) ethyl isocyanate and allyl isocyanate are preferable, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 1,1- (bis). Acryloyloxymethyl) ethyl isocyanate and allyl isothiocyanate are more preferable, and 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate and 1,1- (bisacryloyloxymethyl) ethyl isocyanate are even more preferable.

The reaction between the hydroxyl group of the polyphenylene ether compound having a hydroxyl group represented by the average structural formula (14) and the compound having a functional group and a polymerizable reactive group capable of reacting with the hydroxyl group is carried out by a conventionally known general method. It can be carried out.
For example, a method of introducing a polymerizable reactive group by desalting with a carboxylic acid halide such as methacryloyl chloride in the presence of a basic compound; p-chloromethylstyrene, allyl bromide, epi in the presence of a basic compound. A method for synthesizing asymmetric ethers by nucleophilic substitution reaction with halogenated compounds such as chlorohydrin (Williamson synthesis, Williamson ether synthesis); Iso (thio) cyanate groups such as 2-isocyanatoethylmethacrylate and allyl isothiocyanate. A (thio) urethanization reaction with a contained compound or the like can be adopted.

In particular, when the Williamson synthesis method is used, various basic compounds usually used in the Williamson synthesis method can be used as the basic compound, and the hydroxyl group of the compound represented by the formula (14) can be used. Any one may be used as long as it does not react with anything other than.
Specifically, alkali metals such as metallic sodium and metallic lithium; alkaline earth metals such as metallic calcium; alkali metal hydrides such as sodium hydride, lithium hydride, potassium hydride, and cesium hydride; calcium hydride and the like. Alkaline earth metal hydrides; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide and their aqueous solutions, alkaline earth metal hydroxides such as barium hydroxide and calcium hydroxide. And its aqueous solution; alkali metals and alkaline earth alkoxides such as potassium tertiary butoxide, sodium tertiary butoxide; alkali metals and alkaline earth metal carbonates such as potassium carbonate, sodium carbonate, calcium carbonate; sodium hydrogen carbonate, potassium hydrogen carbonate Alkali metals such as and alkaline earth hydrogen carbonates; examples thereof include tertiary amines such as triethylamine, tributylamine, N, N-diisopropylethylamine, tetramethylethylenediamine, pyridine, N, N-dimethyl-4-aminopyridine and the like.
Among these, from the viewpoint of reaction efficiency, hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, barium hydroxide, calcium hydroxide and alkaline earth metals, or aqueous solutions thereof. Is preferable, and an aqueous solution of sodium hydroxide is more preferable.

The amount of the basic compound used is not particularly limited, but the organosilicon compound obtained by sufficiently advancing the etherification reaction to prevent the residual halogenated compound and preventing the excessive residual of the basic compound. In consideration of enhancing the storage stability and various properties of the compound, the basic compound is preferably 0.5 to 20 mol, more preferably 1 to 10 mol, and 2 to 2 to 1 mol of the hydroxyl group of the compound represented by the formula (14). 8 mol is even more preferable.

In the etherification reaction, a solvent that does not react with the raw material used can be used.
Specific examples thereof include water; hydrocarbon solvents such as pentane, hexane, heptane, octane, decane, and cyclohexane; aromatic solvents such as benzene, toluene, and xylene; formamide, N, N-dimethylformamide, pyrrolidone, and N. -Amid solvents such as methylpyrrolidone; ether solvents such as diethyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran, 1,4-dioxane; nitrile solvents such as acetonitrile, etc., which can be used alone. Two or more types may be used in combination.
Among these, water, toluene, xylene, dimethylformamide, cyclopentyl methyl ether, and tetrahydrofuran are preferable, and a mixed solvent of water and toluene and a mixed solvent of water and xylene are more preferable, from the viewpoint of reaction efficiency.

The reaction temperature during the etherification reaction is not particularly limited, but is preferably 25 to 90 ° C., preferably 40 to 80 ° C., in consideration of suppressing volatilization of the halogenated compound while making the reaction rate appropriate. Preferably, 50-70 ° C. is even more preferable.
The etherification reaction is usually carried out under atmospheric pressure, but may be carried out under pressure for the purpose of suppressing volatilization of the raw materials and improving the reaction rate.
The reaction time is not particularly limited, but is usually 10 minutes to 24 hours.

