Polyphenylene ether resin compositions and mixtures

Abstract

The present invention provides a polyphenylene ether resin composition and a mixture, and provides a polyphenylene ether resin composition that can form a cured product having excellent dielectric properties and good adhesion to copper foil. The polyphenylene ether resin composition is characterized in that it contains a polyphenylene ether resin and at least one of the organosilicon compounds represented by the following structural formulas (1) and (2). (Wherein, R 1 Each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R 2 (each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and m each independently represents an integer of 1 to 3).

Description

Technical Field

[0001] The present invention relates to a polyphenylene ether resin composition and a mixture, and more particularly to a polyphenylene ether resin composition containing a specific organosilicon compound having a reactive group containing a carbon-carbon unsaturated double bond, an isocyanurate skeleton and a hydrolyzable silyl group, and a mixture of the organosilicon compound. Background Art

[0002] In recent years, electronic devices have continued to develop along with the improvement of bonding technology and mounting technology, the high integration of semiconductor devices mounted in electronic devices, the sophistication of packages, and the high-density wiring of printed wiring boards.

[0003] In particular, the development of electronic devices using high frequency bands such as mobile communications is remarkable, and for printed wiring boards constituting such electronic devices, multilayering and fine wiring are being carried out simultaneously. In the high-speed information processing, in order to increase the required signal transmission speed, it is known that reducing the dielectric constant of the material used is effective, and in order to reduce the loss during transmission, it is effective to use a material with a very small dielectric loss tangent (dielectric loss).

[0004] In this regard, polyphenylene ether (PPE) resins have particularly excellent dielectric properties such as dielectric constant and dielectric loss tangent, and therefore have been studied in this field as substrate materials that can cope with high frequencies. In addition, resin compositions using modified polyphenylene ethers have also been proposed (see Patent Documents 1 and 2).

[0005] However, although a substrate formed by curing a resin composition using polyphenylene ether is excellent in dielectric properties, it has a problem of insufficient adhesion with copper foil.

[0006] In order to improve the adhesion between a polyphenylene ether-based cured product and copper foil, a resin composition using a polyphenylene ether compound having an alkoxysilyl group has been proposed (Patent Documents 3 and 4).

[0007] However, although the effect of improving the adhesion to copper foil by using a 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 not sufficient for a composition with a high content of the polyphenylene ether resin that aims at achieving the low dielectric constant and low dielectric loss tangent levels required in recent years.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Publication No. 2004-339328

[0011] Patent Document 2: International Publication No. 2014 / 034103

[0012] Patent Document 3: Japanese Patent Application Publication No. 2018-16709

[0013] Patent Document 4: Japanese Patent Application Publication No. 2019-77761 Summary of the invention

[0014] Problems to be solved by the invention

[0015] The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a polyphenylene ether resin composition that can form a cured product having excellent dielectric properties and good adhesion to copper foil.

[0016] Means for solving problems

[0017] The present inventors have conducted intensive studies to solve the above problems and have found that a specific organosilicon compound having a reactive group containing a carbon-carbon unsaturated double bond, an isocyanurate skeleton and a hydrolyzable silyl group improves the adhesion between a cured product of a polyphenylene ether resin composition and copper foil, thereby completing the present invention.

[0018] That is, the present invention provides:

[0019] 1. A polyphenylene ether resin composition comprising: a polyphenylene ether resin and at least one of the organosilicon compounds represented by the following structural formulas (1) and (2),

[0020]

Chemistry 1

[0021]

[0022] (Where R 1 Each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R 2 Each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and m each independently represents an integer of 1 to 3.

[0023] 2.1 The polyphenylene ether resin composition comprises at least an organosilicon compound represented by the structural formula (1),

[0024] 3. A mixture wherein the ratio determined by the area percentage method of gas chromatography is

[0025] An organic silicon compound represented by the following structural formula (1): 35 to 75%,

[0026] An organic silicon compound represented by the following structural formula (2): 10 to 50%,

[0027] An organic silicon compound represented by the following structural formula (3): less than 15%,

[0028] An organic compound represented by the following structural formula (4): 15 to 50%, and

[0029] The total amount of the compounds represented by the following structural formulae (1) to (4): 96% or more,

[0030]

Chemistry 2

[0031]

[0032] (Where R 1 Each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R 2 Each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and m independently represents an integer of 1 to 3. )

[0033] Effects of the Invention

[0034] The polyphenylene ether resin composition of the present invention contains a specific organosilicon compound having a reactive group containing a carbon-carbon unsaturated double bond, an isocyanurate skeleton and a hydrolyzable silyl group, and thus can improve the adhesion between the cured product of the polyphenylene ether resin composition and copper foil. DETAILED DESCRIPTION

[0035] The present invention is described in detail below.

