JP6988786B2 - Polyphenylene ether resin composition and silane-modified copolymer - Google Patents

Description

The present invention relates to a polyphenylene ether resin composition containing a silane-modified copolymer, and more particularly to a polyphenylene ether resin composition containing a silane-modified copolymer having a polybutadiene skeleton and a polystyrene skeleton.

In recent years, along with the improvement of joining and mounting technology, the electronic equipment has been continuously progressing with the high integration of semiconductor devices mounted on the electronic equipment, the refinement of the package, and the high-density wiring of the printed wiring board. In particular, remarkable progress has been made in electronic devices that use high frequency bands such as mobile communication. In printed wiring boards that make up this type of electronic device, multi-layering and fine wiring are progressing at the same time. It is effective to reduce the dielectric constant of the material to increase the signal transmission speed required for high-speed information processing, and to reduce the loss during transmission, the dielectric loss tangent (dielectric loss) is small. It is effective to use the material.

Polyphenylene ether (PPE) is being studied as a substrate material because it has excellent dielectric properties such as dielectric constant and dielectric loss tangent. Resin compositions using modified polyphenylene ether have also been proposed (Patent Documents 1 and 2).
Although the substrate formed of the resin composition using polyphenylene ether has excellent dielectric properties, there is a problem that the adhesion to the copper foil is insufficient.

On the other hand, it has been reported that a silane-modified copolymer having a polybutadiene skeleton, a polystyrene skeleton, etc. is useful as a component of a filler-filled rubber composition (Patent Documents 3 and 4), but the polyphenylene ether resin composition has a polyphenylene ether resin composition. It was not used.

Japanese Unexamined Patent Publication No. 2004-339328 International Publication No. 2014/034103 U.S. Pat. No. 3,759,869 Japanese Unexamined Patent Publication No. 2017-8301

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polyphenylene ether resin composition that gives a cured product having excellent dielectric properties and improved adhesion to a copper foil.

As a result of diligent studies to solve the above problems, the present inventor has found that the silane-modified copolymer having a polybutadiene skeleton and a polystyrene skeleton improves the adhesion of the cured product of the polyphenylene ether resin composition to the copper foil. Find out and complete the invention.

（式中、Ｒ¹は、互いに独立して、炭素数１〜１０のアルキル基または炭素数６〜１０のアリール基を表し、Ｒ²は、互いに独立して、炭素数１〜１０のアルキル基または炭素数６〜１０のアリール基を表し、ｅ、ｆ、ｇおよびｈは、互いに独立して、０より大きい数を表し、ｍは、１〜３の整数を表す。ただし、各繰り返し単位の順序は任意である。）
２． 式（１）において、ｆ／（ｅ＋ｆ＋ｇ＋ｈ）が０．２２以上である請求項１記載のポリフェニレンエーテル樹脂組成物、
３． 下記式（１）で表されるシラン変性共重合体、

（式中、Ｒ¹は、互いに独立して、炭素数１〜１０のアルキル基または炭素数６〜１０のアリール基を表し、Ｒ²は、互いに独立して、炭素数１〜１０のアルキル基または炭素数６〜１０のアリール基を表し、ｅ、ｆ、ｇおよびｈは、互いに独立して、０より大きい数を表し、ｆ／（ｅ＋ｆ＋ｇ＋ｈ）が０．２２以上であり、ｍは、１〜３の整数を表す。ただし、各繰り返し単位の順序は任意である。）
を提供する。 That is, the present invention
1. 1. A polyphenylene ether resin composition containing a polyphenylene ether resin and a silane-modified copolymer represented by the following formula (1).

(In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms ^{independently of each other, and R 2} represents an alkyl group having 1 to 10 carbon atoms independently of each other. Alternatively, it represents an aryl group having 6 to 10 carbon atoms, e, f, g and h are independent of each other and represent a number greater than 0, and m represents an integer of 1 to 3, where each repeating unit is represented. The order is arbitrary.)
2. 2. The polyphenylene ether resin composition according to claim 1, wherein in the formula (1), f / (e + f + g + h) is 0.22 or more.
3. 3. A silane-modified copolymer represented by the following formula (1),

(In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms ^{independently of each other, and R 2} represents an alkyl group having 1 to 10 carbon atoms independently of each other. Alternatively, it represents an aryl group having 6 to 10 carbon atoms, e, f, g and h are independent of each other and represent a number larger than 0, f / (e + f + g + h) is 0.22 or more, and m is 1. Represents an integer of ~ 3. However, the order of each repeating unit is arbitrary.)
I will provide a.