In the above etherification reaction, a catalyst may be used to improve the reaction rate.
As the catalyst, one that does not react with anything other than the hydroxyl group of the compound represented by the formula (14) may be appropriately selected from those generally used in the Williamson synthesis method.
Specific examples thereof include crown ethers such as 12-crown-4, 15-crown-5, 18-crown-6, dibenzo-18-crown-6; tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodine. Do, quaternary ammonium salts such as tetrabutylammonium hydrogensulfate; alkali metal halides such as potassium iodide and sodium iodide, etc., which may be used alone or in combination of two or more. ..
Among these, 18-crown-6, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydrogensulfate, potassium iodide are preferable, and tetrabutylammonium iodide, from the viewpoint of reactivity and availability. Tetrabutylammonium hydrogensulfate and potassium iodide are more preferable, and tetrabutylammonium hydrogensulfate is even more preferable.
The catalyst can act as a phase transfer catalyst or activate a halogenated compound to improve the reaction rate.

The amount of the catalyst used may be any amount as long as it is a catalyst amount, but is preferably 0.001 to 10% by mass, preferably 0.01 to 1% by mass, based on the total amount of the compound represented by the formula (14) and the halogenated compound. Is more preferable.

In this case, the reaction ratio between the compound represented by the formula (14) and the halogenated compound is not particularly limited, but the reaction is carried out in such an amount that the hydroxyl group of the compound represented by the formula (14) remains. Then, considering that the reaction of forming a urethane bond between the surplus hydroxyl group and the isocyanate group of the isocyanate silane represented by the formula (15) is carried out, the compound represented by the formula (14) The ratio of the halogen atom of the halogenated compound to 1 mol of the hydroxyl group is preferably 0.1 to 0.9 mol, more preferably 0.2 to 0.8 mol, and 0.3 to 0.7 mol. Even more preferable.

Further, when the (thio) urethanization reaction between the hydroxyl group of the compound represented by the formula (14) and the iso (thio) cyanate group-containing compound is carried out, the compound represented by the formula (14) and the iso (thio) cyanate group are carried out. The reaction ratio with the contained compound is not particularly limited, but the reaction is carried out in such an amount that the hydroxyl group of the compound represented by the formula (14) remains, and then the excess hydroxyl group is reacted with the excess hydroxyl group of the formula (15). Considering that the reaction of forming a urethane bond with the isocyanate group of the isocyanate silane represented by is carried out, the iso (thio) cyanate group-containing compound has a 1 mol hydroxyl group of the compound represented by the formula (14). The ratio of the iso (thio) cyanate group is preferably 0.1 to 0.9 mol, more preferably 0.2 to 0.8 mol, and even more preferably 0.3 to 0.7 mol.

Further, in the above (thio) urethanization reaction, a catalyst may be used to improve the reaction rate.
The catalyst may be appropriately selected from those generally used in the (thio) urethanization reaction, and specific examples thereof include dibutyltin oxide, dioctyltin oxide, and tin (II) bis (2-ethylhexano). Ate), dibutyltin dilaurate, dioctyltin dilaurate and the like.
The amount of the catalyst used may be any amount as long as it is the amount of the catalyst, but it is usually 0.001 to 1% by mass with respect to the total of the compound represented by the formula (14) and the isothiocyanate group-containing compound.

Further, in the above (thio) urethanization reaction, a solvent that does not react with the raw material used can be used.
Specific examples thereof include hydrocarbon solvents such as pentane, hexane, heptane, octane, decane, and cyclohexane; aromatic solvents such as benzene, toluene, and xylene; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; formamide. , N, N-dimethylformamide, pyrrolidone, N-methylpyrrolidone and other amide solvents, ethyl acetate, butyl acetate, γ-butyrolactone, propylene glycol-1-monomethyl ether-2-acetate and other ester solvents; diethyl ether, Examples thereof include ether solvents such as dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran, and 1,4-dioxane, and these may be used alone or in combination of two or more.

The reaction temperature during the (thio) urethanization reaction is not particularly limited, but is preferably 25 to 90 ° C. in consideration of suppressing side reactions such as allophanation while making the reaction rate appropriate. ~ 80 ° C. is more preferable.
The reaction time is not particularly limited, but is usually 10 minutes to 24 hours.

In the present invention, after introducing a polymerizable reactive group so that the hydroxyl group of the compound represented by the formula (14) remains based on the above step, the excess hydroxyl group and the isocyanate silane represented by the formula (15) are added. A reaction is carried out to form a urethane bond with the isocyanate group of.
In the reaction of forming a urethane bond between the excess hydroxyl group and the isocyanate group of the isocyanate silane represented by the formula (15), the catalyst, solvent, reaction temperature and reaction time during the (thio) urethanization reaction The reaction conditions such as and the like can be used in the same manner.

