JP2021031612A - Polyphenylene ether resin composition and mixture - Google Patents

Abstract

To provide a polyphenylene ether resin composition which gives a cured product having excellent dielectric characteristics and good adhesion to a copper foil.SOLUTION: The polyphenylene ether resin composition contains a polyphenylene ether resin and at least one of organosilicon compounds represented by structural formulae (1) and (2) (where each R1 independently represents a C1-10 alkyl group or a C6-10 aryl group; each R2 independently represents a C1-10 alkyl group or a C6-10 aryl group; and each m independently represents an integer of 1-3).SELECTED DRAWING: None

Description

The present invention relates to polyphenylene ether resin compositions and mixtures, and more particularly, includes specific organosilicon compounds having a reactive group having a carbon-carbon unsaturated double bond, an isocyanurate skeleton and a hydrolyzable silyl group. The present invention relates to a polyphenylene ether resin composition and a mixture of the organosilicon compound.

In recent years, along with the improvement of joining technology and mounting technology, electronic devices have continued to progress due to the high integration of semiconductor devices mounted on electronic devices, the refinement of packages, and the high-density wiring of printed wiring boards. There is.
In particular, the progress of electronic devices using high frequency bands such as mobile communication is remarkable, and in the printed wiring boards constituting this kind of electronic devices, multi-layering and fine wiring are progressing at the same time. It is known that reducing the dielectric constant of the material used is effective for increasing the required signal transmission speed in speeding up information processing, and reducing the loss during transmission is required. It is effective to use a material having a dielectric loss tangent (dielectric loss) as small as possible.

In this respect, polyphenylene ether (PPE) -based resins are particularly excellent in dielectric properties such as dielectric constant and dielectric loss tangent, and are therefore being studied as substrate materials capable of supporting high frequencies in the same field. Further, a resin composition using modified polyphenylene ether has also been proposed (see Patent Documents 1 and 2).
However, although the substrate formed by curing the resin composition using polyphenylene ether has excellent dielectric properties, there is a problem that the adhesion to the copper foil is insufficient.

In order to improve the adhesion between the polyphenylene ether-based cured product and the copper foil, resin compositions using a polyphenylene ether compound having an alkoxysilyl group have been proposed (Patent Documents 3 and 4).
However, although the effect of improving the adhesion to the copper foil using the polyphenylene ether compound having an alkoxysilyl group is effective when the content of the polyphenylene ether resin in the entire resin composition is low, it is at a level required in recent years. A composition with a high content of polyphenylene ether resin, which is oriented toward low dielectric constant and low dielectric loss tangent, is insufficient.

Japanese Unexamined Patent Publication No. 2004-339328 International Publication No. 2014/034103 Japanese Unexamined Patent Publication No. 2018-16709 Japanese Unexamined Patent Publication No. 2019-77761

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 good adhesion to copper foil.

As a result of diligent studies to solve the above problems, the present inventors have found that a specific organosilicon compound having a reactive group having a carbon-carbon unsaturated double bond, an isocyanurate skeleton and a hydrolyzable silyl group is polyphenylene. The present invention has been completed by finding that the adhesion of the cured product of the ether resin composition to the copper foil is improved.

（式中、Ｒ¹は、それぞれ独立して、炭素原子数１〜１０のアルキル基または炭素原子数６〜１０のアリール基を表し、Ｒ²は、それぞれ独立して、炭素原子数１〜１０のアルキル基または炭素原子数６〜１０のアリール基を表し、ｍは、それぞれ独立して、１〜３の整数を表す。）
２． 少なくとも前記構造式（１）で表される有機ケイ素化合物を含む１のポリフェニレンエーテル樹脂組成物、
３． ガスクロマトグラフィーの面積百分率法により求められる比率が、
下記構造式（１）で表される有機ケイ素化合物：３５〜７５％、
下記構造式（２）で表される有機ケイ素化合物：１０〜５０％、
下記構造式（３）で表される有機ケイ素化合物：１５％未満、
下記構造式（４）で表される有機化合物：１５〜５０％、かつ、
下記構造式（１）〜（４）で表される化合物の合計：９６％以上である混合物

（式中、Ｒ¹は、それぞれ独立して、炭素原子数１〜１０のアルキル基または炭素原子数６〜１０のアリール基を表し、Ｒ²は、それぞれ独立して、炭素原子数１〜１０のアルキル基または炭素原子数６〜１０のアリール基を表し、ｍは、互いに独立して、１〜３の整数を表す。）
を提供する。 That is, the present invention
1. 1. A polyphenylene ether resin composition comprising a polyphenylene ether resin and at least one of an organosilicon compound represented by the following structural formulas (1) and (2).