The polyphenylene ether resin composition of the present invention contains a silane-modified copolymer having a polybutadiene skeleton, a polystyrene skeleton, and a hydrolyzable silyl group, and a cured product is obtained by using this silane-modified copolymer. Adhesion with copper foil can be improved.

Hereinafter, the present invention will be specifically described.
[Polyphenylene ether resin]
The polyphenylene ether resin used in the polyphenylene ether resin composition of the present invention is not particularly limited, but is preferably modified, and is preferably a polyphenylene ether resin terminally modified with a substituent having a carbon-carbon unsaturated double bond. .. As such a polyphenylene ether resin, a commercially available product can be used, and examples thereof include Noyl SA9000 (manufactured by SABIC Innovative Plastics Co., Ltd.) and the like. Even if it is not a commercially available product, a modified polyphenylene ether resin having a vinyl group, a styryl group, a methacrylic group, an acrylic group or the like introduced therein can also be used by using a polyphenylene ether modified with a terminal hydroxyl group.

[Silane-modified copolymer]
The silane-modified copolymer contained in the polyphenylene ether resin composition of the present invention is represented by the formula (1). In the formula (1), the order of each repeating unit is arbitrary.

Here, R ¹ represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms ^{independently of each other, and R 2} represents an alkyl group having 1 to 10 carbon atoms or an alkyl group having 6 to 10 carbon atoms independently of each other. Represents an aryl group having 6 to 10 carbon atoms, e, f, g and h are independent of each other and represent a number greater than 0, and m represents an integer of 1 to 3.

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 and n. -Butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl groups And so on.
Specific examples of the aryl group having 6 to 10 carbon atoms include phenyl, α-naphthyl, β-naphthyl group and the like.

Among these, ^{as R 1} , a linear alkyl group is preferable, and a methyl group and an ethyl group are more preferable.
Further, as R ² , a linear alkyl group is preferable, and a methyl group and an ethyl group are more preferable.

e is preferably 1 to 500, more preferably 5 to 300.
f is preferably 1 to 500, more preferably 5 to 300.
g is preferably 1 to 500, more preferably 2 to 100.
h is preferably 1 to 500, more preferably 5 to 300.

The f / (e + f + g + h) is preferably 0.2 or more, more preferably 0.22 or more, further preferably 0.25 or more, and particularly preferably 0.30 or more. The upper limit is not particularly limited, but is preferably 1 or less, and more preferably 0.8 or less.

The silane-modified copolymer represented by the formula (1) is composed of a butadiene-styrene copolymer represented by the formula (2) and an organosilicon compound represented by the formula (3), as shown in the following scheme. It can be obtained by hydrosilylation in the presence of a platinum compound-containing catalyst, preferably in the presence of a platinum compound-containing catalyst and a co-catalyst.

（式中、Ｒ¹、Ｒ²、ｅ、ｆ、ｇ、ｈおよびｍは、上記と同じ意味を表す。）

(In the formula, R ¹ , R ² , e, f, g, h and m have the same meanings as above.)

The butadiene-styrene copolymer represented by the formula (2) can be synthesized by a known method such as emulsion polymerization or solution polymerization using butadiene and styrene as raw material monomers, but can also be obtained as a commercially available product, for example. , Rion100, Ricon181, Ricon184 (above, manufactured by Polymery), L-SBR-820, L-SBR-841 (above, manufactured by Claret) are on the market.

On the other hand, examples of the organosilicon compound represented by the formula (3) include trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, and dimethylethoxysilane.

The reaction ratio between the copolymer of formula (2) and the compound of formula (3) is:-[CH ₂ = CH-(CH = CH ₂ )] _{f + g} -repeating unit 1 mol in the formula (2). The compound of the formula (3) is preferably less than 1 mol, more preferably 0.8 mol or less. The lower limit is not particularly limited, but 0.01 mol or more is preferable.