The reaction ratio of the excess hydroxyl group to the isocyanate group of the isocyanate silane represented by the formula (15) suppresses by-products during the urethanization reaction and enhances the storage stability and properties of the obtained organic silicon compound. Considering this, the ratio of the isocyanate group of the isocyanate silane represented by the formula (15) is preferably 1 to 1.2 mol, and more preferably 1 to 1.1 mol with respect to the excess 1 mol of the hydroxyl group.

The curable composition of the present invention contains an organosilicon compound represented by the formula (1).
The organosilicon compound represented by the formula (1) of the present invention is derived from the structure of the organosilicon compound, and is a cured product obtained by using a curable composition containing the organosilicon compound as compared with the conventional organosilicon compound. Improves copper foil adhesion and dielectric properties.
In the curable composition of the present invention, the content of the organosilicon compound is not particularly limited, but is preferably about 0.1 to 10% by mass, and 0.5 to 5% in the curable composition. More preferably by mass. When the organosilicon compound contains a solvent, the above-mentioned content means a non-volatile component excluding the solvent.

Further, the curable composition of the present invention preferably contains an organic resin.
The organic resin is not particularly limited, and specific examples thereof include epoxy resin, phenol resin, polycarbonate and polycarbonate blend, acrylic resin, polyester resin, polyamide resin, polyimide resin, polybutadiene, and styrene-butadiene co-weight. Combined, acrylonitrile-styrene copolymer, styrene-acrylonitrile-butadiene copolymer, polyvinyl chloride resin, polystyrene resin, polyphenylene ether resin, polymerizable reactive group-containing polyphenylene ether resin, blend of polystyrene and polyphenylene ether, cellulose acetate butybean It may be appropriately selected from the rate, polyethylene resin, etc. according to the application, but considering that it is used as a substrate material for a printed wiring board provided in an electronic device using an electric signal in a high frequency region, an epoxy resin, a polycarbonate resin, etc. , Polyphenylene ether resin containing polymerizable reactive group, acrylic resin, polybutadiene, styrene-butadiene copolymer or a blend thereof.
In this case, an appropriate curing agent may be blended depending on the organic resin used. For example, when an epoxy resin is used, a curing agent such as an imidazole compound or a polymerizable reactive group-containing polyphenylene ether resin is used. A curing agent such as a peroxide can be blended.
Further, as a cross-linking component, for example, a cyanate ester compound or the like may be appropriately blended, and further, an adhesiveness improver, an ultraviolet absorber, a storage stability improver, a plasticizer, a filler, a pigment, etc. Various additives may be added.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
In the following, the viscosity is a value measured at 25 ° C. by a B-type rotational viscometer, the molecular weight is a polystyrene-equivalent weight average molecular weight obtained by GPC (gel permeation chromatography) measurement, and the non-volatile content is It is a measured value by the heating residual amount method after heating and drying at 105 ° C. for 3 hours on an aluminum petri dish.

[1] Synthesis of organosilicon compound [Example 1-1] Synthesis of organosilicon compound 1 PPO ™ SA90-100 (trademark) was placed in a 200 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. 16 g of SABIC Innovative Plastics Co., Ltd., 80 g of toluene, 0.02 g of dioctyltin dilaurate and 0.02 g of 3,5-ditercious butyl-4-hydroxytoluene were charged and heated to 80 ° C. 1.7 g of 2-isocyanatoethyl methacrylate was added dropwise thereto, and then 2.2 g of 3-isocyanatopropyltrimethoxysilane was added dropwise, and the mixture was heated and stirred at 80 ° C. for 2 hours. It was confirmed by IR measurement that the absorption peak derived from the isocyanate group of the raw material completely disappeared and the absorption peak derived from the urethane bond was generated instead, and the reaction was terminated.
The obtained reaction product was a brown transparent liquid having a weight average molecular weight of 4,900, a viscosity of 4.9 mm ² / s, and a non-volatile content of 23% by mass.
In the obtained reaction product, the polymerizable reactive group corresponds to a methacryloxy group, the hydrolyzable group corresponds to a trimethoxysilyl group, and the polymerizable reactive group: hydrolyzable group = 50:50 (molar ratio).

[Example 1-2] Synthesis of organosilicon compound 2 Example 1-except that the amount of 2-isocyanatoethyl methacrylate was changed to 3.0 g and the amount of 3-isocyanatopropyltrimethoxysilane was changed to 0.4 g. It was synthesized in the same procedure as in 1.
The obtained reaction product was a brown transparent liquid, having a weight average molecular weight of 5,000, a viscosity of 5.5 mm ² / s, and a non-volatile content of 22% by mass.
The obtained reaction product corresponds to a methacryloxy group as a polymerizable reactive group, a trimethoxysilyl group as a hydrolyzable group, and a polymerizable reactive group: hydrolyzable group = 90:10 (molar ratio).

