JP6642325B2 - Resin modifier for high frequency substrate materials composed of organosilicon compounds - 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 and a hydrolyzable group in a molecule, a method for producing the same, and the organosilicon compound. And a cured article thereof.

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

In addition, the polyphenylene ether compound has high heat resistance and excellent dielectric characteristics such as a dielectric constant and a dielectric loss tangent, and particularly has excellent dielectric characteristics in a high frequency band (high frequency range) from a MHz band to a GHz band, that is, high frequency characteristics. It has been known.
For this reason, as an application example of the polyphenylene ether compound, in recent years, it is considered that the use as a high-frequency molding material is suitable. Specifically, as a component of a substrate material for forming a base material (copper-clad laminate) of a printed wiring board provided in an electronic device using an electric signal in a high-frequency region, it may be used in combination with an epoxy resin or the like. Are being considered.

In such applications, electric signals in a high-frequency region tend to be attenuated easily by a wiring circuit, and thus an electronic circuit board having good transmission characteristics is essential.
To obtain an electronic circuit board with good transmission characteristics, use an insulating resin material with a small dielectric loss tangent, such as a polyphenylene ether compound, and at the same time, smooth the surface of the conductor (metal wiring such as copper foil) 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 provided with irregularities to secure the adhesion between the resin material and the copper foil by exhibiting an anchor effect. When the surface of the copper foil is made smooth 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 to improve the adhesiveness, but the adhesiveness cannot be sufficiently satisfied at present.

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 condensate to a dealcoholation condensation reaction.
However, in the compound of Patent Document 1, the alkoxysilyl group which is the most reactive and contributes to the improvement of adhesion is consumed in the dealcoholization condensation reaction due to its production method, so that the adhesion between the resin material and the copper foil is not good. Was enough.

JP 2005-330324 A

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

  The present inventors have conducted intensive studies to solve the above-described problems, and as a result, have found a predetermined organosilicon compound having a polyphenylene ether structure and a hydrolyzable group in a molecule and a method for producing the same, and the present organosilicon compound. The present invention has been found to provide a cured product capable of exhibiting good copper foil adhesion and dielectric properties such as a dielectric constant and a dielectric loss tangent, and thus is suitable as a curable composition for forming a high-frequency substrate material. Was completed.

（式中、Ｘは、ポリフェニレンエーテル構造を含む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、Ａ¹は、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、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、ｎは、１〜１０の数である。）
２． 平均構造式（１）または（２）で表される１の有機ケイ素化合物、

｛式中、Ｒ¹、Ｒ²、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、ａおよびｂは、互いに独立して、１〜１００の数であり、ｃは、０以上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、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、式（１２）または式（１３）で表される１または２の有機ケイ素化合物、

４． 平均構造式（１４）または（１５）

（式中、Ｒ³、Ｒ⁴、ａ、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、式（１６）

（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１〜３のいずれかの有機ケイ素化合物の製造方法、
５． 平均構造式（１４）または式（１５）

（式中、Ｒ³、Ｒ⁴、ａ、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アルケニル基を有する化合物とを反応させてアルケニル化合物を得た後、このアルケニル化合物と、式（１７）

（式中、Ｒ¹、Ｒ²およびｍは、前記と同じ意味を表す。）
で表されるシラン化合物とを、白金化合物含有触媒の存在下でヒドロシリル化反応させることを特徴とする１〜３のいずれかの有機ケイ素化合物の製造方法、
６． １〜３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、
７． ６の硬化性組成物が硬化してなる硬化物品
を提供する。 That is, the present invention
1. An organosilicon compound represented by the average structural formula (i),

(In the formula, X represents an n-valent organic group containing a polyphenylene ether structure, and R ^{1 s} independently represent an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted R ² represents, independently of each other, 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, A ¹ represents a single bond or a divalent linking group containing a hetero atom, and A ² represents an unsubstituted or substituted divalent carbon atom having 1 to 20 carbon atoms which does not contain a hetero atom. Represents a hydrogen group, m is a number of 1 to 3, and n is a number of 1 to 10.)
2. 1 organosilicon compound represented by the average structural formula (1) or (2),

In the formula, R ¹ , R ² , A ¹ , A ² and m represent the same meaning as described above, and R ³ is independently a halogen atom, an unsubstituted or substituted C 1-12 An alkyl group, 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 haloalkoxy group having 1 to 12 carbon atoms. R ⁴ is independently 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, an unsubstituted or Represents a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms or an unsubstituted or substituted haloalkoxy group having 1 to 12 carbon atoms, a and b are each independently a number of 1 to 100, , Numbers from 0 to less than 2, Z represents a linking group represented by the following formula (3).

[Wherein, R ⁴ represents the same meaning as described above, and L represents a linking group selected from the following formulas (4) to (11).]

(Wherein, R ⁵ independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R ⁶ independently represents an alkyl group having 1 to 12 carbon atoms, and k represents , 1 to 12, and j represents a number of 1 to 1,000.)]｝
3. Wherein A ¹ -A ² is an organosilicon compound of 1 or 2 represented by formula (12) or (13),

4. Average structural formula (14) or (15)

(In the formula, R ³ , R ⁴ , a, b and Z represent the same meaning as described above.)
A polyphenylene ether compound having a hydroxyl group represented by the formula:

(In the formula, R ¹ , R ² , A ² and m represent the same meaning as described above.)
Represented by the method for producing an organosilicon compound according to any one of 1 to 3, characterized by reacting with a compound having an isocyanate group and an alkoxysilyl group,
5. Average structural formula (14) or formula (15)

(In the formula, R ³ , R ⁴ , a, b and Z represent the same meaning as described above.)
A polyphenylene ether compound having a hydroxyl group and a compound having a functional group capable of reacting with the hydroxyl group and a compound having an alkenyl group are obtained to obtain an alkenyl compound.