[0036] The polyphenylene ether resin composition according to the present invention is characterized by comprising a polyphenylene ether resin and at least one of organic silicon compounds represented by the following structural formulas (1) and (2).

[0037]

Chemistry 3

[0038]

[0039] [Polyphenylene ether resin]

[0040] The polyphenylene ether resin used in the composition of the present invention is not particularly limited, but is preferably a modified polyphenylene ether resin, and preferably a polyphenylene ether resin terminally modified with a substituent having a carbon-carbon unsaturated double bond.

[0041] As such a polyphenylene ether resin, a commercially available product can be used, and specific examples thereof include Noryl SA9000 (manufactured by SABIC Innovative Plastics Co., Ltd.) and the like.

[0042] In addition, even if it is not a commercially available product, a modified polyphenylene ether resin having a polymerization-reactive carbon-carbon unsaturated double bond group such as a vinyl group, an allyl group, a styryl group, a methacryloyl group, or an acryloyl group introduced through a polyphenylene ether modified by a phenolic hydroxyl group at the terminal can be used. A commercially available product can be used as a specific example thereof, and Noryl SA90, Noryl SA120 (manufactured by SABIC Innovative Plastics Co., Ltd.) and the like can be cited.

[0043] [Organic silicon compounds]

[0044] The organosilicon compound contained in the polyphenylene ether resin composition of the present invention is represented by the formula (1) and / or the formula (2) as described above.

[0045] In the above formulas, R 1 Each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R 2 Each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and m each independently represents an integer of 1 to 3.

[0046] As R 1 and R 2 The alkyl group may be a linear, cyclic or branched alkyl group having 1 to 10 carbon atoms. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups.

[0047] Specific examples of the aryl group having 6 to 10 carbon atoms include phenyl, α-naphthyl, β-naphthyl and the like.

[0048] Among these, R 1 , preferably a straight-chain alkyl group, more preferably a methyl group or an ethyl group.

[0049] In addition, as R 2 , preferably a straight-chain alkyl group, more preferably a methyl group or an ethyl group.

[0050] The organosilicon compounds represented by the above formulae (1) and (2) can be obtained by hydrosilylation of a compound represented by formula (4) and an organosilicon compound represented by formula (5) in the presence of a catalyst containing a platinum compound, preferably in the presence of a catalyst containing a platinum compound and a co-catalyst, as shown in the following scheme.

[0051]

Chemistry 4

[0052]

[0053] (Where R 1 , R 2 and m have the same meanings as above.)

[0054] The compound represented by the formula (4) is triallyl isocyanurate, which is also available as a commercial product, for example, TAIC (manufactured by Mitsubishi Chemical Corporation) is already on the market.

[0055] On the other hand, examples of the organic silicon compound represented by the formula (5) include trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, and dimethylethoxysilane.

[0056] With regard to the reaction ratio of the compound represented by formula (4) and the organosilicon compound represented by formula (5), from the viewpoint of the adhesion between the cured product of the polyphenylene ether resin composition of the present invention and the copper foil, the amount of the organosilicon compound represented by formula (5) is preferably 0.01 mol or more and less than 3.0 mol, more preferably 0.1 mol or more and less than 1.5 mol, and even more preferably 0.6 mol or more and less than 1.2 mol, relative to 1 mol of the compound represented by formula (4).

[0057] The catalyst containing a platinum compound used in the above-mentioned hydrosilylation reaction is not particularly limited. Specific examples thereof include chloroplatinic acid, an alcohol solution of chloroplatinic acid, a toluene or xylene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, tetrakis(triphenylphosphine)platinum, dichlorobis(triphenylphosphine)platinum, dichlorobisacetonitrile platinum, dichlorobisbenzonitrile platinum, dichlorocyclooctadiene platinum, and supported catalysts such as platinum-carbon, platinum-alumina, and platinum-silica.

[0058] In particular, from the viewpoint of selectivity during hydrosilylation, a zero-valent platinum complex is preferred, and a toluene or xylene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex is more preferred.