[Example 1-3] Synthesis of organosilicon compound 3 Example 1-except that the amount of 2-isocyanatoethyl methacrylate was changed to 0.3 g and the amount of 3-isocyanatopropyltrimethoxysilane was changed to 4.0 g. It was synthesized in the same procedure as in 1.
The obtained reaction product was a brown transparent liquid, having a weight average molecular weight of 5,300, a viscosity of 6.2 mm ² / s, and a non-volatile content of 25% by mass.
The obtained reaction product corresponds to a methacryloxy group as a polymerizable reactive group, a trimethoxysilyl group as a hydrolyzable group, and a polymerizable reactive group: hydrolyzable group = 10:90 (molar ratio).

[Example 1-4] PPO ™ resin powder (manufactured by SABIC Innovative Plastics Co., Ltd.) in a 200 mL separable flask equipped with a synthetic stirrer for organosilicon compound 4, a reflux condenser, a dropping funnel, and a thermometer. 40 g, 110 g of toluene, 0.05 g of dioctyltin dilaurate and 0.05 g of 3,5-ditersally butyl-4-hydroxytoluene were charged and heated to 80 ° C. 0.2 g of 2-isocyanatoethyl methacrylate was added dropwise thereto, then 0.25 g of 3-isocyanatopropyltrimethoxysilane was added dropwise, and the mixture was heated and stirred at 80 ° C. for 2 hours. Then, it was confirmed by IR measurement that the absorption peak derived from the isocyanate group of the raw material completely disappeared and the absorption peak derived from the urethane bond was generated instead, and the reaction was terminated.
The obtained reaction product was a brown transparent liquid, having a weight average molecular weight of 102,000, a viscosity of 1,200 mm ² / s, and a non-volatile content of 27% by mass.
In the obtained reaction product, the polymerizable reactive group corresponds to a methacryloxy group, the hydrolyzable group corresponds to a trimethoxysilyl group, and the polymerizable reactive group: hydrolyzable group = 50:50 (molar ratio).

[Example 1-5] Synthesis of organosilicon compound 5 Distribution of noyl640-111 (manufactured by SABIC Innovative Plastics Co., Ltd.) based on the method described in Example "PPE-3" of Japanese Patent Application Laid-Open No. 2015-08632. By rearrangement, a partitioned rearranged polyphenylene ether was obtained.
In a 200 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 40 g of the partitioned rearranged polyphenylene ether obtained above, 110 g of toluene, 0.05 g of dioctyltin dilaurate and 3,5-diter 0.05 g of Charlie Butyl-4-hydroxytoluene was charged and heated to 80 ° C. 10.6 g of 2-isocyanatoethyl methacrylate was added dropwise thereto, and then 13.9 g of 3-isocyanatopropyltrimethoxysilane was added dropwise, and the mixture was heated and stirred at 80 ° C. for 2 hours. Then, it was confirmed by IR measurement that the absorption peak derived from the isocyanate group of the raw material completely disappeared and the absorption peak derived from the urethane bond was generated instead, and the reaction was terminated.
The obtained reaction product was a brown transparent liquid having a weight average molecular weight of 6,200, a viscosity of 49 mm ² / s, and a non-volatile content of 30% by mass.
In the obtained reaction product, the polymerizable reactive group corresponds to a methacryloxy group, the hydrolyzable group corresponds to a trimethoxysilyl group, and the polymerizable reactive group: hydrolyzable group = 50:50 (molar ratio).

[Example 1-6] Synthesis of organosilicon compound 6 2-Isocyanatoethyl methacrylate was synthesized in the same procedure as in Example 1-1 except that it was changed to 1.5 g of 2-isocyanatoethyl acrylate.
The obtained reaction product was a brown transparent liquid, having a weight average molecular weight of 4,800, a viscosity of 4.5 mm ² / s, and a non-volatile content of 22% by mass.
The obtained reaction product corresponds to an acrylic oxy group as a polymerizable reactive group, a trimethoxysilyl group as a hydrolyzable group, and a polymerizable reactive group: hydrolyzable group = 50:50 (molar ratio).