(In the formula, R ¹ , R ² and m represent the same meaning as described above.)
A method for producing an organosilicon compound according to any one of 1 to 3, characterized by performing a hydrosilylation reaction with a silane compound represented by a platinum compound-containing catalyst,
6. Curable composition containing an organosilicon compound according to any one of 1 to 3,
7. 6. A cured article obtained by curing the curable composition of item 6.

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

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

Here, X represents an n-valent organic group containing a polyphenylene ether structure, and R ^{1 s} independently represent an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted carbon group. R ² represents 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; A ¹ represents a single bond or a divalent linking group containing a hetero atom, and A ² represents an unsubstituted or substituted divalent hydrocarbon having 1 to 20 carbon atoms containing no hetero atom. Represents a group, m is a number of 1 to 3, and n is a number of 1 to 10.

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, 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, cyclopropyl, cyclobutyl, And cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.
Specific examples of the aryl group having 6 to 10 carbon atoms of R ¹ and R ² include phenyl, α-naphthyl, β-naphthyl and the like.
Some or all of the hydrogen atoms in each of these groups may be substituted with an alkyl group having 1 to 10 carbon atoms, a halogen atom such as F, Cl, or Br, a cyano group, or the like. Specific examples include 3-chloropropyl, 3,3,3-trifluoropropyl, 2-cyanoethyl, tolyl, and xylyl group.

Among them, R ¹ is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a methyl or ethyl group, and still more preferably a methyl group, from the viewpoint of hydrolyzability.
On the other hand, R ² is preferably a linear alkyl group, more preferably a methyl or ethyl group, and even more preferably a methyl group.
M is an integer of 1 to 3, preferably 2 to 3, and more preferably 3 from the viewpoint of reactivity.

Specific examples of the divalent linking group containing a hetero atom of A ¹ include an ether bond (—O—), a thioether bond (—S—), an amino bond (—NH—), and a sulfonyl bond (—S ( = O) _2- ), a phosphinyl bond (-P (= O) OH-), an oxo bond (-C (= O)-), a thiooxo bond (-C (= S)-), an ester bond (-C ( = O) O-), thioester bond (-C (= O) S-), thionoester bond (-C (= S) O-), dithioester bond (-C (= S) S-), carbonate bond (-OC (= O) O-), thiocarbonate bond (-OC (= S) O-), amide bond (-C (= O) NH-), thioamide bond (-C (= S) NH-) ), Urethane bond (—OC (＝ O) NH—), thiourethane bond (—SC (＝ O) NH—), Nourethane bond (-OC (= S) NH-), dithiourethane bond (-SC (= S) NH-), urea bond (-NHC (= O) NH-), thiourea bond (-NHC (= S) NH-) and the like.
Among them, A ¹ is preferably an ether bond (—O—) or a urethane bond (—OC (＝ O) NH—).

On the other hand, specific examples of the unsubstituted or substituted divalent hydrocarbon group having 1 to 20 carbon atoms not containing the hetero atom of A ² include methylene, ethylene, trimethylene, propylene, isopropylene, tetramethylene, isobutylene, Pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene, heptadecamethylene, octadecamethylene, nonadecame Alkylene groups such as methylene and eicosadecylene groups; cycloalkylene groups such as cyclopentylene and cyclohexylene groups; and arylene groups such as phenylene and α-, β-naphthylene groups.
Of these, trimethylene and octamethylene groups are preferred, and trimethylene groups are more preferred.

X in the formula (i) 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 1 to 10, preferably 1 to 5, and more preferably 1 or 2. If n is less than 1, the reactivity is poor due to a shortage of hydrolyzable groups. On the other hand, when n exceeds 10, the number of reaction points becomes too large, so that the storage stability of the compound may be deteriorated or cracks may be easily generated 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. However, in consideration of enhancing the copper foil adhesion and dielectric properties, the present invention particularly employs the following formula: The groups represented are preferred.

  Therefore, as the organosilicon compound of the present invention, those having an average structural formula represented by Formula (1) or Formula (2) are preferable, and by using these compounds, more excellent copper foil adhesion and dielectric properties are obtained. Is exhibited.

In each of these formulas, R ¹ , R ² , A ¹ , A ² and m represent the same meaning as described above, and R ³ independently of one another is a halogen atom, an unsubstituted or substituted carbon atom 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 haloalkoxy group having 1 to 12 carbon atoms R ⁴ is independently 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, an unsubstituted Or a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, or an unsubstituted or substituted haloalkoxy group having 1 to 12 carbon atoms, and a and b are each independently a number of 1 to 100. , C is a number from 0 to less than 2, Z represents a linking group represented by the following formula (3).

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

R ⁵ independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; R ⁶ independently represents an alkyl group having 1 to 12 carbon atoms; Represents an integer of 12, and j represents a number of 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, i-propyl, Linear or branched such as n-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl Examples of the alkyl group include cycloalkyl groups such as an alkyl group, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.
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, n- Butoxy, s-butoxy, t-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy and the like Examples thereof include a linear or branched alkoxy group, a cycloalkyloxy group such as cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy group.
Some or all of the hydrogen atoms in each of these groups may be substituted with halogen atoms such as F, Cl, and Br, mercapto groups, cyano groups, and the like. Specific examples of such groups include 3 -Chloropropyl, 3,3,3-trifluoropropyl, 3-mercaptopropyl, 2-cyanoethyl and the like.
Examples of the halogen atom of R ³ and R ⁴ include F, Cl, Br and the like.

Among them, R ³ is preferably a methyl group or a methoxy group, more preferably a methyl group, from the viewpoint of ease of production.
On the other hand, R ⁴ is preferably a hydrogen atom, a methyl group, or a methoxy group, and more preferably a hydrogen atom.