[0059] The amount of the catalyst containing the platinum compound is not particularly limited. From the perspective of reactivity, productivity, etc., it is preferred that the amount of platinum atoms contained be 1×10 -7 ~1×10 -2 The molar amount is more preferably 1×10 -7 ~1×10 -3 The amount of moles.

[0060] As the promoter in the above reaction, it is preferred to use one or more selected from ammonium salts of inorganic acids, acid amide compounds and carboxylic acids.

[0061] Specific examples of ammonium salts of inorganic acids include ammonium chloride, ammonium sulfate, ammonium amidosulfate, ammonium nitrate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium diphosphite, ammonium carbonate, ammonium bicarbonate, ammonium sulfide, ammonium borate, and ammonium borofluoride. Among them, ammonium salts of inorganic acids having a pKa of 2 or more are preferred, and ammonium carbonate and ammonium bicarbonate are more preferred.

[0062] Specific examples of the acid amide compound include formamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, acrylamide, malonamide, succinamide, maleamide, fumaramide, benzamide, phthalamide, palmitamide, stearamide, etc. Among these, formamide is more preferred.

[0063] Specific examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, methoxyacetic acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, lactic acid, glycolic acid, and the like. Among these, formic acid, acetic acid, and lactic acid are preferred, and acetic acid is more preferred.

[0064] The amount of the co-catalyst used is not particularly limited, but is preferably 1×10 -5 ~5×10 -1 mole, more preferably 1×10 -4 ~1×10 -1 Moore.

[0065] The above reaction proceeds even without a solvent, but a solvent may be used.

[0066] 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; 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. These solvents may be used alone or in combination of two or more.

[0067] The reaction temperature in the hydrosilylation reaction is not particularly limited, and the reaction can be carried out at a temperature ranging from 0°C to 200°C, preferably 0°C to 200°C.

[0068] In order to obtain an appropriate reaction rate, it is preferred to carry out the reaction under heating. From such a viewpoint, the reaction temperature is more preferably 40 to 110°C, and further preferably 40 to 90°C.

[0069] The reaction time is not particularly limited, but is usually about 1 to 60 hours, preferably 1 to 30 hours, and more preferably 1 to 20 hours.

[0070] The amount of the organosilicon compound represented by formula (1) and / or formula (2) in the polyphenylene ether resin composition of the present invention is preferably 0.001 to 100 parts by mass, more preferably 0.01 to 20 parts by mass, and even more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the resin component (polyphenylene ether resin) in the composition, from the viewpoint of adhesion to copper foil.

[0071] Furthermore, when the organosilicon compound represented by formula (1) and / or formula (2) is produced by the above-mentioned production method, the target product is obtained as a mixture of compounds represented by at least the above-mentioned formulas (1), (2) and (4), and the mixture can be directly used as a component of the polyphenylene ether resin composition of the present invention.

[0072] In this case, the ratio of the compounds represented by formulae (1) to (4) in the mixture as determined by the area percentage method of gas chromatography is not particularly limited as long as the total amount of the organosilicon compounds represented by formulae (1) and (2) is 50% or more. However, in view of improving the adhesion between the cured product of the polyphenylene ether resin composition to which the mixture is added and the copper foil, the organosilicon compound represented by formula (1) is preferably 35 to 75%, the organosilicon compound represented by formula (2) is 10 to 50%, the organosilicon compound represented by formula (3) is less than 15%, the organic compound represented by formula (4) is 15 to 50%, and the total amount of the compounds represented by formulae (1) to (4) is preferably 96% or more, particularly preferably 98% or more, and further preferably 100%.

[0073] [Other ingredients]

[0074] The polyphenylene ether resin composition of the present invention may further contain other components in addition to 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.

[0075] Specific examples of the high molecular weight substance include polybutadiene, butadiene-styrene copolymers, and (meth)acrylic acid-based copolymers.

[0076] Specific examples of the inorganic filler include spherical silica, barium sulfate, silica powder, ground silica, calcined talc, barium titanate, titanium oxide, clay, alumina, mica, boehmite, and the like.

[0077] Specific examples of curing agents include triallyl isocyanurate (TAIC), trimethylallyl isocyanurate (TMAIC) and other triallyl isocyanurate compounds; polyfunctional methacrylate compounds having two or more methacryloyl groups in the molecule; polyfunctional acrylate compounds having two or more acryloyl groups in the molecule; vinylbenzyl compounds such as styrene and divinylbenzene having vinylbenzyl groups in the molecule, and the like.