[Example 1-7] Synthesis of organosilicon compound 7 The same as in Example 1-1 except that 2-isocyanatoethyl methacrylate was changed to 2.6 g of 1,1- (bisacryloyloxymethyl) ethyl isocyanate. Synthesized by the procedure.
The obtained reaction product was a brown transparent liquid, having a weight average molecular weight of 5,500, a viscosity of 6.2 mm ² / s, and a non-volatile content of 20% by mass.
The obtained reaction product corresponds to an acrylic oxy group as a polymerizable reactive group, a trimethoxysilyl group as a hydrolyzable group, and a polymerizable reactive group: hydrolyzable group = 67:33 (molar ratio).

[Example 1-8] Synthesis of organosilicon compound 8 2-Isocyanatoethyl methacrylate was synthesized in the same procedure as in Example 1-1 except that it was changed to 1.1 g of allyl isothiocyanate.
The obtained reaction product was a brown transparent liquid having a weight average molecular weight of 4,500, a viscosity of 4.1 mm ² / s, and a non-volatile content of 21% by mass.
The obtained reaction product corresponds to a vinyl group as a polymerizable reactive group, a trimethoxysilyl group as a hydrolyzable group, and a polymerizable reactive group: hydrolyzable group = 50:50 (molar ratio).

[Example 1-9] Synthesis of organosilicon compound 9 [First step]
PPO ™ SA90-100 (manufactured by SABIC Innovative Plastics Co., Ltd.) 50 g, toluene 130 g, tetrabutylammonium hydrogen sulfate 0 in a 300 mL separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer. .54 g, 0.06 g of 3,5-ditercious butyl-4-hydroxytoluene and 54.1 g of 30% sodium hydroxide aqueous solution were charged and heated to 60 ° C. 4.1 g of allyl bromide was added dropwise thereto, and the mixture was heated and stirred at 60 ° C. for 6 hours. Then, the aqueous layer separated into two layers is separated by allowing it to stand, the organic layer is washed with water until it becomes neutral, and the organic layer is further concentrated under reduced pressure (80 ° C., 5 mmHg) to remove volatile components and polymerize. A compound having a vinyl group introduced as a sex reactive group was obtained as a brown solid.

[Second stage]
In a 200 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 16 g of the compound having the vinyl group obtained in the first step, 80 g of toluene, 0.02 g of dioctyltin dilaurate and 3, 0.02 g of 5-ditercious butyl-4-hydroxytoluene was charged and heated to 80 ° C. 2.2 g of 3-isocyanatepropyltrimethoxysilane was added dropwise thereto, and the mixture was heated and stirred at 80 ° C. for 2 hours. It was confirmed by IR measurement that the absorption peak derived from the isocyanate group of the raw material completely disappeared and the absorption peak derived from the urethane bond was generated instead, and the reaction was terminated.
The obtained reaction product was a brown transparent liquid, having a weight average molecular weight of 4,600, a viscosity of 2.7 mm ² / s, and a non-volatile content of 23% by mass.
The obtained reaction product corresponds to a vinyl group as a polymerizable reactive group, a trimethoxysilyl group as a hydrolyzable group, and a polymerizable reactive group: hydrolyzable group = 50:50 (molar ratio).

[Example 1-10] Synthesis of organosilicon compound 10 Allyl bromide was synthesized in the same procedure as in Example 1-9, except that the allyl bromide was changed to 5.2 g of p-chloromethylstyrene.
The obtained reaction product was a brown transparent liquid, having a weight average molecular weight of 5,700, a viscosity of 3.8 mm ² / s, and a non-volatile content of 21% by mass.
The obtained reaction product corresponds to a styryl group as a polymerizable reactive group, a trimethoxysilyl group as a hydrolyzable group, and a polymerizable reactive group: hydrolyzable group = 50:50 (molar ratio).

[Example 1-11] Synthesis of organosilicon compound 11 [First step]
PPO ™ SA90-100 (manufactured by SABIC Innovative Plastics Co., Ltd.) 50 g, toluene 130 g, 3,5-ditershally butyl in a 300 mL separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer. 0.06 g of -4-hydroxytoluene and 3.8 g of triethylamine were charged and heated to 60 ° C. 3.5 g of methacryloyl chloride was added dropwise thereto, and the mixture was heated and stirred at 60 ° C. for 6 hours. Then, 150 g of water was added to stop the reaction. Subsequently, the aqueous layer separated into two layers was separated by allowing it to stand, the organic layer was washed with water until it became neutral, and the organic layer was further concentrated under reduced pressure (80 ° C., 5 mmHg) to remove volatile components. A compound having a methacryloxy group introduced as a polymerizable reactive group was obtained as a brown solid.

