KR102356533B1 - Organosilicon compound and method for producing the same, and curable composition - Google Patents

Abstract

(식 중, X는 폴리페닐렌에테르 구조를 포함하는 n가의 유기기를 나타내고, R¹은 서로 독립적으로, 비치환 또는 치환된 탄소 원자수 1 내지 10의 알킬기, 또는 비치환 또는 치환된 탄소 원자수 6 내지 10의 아릴기를 나타내고, R²는 서로 독립적으로, 비치환 또는 치환된 탄소 원자수 1 내지 10의 알킬기, 또는 비치환 또는 치환된 탄소 원자수 6 내지 10의 아릴기를 나타내고, A¹은, 단결합, 또는 헤테로 원자를 함유하는 2가의 연결기를 나타내고, A²는, 헤테로 원자를 포함하지 않은, 비치환 또는 치환된 탄소 원자수 1 내지 20의 2가 탄화수소기를 나타내고, m은 1 내지 3의 수이고, n은 1 내지 10의 수임)[Problem] To provide an organosilicon compound effective as a resin modifier or the like for a high-frequency substrate material, a method for producing the same, and a curable composition containing the organosilicon compound.
[Solutions] An organosilicon compound represented by the average structural formula (i).

(Wherein, X represents an n-valent organic group including a polyphenylene ether structure, and R ¹ is each independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or unsubstituted or substituted carbon atoms. represents an aryl group of 6 to 10, 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 is, Represents a single bond or a divalent linking group containing a hetero atom, A ² represents an unsubstituted or substituted divalent hydrocarbon group having 1 to 20 carbon atoms that does not contain a hetero atom, and m is 1 to 3 number, and n is a number from 1 to 10)

Description

An organosilicon compound, its manufacturing method, and a curable composition

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 It relates to a curable composition comprising a, and a cured article thereof.

A silane coupling agent is a compound that has both a moiety having reactivity with an inorganic substance (a hydrolyzable group bonded to a Si atom) and a moiety rich in reactivity or solubility with respect to an organic substance in one molecule, and an adhesion aid at the interface between the inorganic substance and the organic substance. Because it acts as a compound resin modifier, it is widely used.

In addition, polyphenylene ether compounds are known to have high heat resistance and excellent dielectric properties such as dielectric constant and dielectric loss tangent, and in particular, excellent dielectric properties in the high frequency band (high frequency region) from MHz to GHz, that is, high frequency characteristics. have.

For this reason, as an application example of a polyphenylene ether compound, use as a molding material for high frequency use is considered suitable in recent years. Specifically, as one component of a substrate material for constituting a substrate (copper clad laminate) of a printed wiring board provided in an electronic device using an electric signal in a high-frequency region, using together with an epoxy resin or the like is being studied.

In such applications, since electric signals in the high-frequency region tend to be attenuated in the wiring circuit, an electronic circuit board with good transmission characteristics is essential.

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 the surface of the conductor (metal wiring such as copper foil) is smoothed, and the roughness is reduced and low. It is effective to make skin resistance small by thickness increase.

However, in the conventional copper clad laminate, the adhesion between the resin material and the copper foil was secured by forming an anchor effect by forming irregularities on the surface of the copper foil. When it was made smooth, there existed a problem that the anchor effect was weakened and the adhesiveness of a resin material and copper foil deteriorated.

Therefore, although the use of a general silane coupling agent is also examined for adhesive improvement, the adhesiveness cannot fully be satisfied in the present situation.

Further, Patent Document 1 discloses an alkoxysilyl group-containing silane-modified phenylene ether resin obtained by carrying out a dealcoholization condensation reaction between a bifunctional phenylene ether resin and an alkoxysilane partial condensate.

However, in the compound of patent document 1, since the alkoxysilyl group which has the highest reactivity and contributes to an adhesive improvement on the manufacturing method is consumed by dealcoholization condensation reaction, the adhesiveness of a resin material and copper foil was inadequate.

Japanese Patent Laid-Open 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 high-frequency substrate materials, a method for producing the same, and a curable composition containing the organosilicon compound.

MEANS TO SOLVE THE PROBLEM As a result of earnest examination in order to solve the said subject, the present inventors discovered the predetermined organosilicon compound which has a polyphenylene ether structure and a hydrolysable group in a molecule|numerator, and its manufacturing method, and contains this organosilicon compound Since the composition imparts a cured product capable of exhibiting good copper foil adhesion and dielectric properties such as dielectric constant and dielectric loss tangent, it has been found to be suitable as a curable composition for forming a high-frequency substrate material, and the present invention has been completed.

That is, the present invention

1. An organosilicon compound characterized by being represented by the average structural formula (i);

(Wherein, X represents an n-valent organic group including a polyphenylene ether structure, and R ¹ is each independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or unsubstituted or substituted carbon atoms. represents an aryl group of 6 to 10, 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 is, Represents a single bond or a divalent linking group containing a hetero atom, A ² represents an unsubstituted or substituted divalent hydrocarbon group having 1 to 20 carbon atoms that does not contain a hetero atom, and m is 1 to 3 number, and n is a number from 1 to 10)

2. The organosilicon compound of 1 represented by the average structural formula (1) or (2);

{Wherein, R ¹ , R ² , A ¹ , A ² and m have the same meaning as above, and R ³ are each independently a halogen atom, an unsubstituted or substituted C 1 to C 12 alkyl group, unsubstituted represents a ring 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 are each independently a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-C12 alkyl group, an unsubstituted or substituted C1-C12 alkoxy group, an unsubstituted or substituted C1-C12 12 alkylthio group, or unsubstituted or substituted haloalkoxy group having 1 to 12 carbon atoms, a and b are each independently a number from 1 to 100, c is a number from 0 to less than 2, and Z is Representing a linking group represented by the following formula (3),