  A and b are each independently 1 to 100, preferably 3 to 50, more preferably 5 to 20, from the viewpoint of copper foil adhesion and dielectric properties of the organosilicon compound. When a and b are smaller than 1, good copper foil adhesion and dielectric properties may not be obtained, and when a and b are larger than 100, the compatibility of the organosilicon compound with the organic resin is deteriorated. May be.

Further, in the present invention, as the -A ¹ -A ² -group, a trimethylene group having a urethane bond (—OC (ＯO) NH—) represented by the formula (12) and a formula (13) A trimethylene group having an ether bond (—O—) is preferred.

  The weight average molecular weight of the organosilicon compound of the present invention is not particularly limited, and the workability is improved by setting the viscosity and the like of the curable composition containing the compound to an appropriate range. In consideration of imparting sufficient copper foil adhesion and dielectric properties, the weight average molecular weight is preferably from 500 to 50,000, more preferably from 1,000 to 20,000, and still more preferably from 4,000 to 10,000. The weight average molecular weight in the present invention is a value in terms of polystyrene measured by gel permeation chromatography (GPC).

The organosilicon compound of the present invention may be used in a state containing a solvent.
The solvent is not particularly limited as long as it has the ability to dissolve the organosilicon compound represented by the formula (i). From the viewpoint of solubility and volatility, aromatic solvents 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 among them, toluene and xylene are more preferable.
The amount of the solvent to be added is preferably 100 to 20,000 parts by mass, more preferably 200 to 10,000 parts by mass, per 100 parts by mass of the organosilicon compound represented by the formula (i).

Among the organosilicon compounds represented by the above formula (i), those in which A ¹ has a urethane bond include those having a polyphenylene ether structure in one molecule whose average structural formula is represented by the formula (14) or (15). It can be obtained by reacting a compound having a group and a hydroxyl group with a compound having an isocyanate group and an alkoxysilyl group represented by the formula (16) (hereinafter referred to as isocyanate silane).
More specifically, a reaction for forming a urethane bond between the hydroxyl group of the compound represented by the average structural formula (14) or (15) and the isocyanate group of the isocyanate silane is performed.

（式中、Ｒ³、Ｒ⁴、ａ、ｂおよびＺは、上記と同じ。）

(In the formula, R ³ , R ⁴ , a, b and Z are the same as described 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 compounds represented by the formulas (14) and (15) are commercially available, and such commercially available products include, for example, PPO ™ SA120-100 manufactured by SABIC Innovative Plastics. , PPO (trademark) SA90-100 and the like.

On the other hand, specific examples of the isocyanate silane represented by the formula (16) include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropyldimethylmethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatopropyldimethylethoxysilane and the like can be mentioned.
Among these, from the viewpoint of hydrolyzability, 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropyltrimethoxysilane are preferable, and 3-isocyanatopropyltrimethoxysilane is more preferable.

  The reaction ratio between the compound having a group having a polyphenylene ether structure and a hydroxyl group in one molecule represented by the formula (14) or the formula (15) and the isocyanate silane represented by the formula (16) is as follows. In consideration of suppressing the by-product of the formula (I) and enhancing the storage stability and properties of the obtained organosilicon compound, 1 mol of the hydroxyl group in the compound represented by the formula (14) or (15) is added to the formula (16) ) Is preferably 0.01 to 1.2 mol, more preferably 0.1 to 1.1 mol, and even more preferably 0.4 to 1 mol. .

In addition, a catalyst may be used in the urethanization reaction to improve the reaction rate.
The catalyst may be appropriately selected from those generally used in a urethanation reaction, and specific examples thereof include dibutyltin oxide, dioctyltin oxide, tin (II) bis (2-ethylhexanoate), Examples thereof include dibutyltin dilaurate and dioctyltin dilaurate.
The amount of the catalyst used may be a catalytic amount, but is usually 0.001 to 1 based on the total of the compound represented by the formula (14) or the formula (15) and the isocyanate silane represented by the formula (16). % By mass.

Further, a solvent that does not react with the raw materials to be used can be used in the urethanization reaction.
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; , Amide solvents such as N, N-dimethylformamide, pyrrolidone and N-methylpyrrolidone; ester solvents such as ethyl acetate, butyl acetate, γ-butyrolactone, propylene glycol-1-monomethyl ether-2-acetate; 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 urethanization reaction is not particularly limited, but is preferably 25 to 90 ° C, and is preferably 40 to 80 ° C in consideration of suppressing the side reactions such as allophanation while keeping the reaction rate appropriate. Is more preferred.
Although the reaction time is not particularly limited, it is generally 10 minutes to 24 hours.

Further, among the organosilicon compounds represented by the formula (i), those in which A ¹ is an ether bond have, as a first step, one molecule having an average structural formula represented by the above formula (14) or (15). A compound having a group having a polyphenylene ether structure and a hydroxyl group therein, and a compound having a functional group capable of reacting with the hydroxyl group and a compound having an alkenyl group are reacted to form an alkenyl compound. It can be obtained by reacting the obtained alkenyl compound with a silane compound represented by the formula (17).
More specifically, in the first step, a functional group capable of reacting with a hydroxyl group is reacted with a hydroxyl group, and a compound having an average structural formula represented by Formula (14) or Formula (15) is compounded with a compound having an alkenyl group. Is coupled with an ether bond. In the second step, the alkenyl compound obtained in the first step and the silane compound represented by the formula (17) are hydrosilylated in the presence of a platinum compound-containing catalyst to form an alkenyl group. The hydrosilyl group is added to form a carbon-silicon bond.