(In the formula, R ¹ independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ² independently represents 1 to 10 carbon atoms. Represents an alkyl group or an aryl group having 6 to 10 carbon atoms, and m independently represents an integer of 1 to 3).
2. 1. The polyphenylene ether resin composition of 1 containing at least the organosilicon compound represented by the structural formula (1).
3. 3. The ratio determined by the area percentage method of gas chromatography is
Organosilicon compound represented by the following structural formula (1): 35-75%,
Organosilicon compound represented by the following structural formula (2): 10 to 50%,
Organosilicon compound represented by the following structural formula (3): less than 15%,
Organic compound represented by the following structural formula (4): 15 to 50% and
Total of compounds represented by the following structural formulas (1) to (4): Mixture of 96% or more

(In the formula, R ¹ independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ² independently represents 1 to 10 carbon atoms. Represents an alkyl group or an aryl group having 6 to 10 carbon atoms, and m represents an integer of 1 to 3 independently of each other.)
I will provide a.

The polyphenylene ether resin composition of the present invention contains a specific organosilicon compound having a reactive group having a carbon-carbon unsaturated double bond, an isocyanurate skeleton and a hydrolyzable silyl group, and thus the polyphenylene ether resin. The adhesion of the cured product of the composition to the copper foil can be improved.

Hereinafter, the present invention will be specifically described.
The polyphenylene ether resin composition according to the present invention is characterized by containing a polyphenylene ether resin and at least one of the organosilicon compounds represented by the following structural formulas (1) and (2).

[Polyphenylene ether resin]
The polyphenylene ether resin used in the composition of the present invention is not particularly limited, but is preferably modified, and the polyphenylene ether resin terminally modified by a substituent having a carbon-carbon unsaturated double bond. Is preferable.
As such a polyphenylene ether resin, a commercially available product can be used, and specific examples thereof include Noyl SA9000 (manufactured by SABIC Innovative Plastics Co., Ltd.) and the like.
In addition, even if it is not a commercially available product, a polymerization-reactive carbon-carbon unsaturated double such as a vinyl group, an allyl group, a styryl group, a methacryl group, or an acrylic group is used by using a polyphenylene ether whose terminal is modified with a phenolic hydroxyl group. A modified polyphenylene ether resin having a binding group introduced can also be used. Commercially available products can be used as the polyphenylene ether having the terminal modified with a phenolic hydroxyl group, and specific examples thereof include Noyl SA90 and Noyl SA120 (manufactured by SABIC Innovative Plastics).

[Organosilicon compound]
The organosilicon compound contained in the polyphenylene ether resin composition of the present invention is represented by the formulas (1) and / or the formula (2) as described above.
In each of the above formulas, R ¹ independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ² independently represents 1 to 1 carbon atoms. It represents an alkyl group of 10 or an aryl group having 6 to 10 carbon atoms, and m independently 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 and i-propyl. n-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl Group etc. can be mentioned.
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.

The organosilicon compounds represented by the above formulas (1) and (2) include a compound represented by the formula (4) and an organosilicon compound represented by the formula (5), as shown in the following scheme. 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およびｍは、上記と同じ意味を表す。）

(In the formula, R ¹ , R ² and m have the same meaning as above.)

The compound represented by the formula (4) is triallyl isocyanurate, but it can also be obtained as a commercially available product. For example, TAIC (manufactured by Mitsubishi Chemical Holdings, Inc.) is on the market.

On the other hand, examples of the organosilicon compound represented by the formula (5) include trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, and dimethylethoxysilane.

The reaction ratio between the compound represented by the formula (4) and the organosilicon compound represented by the formula (5) is determined from the viewpoint of the adhesion between the cured product of the polyphenylene ether resin composition of the present invention and the copper foil. With respect to 1 mol of the compound represented by (4), 0.01 mol or more and less than 3.0 mol of the organosilicon compound represented by the formula (5) is preferable, and more preferably 0.1 mol or more and 1.5 mol. It is less than, more preferably 0.6 mol or more and less than 1.2 mol.