[( ^{wherein, R 4} represents the same meaning as 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 an integer of 1 to 12. and j represents a number from 1 to 1,000)]}

3. The ^{organosilicon compound of 1 or 2, wherein A 1} -A ² is represented by Formula (12) or Formula (13);

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

(wherein R ³ , R ⁴ , a, b and Z have the same meanings as above)

A polyphenylene ether compound having a hydroxyl group represented by the formula (16)

(Wherein, R ¹ , R ² , A ² and m have the same meanings as above)

A method for producing an organosilicon compound of any one of 1 to 3, characterized in that the compound having an isocyanate group and an alkoxysilyl group is reacted,

5. Average Structural Formula (14) or Formula (15)

(wherein R ³ , R ⁴ , a, b and Z have the same meanings as above)

After reacting a polyphenylene ether compound having a hydroxyl group represented by

(Wherein, R ¹ , R ² and m have the same meaning as above)

A method for producing an organosilicon compound according to any one of 1 to 3, characterized in that the silane compound represented by is subjected to a hydrosilylation reaction in the presence of a catalyst containing a platinum compound;

6. A curable composition containing the organosilicon compound of any one of 1 to 3;

7. Cured article made by curing the curable composition of 6

provides

The organosilicon compound of the present invention has a polyphenylene ether structure and a highly reactive hydrolyzable group in the molecule, and has excellent adhesion to copper foil and dielectric properties such as dielectric constant and dielectric loss tangent compared to conventional silane coupling agents. have it

The composition containing the organosilicon compound of this invention which has such a characteristic can be used suitably as a curable composition, especially a curable composition which forms a high frequency board|substrate material.

Hereinafter, the present invention will be specifically described.

The organosilicon compound which concerns on this invention is represented by average structural formula (i).

Here, X represents an n-valent organic group including a polyphenylene ether structure, and R ¹ is, independently of each other, an unsubstituted or substituted C 1 to C 10 alkyl group, or an unsubstituted or substituted C 6 to C 6 group. represents an aryl group of 10, 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 is a single bond , or represents a divalent linking group containing a hetero atom, A ² represents an unsubstituted or substituted divalent hydrocarbon group having 1 to 20 carbon atoms that does not contain a hetero atom, and m is a number of 1 to 3 , n is a number from 1 to 10.

The alkyl group having 1 to 10 carbon atoms for R ¹ and R ² may be any of linear, cyclic, or branched, and specific examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl, and s-butyl. , t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl straight-chain or branched alkyl group, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and a cycloalkyl group such as a cyclooctyl group.

Specific examples of the aryl group having 6 to 10 carbon atoms for R ¹ and R ^{2 include phenyl, α-naphthyl and β-naphthyl groups.}

In addition, some 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 or Br, a cyano group, or the like, and a specific example of such a group is 3-chloro propyl, 3,3,3-trifluoropropyl, 2-cyanoethyl, tolyl, xylyl group and the like can be exemplified.

Among these, as R<^1> , a C1-C5 linear alkyl group from a hydrolysable viewpoint is preferable, methyl and an ethyl group are more preferable, and a methyl group is still more preferable.

On the other hand, as R<^2> , a linear alkyl group is preferable, methyl and an ethyl group are more preferable, and a methyl group is still more preferable.

Moreover, m is an integer of 1-3, 2-3 are preferable from a reactive viewpoint, and 3 is more preferable.

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-), a sulfonyl bond (-S (= O) ) ₂ -), phosphinyl bond (-P(=O)OH-), oxo bond (-C(=O)-), thiooxo bond (-C(=S)-), 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-), thionourethane bond (-OC(=S)NH-), DT urethane bond (-SC(=S)NH-), urea bond (-NHC(=O)NH-), thiourea bond (-NHC(=S)NH-), and the like.

Among these, as A ¹ , 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 that do not contain a heteroatom 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, alkylene groups such as nonadecamethylene and eicosadecylene; cycloalkylene groups such as cyclopentylene and cyclohexylene; and arylene groups such as phenylene, α-, and β-naphthylene groups.

Among these, trimethylene and an octamethylene group are preferable, and a trimethylene group is more preferable.

X in Formula (i) represents an n-valent coupling group containing a polyphenylene ether structure, and may have a linear structure, a branched structure, or a crosslinked structure in it.

Although the average of n per molecule is 1-10, 1-5 are preferable and 1-2 are more preferable. If n is less than 1, the hydrolyzable group is insufficient and the reactivity is deteriorated. On the other hand, when n exceeds 10, since reaction points increase too much, the storage stability of a compound may deteriorate or it may become easy to generate|occur|produce a crack in hardened|cured material.

Although it will not specifically limit as said X, if it is an n-valent coupling group containing a polyphenylene ether structure, Considering improving copper foil adhesiveness and dielectric property, in this invention, the group represented by a following formula is especially suitable.

Therefore, as an organosilicon compound of this invention, it is preferable that an average structural formula is represented by Formula (1) or Formula (2), and more favorable copper foil adhesiveness and dielectric property are exhibited by using these compounds.