（式中、Ｒ¹、Ｒ²およびｍは、上記と同じ。）

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

  The functional group of the compound having a functional group capable of reacting with a hydroxyl group and an alkenyl group used in the first step is not particularly limited as long as the functional group selectively reacts with a hydroxyl group. Examples thereof include a methanesulfonate group, a trifluoromethanesulfonate group, and a p-toluenesulfonate group, with a halogen atom being preferred, and a chlorine atom, a bromine atom and an iodine atom being more preferred.

Specific examples of the compound having a halogen atom and an alkenyl group (hereinafter, referred to as an alkenyl halide compound) include allyl chloride, methallyl chloride, butenyl chloride, pentenyl chloride, hexenyl chloride, heptenyl chloride, octenyl chloride, nonenyl chloride and the like. Alkenyl compounds; alkenyl bromide compounds such as allyl bromide, methallyl bromide, butenyl bromide, pentenyl bromide, hexenyl bromide, heptenyl bromide, octenyl bromide, and nonenyl bromide; allyl iodide, methallyl iodide, iodine Alkenyl iodide compounds such as butenyl iodide, pentenyl iodide, hexenyl iodide, heptenyl iodide, octenyl iodide, and nonenyl iodide.
Among these, from the viewpoint of reactivity and availability, allyl chloride, hexenyl chloride, octenyl chloride, allyl bromide, allyl iodide are preferred, allyl chloride, octenyl chloride, allyl bromide is more preferred, and allyl bromide is preferred. Even more preferred.

The reaction of the first step can be carried out by a conventionally known general method, for example, a method for synthesizing an asymmetric ether by a nucleophilic substitution reaction between a hydroxyl group and an alkenyl halide compound in the presence of a basic compound (William Sonson synthesis, Williamson ether synthesis) and the like.
In this case, the reaction ratio between the compound represented by the formula (14) or the formula (15) and the alkenyl halide compound is not particularly limited. In consideration of enhancing the storage stability and various properties of the silicon compound, the halogen atom of the alkenyl halide compound is 0.1 to 10 mol per 1 mol of the hydroxyl group of the compound represented by the formula (14) or (15). Is preferably, more preferably 0.2 to 5 mol, even more preferably 0.4 to 1.2 mol.

In addition, as the basic compound, various basic compounds generally used in the Williamson synthesis method can be used, and do not react with any other than the hydroxyl group of the compound represented by the formula (14) or (15). Any of these may be used.
Specifically, alkali metals such as sodium metal and lithium metal; alkaline earth metals such as calcium metal; 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 and cesium hydroxide and aqueous solutions thereof, and alkaline earth metal hydroxides such as barium hydroxide and calcium hydroxide And aqueous solutions thereof; alkali metal and alkaline earth alkoxides such as potassium tertiary butoxide and sodium tertiary butoxide; alkali metal and alkaline earth metal carbonates such as potassium carbonate, sodium carbonate and calcium carbonate; sodium hydrogen carbonate and potassium hydrogen carbonate Etc. Alkali gold And alkaline earth bicarbonates, triethylamine, tributylamine, N, N- diisopropylethylamine, tetramethylethylenediamine, pyridine, N, etc. tertiary amine such as N- dimethyl-4-aminopyridine.
Among these, from the viewpoint of reaction efficiency, hydroxides of alkali metals and alkaline earth metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, barium hydroxide, and calcium hydroxide, 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 etherification reaction is sufficiently advanced to prevent the remaining of the raw material, and the storage of the organosilicon compound obtained by preventing the excessive remaining of the basic compound. In consideration of enhancing the stability and various properties, the basic compound is preferably 0.5 to 20 mol, more preferably 1 to 10 mol, per 1 mol of the hydroxyl group of the compound represented by the formula (14) or (15). , 2 to 8 mol are even more preferred.

In the above etherification reaction, a solvent that does not react with the raw materials to be used can be used.
Specific examples 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, N Amide solvents such as -methylpyrrolidone; ether solvents such as diethyl ether, dibutyl ether, cyclopentylmethyl ether, tetrahydrofuran, and 1,4-dioxane; nitrile solvents such as acetonitrile; and the like. You may use in combination of 2 or more types.
Among these, water, toluene, xylene, dimethylformamide, cyclopentyl methyl ether, and tetrahydrofuran are preferable from the viewpoint of reaction efficiency, and a mixed solvent of water and toluene, and a mixed solvent of water and xylene are more preferable.

The reaction temperature at the time of the etherification reaction is not particularly limited, but is preferably 25 to 90 ° C, and more preferably 40 to 80 ° C in consideration of suppressing the volatilization of the alkenyl halide compound while keeping the reaction rate appropriate. Is preferred, and 50 to 70 ° C. is even more preferred.
The etherification reaction is usually performed under atmospheric pressure, but may be performed under pressure for the purpose of suppressing the volatilization of the alkenyl halide compound and improving the reaction rate.
Although the reaction time is not particularly limited, it is generally 10 minutes to 24 hours.

In the etherification reaction, a catalyst may be used to improve the reaction rate.
As the catalyst, a catalyst that does not react with any other than the hydroxyl group of the compound represented by the formula (14) or (15) 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, and dibenzo-18-crown-6; tetrabutylammonium chloride, tetrabutylammonium bromide, and tetrabutylammonium iodide. And quaternary ammonium salts such as tetrabutylammonium hydrogen sulfate; and alkali metal halides such as potassium iodide and sodium iodide. These may be used alone or in combination of two or more. .
Among them, from the viewpoint of reactivity and availability, 18-crown-6, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydrogensulfate, and potassium iodide are preferable, and tetrabutylammonium iodide, Tetrabutylammonium hydrogen sulfate and potassium iodide are more preferred, and tetrabutylammonium hydrogen sulfate is even more preferred.
The above catalyst can act as a phase transfer catalyst or activate an alkenyl halide compound to improve the reaction rate.