The platinum compound-containing catalyst used in the hydrosilylation reaction is not particularly limited, and specific examples thereof include platinum chloride, an alcohol solution of platinum chloride, and platinum-1,3-divinyl-1,1. , 3,3-Tetramethyldisiloxane complex in toluene or xylene, tetraxtriphenylphosphine platinum, dichlorobistriphenylphosphine platinum, dichlorobis acetonitrile platinum, dichlorobisbenzonitrile platinum, dichlorocyclooctadien platinum, etc., platinum-carbon , Platinum-alumina, platinum-silica and other supported catalysts.
From the viewpoint of selectivity during hydrosilylation, a 0-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, productivity, etc., 1 mol of the organic silicon compound represented by the formula (3) contains 1 platinum atom. An amount of × 10 ^-7 to 1 × 10 ⁻² mol is preferable, and an amount of 1 × 10 ^-7 to 1 × 10 ^-3 mol is more preferable.

As the co-catalyst in the above reaction, it is preferable to use one or more selected from an ammonium salt of an inorganic acid, an acid amide compound and a carboxylic acid.
Specific examples of ammonium salts of inorganic acids include ammonium chloride, ammonium sulfate, ammonium ammonium sulfate, ammonium nitrate, monoammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium diaphosphate, ammonium carbonate, and 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 hydrogencarbonate are more preferable.

Specific examples of the acid amide compound include formamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, acrylamide, malonamide, succinamide, maleamide, fumalamide, benzamide, phthalamide, palmitate amide, stearate amide and the like. Can be mentioned.

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

^{The amount of the co-catalyst used is not particularly limited, but 1 × 10 -5 to} 5 × 10 per mol of the organosilicon compound represented by the formula (3) from the viewpoint of reactivity, selectivity, cost and the like. ^-1 mol is preferable, and 1 × 10 ^-4 to 1 × 10 ^-1 mol is more preferable.

Although the above reaction proceeds without a solvent, a solvent can 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; ethyl acetate, butyl acetate and the like. Ester-based solvents; aprotonic polar solvents such as N, N-dimethylformamide; chlorinated hydrocarbon-based solvents such as dichloromethane and chloroform, and the like, even if one of these solvents is used alone, 2 A mixture of seeds or more may be used.

The reaction temperature in the hydrosilylation reaction is not particularly limited and can be carried out from 0 ° C. under heating, but 0 to 200 ° C. is preferable.
In order to obtain an appropriate reaction rate, the reaction is preferably carried out under heating, and from such a viewpoint, the reaction temperature is more preferably 40 to 110 ° C, and even more preferably 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.

Considering the handleability of the polyphenylene ether resin composition of the present invention, the number average molecular weight of the silane-modified copolymer represented by the formula (1) is preferably 500 to 100,000, preferably 1,000 to 20, It is more preferably 000.
The number average molecular weight is a polystyrene-equivalent value obtained by gel permeation chromatography.

The blending amount of the silane-modified copolymer represented by the formula (1) in the polyphenylene ether resin composition of the present invention is 100 parts by mass of the resin component (polyphenylene ether resin) in the composition from the viewpoint of adhesiveness to the copper foil. It is preferably 0.001 to 20 parts by mass, and more preferably 0.1 to 5 parts by mass.

[Other ingredients]
The polyphenylene ether resin composition of the present invention may further contain components other than the above-mentioned components. Examples of other components include high molecular weight substances, inorganic fillers, flame retardants, additives, curing agents, and reaction initiators.

Examples of the high molecular weight polymer include polybutadiene, a butadiene-styrene copolymer other than the formula (1), a (meth) acrylic copolymer and the like.
Examples of the inorganic filler include spherical silica, barium sulfate, silicon oxide powder, crushed silica, calcined talc, barium titanate, titanium oxide, clay, alumina, mica, boehmite and the like.
Examples of the curing agent include a trialkenyl isocyanurate compound such as triallyl isocyanurate (TAIC), a polyfunctional methacrylate compound having two or more methacrylic groups in the molecule, and a polyfunctional acrylate having two or more acrylic groups in the molecule. Examples thereof include compounds and vinylbenzyl compounds such as styrene and divinylbenzene having a vinylbenzyl group in the molecule.

[Method for producing composition]
The composition of the present invention can be produced by dissolving a polyphenylene ether resin in a solvent according to a conventional method, and then mixing a silane-modified copolymer and other components. As the solvent, 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 among these, toluene and xylene are more preferable.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
The molecular weight is a polystyrene-equivalent number average molecular weight obtained by gel permeation chromatography (GPC) measurement. The viscosity is a value at 25 ° C. measured using a rotary viscometer.