In each of these formulas, R ¹ , R ² , A ¹ , A ² and m represent the same meanings as above, and R ³ are each independently a halogen atom, an unsubstituted or substituted C 1 to C 12 alkyl group, represents 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 of each other a hydrogen atom, a halogen atom, an unsubstituted or substituted C 1 to C 12 alkyl group, an unsubstituted or substituted C 1 to C 12 alkoxy group, or an unsubstituted or substituted C 1 to 12 alkylthio group, or unsubstituted or substituted haloalkoxy group having 1 to 12 carbon atoms, a and b are each independently a number from 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 above, and L represents a linking group selected from the following formulas (4) to (11).

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

The alkyl group having 1 to 12 carbon atoms for R ³ and R ⁴ may be any of linear, cyclic, or branched, and specific examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl, and s-butyl. , t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl straight chain or branched alkyl group, cyclopropyl, cyclo and cycloalkyl groups such as butyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups.

The alkoxy group having 1 to 12 carbon atoms for R ³ and R ⁴ may be any of 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 -A linear or branched alkoxy group, such as dodecyloxy, and cycloalkyloxy groups, such as a cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, a cyclooctyloxy group, are mentioned.

In addition, a part or all of the hydrogen atoms of these groups may be substituted with halogen atoms, such as F, Cl, Br, a mercapto group, a cyano group, etc., As a specific example of such a group, 3-chloropropyl, 3,3,3 -trifluoropropyl, 3-mercaptopropyl, 2-cyanoethyl group, etc. can be illustrated.

Examples ^{of the halogen atom for R 3} and R ⁴ include F, Cl, Br, and the like.

Among these, as R<^3> , a methyl group and a methoxy group are preferable from a viewpoint of manufacturing easiness, and a methyl group is more preferable.

On the other hand, as R ⁴ , a hydrogen atom, a methyl group or a methoxy group is preferable, and a hydrogen atom is more preferable.

Moreover, although a and b are the numbers of 1-100 mutually independently, from a viewpoint of the copper foil adhesiveness of an organosilicon compound, and a dielectric characteristic, 3-50 are preferable and 5-20 are more preferable. When a and b are smaller than 1, there exists a possibility that favorable copper foil adhesiveness and a dielectric characteristic may not be acquired, and when a and b are larger than 100, the compatibility with respect to the organic resin of an organosilicon compound may deteriorate.

Moreover, in this invention, as -A ¹ -A ² - group, the trimethylene group which has a urethane bond (-OC(=O)NH-) represented by Formula (12), and an ether represented by Formula (13). A trimethylene group having a bond (-O-) is suitable.

Although the weight average molecular weight of the organosilicon compound of this invention is not specifically limited, While making the viscosity of a curable composition containing the said compound into an appropriate range, and improving workability, copper foil adhesiveness sufficient to the hardened|cured material obtained And in consideration of imparting dielectric properties, weight average molecular weights of 500 to 50,000 are preferable, 1,000 to 20,000 are more preferable, and 4,000 to 10,000 are still more preferable. In addition, the weight average molecular weight in this invention is a polystyrene conversion value by gel permeation chromatography (GPC).

In addition, you may use the organosilicon compound of this invention in the state containing a solvent.

Although it will not specifically limit as long as it has the solubility of the organosilicon compound represented by Formula (i) as a solvent, From a viewpoint of solubility, volatility, etc., aromatic solvents, such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; Ether solvents, such as tetrahydrofuran, are preferable, and especially, toluene and xylene are more preferable.

100-20,000 mass parts is preferable with respect to 100 mass parts of organosilicon compounds represented by Formula (i), and, as for the addition amount of a solvent, 200-10,000 mass parts is more preferable.

Among the organosilicon compounds represented by the formula (i), in which A ¹ is a urethane bond, the average structural formula is a group containing a polyphenylene ether structure in one molecule represented by the formula (14) or formula (15) and a hydroxyl group It can obtain by making the compound which has and the compound which has an isocyanate group and alkoxysilyl group represented by Formula (16) (henceforth isocyanate silane) react.

More specifically, a reaction is performed to form 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.

(wherein R ³ , R ⁴ , a, b and Z are the same as above)

(wherein R ¹ , R ² , A ² and m are the same as above)

As a compound represented by Formula (14) and Formula (15), it can obtain as a commercial item, As such a commercial item, SABIC Innovative Plastics PPO (trademark) SA120-100, PPO (trademark) SA90, for example, -100 and the like.

On the other hand, as a specific example of the isocyanate silane represented by Formula (16), 3-isocyanate propyl trimethoxysilane, 3-isocyanate propylmethyl dimethoxysilane, 3-isocyanate propyl dimethyl methoxysilane, 3-isocyanate propyl triethoxysilane , 3-isocyanate propylmethyl diethoxy silane, 3-isocyanate propyl dimethyl ethoxy silane, etc. are mentioned.

Among these, 3-isocyanate propyl triethoxysilane and 3-isocyanate propyl trimethoxysilane are preferable from a hydrolysable viewpoint, and 3-isocyanate propyl trimethoxysilane is more preferable.

The reaction ratio of the compound having a group containing a polyphenylene ether structure and a hydroxyl group in one molecule represented by the formula (14) or (15) and the isocyanate silane represented by the formula (16) is, The isocyanate represented by Formula (16) with respect to 1 mol of hydroxyl groups in the compound represented by Formula (14) or Formula (15) in consideration of suppressing a by-product and improving the storage stability and characteristics of the organosilicon compound obtained The ratio used as 0.01-1.2 mol of the isocyanate group of a silane is preferable, the ratio used as 0.1-1.1 mol is more preferable, The ratio used as 0.4-1 mol is still more preferable.

In addition, you may use a catalyst for the said urethanation reaction in order to improve reaction rate.