  The amount of the catalyst used may be a catalytic amount, but is preferably 0.001 to 10% by mass based on the total of the compound represented by the formula (14) or (15) and the alkenyl halide compound. 0.01-1 mass% is more preferable.

  In the second step, specific examples of the silane compound represented by the formula (17) used for the reaction with the alkenyl compound obtained in the first step include trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, and triethoxysilane. Examples thereof include silane, methyldiethoxysilane, and dimethylethoxysilane. From the viewpoint of hydrolyzability, trimethoxysilane and triethoxysilane are preferable, and trimethoxysilane is more preferable.

The platinum compound-containing catalyst used in the second-stage hydrosilylation is not particularly limited, and specific examples thereof include chloroplatinic acid, an alcohol solution of chloroplatinic acid, platinum-1,3-divinyl-1,1 , 3,3-tetramethyldisiloxane complex in toluene or xylene, tetrakistriphenylphosphine platinum, dichlorobistriphenylphosphine platinum, dichlorobisacetonitrile platinum, dichlorobisbenzonitrile platinum, dichlorocyclooctadiene platinum, platinum-carbon, platinum Supported catalysts such as alumina and platinum-silica;
Among these, from the viewpoint of selectivity, a zero-valent platinum complex is preferable, and a toluene or xylene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex is more preferable.

The amount of the platinum compound-containing catalyst used is not particularly limited, but from the viewpoint of reactivity and productivity, 1 × 10 ^{−7 of} platinum atoms contained per 1 mol of the silane compound represented by the formula (17). The amount is preferably from 1 × 10 ⁻² mol to 1 × 10 ⁻² mol, more preferably from 1 × 10 ⁻⁷ to 1 × 10 ⁻³ mol.

Further, a co-catalyst may be used for improving the reactivity of hydrosilylation. As the co-catalyst, a co-catalyst generally used for hydrosilylation can be used, but in the present invention, an ammonium salt of an inorganic acid, an acid amide compound, and a carboxylic acid are preferable.
Specific examples of the ammonium salt of an inorganic acid include ammonium chloride, ammonium sulfate, ammonium amido sulfate, ammonium nitrate, monoammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium diphosphite, ammonium carbonate, hydrogen carbonate Examples thereof include ammonium, ammonium sulfide, ammonium borate, and ammonium borofluoride. Among them, ammonium salts of inorganic acids having a pKa of 2 or more are preferable, and ammonium carbonate and ammonium hydrogen carbonate are more preferable.

  Specific examples of the acid amide compound include formamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, acrylamide, malonamide, succinamide, maleamide, fumaramide, benzamide, phthalamide, palmitic amide, stearic amide and the like. Is mentioned.

  Specific examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, methoxyacetic acid, pentanoic acid, caproic acid, heptanoic acid, octanoic acid, lactic acid, glycolic acid and the like. Among these, formic acid, acetic acid, lactic acid Is preferred, and acetic acid is more preferred.

The amount of the cocatalyst used is not particularly limited, but from the viewpoint of reactivity, selectivity, cost and the like, 1 × 10 ⁻⁵ to 1 × 10 ⁻¹ per 1 mol of the silane compound represented by the formula (17). mol is preferable, and 1 × 10 ^{−4 to} 5 × 10 ⁻¹ mol is more preferable.

The above hydrosilylation reaction proceeds without a solvent, but a solvent can also be used.
Specific examples of usable solvents include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene and xylene; ether solvents such as diethyl ether, tetrahydrofuran and dioxane; ethyl acetate, butyl acetate and the like. Ester solvents; aprotic polar solvents such as N, N-dimethylformamide; chlorinated hydrocarbon solvents such as dichloromethane, chloroform and the like. Mixtures of more than one species may be used.

The reaction temperature in the above hydrosilylation reaction is not particularly limited, and the reaction can be carried out under heating from 0 ° C, but is preferably 0 to 200 ° C.
In order to obtain an appropriate reaction rate, it is preferable to carry out the reaction under heating, and from such a viewpoint, the reaction temperature is more preferably from 40 to 110 ° C, and still more preferably from 40 to 90 ° C.
The reaction time is not particularly limited, and is usually about 1 to 60 hours, preferably 1 to 30 hours, more preferably 1 to 20 hours.

The curable composition of the present invention contains an organosilicon compound represented by the formula (i).
The organosilicon compound represented by the formula (i) of the present invention is derived from the structure of the organosilicon compound, and has a higher molecular weight than a 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 in the curable composition, and 0.5 to 5% by mass. % Is more preferred. When the organosilicon compound contains a solvent, the above content means a non-volatile content excluding the solvent.

The curable composition of the present invention preferably contains an organic resin.
The organic resin is not particularly limited, and specific examples thereof include an epoxy resin, a phenol resin, a polycarbonate and a polycarbonate blend, an acrylic resin, a polyester resin, a polyamide resin, a polyimide resin, an acrylonitrile-styrene copolymer, Styrene-acrylonitrile-butadiene copolymer, polyvinyl chloride resin, polystyrene resin, polyphenylene ether resin, a blend of polystyrene and polyphenylene ether, cellulose acetate butyrate, may be appropriately selected depending on the application and the like from the polyethylene resin, etc. Considering the use as a substrate material of a printed wiring board provided in an electronic device utilizing an electric signal in a high frequency region, an epoxy resin, a polyphenylene ether resin, or a blend of these resins. It is preferred.
In this case, an appropriate curing agent may be blended according to the organic resin used. For example, when an epoxy resin is used, a curing agent such as an imidazole compound can be blended.
In addition, as a crosslinking component, for example, a cyanate ester compound or the like may be appropriately compounded, and further, depending on the purpose of use, an adhesion improver, an ultraviolet absorber, a storage stability improver, a plasticizer, a filler, a pigment, and the like. May be added.