[Second stage]
16 g of the compound having the methacryloxy group obtained in the first step, 80 g of toluene, 0.02 g of dioctyltin dilaurate and 3 in a 200 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. , 5-Ditershaly butyl-4-hydroxytoluene 0.02 g was charged and heated to 80 ° C. 2.2 g of 3-isocyanatepropyltrimethoxysilane was added dropwise thereto, and the mixture was heated and stirred at 80 ° C. for 2 hours. It was confirmed by IR measurement that the absorption peak derived from the isocyanate group of the raw material completely disappeared and the absorption peak derived from the urethane bond was generated instead, and the reaction was terminated.
The obtained reaction product was a brown transparent liquid, having a weight average molecular weight of 5,000, a viscosity of 3.0 mm ² / s, and a non-volatile content of 20% by mass.
In the obtained reaction product, the polymerizable reactive group corresponds to a methacryloxy group, the hydrolyzable group corresponds to a trimethoxysilyl group, and the polymerizable reactive group: hydrolyzable group = 50:50 (molar ratio).

[Example 1-12] Synthetic allyl bromide of organosilicon compound 12 was changed to 3.1 g of epichlorohydrin, and 3,5-ditercious butyl-4-hydroxytoluene in the first and second steps was added. It was synthesized in the same procedure as in Example 1-9 except that it was not used.
The obtained reaction product was a brown transparent liquid having a weight average molecular weight of 5,200, a viscosity of 2.9 mm ² / s, and a non-volatile content of 20% by mass.
The obtained reaction product corresponds to an epoxy group as a polymerizable reactive group, a trimethoxysilyl group as a hydrolyzable group, and a polymerizable reactive group: hydrolyzable group = 50:50 (molar ratio).

[Comparative Example 1-1] A bifunctional phenylene ether resin (manufactured by Mitsubishi Gas Chemical Co., Inc., OPE-1000) is used in a reaction apparatus equipped with a synthetic stirrer, a reflux condenser, a dropping funnel and a thermometer for an organosilicon compound 13. ) 500 g and 447 g of polytetramethoxysilane (M silicate 51 manufactured by Tama Chemical Co., Ltd.) were charged, heated to 90 ° C., melted and mixed to prepare a uniform solution. 0.22 g of dibutyltin dilaurate was added thereto as a catalyst, and a demethanol reaction was carried out at 90 ° C. for 15 hours to obtain a corresponding organosilicon compound.

[Comparative Example 1-2] A bifunctional phenylene ether resin (manufactured by Mitsubishi Gas Chemical Co., Inc., OPE-1000) is used in a reaction device equipped with a synthetic stirrer, a reflux condenser, a dropping funnel and a thermometer for an organosilicon compound 14. ) 71.8 g and 45.3 g of polymethyltrimethoxysilane (MTMS-A manufactured by Tama Chemical Co., Ltd.) were charged, heated to 90 ° C., melted and mixed to prepare a uniform solution. 0.02 g of dibutyltin dilaurate was added thereto as a catalyst, and a demethanol reaction was carried out at 90 ° C. for 15 hours to obtain a corresponding organosilicon compound.

[2] Preparation of curable composition and cured article thereof Each component used when preparing the curable composition and the cured article thereof will be described.
[PPE]
-PPO (trademark) SA9000 manufactured by SABIC Innovative Plastics Co., Ltd. (polyphenylene ether resin containing a methacrylicoxy group as a polymerizable reactive group)
[Crosslinking agent]
・ Crosslinking agent 1: DCP (tricyclodecanedimethanol dimethacrylate) manufactured by Shin Nakamura Chemical Industry Co., Ltd.
-Crosslinking agent 2: TAIC (trademark) (triallyl isocyanurate) manufactured by Nihon Kasei Corporation
[Organic resin]
-Organic resin 1: Ricon 156 (polybutadiene) manufactured by Cray Valley.
-Organic resin 2: Ricon100 (styrene-butadiene copolymer) manufactured by Cray Valley.
[filler]
-SC2300-SVJ manufactured by Admatex Co., Ltd. (spherical silica surface-treated with vinylsilane)
[Curing agent]
・ Perbutyl P manufactured by NOF CORPORATION (1,3-bis (butylperoxyisopropyl) benzene, peroxide)
[Organosilicon compound]
-Organosilicon compound: The organosilicon compound obtained in Examples 1-1 to 1-12 and Comparative Examples 1-1 and 1-2.