The catalyst may be appropriately selected from those generally used in the urethanation reaction, and specific examples thereof include dibutyltin oxide, dioctyltin oxide, tin(II)bis(2-ethylhexanoate), and dibutyltindilau. rate, dioctyltin dilaurate, and the like.

Although what is necessary is just a catalyst amount, the usage-amount of a catalyst is 0.001-1 mass % with respect to the sum total of the compound represented by Formula (14) or Formula (15), and the isocyanate silane represented by Formula (16) normally.

In addition, the solvent which does not react with the raw material used can be used for the said urethanation 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 formamide, N,N-dimethylformamide, pyrrolidone and N-methylpyrrolidone, ethyl acetate, butyl acetate, γ-butyrolactone, propylene glycol-1-monomethyl ether-2- ester solvents such as acetate; Ether solvents, such as diethyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran, 1, 4- dioxane, etc. are mentioned, These may be used individually or in combination of 2 or more types.

The reaction temperature at the time of the urethanation reaction is not particularly limited, but considering suppressing side reactions such as allophanation while controlling the reaction rate, it is preferably 25 to 90°C, more preferably 40 to 80°C do.

The reaction time is not particularly limited, but is usually 10 minutes to 24 hours.

In addition, among the organosilicon compounds represented by formula (i), those in which A ¹ is an ether bond are a first step, and polyphenylene ether in one molecule whose average structural formula is represented by the formula (14) or (15) above. After reacting a compound having a group containing a structure and a hydroxyl group with a compound having a functional group capable of reacting with a hydroxyl group and an alkenyl group to obtain an alkenyl compound, in the second step, the alkenyl compound obtained in the first step It can be obtained by making the silane compound represented by and Formula (17) react.

More specifically, in the first step, a functional group capable of reacting with a hydroxyl group is reacted with a hydroxyl group, and the compound represented by the average structural formula of Formula (14) or Formula (15) and the compound having an alkenyl group are coupled by 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 catalyst containing a platinum compound, and a hydrosilyl group is added to the alkenyl group to form a carbon- form silicon bonds.

( ^{wherein R 1} , R ² and m are the same as above)

The functional group of the compound having an alkenyl group and a functional group capable of reacting with a hydroxyl group used in the first step is not particularly limited as long as it is a functional group that selectively reacts with a hydroxyl group, and a halogen atom, a methanesulfonate group, trifluoro Although a methanesulfonate group, p-toluenesulfonate group, etc. are mentioned, A halogen atom is preferable, and a chlorine atom, a bromine atom, and an iodine atom are more preferable.

Specific examples of the compound having a halogen atom and an alkenyl group (hereinafter referred to as a halogenated alkenyl compound) include allyl chloride, methallyl chloride, butenyl chloride, pentenyl chloride, hexenyl chloride, heptenyl chloride, octenyl chloride, nonenyl chloride alkenyl chloride compounds, such as; alkenyl bromide compounds such as allyl bromide, methallyl bromide, butenyl bromide, pentenyl bromide, hexenyl bromide, heptenyl bromide, octenyl bromide, and nonenyl bromide; and alkenyl iodide compounds such as allyl iodide, methallyl iodide, 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, and allyl iodide are preferable, allyl chloride, octenyl chloride, and allyl bromide are more preferable, and allyl bromide is still more preferable .

The reaction in 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 a halogenated alkenyl compound in the presence of a basic compound (Williamson Synthesis, Williamson Ether Synthesis) ) can be employed.

In this case, the reaction ratio of the compound represented by the formula (14) or (15) and the halogenated alkenyl compound is not particularly limited, but the amount of unreacted raw material is reduced and the storage stability and various characteristics of the obtained organosilicon compound In consideration of increasing It is preferable, and the ratio used as 0.4-1.2 mol is still more preferable.

In addition, as said basic compound, various basic compounds normally used for the Williamson synthesis method can be used, Any thing may be used as long as it does not react with anything other than the hydroxyl group of the compound represented by Formula (14) or Formula (15).

Specifically, alkali metals, such as metallic sodium and metallic lithium; alkaline earth metals such as metal calcium; alkali metal hydrides such as sodium hydride, lithium hydride, potassium hydride, and cesium hydride; alkaline earth metal hydrides such as calcium hydride; alkali metal hydroxides and aqueous solutions thereof, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; 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; alkali metal and alkaline earth hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; and tertiary amines such as triethylamine, tributylamine, N,N-diisopropylethylamine, tetramethylethylenediamine, pyridine, and N,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, and aqueous solutions of sodium hydroxide are more preferable. .

The amount of the basic compound to be used is not particularly limited, but when the etherification reaction is sufficiently advanced to prevent the residual of the raw material and to prevent excessive residual of the basic compound, the storage stability and various properties of the obtained organosilicon compound are improved. , 0.5-20 mol is preferable with respect to 1 mol of hydroxyl groups of the compound represented by Formula (14) or Formula (15), 1-10 mol is more preferable, 2-8 mol is still more preferable.

In the said etherification reaction, the solvent which 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; amide solvents such as formamide, N,N-dimethylformamide, pyrrolidone, and N-methylpyrrolidone; ether solvents such as diethyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran, and 1,4-dioxane; Nitrile solvents, such as acetonitrile, etc. are mentioned, These may be used independently, or may be used in combination of 2 or more types.

Among these, from the viewpoint of reaction efficiency, water, toluene, xylene, dimethylformamide, cyclopentylmethyl ether, and tetrahydrofuran are preferable, 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 considering suppressing volatilization of the halogenated alkenyl compound while controlling the reaction rate, it is preferably 25 to 90°C, preferably 40 to 80°C, , 50-70 degreeC is still more preferable.

