CN112442267A - Polyphenylene ether resin composition and mixture - Google Patents

Polyphenylene ether resin composition and mixture Download PDF

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Publication number
CN112442267A
CN112442267A CN202010871018.4A CN202010871018A CN112442267A CN 112442267 A CN112442267 A CN 112442267A CN 202010871018 A CN202010871018 A CN 202010871018A CN 112442267 A CN112442267 A CN 112442267A
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polyphenylene ether
compound represented
carbon atoms
ether resin
group
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山田哲郎
广神宗直
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Shin Etsu Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C08K5/5477—Silicon-containing compounds containing nitrogen containing nitrogen in a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen

Abstract

The invention provides a polyphenylene ether resin composition and a mixture thereof, which can form a cured product with excellent dielectric characteristics and good adhesion with a copper foil. A polyphenylene ether resin composition characterized by comprising a polyphenylene ether resin and at least one of organic silicon compounds represented by the following structural formulae (1) and (2).
Figure DDA0002651091300000011
(in the formula, R1Each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R2Each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and each m independently represents an integer of 1 to 3).

Description

Polyphenylene ether resin composition and mixture
Technical Field
The present invention relates to a polyphenylene ether resin composition and a mixture thereof, and more particularly to a polyphenylene ether resin composition containing a specific organic silicon 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 organic silicon compound.
Background
In recent years, with the improvement of bonding technology and mounting technology, electronic devices have been developed in association with the high integration of semiconductor devices mounted on the electronic devices, the refinement of packaging, the high-density wiring of printed wiring boards, and the like.
In particular, electronic devices utilizing high frequency bands such as mobile communications have been developed remarkably, and multilayer formation and fine wiring have been performed simultaneously on printed wiring boards constituting such electronic devices. In order to increase the signal transmission speed required for high-speed information processing, it is known that it is effective to reduce the dielectric constant of the material used, and it is effective to use a material having an extremely low dielectric loss tangent (dielectric loss) in order to reduce the loss during transmission.
In this respect, polyphenylene ether (PPE) based resins are particularly excellent in dielectric properties such as dielectric constant and dielectric loss tangent, and therefore, they have been studied in this field as substrate materials that can cope with high frequencies. Resin compositions using modified polyphenylene ether have also been proposed (see patent documents 1 and 2).
However, a substrate molded by curing a resin composition using polyphenylene ether has a problem that adhesion to a copper foil is insufficient, although the substrate has excellent dielectric characteristics.
Resin compositions using a polyphenylene ether compound having an alkoxysilyl group have been proposed in order to improve adhesion between a polyphenylene ether-based cured product and a copper foil (patent documents 3 and 4).
However, the effect of improving adhesion to copper foil 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, but is not sufficient for a composition having a high content of the polyphenylene ether resin aimed at a low dielectric constant and a low dielectric loss tangent, which are required in recent years.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2004-339328
Patent document 2: international publication No. 2014/034103
Patent document 3: japanese patent laid-open publication No. 2018-16709
Patent document 4: japanese patent laid-open publication No. 2019-77761
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide a polyphenylene ether resin composition which can form a cured product having excellent dielectric characteristics and good adhesion to a copper foil.
Means for solving the problems
The present inventors have intensively studied to solve the above problems, and as a result, have found that: the 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 the polyphenylene ether resin composition and the copper foil, and the present invention has been completed.
Namely, the present invention provides:
1. a polyphenylene ether resin composition characterized by comprising: at least one of a polyphenylene ether resin and an organosilicon compound represented by the following structural formulae (1) and (2),
[ CHEM 1]
Figure BDA0002651091290000031
(in the formula, R1Each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R2Each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and each m independently represents an integer of 1 to 3. )
2.1A polyphenylene ether resin composition comprising at least an organosilicon compound represented by the structural formula (1),
3. a mixture of compounds in which the ratio determined by the area percentage method of gas chromatography is
An organosilicon compound represented by the following structural formula (1): 35 to 75 percent,
An organosilicon compound represented by the following structural formula (2): 10 to 50 percent,
An organosilicon compound represented by the following structural formula (3): less than 15 percent,
An organic compound represented by the following structural formula (4): 15 to 50%, and
the total of compounds represented by the following structural formulae (1) to (4): more than 96 percent of the total weight of the composition,
[ CHEM 2]
Figure BDA0002651091290000032
(in the formula, R1Each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R2Each 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. ).
ADVANTAGEOUS EFFECTS OF INVENTION
The polyphenylene ether resin composition of the present invention contains a specific organic silicon compound having a reactive group containing a carbon-carbon unsaturated double bond, an isocyanurate skeleton and a hydrolyzable silyl group, and therefore, the adhesion of a cured product of the polyphenylene ether resin composition to a copper foil can be improved.
Detailed Description
The present invention will be specifically described below.
The polyphenylene ether resin composition according to the present invention is characterized by comprising a polyphenylene ether resin and at least one of the organosilicon compounds represented by the following structural formulae (1) and (2).
[ CHEM 3]
Figure BDA0002651091290000041
[ polyphenylene ether resin ]
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 is preferably a polyphenylene ether resin end-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 specific examples thereof include Noryl SA9000 (manufactured by SABIC Innovative Plastics co., ltd.).