[Example 2-1]
After mixing PPE and toluene in a mass ratio of 1: 1, the mixed solution is heated and stirred at 80 ° C. for 1 hour to completely dissolve PPE in toluene, and then cooled to 25 ° C. to obtain PPE. A 50 mass% toluene solution was obtained.
Subsequently, according to the compounding ratio (parts by mass, but the organosilicon compound is a non-volatile content equivalent value) shown in Table 1, a 50 mass% toluene solution of PPE (non-volatile content equivalent value), a cross-linking agent, an organic resin, a filler, The curing agent and the organosilicon compound 1 obtained in Example 1-1 were mixed and stirred for 30 minutes to completely dissolve the mixture to obtain a varnish-like curable composition (resin varnish).
Subsequently, the obtained resin varnish was impregnated with glass cloth (manufactured by Nitto Boseki Co., Ltd., # 1078 type, WEA1078) and then heated and dried at 120 ° C. for 3 minutes to obtain a prepreg. At this time, the thickness after curing was adjusted to be about 60 μm.
Both sides of the obtained prepreg were sandwiched between copper foils (GT-MP manufactured by Furukawa Electric Co., Ltd., thickness 12 μm) and laminated, and under vacuum conditions, at 220 ° C. for 90 minutes and at a pressure of 40 kgf / cm ² . By heating and pressurizing under the conditions, an evaluation substrate 1 which is a cured article was obtained.
Further, 12 prepregs obtained above were stacked and heated and pressed in the same manner as described above to obtain an evaluation substrate 2 which is a cured product.

[Examples 2-2-2-12 and Comparative Examples 2-1 and 2-2]
As shown in Tables 1 and 2, the organosilicon compound 1 was changed to the organosilicon compounds 2 to 14 obtained in Examples 1-2 to 1-12 and Comparative Examples 1-1 to 1-2, respectively. Made a curable composition and a cured article thereof in the same manner as in Example 2-1.

[Comparative Examples 2-3, 2-4]
As shown in Table 2, organosilicon compound 1 was used as Comparative Example 2-3 with γ-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) and Comparative Example 2-4 with phenyl. A curable composition and a cured article thereof were prepared in the same manner as in Example 2-1 except that they were changed to trimethoxysilane (KBM-103, manufactured by Shin-Etsu Chemical Co., Ltd.).

[Comparative Example 2-5]
As shown in Table 2, a curable composition and a cured article thereof were prepared in the same manner as in Example 2-1 except that the organosilicon compound 1 was not used.

Each evaluation substrate 1 or 2 prepared by the above procedure was evaluated by the method shown below.
[Dielectric property]
Using "N5230A" manufactured by Agilent Technologies, Inc., the relative permittivity and dielectric loss tangent of the copper-clad laminate at 10 GHz were measured by the cavity resonator perturbation method. As the copper-clad laminate, the one obtained by removing the copper foil from the evaluation substrate 2 produced above was used. The results are also shown in Tables 1 and 2 below.
[Copper foil adhesion strength]
The peeling strength of the copper foil on the surface of the copper-clad laminate (copper foil adhesion strength) was measured by a method in accordance with JIS C 6481. At this time, a pattern having a width of 10 mm and a length of 100 mm is formed on a test piece having a width of 20 mm and a length of 100 mm, and the copper foil is peeled off at a speed of 50 mm / min using a tensile tester. (KN / m) was evaluated as the copper foil adhesion strength. The results are also shown in Tables 1 and 2 below.

As shown in Tables 1 and 2, the organosilicon compounds obtained in Examples 1-1 to 1-12 are the organosilicon compounds obtained in Comparative Examples 1-1 and 1-2, γ-glycidoxy. It can be seen that, as compared with propyltrimethoxysilane and phenyltrimethoxysilane, it provides a cured product having excellent dielectric properties such as copper foil adhesion, relative permittivity and dielectric loss tangent.

Claims (9)

An organosilicon compound represented by the average structural formula (1).

(In the formula, X represents an n-valent organic group having a polyphenylene ether structure, and R ¹ is an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted alkyl group. Represents an aryl group having 6 to 10 carbon atoms, and R ² is an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aryl group having 6 to 10 carbon atoms independently of each other. Representing a group, R ⁷ represents a monovalent hydrocarbon group containing a polymerizable reactive group ^{independently of each other, and A 1} represents a divalent linkage containing a single bond or a hetero atom independently of each other. Representing a group, A ² represents an unsubstituted or substituted divalent hydrocarbon group having 1 to 20 carbon atoms, which is independent of each other and does not contain a single bond or a hetero atom, and m represents a divalent hydrocarbon group having 1 to 20 carbon atoms. A number, p is a number from 1 to 10, q is a number from 1 to 10, n = p + q, and n is a number from 2 to 20.) The organosilicon compound according to claim 1, which is represented by the average structural formula (2).