[Examples 1-1 to 1-4, Reference Examples 1 to 5 to 1-8]
[1] Production of silane-modified copolymer [Example 1-1]
In a 2L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, Ricon100 (e = 19, (f + g) = 44, h = 11 in the above formula (2); number average molecular weight 4,500; .. Cray Vally Co. hereinafter the same) 1,000 g, toluene 200 g, a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of a toluene solution (3.1 × 10 platinum atoms ^{- 4} mol) and 0.2 g of acetic acid (3.1 × 10 ^-3 mol) were charged. 122 g (1.0 mol) of trimethoxysilane was added dropwise thereto at an internal temperature of 75 to 85 ° C. over 2 hours, and then the mixture was stirred at 80 ° C. for 3 hours.
After the stirring was completed, the mixture was concentrated under reduced pressure and filtered to obtain a yellow transparent liquid having a viscosity of 600,000 mPa · s and a number average molecular weight of 5,000.
The average structure obtained from the molecular weight of the product and the ¹ H-NMR spectrum was a silane-modified copolymer represented by e = 19, f = 40, g = 4, h = 11 in the above formula (1). .. f / (e + f + g + h) is 0.54. This is referred to as a silane-modified copolymer A.

[Example 1-2]
1,000 g of Ricon 100, 200 g of toluene, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane in a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. A toluene solution of the complex (3.1 × 10 ^-4 mol as platinum atom) and 0.2 g of acetic acid (3.1 × 10 ^-3 mol) were charged. To this, 244 g (2.0 mol) of trimethoxysilane was added dropwise at an internal temperature of 75 to 85 ° C. over 2 hours, and then the mixture was stirred at 80 ° C. for 3 hours.
After completion of stirring, the mixture was concentrated under reduced pressure and filtered to obtain a yellow transparent liquid having a viscosity of 650,000 mPa · s and a number average molecular weight of 5,600.
The average structure obtained from the molecular weight of the product and the ¹ H-NMR spectrum was a silane-modified copolymer represented by e = 19, f = 36, g = 8, h = 11 in the above formula (1). .. f / (e + f + g + h) is 0.49. This is referred to as a silane-modified copolymer B.

[Example 1-3]
1,000 g of Ricon 100, 200 g of toluene, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane in a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. A toluene solution of the complex (3.1 × 10 ^-4 mol as platinum atom) and 0.2 g of acetic acid (3.1 × 10 ^-3 mol) were charged. To this, 366 g (3.0 mol) of trimethoxysilane was added dropwise at an internal temperature of 75 to 85 ° C. over 2 hours, and then the mixture was stirred at 80 ° C. for 3 hours.
After completion of stirring, the mixture was concentrated under reduced pressure and filtered to obtain a yellow transparent liquid having a viscosity of 700,000 mPa · s and a number average molecular weight of 6,100.
The average structure obtained from the molecular weight of the product and the ¹ H-NMR spectrum was a silane-modified copolymer represented by e = 19, f = 31, g = 13, h = 11 in the above formula (1). .. f / (e + f + g + h) is 0.42. This is referred to as a silane-modified copolymer C.

[Example 1-4]
1,000 g of Ricon 100, 200 g of toluene, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane in a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. A toluene solution of the complex (3.1 × 10 ^-4 mol as platinum atom) and 0.2 g of acetic acid (3.1 × 10 ^-3 mol) were charged. To this, 610 g (5.0 mol) of trimethoxysilane was added dropwise at an internal temperature of 75 to 85 ° C. over 2 hours, and then the mixture was stirred at 80 ° C. for 3 hours.
After the stirring was completed, the mixture was concentrated under reduced pressure and filtered to obtain a yellow transparent liquid having a viscosity of 800,000 mPa · s and a number average molecular weight of 7,200.
The average structure obtained from the molecular weight of the product and the ¹ H-NMR spectrum was a silane-modified copolymer represented by e = 19, f = 22, g = 22, and h = 11 in the above formula (1). .. f / (e + f + g + h) is 0.29. This is referred to as a silane-modified copolymer D.