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 solution, tetraxtriphenylphosphine platinum, dichlorobistriphenylphosphine platinum, dichlorobis acetonitrile platinum, dichlorobisbenzonitrile platinum, dichlorocyclooctadiene platinum, etc., platinum-carbon , Platinum-alumina, platinum-silica and other supported catalysts.
In particular, from the viewpoint of selectivity during hydrosilylation, 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 viewpoints of reactivity, productivity, etc., the platinum atom contained in 1 mol of the organosilicon compound represented by the formula (5) is contained. An amount of 1 × 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 ammonium salts of inorganic acids, acid amide compounds and carboxylic acids.
Specific examples of ammonium salts of inorganic acids include ammonium chloride, ammonium sulfate, ammonium amide 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. Among these, formamide is more preferable.

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. 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 × per 1 mol of the organosilicon compound represented by the formula (5) from the viewpoint of reactivity, selectivity, cost and the like. 10 ^-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 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-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 also not particularly limited, and is usually about 1 to 60 hours, preferably 1 to 30 hours, more preferably 1 to 20 hours.

The blending amount of the organosilicon compound represented by the formula (1) and / or the formula (2) in the polyphenylene ether resin composition of the present invention is the resin component (polyphenylene ether) in the composition from the viewpoint of adhesiveness to the copper foil. Resin) 0.001 to 100 parts by mass is preferable, 0.01 to 20 parts by mass is more preferable, and 0.1 to 5 parts by mass is even more preferable with respect to 100 parts by mass.

When the organosilicon compound represented by the formula (1) and / or the formula (2) is produced by the above production method, at least as a mixture of the compounds represented by the above formulas (1), (2) and (4). The desired product is obtained, and this mixture can be used as it is as a component of the polyphenylene ether resin composition of the present invention.
In this case, the ratio of the compounds represented by the formulas (1) to (4) obtained by the area percentage method of gas chromatography in this mixture is the ratio of the organic silicon compounds represented by the formulas (1) and (2). The total amount is not particularly limited as long as it is 50% or more, but it is represented by the formula (1) in consideration of enhancing the adhesion of the cured product of the polyphenylene ether resin composition to which the mixture is added to the copper foil. Organic silicon compound: 35 to 75%, organic silicon compound represented by the formula (2): 10 to 50%, organic silicon compound represented by the formula (3): less than 15%, represented by the formula (4). 15 to 50% of the organic compounds, and the total of the compounds represented by the formulas (1) to (4): 96% or more, particularly 98% or more, more preferably 100%.

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

Specific examples of the high molecular weight polymer include polybutadiene, butadiene-styrene copolymer, (meth) acrylic copolymer and the like.
Specific 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.
Specific examples of the curing agent include trialkenyl isocyanurate compounds such as triallyl isocyanurate (TAIC) and trimetalyl isocyanurate (TMAIC); polyfunctional methacrylate compounds having two or more methacryl groups in the molecule; acrylic in the molecule. Polyfunctional acrylate compounds having two or more groups; vinylbenzyl compounds such as styrene and divinylbenzene having a vinylbenzyl group in the molecule can be mentioned.

[Method for producing composition]
The polyphenylene ether resin composition of the present invention is prepared by dissolving the polyphenylene ether resin in a solvent according to a conventional method, and then mixing the organosilicon compounds represented by the formulas (1) and / or the formula (2), and other components. Can be manufactured.
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, aromatic solvents are more preferable, and toluene and xylene are more preferable. Even more preferable.

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples.
The viscosity is a value measured by an Ostwald viscometer at 25 ° C., and the area percentage in gas chromatography was measured under the following conditions and calculated based on the peak area of each component obtained.
(Gas chromatography measurement conditions)
Gas chromatograph: 6890N (manufactured by Agilent Technologies, Inc.)
Column: HP-5 (5% -Phenyl-95% -Methylpolysiloxane, manufactured by Agilent Technologies, Inc.)
Column size: length 30 m, inner diameter 0.53 mm, film thickness 1.5 μm
Carrier gas: Helium Carrier gas Flow rate: 1 ml / min Oven temperature: 50 ° C to 300 ° C
Heating conditions: 10 ° C / min Split ratio: 100: 1
Detection method, temperature: hydrogen flame ionization detector (FID), 300 ° C
Sample injection volume: 1 μl

[1] Production of (mixture of) an organosilicon compound [Example 1-1]
250 g (1.0 mol) of triallyl isocyanurate, platinum-1,3-divinyl-1,1,3,3-tetra in a 3 L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer. A toluene solution of the methyldisiloxane complex (5.0 × 10 ^-5 mol as platinum atom) and 0.2 g of formamide (5.0 × 10 ^-3 mol) were charged. To this, 122 g (1.0 mol) of trimethoxysilane was added dropwise at an internal temperature of 80 to 90 ° C. over 1 hour, 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 pale yellow transparent liquid having ^{a viscosity of 175 mm 2 / s.} The area percentage of the product in gas chromatography is 46% for the organosilicon compound represented by the above formula (1), 24% for the organosilicon compound represented by the above formula (2), and is represented by the above formula (3). The content of the organosilicon compound was 4%, and the proportion of the organosilicon compound represented by the above formula (4) was 26%. This is referred to as mixture A.