{In the formula, R ¹ , R ² , R ⁷ , A ¹ , A ² and m have the same meanings as described above, and R ³ is independent of each other and has 1 halogen atom, unsubstituted or substituted carbon atom number 1. Alkyl groups of ~ 12, unsubstituted or substituted alkoxy groups with 1 to 12 carbon atoms, unsubstituted or substituted alkylthio groups with 1 to 12 carbon atoms, or unsubstituted or substituted halos with 1 to 12 carbon atoms Representing an alkoxy group, R ⁴ is a hydrogen atom, a halogen atom, an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms, an unsubstituted or substituted alkoxy group having 1 to 12 carbon atoms, and the like. Represents an unsubstituted or substituted alkylthio group having 1 to 12 carbon atoms or an unsubstituted or substituted haloalkoxy group having 1 to 12 carbon atoms, and b is a number of 1 to 100 independently of each other. c is a number greater than 0 and less than 2, and Z represents a linking group represented by the following formula (3).

[(In the formula, R ⁴ represents the same meaning as described above, and L represents a single bond or a linking group selected from the following formulas (4) to (11).)

(In the formula, R ⁵ represents an alkyl group having a hydrogen atom or 1 to 12 carbon atoms ^{independently of each other, R 6} represents an alkyl group having 1 to 12 carbon atoms independently of each other, and k represents an alkyl group having 1 to 12 carbon atoms. , 1-12, where j represents a number from 1 to 1,000.)]} The organosilicon compound according to claim 1 or 2, wherein A ^1- A ² is a single bond, a linking group represented by the formula (12) or a linking group represented by the formula (13).

(In the formula, a is a number of 1 to 20 independently of each other, Y is an oxygen atom or a sulfur atom independently of each other, and * represents a binding site with X or a phenylene group.) The ^{organosilicon compound according to any one of claims 1 to 3, wherein the polymerizable reactive group of R 7} is an acryloyloxy group, a methacryloyloxy group, a styryl group, a vinyl group or an epoxy group. The organosilicon compound according to any one of claims 1 to 4, ^{wherein the polymerizable reactive group of R 7 is an acryloyloxy group or a methacryloyloxy group.} Average structural formula (14)

{In the formula, R ³ are independent of each other, halogen atoms, unsubstituted or substituted alkyl groups having 1 to 12 carbon atoms, unsubstituted or substituted alkoxy groups having 1 to 12 carbon atoms, unsubstituted or substituted. Represents an alkylthio group having 1 to 12 carbon atoms, or an unsubstituted or substituted haloalkoxy group having 1 to 12 carbon atoms, and R ⁴ is independent of each other and is hydrogen atom, halogen atom, unsubstituted or substituted. An alkyl group having 1 to 12 carbon atoms, an unsubstituted or substituted alkoxy group having 1 to 12 carbon atoms, an unsubstituted or substituted alkylthio group having 1 to 12 carbon atoms, or an unsubstituted or substituted carbon atom number 1 Represents haloalkoxy groups of ~ 12, b is a number of 1 to 100 independently of each other, and Z represents a linking group represented by the following formula (3).

[(In the formula, R ⁴ represents the same meaning as described above, and L represents a single bond or a linking group selected from the following formulas (4) to (11).)

(In the formula, R ⁵ represents an alkyl group having a hydrogen atom or 1 to 12 carbon atoms ^{independently of each other, R 6} represents an alkyl group having 1 to 12 carbon atoms independently of each other, and k represents an alkyl group having 1 to 12 carbon atoms. , 1-12, where j represents a number from 1 to 1,000.)] }.
A polyphenylene ether compound having a hydroxyl group represented by the above, a compound having a functional group capable of reacting with the hydroxyl group and a polymerizable reactive group, and the formula (15).

(In the formula, R ¹ , R ² , A ² and m have the same meanings as described above.)
The method for producing an organosilicon compound according to any one of claims 1 to 5, wherein the compound having an isocyanate group and an alkoxysilyl group represented by the above is reacted. The compound having a functional group capable of reacting with the hydroxyl group and a polymerizable reactive group is represented by the formula (16).

(In the formula, R ⁷ and A ² have the same meanings as described above.)
The method for producing an organosilicon compound according to claim 6, which is a compound having an isocyanate group and a polymerizable reactive group represented by. A curable composition containing the organosilicon compound according to any one of claims 1 to 5. An article obtained by curing the curable composition according to claim 8.