In addition, although the etherification reaction is normally performed under atmospheric pressure, you may carry out under pressure for the purpose of suppression of volatilization of the said halogenated alkenyl compound, improvement of reaction rate, etc.

The reaction time is not particularly limited, but is usually 10 minutes to 24 hours.

Moreover, in the said etherification reaction, you may use a catalyst in order to improve reaction rate.

What is necessary is just to select suitably what does not react with anything other than the hydroxyl group of the compound represented by Formula (14) or Formula (15) from what is generally used for the Williamson synthesis method as a catalyst.

Specific examples thereof include crown ethers such as 12-crown-4, 15-crown-5, 18-crown-6 and dibenzo-18-crown-6; quaternary ammonium salts such as tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, and tetrabutylammonium hydrogen sulfate; Alkali metal halides, such as potassium iodide and sodium iodide, etc. are mentioned, These may be used individually or may be used in combination of 2 or more types.

Among these, 18-crown-6, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydrogensulfate, and potassium iodide are preferable from the viewpoint of reactivity and availability, and tetrabutylammonium iodide and tetrabutyl Ammonium hydrogensulfate and potassium iodide are more preferable, and tetrabutylammonium hydrogensulfate is still more preferable.

The catalyst may act as a phase transfer catalyst, or may activate a halogenated alkenyl compound to improve the reaction rate.

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

In the second step, specific examples of the silane compound represented by formula (17) used in the reaction with the alkenyl compound obtained in the first step include trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxy Although silane, methyldiethoxysilane, dimethylethoxysilane, etc. are mentioned, From a hydrolysable viewpoint, trimethoxysilane and triethoxysilane are preferable and trimethoxysilane is more preferable.

The platinum compound-containing catalyst used in the hydrosilylation of the second step 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- Toluene or xylene solution of tetramethyldisiloxane complex, tetrakistriphenylphosphine platinum, dichlorobistriphenylphosphine platinum, dichlorobisacetonitrile platinum, dichlorobisbenzonitrile platinum, dichlorocyclooctadiene platinum, platinum-carbon, platinum -Alumina, platinum-silica, etc. supported catalysts, etc. are mentioned.

Among these, a zero-valent platinum complex is preferable from the point of selectivity, and the 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 to be used is not particularly limited, but from the viewpoint of reactivity and productivity, the amount of platinum contained is 1×10 ^-7 to 1×10 ^-2 mol with respect to 1 mol of the silane compound represented by Formula (17). The amount used is preferably 1×10 ^-7 to 1×10 ^-3 mol, more preferably.

In addition, a cocatalyst may be used to improve the reactivity of hydrosilylation. As this promoter, a promoter 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 amide sulfate, ammonium nitrate, dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium diphosphate, ammonium carbonate, ammonium hydrogen carbonate, ammonium sulfide, ammonium borate, Although ammonium borofluoride etc. are mentioned, Among these, the ammonium salt of an inorganic acid whose pKa is 2 or more is preferable, and ammonium carbonate and ammonium hydrogencarbonate 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 acid amide, stearic acid amide, etc. are 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 and glycolic acid. Among these, formic acid, acetic acid and lactic acid are preferable. and acetic acid is more preferable.

The amount of the co-catalyst is not particularly limited, but from the viewpoint of reactivity, selectivity, cost, etc., 1×10 ^-5 to 1×10 ^-1 mol is preferable with respect to 1 mol of the silane compound represented by Formula (17), 1 x10 ^-4 to 5x10 ^-1 mol is more preferable.

In addition, although the hydrosilylation reaction proceeds without a solvent, a solvent may also be used.

Specific examples of the solvent that can be used include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene, and xylene; ether solvents such as diethyl ether, tetrahydrofuran and dioxane; ester solvents such as ethyl acetate and butyl acetate; aprotic polar solvents such as N,N-dimethylformamide; Chlorinated hydrocarbon solvents, such as dichloromethane and chloroform, etc. are mentioned, These solvent may be used individually by 1 type, or may mix and use 2 or more types.

The reaction temperature in the said hydrosilylation reaction is not specifically limited, Although it can carry out under heating from 0 degreeC, 0-200 degreeC is preferable.

In order to obtain a suitable reaction rate, it is preferable to react under heating, and from this viewpoint, 40-110 degreeC is more preferable, and, as for the reaction temperature, 40-90 degreeC is still more preferable.

Moreover, reaction time is not specifically limited, either, Usually, although it is about 1 to 60 hours, 1 to 30 hours are preferable and 1 to 20 hours are more preferable.

The curable composition of this invention contains the organosilicon compound represented by Formula (i).

The organosilicon compound represented by the formula (i) of the present invention is derived from the structure of the organosilicon compound, and compared with a conventional organosilicon compound, copper foil adhesion and dielectric properties of a cured product obtained using a curable composition containing this to improve

Curable composition of this invention WHEREIN: Although content of an organosilicon compound is not specifically limited, About 0.1-10 mass % is preferable in a curable composition, and its 0.5-5 mass % is more preferable. In addition, when an organosilicon compound contains a solvent, the said content means the non-volatile matter except a solvent.

Moreover, it is preferable that the curable composition of this invention contains an organic resin.

The organic resin is not particularly limited, and specific examples thereof include epoxy resins, phenol resins, polycarbonates and polycarbonate blends, acrylic resins, polyester resins, polyamide resins, polyimide resins, acrylonitrile-styrene Copolymer, styrene-acrylonitrile-butadiene copolymer, polyvinyl chloride resin, polystyrene resin, polyphenylene ether resin, polystyrene and polyphenylene ether blend, cellulose acetate butyrate, polyethylene resin, etc. are appropriately selected according to the application However, in consideration of use 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 polyphenylene ether resin, or a blend thereof is preferable.