Hereinafter, the present invention will be described more specifically 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. using a B-type rotational viscometer, and the molecular weight is a weight average molecular weight in terms of polystyrene determined by GPC (gel permeation chromatography) measurement. This is a value measured by a residual heating 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 In a 200 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, PPO (trademark) SA120-100 ( 40 g (manufactured by SABIC Innovative Plastics), 110 g of toluene and 0.05 g of dioctyltin dilaurate were charged and heated to 80 ° C. 7.6 g of 3-isocyanatopropyltrimethoxysilane was dropped therein, 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 instead, an absorption peak derived from a urethane bond was generated.
The obtained reaction product was a transparent brown liquid, and had a weight average molecular weight of 6,700, a viscosity of 23 mm ² / s, and a nonvolatile content of 34% by mass.

[Example 1-2] Synthesis of organosilicon compound 2 Synthesis was performed in the same manner as in Example 1-1, except that the amount of 3-isocyanatopropyltriethoxysilane was changed to 9.2 g.
The obtained reaction product was a transparent brown liquid, had a weight average molecular weight of 6,800, a viscosity of 30 mm ² / s, and a nonvolatile content of 30% by mass.

[Example 1-3] Synthesis of organosilicon compound 3 Synthesis was performed in the same manner as in Example 1-1, except that the amount of toluene was changed to 120 g and the amount of 3-isocyanatopropyltrimethoxysilane was changed to 11.1 g. .
The obtained reaction product was a brown transparent liquid, and had a weight average molecular weight of 5,300, a viscosity of 21 mm ² / s, and a nonvolatile content of 29% by mass.

[Example 1-4] Synthesis of organosilicon compound 4 Synthesis was performed in the same manner as in Example 1-1, except that the amount of 3-isocyanatopropyltrimethoxysilane was changed to 5.6 g.
The obtained reaction product was a brown transparent liquid, and had a weight average molecular weight of 4,200, a viscosity of 12 mm ² / s, and a nonvolatile content of 30% by mass.

[Example 1-5] Synthesis of organosilicon compound 5 PPO (trademark) resin powder (manufactured by SABIC Innovative Plastics) in a 200 mL separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer. 40 g, 110 g of toluene and 0.05 g of dioctyltin dilaurate were charged and heated to 80 ° C. 0.5 g of 3-isocyanatopropyltrimethoxysilane was added dropwise thereto, and the mixture was heated and stirred at 80 ° C. for 2 hours. After that, it was confirmed by IR measurement that the absorption peak derived from the isocyanate group of the raw material completely disappeared and an absorption peak derived from a 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 nonvolatile content of 28% by mass.

[Example 1-6] Synthesis of organosilicon compound 6 Distribution of noryl 640-111 (manufactured by SABIC Innovative Plastics Co., Ltd.) based on the method described in Example "PPE-3" of JP-A-2005-086329. Rearrangement yielded a distributed rearranged polyphenylene ether.
A 200 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 40 g of the polyphenylene ether thus distributed and rearranged, 110 g of toluene and 0.05 g of dioctyltin dilaurate, and heated to 80 ° C. did. 27.8 g of 3-isocyanatopropyltrimethoxysilane was dropped therein, and the mixture was heated and stirred at 80 ° C. for 2 hours. After that, it was confirmed by IR measurement that the absorption peak derived from the isocyanate group of the raw material completely disappeared and an absorption peak derived from a urethane bond was generated instead, and the reaction was terminated.
The resulting 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 nonvolatile content of 30% by mass.

[Example 1-7] Synthesis of organosilicon compound 7 In a 200 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 40 g of polyphenylene ether distributed and rearranged in Example 1-6 and 110 g of toluene. And 0.05 g of dioctyltin dilaurate were charged and heated to 80 ° C. 13.9 g of 3-isocyanatopropyltrimethoxysilane was dropped therein, and the mixture was heated and stirred at 80 ° C. for 2 hours. After that, it was confirmed by IR measurement that the absorption peak derived from the isocyanate group of the raw material completely disappeared and an absorption peak derived from a urethane bond was generated instead, and the reaction was terminated.
The obtained reaction product was a brown transparent liquid, and had a weight average molecular weight of 5,000, a viscosity of 35 mm ² / s, and a nonvolatile content of 30% by mass.

[Example 1-8] Synthesis of organosilicon compound 8 [First step]
In a 300 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 50 g of PPO (trademark) SA120-100 (manufactured by SABIC Innovative Plastics), 120 g of toluene, 120 g of tetrabutylammonium hydrogensulfate 0 .56 g and 37.6 g of a 30% aqueous sodium hydroxide solution were charged and heated to 60 ° C. 5.7 g of allyl bromide was dropped therein, and the mixture was heated and stirred at 60 ° C. for 6 hours. Thereafter, the aqueous layer separated by standing and separated into two layers is separated, the organic layer is washed with water until neutral, and the organic layer is concentrated under reduced pressure (80 ° C., 5 mmHg) to remove volatile components. The corresponding alkenyl compound 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, 30 g of the alkenyl compound obtained in the first step, 70 g of toluene, platinum-1,3-divinyl-1,1,3,3. 0.08 g of a toluene solution of 3-tetramethyldisiloxane complex (5.0 × 10 ⁻⁵ mol of platinum atom per mol of trimethoxysilane) is charged, and 3.5 g of trimethoxysilane is charged at an internal temperature of 75 to 85 ° C. After that, the mixture was stirred at 80 ° C. for 1 hour.
The resulting reaction product was a brown transparent liquid, having a weight average molecular weight of 6,000, a viscosity of 15 mm ² / s, and a nonvolatile content of 31% by mass.