[Reference Example 1-5]
In a 2L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, Ricon181 (e = 30, (f + g) = 13, h = 9 in the above formula (2); number average molecular weight 3,200; .. Cray Vally Co. hereinafter the same) 1,000 g, toluene 200 g, a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of a toluene solution (0.5 × 10 platinum atoms ^{- 4} mol) and 0.4 g (0.5 × 10 ⁻² mol) of acetic acid were charged. 73 g (0.6 mol) of trimethoxysilane was added dropwise thereto at an internal temperature of 75 to 85 ° C. over 2 hours, and then the mixture was stirred at 80 ° C. for 1 hour.
After the stirring was completed, the mixture was concentrated under reduced pressure and filtered to obtain a yellow transparent liquid having a viscosity of 12,500 mPa · s and a number average molecular weight of 3,400.
The average structure obtained from the molecular weight of the product and the ¹ H-NMR spectrum was a silane-modified copolymer represented by e = 30, f = 11, g = 2, and h = 9 in the above formula (1). .. f / (e + f + g + h) is 0.21. This is referred to as a silane-modified copolymer E.

[Reference Example 1-6]
1,000 g of Ricon 100, 200 g of toluene, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane in a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. A toluene solution of the complex (3.1 × 10 ^-4 mol as platinum atom) and 0.2 g of acetic acid (3.1 × 10 ^-3 mol) were charged. To this, 976 g (8.0 mol) of trimethoxysilane was added dropwise at an internal temperature of 75 to 85 ° C. over 2 hours, and then the mixture was stirred at 80 ° C. for 3 hours.
After the stirring was completed, the mixture was concentrated under reduced pressure and filtered to obtain a yellow transparent liquid having a viscosity of 1,200,000 mPa · s and a number average molecular weight of 8,900.
The average structure obtained from the molecular weight of the product and the ¹ H-NMR spectrum was a silane-modified copolymer represented by e = 19, f = 9, g = 35, h = 11 in the above formula (1). .. f / (e + f + g + h) is 0.12. Let it be a silane-modified copolymer F.

[Reference Example 1-7]
1,000 g of Ricon 100, 200 g of toluene, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane in a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. A toluene solution of the complex (3.1 × 10 ^-4 mol as platinum atom) and 0.2 g of acetic acid (3.1 × 10 ^-3 mol) were charged. To this, 854 g (7.0 mol) of trimethoxysilane was added dropwise at an internal temperature of 75 to 85 ° C. over 2 hours, and then the mixture was stirred at 80 ° C. for 3 hours.
After the stirring was completed, the mixture was concentrated under reduced pressure and filtered to obtain a yellow transparent liquid having a viscosity of 1,100,000 mPa · s and a number average molecular weight of 8,300.
The average structure obtained from the molecular weight of the product and the ¹ H-NMR spectrum was a silane-modified copolymer represented by e = 19, f = 13, g = 31, h = 11 in the above formula (1). .. f / (e + f + g + h) is 0.18. It is a silane-modified copolymer G.

[Reference Example 1-8]
1,000 g of Ricon181, 200 g of toluene, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane in a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. A toluene solution of the complex (0.5 × 10 ^-4 mol as platinum atom) and 0.4 g (0.5 × 10 ⁻² mol) of acetic acid were charged. To this, 244 g (2.0 mol) of trimethoxysilane was added dropwise at an internal temperature of 75 to 85 ° C. over 2 hours, and then the mixture was stirred at 80 ° C. for 1 hour.
After the stirring was completed, the mixture was concentrated under reduced pressure and filtered to obtain a yellow transparent liquid having a viscosity of 14,500 mPa · s and a number average molecular weight of 3,900.
The average structure obtained from the molecular weight of the product and the ¹ H-NMR spectrum was a silane-modified copolymer represented by e = 30, f = 6, g = 7, and h = 9 in the above formula (1). .. f / (e + f + g + h) is 0.12. It is a silane-modified copolymer H.

[Examples 2-1 to 2-8, Comparative Examples 2-1 to 2-5]
[2] Production of Polyphenylene Ether Resin Composition (Polyphenylene Ether)
Modified polyphenylene ether whose terminal is modified with a methacrylic group (Noyl SA9000: manufactured by SABIC Innovative Plastics Co., Ltd.)
(High molecular weight body)
High molecular weight body having a methacryl skeleton (ARUFON UP-1080; weight average molecular weight 6,000: manufactured by Toagosei Co., Ltd.)
(Crosslink type curing agent)
Triallyl Isocyanurate (TAIC: manufactured by Nihon Kasei Corporation)
(Inorganic filler)
Silica surface-treated with vinylsilane (SC2300-SVJ: manufactured by Admatex Co., Ltd.)
(Reaction initiator)
1,3-Bis (t-butylperoxydiisopropyl) benzene (Perbutyl P: manufactured by NOF CORPORATION)