In this case, an appropriate hardening|curing agent may be mix|blended according to the organic resin to be used, for example, when using an epoxy resin, hardening|curing agents, such as an imidazole compound, can be mix|blended.

Moreover, as a crosslinking component, for example, a cyanate ester compound etc. may be mix|blended suitably, Furthermore, depending on the purpose of use, various additives, such as an adhesion improving agent, a ultraviolet absorber, storage stability improving agent, a plasticizer, a filler, a pigment, may be added. do.

[ Example ]

Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to these Examples.

In addition, in the following, a viscosity is a measurement value at 25 degreeC with a B-type rotational viscometer, a molecular weight is a polystyrene conversion weight average molecular weight calculated|required by GPC (gel permeation chromatograph) measurement, and a non-volatile matter is an aluminum petri dish. It is the measured value by the heating residual quantity method after heat-drying at 105 degreeC for 3 hours.

[1] Synthesis of organosilicon compounds

[Example 1-1] Synthesis of organosilicon compound 1

In a 200 mL separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 40 g of PPO (trademark) SA120-100 (manufactured by SABIC Innovative Plastics Co., Ltd.), 110 g of toluene and 0.05 g of dioctyltin dilaurate was added and heated to 80°C. In it, 7.6 g of 3-isocyanate propyl trimethoxysilane was added dropwise, and it heat-stirred at 80 degreeC for 2 hours. By IR measurement, it was confirmed that the absorption peak derived from the isocyanate group as the raw material was completely lost, 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, and had a weight average molecular weight of 6,700, a viscosity of 23 mm<2>/s, and 34 mass % of nonvolatile matter.

[Example 1-2] Synthesis of organosilicon compound 2

It was synthesized in the same procedure as in Example 1-1, except that the amount of 3-isocyanate propyltriethoxysilane was changed to 9.2 g.

The obtained reaction product was a brown transparent liquid, and had a weight average molecular weight of 6,800, a viscosity of 30 mm<2>/s, and 30 mass % of nonvolatile matter.

[Example 1-3] Synthesis of organosilicon compound 3

It synthesized in the same procedure as in Example 1-1, except that the amount of toluene was changed to 120 g and the amount of 3-isocyanate propyltrimethoxysilane 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 29 mass % of nonvolatile matter.

[Example 1-4] Synthesis of organosilicon compound 4

It was synthesized in the same procedure as in Example 1-1, except that the amount of 3-isocyanate propyltrimethoxysilane 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 30 mass % of nonvolatile matter.

[Example 1-5] Synthesis of organosilicon compound 5

In a 200 mL separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 40 g of PPO (trademark) resin powder (manufactured by SABIC Innovative Plastics), 110 g of toluene, and 0.05 g of dioctyltin dilaurate were added and heated to 80°C. In that, 0.5 g of 3-isocyanate propyl trimethoxysilane was added dropwise, and it heat-stirred at 80 degreeC for 2 hours. Then, by IR measurement, it was confirmed that the absorption peak derived from the isocyanate group which is a raw material disappeared completely, and the absorption peak derived from a urethane bond was produced|generated instead, and it was set as reaction completion|finish.

The obtained reaction product was a brown transparent liquid, and had a weight average molecular weight of 102,000, a viscosity of 1,200 mm<2>/s, and 28 mass % of nonvolatile matter.

[Example 1-6] Synthesis of organosilicon compound 6

Based on the method described in Example "PPE-3" of Japanese Patent Application Laid-Open No. 2015-086329, polyphenyl which was distributively rearranged by distributive rearrangement of noryl640-111 (manufactured by SABIC Innovative Plastics) Renether was obtained.

In a 200 mL separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 40 g of the distributive rearranged polyphenylene ether obtained above, 110 g of toluene, and 0.05 g of dioctyltin dilaurate were added, and heated to 80 ° C. did In that, 27.8 g of 3-isocyanate propyltrimethoxysilane was added dropwise, and it heat-stirred at 80 degreeC for 2 hours. Then, by IR measurement, it was confirmed that the absorption peak derived from the isocyanate group which is a raw material disappeared completely, and the absorption peak derived from a urethane bond was produced|generated instead, and it was set as reaction completion|finish.

The obtained reaction product was a brown transparent liquid, and had a weight average molecular weight of 6,200, a viscosity of 49 mm<2>/s, and 30 mass % of nonvolatile matter.

[Example 1-7] Synthesis of organosilicon compound 7

In a 200 mL separable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 40 g of polyphenylene ether, 110 g of toluene, and 0.05 g of dioctyltin dilaurate, which were rearranged by distribution in Example 1-6, were placed at 80 ° C. heated with In it, 13.9 g of 3-isocyanate propyl trimethoxysilane was added dropwise, and it heat-stirred at 80 degreeC for 2 hours. Then, by IR measurement, it was confirmed that the absorption peak derived from the isocyanate group which is a raw material disappeared completely, and the absorption peak derived from a urethane bond was produced|generated instead, and it was set as reaction completion|finish.

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 30 mass % of nonvolatile matter.