[Example 1-9] Synthesis of organosilicon compound 9 [First step]
In a 300 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 50 g of PPO (trademark) SA120-100 (manufactured by SABIC Innovative Plastics), 120 g of toluene, and 0.1 g of tetrabutylammonium iodide. 56 g and 37.6 g of a 30% aqueous sodium hydroxide solution were charged and heated to 60 ° C. Into this, 6.9 g of octenyl chloride was dropped and heated and stirred at 60 ° C. for 6 hours. Thereafter, the aqueous layer separated by standing still is separated into two layers, the organic layer is washed with water until neutral, and the organic layer is concentrated under reduced pressure (80 ° C., 5 mmHg) to remove volatile components. The resulting alkenyl compound 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, 30 g of the alkenyl compound obtained in the first step, 70 g of toluene, platinum-1,3-divinyl-1,1,3,3. 0.08 g of a toluene solution of a 3-tetramethyldisiloxane complex (5.0 × 10 ⁻⁵ mol of platinum atom per mol of trimethoxysilane) and 0.003 g of acetic acid were placed therein, and 3.4 g of trimethoxysilane was heated at an internal temperature. After charging at 75 to 85 ° C, the mixture was stirred at 80 ° C for 1 hour.
The obtained reaction product was a brown transparent liquid, and had a weight average molecular weight of 6,100, a viscosity of 17 mm ² / s, and a nonvolatile content of 30% by mass.

[Example 1-10] Synthesis of organosilicon compound 10 [First step]
In a 300 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 50 g of PPO (trademark) SA90-100 (manufactured by SABIC Innovative Plastics), 130 g of toluene, 130 g of tetrabutylammonium hydrogen sulfate .58 g and 54.1 g of a 30% aqueous sodium hydroxide solution were charged and heated to 60 ° C. 8.2 g of allyl bromide was dropped therein, and the mixture was heated and stirred at 60 ° C. for 6 hours. Thereafter, the aqueous layer separated by standing still is separated into two layers, the organic layer is washed with water until neutral, and the organic layer is concentrated under reduced pressure (80 ° C., 5 mmHg) to remove volatile components. The resulting alkenyl compound was obtained as a brown solid.

[Second stage]
In a 200 mL separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 40 g of the alkenyl compound obtained in the first step, 60 g of toluene, platinum-1,3-divinyl-1,1,3,3 were added. 0.10 g of a toluene solution of 3-tetramethyldisiloxane complex (5.0 × 10 ⁻⁵ mol of platinum atom per mol of trimethoxysilane) is charged, and 6.3 g of trimethoxysilane is charged at an internal temperature of 75 to 85 ° C. After that, the mixture was stirred at 80 ° C. for 1 hour.
The obtained reaction product was a brown transparent liquid, having a weight average molecular weight of 4,800, a viscosity of 13 mm ² / s, and a nonvolatile content of 31% by mass.

[Example 1-11] Synthesis of organosilicon compound 11 [First step]
In a 300 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 50 g of PPO (trademark) SA90-100 (manufactured by SABIC Innovative Plastics), 130 g of toluene, 130 g of tetrabutylammonium hydrogen sulfate .54 g and 54.1 g of a 30% aqueous sodium hydroxide solution were charged and heated to 60 ° C. 4.1 g of allyl bromide was dropped therein, and the mixture was heated and stirred at 60 ° C. for 6 hours. Thereafter, the aqueous layer separated by standing still is separated into two layers, the organic layer is washed with water until neutral, and the organic layer is concentrated under reduced pressure (80 ° C., 5 mmHg) to remove volatile components. The resulting alkenyl compound 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, 25 g of the alkenyl compound obtained in the first step, 75 g of toluene, platinum-1,3-divinyl-1,1,3,3. 0.06 g of a toluene solution of 3-tetramethyldisiloxane complex (5.0 × 10 ⁻⁵ mol of platinum atom per mol of trimethoxysilane) is charged, and 3.7 g of trimethoxysilane is charged at an internal temperature of 75 to 85 ° C. After that, the mixture was stirred at 80 ° C. for 1 hour.
The obtained reaction product was a brown transparent liquid, having a weight average molecular weight of 6,100, a viscosity of 18 mm ² / s, and a nonvolatile content of 30% by mass.

[Comparative Example 1-1] Synthesis of organosilicon compound 12 A bifunctional phenylene ether resin (OPE-1000, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was placed in a reactor equipped with a stirrer, reflux condenser, dropping funnel and thermometer. ) And 447 g of polytetramethoxysilane (manufactured by Tama Chemical Co., Ltd., M silicate 51) were charged, heated to 90 ° C. and melted and mixed to obtain a uniform solution. Thereto, 0.22 g of dibutyltin dilaurate was added as a catalyst, and a methanol removal reaction was performed at 90 ° C. for 15 hours to obtain a corresponding organosilicon compound.

[Comparative Example 1-2] Synthesis of organosilicon compound 13 A bifunctional phenylene ether resin (OPE-1000, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was placed in a reactor equipped with a stirrer, reflux condenser, dropping funnel and thermometer. 71.8 g) and 45.3 g of polymethyltrimethoxysilane (manufactured by Tama Chemical Co., Ltd., MTMS-A) were charged, heated to 90 ° C., melted and mixed to form a uniform solution. Therein, 0.02 g of dibutyltin dilaurate was added as a catalyst, and a methanol removal reaction was performed at 90 ° C. for 15 hours to obtain a corresponding organosilicon compound.