[Example 1-2]
250 g (1.0 mol) of triallyl isocyanurate, platinum-1,3-divinyl-1,1,3,3-tetra in a 3 L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer. A toluene solution of the methyldisiloxane complex (5.0 × 10 ^-5 mol as platinum atom) and 0.2 g of formamide (5.0 × 10 ^-3 mol) were charged. 61 g (0.5 mol) of trimethoxysilane was added dropwise thereto at an internal temperature of 80 to 90 ° C. over 0.5 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 pale yellow transparent liquid having ^{a viscosity of 135 mm 2 / s.} The area percentage of the product in gas chromatography is 43% for the organosilicon compound represented by the above formula (1), 10% for the organosilicon compound represented by the above formula (2), and is represented by the above formula (3). The proportion of the organosilicon compound to be produced was 0%, and the proportion of the organosilicon compound represented by the above formula (4) was 47%. This is referred to as mixture B.

[Example 1-3]
250 g (1.0 mol) of triallyl isocyanurate, platinum-1,3-divinyl-1,1,3,3-tetra in a 3 L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer. A toluene solution of the methyldisiloxane complex (5.0 × 10 ^-5 mol as platinum atom) and 0.2 g of formamide (5.0 × 10 ^-3 mol) were charged. To this, 183 g (1.5 mol) of trimethoxysilane was added dropwise at an internal temperature of 80 to 90 ° C. over 1.5 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 pale yellow transparent liquid having ^{a viscosity of 285 mm 2 / s.} The area percentage of the product in gas chromatography is 38% for the organosilicon compound represented by the above formula (1), 34% for the organosilicon compound represented by the above formula (2), and the above formula (3). The content of the organosilicon compound was 12%, and the proportion of the organosilicon compound represented by the above formula (4) was 16%. This is referred to as mixture C.

[Synthesis Example 1-1]
250 g (1.0 mol) of triallyl isocyanurate, platinum-1,3-divinyl-1,1,3,3-tetra in a 3 L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer. A toluene solution of the methyldisiloxane complex (5.0 × 10 ^-5 mol as platinum atom) and 0.2 g of formamide (5.0 × 10 ^-3 mol) were charged. To this, 244 g (2.0 mol) of trimethoxysilane was added dropwise at an internal temperature of 80 to 90 ° 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 pale yellow transparent liquid having ^{a viscosity of 391 mm 2 / s.} The area percentage of the product in gas chromatography is 28% for the organosilicon compound represented by the above formula (1), 41% for the organosilicon compound represented by the above formula (2), and is represented by the above formula (3). The content of the organosilicon compound was 19%, and the proportion of the organosilicon compound represented by the above formula (4) was 6%. This is referred to as the mixture D.

[Comparative Example 1-1]
250 g (1.0 mol) of triallyl isocyanurate, platinum-1,3-divinyl-1,1,3,3-tetra in a 3 L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer. A toluene solution of the methyldisiloxane complex (5.0 × 10 ^-5 mol as platinum atom) and 0.2 g of formamide (5.0 × 10 ^-3 mol) were charged. To this, 366 g (3.0 mol) of trimethoxysilane was added dropwise at an internal temperature of 80 to 90 ° C. over 3 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 pale yellow transparent liquid having ^{a viscosity of 305 mm 2 / s.} The area percentage of the product in gas chromatography is 0% for the organosilicon compound represented by the above formula (1), 0% for the organosilicon compound represented by the above formula (2), and is represented by the above formula (3). The amount of the organosilicon compound to be used was 100%, and the amount of the organosilicon compound represented by the above formula (4) was 0%. This is referred to as organosilicon compound E.