[Example 1-8] Synthesis of organosilicon compound 8

[Step 1]

In a 300 mL separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 50 g of PPO (trademark) SA120-100 (manufactured by SABIC Innovative Plastics Co., Ltd.), 120 g of toluene, 0.56 g and 30 of tetrabutylammonium hydrogensulfate % Sodium hydroxide aqueous solution 37.6g was thrown in, and it heated to 60 degreeC. In it, 5.7 g of allyl bromide was added dropwise, and it heat-stirred at 60 degreeC for 6 hours. Thereafter, the aqueous layer separated into two layers was separated by standing still, 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 to turn the corresponding alkenyl compound into brown color. obtained as a solid.

[Step 2]

In a 200 mL separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 30 g of the alkenyl compound obtained in the first step, 70 g of toluene, platinum-1,3-divinyl-1,1,3,3-tetra 0.08 g of a toluene solution of the methyldisiloxane complex (5.0 × 10 ^-5 mol as platinum atoms per 1 mol of trimethoxysilane) was added, and 3.5 g of trimethoxysilane was added at an internal temperature of 75 to 85° C., and then at 80° C. Stirred for 1 hour.

The obtained reaction product was a brown transparent liquid, and had a weight average molecular weight of 6,000, a viscosity of 15 mm<2>/s, and 31 mass % of nonvolatile matter.

[Example 1-9] Synthesis of organosilicon compound 9

[Step 1]

In a 300 mL separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 50 g of PPO (trademark) SA120-100 (manufactured by SABIC Innovative Plastics Co., Ltd.), 120 g of toluene, 0.56 g of tetrabutylammonium iodide and 37.6 g of 30% aqueous sodium hydroxide solution was put thereinto, and the mixture was heated to 60°C. In that, 6.9 g of octenyl chloride was added dropwise, and the mixture was heated and stirred at 60°C for 6 hours. After that, the aqueous layer separated into two layers was separated by standing still, 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, and the corresponding alkenyl compound obtained as a brown solid.

[Step 2]

In a 200 mL separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 30 g of the alkenyl compound obtained in the first step, 70 g of toluene, platinum-1,3-divinyl-1,1,3,3-tetra 0.08 g of a toluene solution of the methyldisiloxane complex (5.0 × 10 ^-5 mol as platinum atoms per 1 mol of trimethoxysilane) and 0.003 g of acetic acid were added, and 3.4 g of trimethoxysilane was added at an internal temperature of 75 to 85° C. , and 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 30 mass % of nonvolatile matter.

[Example 1-10] Synthesis of organosilicon compound 10

[Step 1]

In a 300 mL separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 50 g of PPO (trademark) SA90-100 (manufactured by SABIC Innovative Plastics Co., Ltd.), 130 g of toluene, 0.58 g of tetrabutylammonium hydrogen sulfate and 30 % Sodium hydroxide aqueous solution 54.1g was thrown in, and it heated to 60 degreeC. In it, 8.2 g of allyl bromide was added dropwise, and it heat-stirred at 60 degreeC for 6 hours. After that, the aqueous layer separated into two layers was separated by standing still, 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, and the corresponding alkenyl compound obtained as a brown solid.

[Step 2]

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-tetra 0.10 g of a toluene solution of the methyldisiloxane complex (5.0 × 10 ^-5 mol as platinum atoms per 1 mol of trimethoxysilane) was added, and 6.3 g of trimethoxysilane was added at an internal temperature of 75 to 85° C., and then at 80° C. Stirred for 1 hour.

The obtained reaction product was a brown transparent liquid, and had a weight average molecular weight of 4,800, a viscosity of 13 mm<2>/s, and 31 mass % of nonvolatile matter.

[Example 1-11] Synthesis of organosilicon compound 11

[Step 1]

In a 300 mL separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 50 g of PPO (trademark) SA90-100 (manufactured by SABIC Innovative Plastics, Ltd.), 130 g of toluene, 0.54 g and 30 of tetrabutylammonium hydrogensulfate % Sodium hydroxide aqueous solution 54.1g was thrown in, and it heated to 60 degreeC. In it, 4.1 g of allyl bromide was added dropwise, and it heat-stirred at 60 degreeC for 6 hours. After that, the aqueous layer separated into two layers was separated by standing still, 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, and the corresponding alkenyl compound obtained as a brown solid.

[Step 2]

In a 200 mL separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 25 g of the alkenyl compound obtained in the first step, 75 g of toluene, platinum-1,3-divinyl-1,1,3,3-tetra 0.06 g of a toluene solution of the methyldisiloxane complex (5.0 × 10 ^-5 mol as platinum atoms per 1 mol of trimethoxysilane) was added, and 3.7 g of trimethoxysilane was added at an internal temperature of 75 to 85° C., and then at 80° C. Stirred 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 18 mm<2>/s, and 30 mass % of nonvolatile matter.

[Comparative Example 1-1] Synthesis of organosilicon compound 12

In a reaction apparatus equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 500 g of bifunctional phenylene ether resin (Mitsubishi Gas Chemical Co., Ltd., OPE-1000), polytetramethoxysilane (Tama Chemical Co., Ltd.) ) agent, 447 g of M silicate 51) was added, heated to 90° C., and melt-mixed to obtain a homogeneous solution. In it, 0.22 g of dibutyltin dilaurate was added as a catalyst, and the corresponding organosilicon compound was obtained by demethanol-reacting at 90 degreeC for 15 hours.

[Comparative Example 1-2] Synthesis of organosilicon compound 13

In a reaction apparatus equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 71.8 g of bifunctional phenylene ether resin (Mitsubishi Gas Chemical Co., Ltd., OPE-1000), polymethyltrimethoxysilane (Tama Chemical) 45.3 g (manufactured by Co., Ltd., MTMS-A) was added, heated to 90° C., and melt-mixed to obtain a homogeneous solution. In it, 0.02 g of dibutyltin dilaurate was added as a catalyst, and the corresponding organosilicon compound was obtained by demethanol-reacting at 90 degreeC for 15 hours.