[0078] [Method for producing composition]

[0079] The polyphenylene ether resin composition of the present invention can be produced by dissolving a polyphenylene ether resin in a solvent and then mixing the organosilicon compound represented by formula (1) and / or formula (2) and other components according to a conventional method.

[0080] As the solvent, aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; and ether solvents such as tetrahydrofuran are preferred. Among these, aromatic solvents are more preferred, and toluene and xylene are further preferred.

[0081] Example

[0082] The present invention will be described in more detail below with reference to synthesis examples, examples and comparative examples, but the present invention is not limited to these examples.

[0083] The viscosity is a value measured at 25° C. using an Ostwald viscometer, and the area percentage in gas chromatography was measured under the following conditions and calculated based on the peak area of ​​each component obtained.

[0084] (Gas chromatography measurement conditions)

[0085] Gas chromatograph: 6890N (manufactured by Agilent Technologies, Inc.)

[0086] Column: HP-5 (5%-phenyl-95%-methylpolysiloxane, manufactured by Agilent Technologies, Inc.)

[0087] Column dimensions: 30m long, 0.53mm inner diameter, 1.5μm film thickness

[0088] Carrier gas: Helium

[0089] Carrier gas flow rate: 1ml / min

[0090] Oven temperature: 50℃~300℃

[0091] Heating conditions: 10℃ / min

[0092] Split ratio: 100:1

[0093] Detection method, temperature: hydrogen flame ionization detector (FID), 300℃

[0094] Sample injection volume: 1μl

[0095] [1] Manufacture of organosilicon compounds (mixtures)

[0096] [Example 1-1]

[0097] In a 3 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 250 g (1.0 mol) of triallyl isocyanurate and a toluene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (5.0 × 10 -5 mol) and formamide 0.2 g (5.0×10 -3 122 g (1.0 mol) of trimethoxysilane was added dropwise thereto at an internal temperature of 80 to 90°C over 1 hour, followed by stirring at 80°C for 3 hours.

[0098] After stirring, the mixture was concentrated under reduced pressure and filtered to obtain a product with a viscosity of 175 mm 2 / s of light yellow transparent liquid. As for the area percentage in the gas chromatogram of the product, the organosilicon compound represented by the above formula (1) is 46%, the organosilicon compound represented by the above formula (2) is 24%, the organosilicon compound represented by the above formula (3) is 4%, and the organic compound represented by the above formula (4) is 26%. This is referred to as mixture A.

[0099] [Example 1-2]

[0100] In a 3 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 250 g (1.0 mol) of triallyl isocyanurate and a toluene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (5.0 × 10 -5 mol) and formamide 0.2 g (5.0×10 -3 61 g (0.5 mol) of trimethoxysilane was added dropwise thereto at an internal temperature of 80 to 90°C over 0.5 hours, followed by stirring at 80°C for 3 hours.

[0101] After stirring, the mixture was concentrated under reduced pressure and filtered to obtain a product with a viscosity of 135 mm 2 / s of light yellow transparent liquid. As for the area percentage in the gas chromatogram of the product, the organosilicon compound represented by the above formula (1) is 43%, the organosilicon compound represented by the above formula (2) is 10%, the organosilicon compound represented by the above formula (3) is 0%, and the organic compound represented by the above formula (4) is 47%. This is referred to as mixture B.

[0102] [Examples 1-3]

[0103] In a 3 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 250 g (1.0 mol) of triallyl isocyanurate and a toluene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (5.0 × 10 -5 mol) and formamide 0.2 g (5.0×10 -3 183 g (1.5 mol) of trimethoxysilane was added dropwise thereto at an internal temperature of 80 to 90°C over 1.5 hours, followed by stirring at 80°C for 3 hours.

[0104] After stirring, the mixture was concentrated under reduced pressure and filtered to obtain a product with a viscosity of 285 mm 2 / s of light yellow transparent liquid. As for the area percentage in the gas chromatogram of the product, the organosilicon compound represented by the above formula (1) was 38%, the organosilicon compound represented by the above formula (2) was 34%, the organosilicon compound represented by the above formula (3) was 12%, and the organic compound represented by the above formula (4) was 16%. This was referred to as mixture C.