[Examples 2-1 to 2-4, Comparative Examples 2-1 to 2-6]
[2] Production of polyphenylene ether resin composition and cured product thereof (polyphenylene ether)
Modified polyphenylene ether whose terminal is modified with a methacrylic group (Noryl SA9000: manufactured by SABIC Innovative Plastics Co., Ltd.)
(High molecular weight body)
High molecular weight body having a methacrylic skeleton (ARUFON UP-1080; weight average molecular weight 6,000: manufactured by Toagosei Co., Ltd.)
(Crosslink type curing agent)
Triallyl Isocyanurate (TAIC: manufactured by Mitsubishi Chemical 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 of resin composition]
Modified polyphenylene ether (Noryl SA9000) and toluene were mixed, and the mixed solution was heated to 80 ° C. and dissolved to obtain a 50 mass% toluene solution. Then, in the obtained toluene solution, the high molecular weight compound (ARUFON UP-1080), the cross-linking agent (TAIC), the mixtures AD and the organosilicon were added so as to have the ratios (parts by mass) shown in Tables 1 and 2. After adding any one of the compounds E to I (Comparative Example 2-1 did not add the organosilicon compound), the mixture was stirred for 30 minutes to completely dissolve the compound. 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.

[Making prepreg]
A prepreg was prepared using each of the above varnishes and used for later evaluation.
To prepare the prepreg, a glass cloth of # 1078 type, WEA1078 manufactured by Nitto Boseki Co., Ltd. was used as the woven fabric base material.
Each of the resin compositions obtained above was impregnated into a woven fabric base material so that the thickness after curing was 60 μm, and this was heated and dried at 120 ° C. for 3 minutes until it became a semi-cured state to obtain a prepreg. ..

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

Using the evaluation laminated plates 1 and 2 produced as described above, the copper foil adhesive strength and the dielectric properties were evaluated by the following methods. The results are also shown in Tables 1 and 2.
(1) Evaluation of Copper Foil Adhesive Strength In the laminated board 1, the peeling strength of the copper foil from the insulating layer was measured according to JIS C 6488: 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 with a tensile tester, the peeling strength (peel strength) at that time is measured, and the obtained peel strength is determined by the copper foil adhesive strength. (Adhesion strength). The unit of measurement is kN / m.

(2) Dielectric properties (relative permittivity and dielectric loss tangent)
The relative permittivity and dielectric loss tangent of the evaluation substrate at 10 GHz were measured by the cavity resonator perturbation method. The evaluation laminate 2 described above 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Ｆ：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Ｇ：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）
＊３ 有機ケイ素化合物Ｈ：特開２０１８−１６７０９号公報、実施例１−１の有機ケイ素化合物１
＊４ 有機ケイ素化合物Ｉ：特開２０１９−７７７６１号公報、実施例１−１の有機ケイ素化合物１

* 1 Organosilicon compound F: Vinyl trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-1003)
* 2 Organosilicon compound G: 3-methacrylpropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503)
* 3 Organosilicon compound H: Organosilicon compound 1 of JP-A-2018-16709, Example 1-1
* 4 Organosilicon compound I: Organosilicon compound 1 of JP-A-2019-77761, Example 1-1

As shown in Table 1, the cured product made of the polyphenylene ether resin composition containing the organosilicon compound of the present invention exhibited excellent dielectric properties and adhesion to copper foil. On the other hand, as shown in Table 2, the polyphenylene ether resin composition containing no organosilicon compound of the present invention resulted in inferior adhesion to the copper foil.

Claims (3)

A polyphenylene ether resin composition comprising a polyphenylene ether resin and at least one of an organosilicon compound represented by the following structural formulas (1) and (2).

(In the formula, R ¹ independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ² independently represents 1 to 10 carbon atoms. Represents an alkyl group or an aryl group having 6 to 10 carbon atoms, and m independently represents an integer of 1 to 3). The polyphenylene ether resin composition according to claim 1, which comprises at least the organosilicon compound represented by the structural formula (1). The ratio determined by the area percentage method of gas chromatography is
Organosilicon compound represented by the following structural formula (1): 35-75%,
Organosilicon compound represented by the following structural formula (2): 10 to 50%,
Organosilicon compound represented by the following structural formula (3): less than 15%,
Organic compound represented by the following structural formula (4): 15 to 50% and
The total of the compounds represented by the following structural formulas (1) to (4): 96% or more of the mixture.

(In the formula, R ¹ independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ² independently represents 1 to 10 carbon atoms. Represents an alkyl group or an aryl group having 6 to 10 carbon atoms, and m represents an integer of 1 to 3 independently of each other.)