[2] Preparation of Curable Composition and Cured Article Thereof Each component used for preparing the curable composition and the cured article thereof will be described.
[PPE]
-PPO (trademark) SA90-100 manufactured by SABIC Innovative Plastics
[Epoxy resin]
・ Epoxy resin 1: Epicron HP7200 (dicyclopentadiene type epoxy compound) manufactured by DIC Corporation
Epoxy resin 2: Epicron 850S (bisphenol A type epoxy resin) manufactured by DIC Corporation
[Curing agent]
・ 2E4MZ (2-ethyl-4-imidazole) manufactured by Shikoku Chemical Industry Co., Ltd.
[Cyanate ester compound]
-BADCy (2,2-bis (4-cyanatophenyl) propane) manufactured by Lonza Japan K.K.
[Organic metal salt]
・ Cu-NAPHTENATE (copper naphthenate) manufactured by DIC Corporation
[Organic silicon compound]
-Organosilicon compound: the organosilicon compounds obtained in Examples 1-1 to 1-11 and Comparative examples 1-1 and 1-2

[Example 2-1]
PPE, epoxy resin, curing agent, and organosilicon compound 1 obtained in Example 1-1 were mixed in accordance with the mixing ratio (parts by mass, where the organosilicon compound is a nonvolatile content value) described in Tables 1 and 2. Then, the obtained mixed solution was heated to 60 ° C. After the cyanate ester compound and the organic metal salt were added thereto, the mixture was stirred for 30 minutes and completely dissolved to obtain a varnish-like curable composition (resin varnish).
Subsequently, the obtained resin varnish was impregnated into a glass cloth (# 2116 type, WEA116E, E glass, manufactured by Nitto Boseki Co., Ltd.), and dried by heating at 160 ° C. for 10 minutes to obtain a prepreg. At this time, the content was adjusted so that the content of the resin component was about 55% by mass.
Each of the obtained prepregs is laminated on six sheets, laminated between copper foils (GT-MP manufactured by Furukawa Circuit Foil Co., Ltd.), and heated and pressed at 200 ° C. for 2 hours under a pressure of 3 MPa to obtain a cured product. A certain evaluation substrate was obtained.

[Examples 2-2 to 2-11 and Comparative Examples 2-1 and 2-2]
Except that the organosilicon compound 1 was changed to the organosilicon compounds 2 to 13 obtained in Examples 1-2 to 1-11 and Comparative examples 1-1 to 1-2, respectively, in the same manner as in Example 2-1. Thus, a curable composition and a cured article thereof were prepared.

[Comparative Examples 2-3 and 2-4]
Organosilicon compound 1 was obtained by using γ-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) as Comparative Example 2-3, and phenyltrimethoxysilane (KBM-103; A curable composition and a cured product thereof were produced in the same manner as in Example 2-1 except that the composition was changed to Shin-Etsu Chemical Co., Ltd., respectively.

[Comparative Example 2-5]
A curable composition and a cured product thereof were produced in the same manner as in Example 2-1 except that the organosilicon compound 1 was not used.

Each evaluation substrate prepared by the above procedure was evaluated by the following method.
[Dielectric properties]
Using the cavity resonance “CP461” manufactured by Kanto Electronics Application Development Co., Ltd., the dielectric constant and the dielectric loss tangent of the copper-clad laminate at 2 GHz were measured. The results are shown in Tables 1 and 2 below.
[Copper foil adhesion strength]
The peel strength (copper foil adhesion strength) of the copper foil on the surface of the copper-clad laminate was measured by a method according to JIS C6481. At this time, a pattern having a width of 10 mm and a length of 100 mm was formed on a test piece having a width of 20 mm and a length of 100 mm, and the copper foil was peeled off at a rate of 50 mm / min using a tensile tester. (Kgf / cm) was evaluated as copper foil adhesion strength. The results are shown in Tables 1 and 2 below.

  As shown in Tables 1 and 2, the organosilicon compounds obtained in Examples 1-1 to 1-11, the organosilicon compounds obtained in Comparative Examples 1-1 and 1-2, γ-glycidoxy It can be seen that compared to propyltrimethoxysilane and phenyltrimethoxysilane, a cured product excellent in copper foil adhesion and dielectric properties such as dielectric constant and dielectric loss tangent is provided.

Claims (7)

Resin modifier of the high-frequency substrate materials consisting of organic silicon compounds you express by average structural formula (i).

(In the formula, X represents an n-valent organic group containing a polyphenylene ether structure, and R ^{1 s} independently represent an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted R ² represents, independently of each other, 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, A ¹ -A ² represents a divalent linking group represented by the formula (12) or (13), m is a number of 1 to 3, and n is 1 to 10 Is a number.)

The resin modifier for a high-frequency substrate material according to claim 1 , wherein the organosilicon compound is represented by an average structural formula (1) or (2).

In the formula, R ¹ , R ² , A ¹ , A ² and m represent the same meaning as described above, and R ³ is independently a halogen atom, an unsubstituted or substituted C 1-12 An alkyl group, 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 haloalkoxy group having 1 to 12 carbon atoms. R ⁴ is independently 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, an unsubstituted or Represents a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms or an unsubstituted or substituted haloalkoxy group having 1 to 12 carbon atoms, a and b are each independently a number of 1 to 100, , Numbers from 0 to less than 2, Z represents a linking group represented by the following formula (3).

[Wherein, R ⁴ represents the same meaning as described above, and L represents a linking group selected from the following formulas (4) to (11). ]

(Wherein, R ⁵ independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R ⁶ independently represents an alkyl group having 1 to 12 carbon atoms, and k represents , 1 to 12, and j represents a number of 1 to 1,000.)]｝ The resin modifier according to claim 1, wherein A ¹ -A ² is represented by Formula (12 ) . 3. The resin modifier for a high-frequency substrate material according to claim 2, wherein a and b are 3 to 50 . A curable composition for forming a high-frequency substrate, comprising the resin modifier for a high-frequency substrate material according to claim 1 . The curable composition for forming a high-frequency substrate according to claim 5, comprising at least one organic resin selected from an epoxy resin and a polyphenylene ether resin . A high-frequency substrate obtained by curing the curable composition according to claim 5 .