[Preparation method]
(varnish)
First, modified polyphenylene ether (Noryl SA9000) and toluene were mixed, and the mixture was dissolved by heating to 80 ° C. to obtain a 50% by mass toluene solution. Then, in the obtained toluene solution, a high molecular weight substance (ARUFON UP-1080), a cross-linking agent (TAIC), and a silane-modified copolymer A to so that the ratios (parts by mass) shown in Tables 1 and 2 are obtained. After adding H, it was completely dissolved by stirring for 30 minutes. Further, an inorganic filler (SC2300-SVJ) and a reaction initiator (perbutyl P) were added and dispersed by a bead mill to obtain a varnish-like resin composition.

(Prepreg)
A prepreg was prepared using the above varnish and used for later evaluation.
For the prepreg, a glass cloth of # 1078 type, WEA1078 manufactured by Nitto Boseki Co., Ltd. was used as the woven fabric base material. Then, the woven fabric base material was impregnated with the above resin varnish so as to have a thickness of 60 μm after curing, and this was heated and dried at 120 ° C. for 3 minutes until it became a semi-cured state to obtain a prepreg.

(Laminated board)
A 12 μm-thick copper foil (GT-MP manufactured by Furukawa Electric Co., Ltd.) was placed on both sides of one of the above prepregs to form a pressure-bearing body, and under vacuum conditions, the temperature was 220 ° C. and the pressure was 40 kgf / cm ^2. The evaluation laminated plate 1 having a thickness of 84 μm was obtained by heating and pressurizing for 90 minutes under the above conditions and having copper foil adhered to both sides.
Further, the above 12 prepregs are stacked, copper foils are arranged on the uppermost surface and the lowermost surface, and heat molding is performed by the same method as described above. An evaluation laminated plate 2 having a thickness of 720 μm was obtained.

[Evaluation method]
The evaluation laminated boards 1 and 2 prepared as described above were evaluated by the methods shown below.
(Copper foil adhesive strength)
In the evaluation laminated board 1, the peeling strength of the copper foil from the insulating layer was measured according to JIS C 6481: 1996. A pattern with a width of 10 mm and a length of 100 mm is formed, peeled off at a speed of 50 mm / min by a tensile tester, the peeling strength (peel strength) at that time is measured, and the obtained peel strength is used as the copper foil adhesive force. (Adhesion strength). The measurement unit is kN / m.

(Dielectric properties (relative permittivity and dielectric loss tangent))
The relative permittivity and the dielectric loss tangent of the evaluation substrate at 10 GHz were measured by the cavity resonator perturbation method. The above-mentioned evaluation laminated board 2 was used as the evaluation substrate. Specifically, a network analyzer (N5230A: manufactured by Agilent Technologies, Inc.) was used to measure the relative permittivity (DK) and the dielectric loss tangent (Df) of the evaluation substrate at 10 GHz.

＊１ 有機ケイ素化合物Ｉ：ビニルトリメトキシシラン（信越化学工業（株）製ＫＢＭ−１００３）
＊２ 有機ケイ素化合物Ｊ：３−メタクリルプロピルトリメトキシシラン（信越化学工業（株）製ＫＢＭ−５０３）

* 1 Organosilicon compound I: Vinyltrimethoxysilane (KBM-1003 manufactured by Shin-Etsu Chemical Co., Ltd.)
* 2 Organosilicon compound J: 3-methacrylpropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.)

Claims (3)

A polyphenylene ether resin composition containing a polyphenylene ether resin and a silane-modified copolymer represented by the following formula (1).

(In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms ^{independently of each other, and R 2} represents an alkyl group having 1 to 10 carbon atoms independently of each other. Alternatively, it represents an aryl group having 6 to 10 carbon atoms, e, f, g and h are independent of each other and represent a number greater than 0, and m represents an integer of 1 to 3, where each repeating unit is represented. The order is arbitrary.) The polyphenylene ether resin composition according to claim 1, wherein in the formula (1), f / (e + f + g + h) is 0.22 or more. The polyphenylene ether resin composition according to claim 1 or 2, wherein the blending amount of the silane-modified copolymer represented by the above formula (1) is 0.001 to 20 parts by mass with respect to 100 parts by mass of the polyphenylene ether resin .