[2] Preparation of curable composition and cured product thereof

Each component used when manufacturing a curable composition and its hardened|cured material is demonstrated.

[PPE]

· SABIC Innovative Plastics PPO (trademark) SA90-100

[Epoxy Resin]

Epoxy resin 1: DIC Corporation Epiclon HP7200 (dicyclopentadiene type epoxy compound)

Epoxy resin 2: DIC Corporation Epiclon 850S (bisphenol A type epoxy resin)

[hardener]

Shikoku Kasei High School Co., Ltd. 2E4MZ (2-ethyl-4-imidazole)

[Cyanate Ester Compound]

· BADCy (2,2-bis(4-cyanatophenyl)propane) manufactured by Lonza Japan Co., Ltd.

[Organic metal salt]

・DIC Co., Ltd. Cu-NAPHTENATE (copper naphthenate)

[organosilicon compound]

Organosilicon compound: the organosilicon compound obtained in Examples 1-1 to 1-11 and Comparative Examples 1-1 and 1-2

[Example 2-1]

According to the blending ratios (parts by mass, provided that the organosilicon compound is a non-volatile content conversion value) shown in Tables 1 and 2, PPE, an epoxy resin, a curing agent, and the organosilicon compound 1 obtained in Example 1-1 are mixed, and the obtained mixture The solution was heated to 60°C. In that, after adding a cyanate ester compound and an organometallic salt, it stirred for 30 minutes, it was made to melt|dissolve completely, and the varnish-shaped curable composition (resin varnish) was obtained.

Then, the obtained resin varnish was impregnated with glass cloth (Nitoboseki Co., Ltd. product, #2116 type, WEA116E, E glass), Then, it heat-dried at 160 degreeC for 10 minutes, and obtained the prepreg. At this time, it adjusted so that content of a resin component might be about 55 mass %.

Each of the obtained prepregs was stacked by 6, sandwiched between copper foils (GT-MP manufactured by Furukawa Circuit Foil Co., Ltd.) and laminated, and heated and pressurized at 200°C for 2 hours and under a pressure of 3 MPa to obtain an evaluation substrate as a cured product. got it

[Examples 2-2 to 2-11 and Comparative Examples 2-1 and 2-2]

It carried out similarly to Example 2-1 except having changed the organosilicon compound 1 into the organosilicon compounds 2-13 obtained in Examples 1-2 to 1-11 and Comparative Examples 1-1 to 1-2, respectively, and curable. A composition and a cured product thereof were prepared.

[Comparative Examples 2-3, 2-4]

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

[Comparative Example 2-5]

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

About each evaluation board|substrate manufactured by said procedure, the method shown below evaluated.

[Genetic Characteristics]

The dielectric constant and dielectric loss tangent of the copper clad laminate in 2 GHz were measured using the cavity resonance "CP461" manufactured by Kanto Denshi Ouyou Kaihatsu. The results are shown in Tables 1 and 2 below.

[Copper Foil Adhesion Strength]

The copper foil peeling strength (copper foil adhesion strength) on the surface of a copper clad laminated board was measured by the method based on JISC6481. At this time, on a test piece having a width of 20 mm and a length of 100 mm, a pattern having a width of 10 mm and a length of 100 mm is formed, and the copper foil is peeled off at a rate of 50 mm / min using a tensile tester, and the peel strength (kgf / cm) at that time It evaluated as copper foil adhesive 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 include the organosilicon compounds obtained in Comparative Examples 1-1 and 1-2, γ-glycidoxypropyltrimethoxysilane and Compared with phenyltrimethoxysilane, it turned out that the hardened|cured material excellent in copper foil adhesiveness, dielectric constant, and dielectric characteristics, such as a dielectric loss tangent, was provided.

Claims (7)

A resin modifier for a high-frequency substrate material comprising an organosilicon compound represented by the average structural formula (i).

(Wherein, X represents an n-valent organic group including a polyphenylene ether structure, and R ¹ is each independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or unsubstituted or substituted carbon atoms. represents an aryl group of 6 to 10, 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 following formula (12) or (13), m is a number from 1 to 3, and n is a number from 1 to 10)

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

{Wherein, R ¹ , R ² , A ¹ , A ² and m have the same meaning as above, and R ³ are each independently a halogen atom, an unsubstituted or substituted C 1 to C 12 alkyl group, unsubstituted represents a ring 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 are each independently a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-C12 alkyl group, an unsubstituted or substituted C1-C12 alkoxy group, an unsubstituted or substituted C1-C12 12 alkylthio group, or unsubstituted or substituted haloalkoxy group having 1 to 12 carbon atoms, a and b are each independently a number from 1 to 100, c is a number from 0 to less than 2, and Z is Representing a linking group represented by the following formula (3),

[( ^{wherein R 4} represents the same meaning as 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 an integer of 1 to 12. and j represents a number from 1 to 1,000)]} The resin modifier for a high frequency substrate material according to claim 1 or 2, wherein the A ¹ -A ² is represented by the formula (12). The resin modifier for a high-frequency substrate material according to claim 2, wherein a and b are numbers from 3 to 50. The curable composition for high frequency board|substrate formation containing the resin modifier of the high frequency board|substrate material in any one of Claims 1, 2, and 4. 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 board|substrate formed by hardening|curing the curable composition of Claim 5.