[0105] [Synthesis Example 1-1]

[0106] In a 3 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 250 g (1.0 mol) of triallyl isocyanurate and a toluene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (5.0 × 10 -5 mol) and formamide 0.2 g (5.0×10 -3 244 g (2.0 mol) of trimethoxysilane was added dropwise thereto at an internal temperature of 80 to 90°C over 2 hours, followed by stirring at 80°C for 3 hours.

[0107] After stirring, the mixture was concentrated under reduced pressure and filtered to obtain a solution with a viscosity of 391 mm 2 / s of light yellow transparent liquid. As for the area percentage in the gas chromatogram of the product, the organosilicon compound represented by the above formula (1) was 28%, the organosilicon compound represented by the above formula (2) was 41%, the organosilicon compound represented by the above formula (3) was 19%, and the organic compound represented by the above formula (4) was 6%. This was referred to as mixture D.

[0108] [Comparative Example 1-1]

[0109] In a 3 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 250 g (1.0 mol) of triallyl isocyanurate and a toluene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (5.0 × 10 -5 mol) and formamide 0.2 g (5.0×10 -3 366 g (3.0 mol) of trimethoxysilane was added dropwise thereto at an internal temperature of 80 to 90°C over 3 hours, followed by stirring at 80°C for 3 hours.

[0110] After stirring, the mixture was concentrated under reduced pressure and filtered to obtain a product with a viscosity of 305 mm 2 / s of light yellow transparent liquid. As for the area percentage in the gas chromatogram of the product, the organic silicon compound represented by the above formula (1) is 0%, the organic silicon compound represented by the above formula (2) is 0%, the organic silicon compound represented by the above formula (3) is 100%, and the organic compound represented by the above formula (4) is 0%. This is referred to as organic silicon compound E.

[0111] [Examples 2-1 to 2-4, Comparative Examples 2-1 to 2-6]

[0112] [2] Production of polyphenylene ether resin composition and cured product thereof

[0113] (Polyphenylene ether)

[0114] Modified polyphenylene ether (Noryl SA9000: manufactured by SABIC Innovative Plastics Co., Ltd.) whose terminal is modified with a methacryloyl group

[0115] (High molecular weight substance)

[0116] High molecular weight product having a methacrylic acid-based skeleton (ARUFON UP-1080; weight average molecular weight 6000: manufactured by Toagosei Co., Ltd.)

[0117] (Cross-linking curing agent)

[0118] Triallyl isocyanurate (TAIC: manufactured by Mitsubishi Chemical Corporation)

[0119] (Inorganic filler)

[0120] Silica surface-treated with vinyl silane (SC2300-SVJ: manufactured by Admatechs Co., Ltd.)

[0121] (Reaction initiator)

[0122] 1,3-Bis(tert-butylperoxydiisopropyl)benzene (Perbutyl P: manufactured by NOF Corporation)

[0123] [Preparation of resin composition]

[0124] Modified polyphenylene ether (Noryl SA9000) was mixed with toluene, and the mixture was heated to 80°C to dissolve it, thereby obtaining a 50% by mass toluene solution. Then, a high molecular weight substance (ARUFON UP-1080), a crosslinking agent (TAIC), any one of mixtures A to D and organosilicon compounds E to I were added to the obtained toluene solution in the proportions (parts by mass) described in Tables 1 and 2 (no organosilicon compound was added in Comparative Example 2-1), and the mixture was stirred for 30 minutes to completely dissolve it. Furthermore, an inorganic filler (SC2300-SVJ) and a reaction initiator (Perbutyl P) were added, and dispersed using a bead mill to obtain a varnish-like resin composition.

[0125] [Preparation of prepreg]

[0126] Using each of the above varnishes, a prepreg was prepared and used for the following evaluation.

[0127] In the preparation of the prepreg, glass cloth of type #1078, WEA1078, manufactured by Nitto Bosho Co., Ltd. was used as a woven cloth base material.

[0128] Each resin composition obtained above was impregnated into a woven fabric substrate so as to have a thickness of 60 μm after curing, and then heated and dried at 120° C. for 3 minutes until it became a semi-cured state, thereby obtaining a prepreg.

[0129] [Production of laminated boards]

[0130] A prepreg prepared as described above was subjected to a press at a temperature of 220°C and a pressure of 40 kgf / cm2 under vacuum conditions. A copper foil (GT-MP manufactured by Furukawa Electric Co., Ltd.) with a thickness of 12 μm was placed on both sides of the prepreg to form a pressed body. 2 The laminate was heated and pressed for 90 minutes under the conditions of , and an evaluation laminate 1 having a thickness of 84 μm and copper foil bonded to both surfaces was obtained.

[0131] Furthermore, 12 sheets of the above-mentioned prepreg were stacked, copper foils were placed on the uppermost and lowermost surfaces, and heat-molded in the same manner as above to obtain a copper-clad laminate. The copper foils were then peeled off to obtain an evaluation laminate 2 having a thickness of 720 μm.

[0132] The copper foil adhesion and dielectric properties were evaluated by the following methods using the evaluation laminated boards 1 and 2 produced as described above. The results are shown in Tables 1 and 2.

[0133] (1) Copper foil adhesion

[0134] In the evaluation laminate 1, the peel 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 was formed, and the peel strength (peel strength) was measured at a speed of 50 mm / min using a tensile tester. The obtained peel strength was defined as the copper foil adhesion (adhesion). The measurement unit is kN / m.

[0135] (2) Dielectric properties (relative dielectric constant and dielectric loss tangent)

[0136] The relative dielectric constant and dielectric loss tangent of the evaluation substrate at 10 GHz were measured by the cavity resonator perturbation method. As the evaluation substrate, the above-mentioned evaluation laminated plate 2 was used.

[0137] Specifically, the relative dielectric constant (DK) and dielectric loss tangent (Df) of the evaluation substrate at 10 GHz were measured using a Network Analyzer (N5230A: manufactured by Agilent Technologies, Inc.).

[0138]

Table 1

[0139]

[0140]

Table 2

[0141]

[0142] *1 Organic silicon compound F: Vinyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-1003)

[0143] *2 Organic silicon compound G: 3-methacryloylpropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503)

[0144] *3 Organic silicon compound H: Organic silicon compound 1 of JP-A-2018-16709 and Example 1-1

[0145] *4 Organic silicon compound I: Organic silicon compound 1 of JP-A-2019-77761 and Example 1-1

[0146] As shown in Table 1, the cured product composed 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 not containing the organosilicon compound of the present invention showed poor adhesion to copper foil.

Claims

1. A polyphenylene ether resin composition, characterized in that: A mixture comprising: a polyphenylene ether resin terminally modified with a substituent having a carbon-carbon unsaturated double bond, and wherein the ratio of An organic silicon compound represented by the following structural formula (1): 35 to 75%, The organosilicon compound represented by the following structural formula (2): 10 to 50%, and the total amount of the organosilicon compounds represented by the formula (1) and the formula (2) is 50% or more, An organic silicon compound represented by the following structural formula (3): less than 15%, An organic compound represented by the following structural formula (4): 15% or more and less than 50% and The total amount of the compounds represented by the following structural formulae (1) to (4) is 96% or more, the amount of the organic silicon compounds represented by the formulae (1) and (2) is 0.1 to 5 parts by mass relative to 100 parts by mass of the polyphenylene ether resin, In the formula, R 1 Each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R 2 Each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and m independently represents an integer of 1 to 3.

2. The polyphenylene ether resin composition according to claim 1, wherein The organosilicon compounds represented by the above formulae (1) and (2) are hydrosilylated with a compound represented by the above formula (4) and an organosilicon compound represented by the following formula (5) in the presence of a catalyst containing a platinum compound as shown in the following scheme to obtain a target product in the form of a mixture of compounds represented by at least the above formulae (1), (2) and (4), and the mixture is used as one of the components of the polyphenylene ether resin composition. In the formula, R 1 , R 2 and m have the same meanings as in claim 1. The polyphenylene ether resin composition according to claim 1 , further comprising a curing agent. The polyphenylene ether resin composition according to claim 1 , further comprising a reaction initiator. The polyphenylene ether resin composition according to claim 1 , further comprising a high molecular weight substance.

6. The method for producing a polyphenylene ether resin composition according to claim 1, wherein The organosilicon compounds represented by the above formulae (1) and (2) are hydrosilylated with a compound represented by the above formula (4) and an organosilicon compound represented by the following formula (5) in the presence of a catalyst containing a platinum compound as shown in the following scheme to obtain a target product in the form of a mixture of compounds represented by at least the above formulae (1), (2) and (4), and the mixture is used as one of the components of the polyphenylene ether resin composition. In the formula, R 1 , R 2 and m have the same meanings as in claim 1.

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