Further, even if it is not a commercially available product, a modified polyphenylene ether resin in which a carbon-carbon unsaturated double bond group having a polymerization reactivity such as a vinyl group, an allyl group, a styryl group, a methacryl group, and an acryloyl group is introduced through a polyphenylene ether whose terminal is modified with a phenolic hydroxyl group can be used. A commercially available polyphenylene ether having a phenolic hydroxyl group at the end thereof can be used, and specific examples thereof include Noryl SA90 and Noryl SA120 (manufactured by SABIC Innovative Plastics co.
[ organosilicon Compound ]
The organic silicon compound contained in the polyphenylene ether resin composition of the present invention is represented by formula (1) and/or formula (2) as described above.
In the above formulae, R1Each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R2Each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and each m independently represents an integer of 1 to 3.
As R1And R2The alkyl group having 1 to 10 carbon atoms may be any of linear, cyclic and branched ones, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group.
Specific examples of the aryl group having 6 to 10 carbon atoms include phenyl group, α -naphthyl group, β -naphthyl group and the like.
Among these, as R1The alkyl group is preferably a linear alkyl group, and more preferably a methyl group or an ethyl group.
In addition, as R2The alkyl group is preferably a linear alkyl group, and more preferably a methyl group or an ethyl group.
The organosilicon compounds represented by the above formulae (1) and (2) can be obtained by hydrosilylation of a compound represented by the formula (4) with an organosilicon compound represented by the 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 schemes.
[ CHEM 4 ]
Figure BDA0002651091290000061
(in the formula, R1、R2And m represents the same meaning as described above. )
The compound represented by formula (4) is triallyl isocyanurate, and is also available as a commercially available product, and is commercially available, for example, TAIC (manufactured by mitsubishi chemical corporation).
On the other hand, examples of the organosilicon compound represented by the formula (5) include trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, dimethylethoxysilane and the like.
The reaction ratio of the compound represented by formula (4) and 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 still more preferably 0.6 mol or more and less than 1.2 mol of the organosilicon compound represented by formula (5) relative to 1 mol of the compound represented by formula (4), from the viewpoint of adhesion between a cured product of the polyphenylene ether resin composition of the present invention and a copper foil.
The catalyst containing a platinum compound used in the hydrosilylation reaction is not particularly limited, and 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 acetonitrile platinum, dichlorobis benzonitrile platinum, dichlorocyclooctadiene platinum, and supported catalysts such as platinum-carbon, platinum-alumina, and platinum-silica.
In particular, from the viewpoint of selectivity in 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 catalyst containing a platinum compound used is not particularly limited, and it is preferable that the platinum atom contained is 1 × 10 to 1 mol of the organosilicon compound represented by the formula (5) from the viewpoints of reactivity, productivity, and the like-7～1×10-2The molar amount is more preferably 1X 10-7～1×10-3Molar amount.
As the cocatalyst in the above reaction, 1 or more selected from an ammonium salt of an inorganic acid, an acid amide compound and a carboxylic acid is preferably used.
Specific examples of the ammonium salt of the inorganic acid include ammonium chloride, ammonium sulfate, ammonium sulfamate, ammonium nitrate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium diphosphite, ammonium carbonate, ammonium hydrogen carbonate, ammonium sulfide, ammonium borate, ammonium borofluoride and the like, among which ammonium salts of inorganic acids having a pKa of 2 or more are preferable, and ammonium carbonate and ammonium hydrogen carbonate are more preferable.
Specific examples of the acid amide compound include formamide, acetamide, N-methylacetamide, N-dimethylacetamide, propionamide, acrylamide, malonamide, succinamide, maleamide, fumaramide, benzamide, phthalic diamide, palmitamide, and stearamide, and of these, formamide is more preferable.
Specific examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, methoxyacetic acid, valeric acid, caproic acid, enanthic acid, caprylic acid, lactic acid, and glycolic acid, and among these, formic acid, acetic acid, and lactic acid are preferable, and acetic acid is more preferable.
The amount of the co-catalyst to be used is not particularly limited, but is preferably 1 × 10 with respect to 1 mol of the organosilicon compound represented by the formula (5) from the viewpoints of reactivity, selectivity, cost, and the like-5～5×10-1Molal, more preferably 1X 10-4～1×10-1And (3) mol.
The reaction is carried out without a solvent, but a solvent may be used.
Specific examples of the solvent that can be used include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene, and xylene; ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; ester solvents such as ethyl acetate and butyl acetate; aprotic polar solvents such as N, N-dimethylformamide; and chlorinated hydrocarbon solvents such as dichloromethane and chloroform, and these solvents may be used alone in 1 kind or in a mixture of 2 or more kinds.
The reaction temperature in the hydrosilylation reaction is not particularly limited, and may be from 0 ℃ to 0 ℃ under heating, and is preferably 0 to 200 ℃.
In order to obtain an appropriate reaction rate, it is preferable to react the reaction mixture under heating, and from such a viewpoint, the reaction temperature is more preferably 40 to 110 ℃, and still more preferably 40 to 90 ℃.
The reaction time is not particularly limited, and is usually about 1 to 60 hours, preferably 1 to 30 hours, and more preferably 1 to 20 hours.
The amount of the organic silicon compound represented by the formula (1) and/or the formula (2) to be blended 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 still 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 adhesiveness to a copper foil.
Furthermore, in the case of producing the organosilicon compound represented by formula (1) and/or formula (2) by the above-mentioned production method, the target product is obtained as a mixture of at least compounds represented by the above-mentioned formulae (1), (2) and (4), and the mixture can be used as it is as one component of the polyphenylene ether resin composition of the present invention.
In this case, the ratio of the compounds represented by formulae (1) to (4) in the mixture, which is determined by the area percentage method using 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, and if the adhesion between the copper foil and the cured product of the polyphenylene ether resin composition to which the mixture is added is improved, the organosilicon compound represented by formula (1) is preferred: 35 to 75%, an organosilicon compound represented by the formula (2): 10 to 50% of an organosilicon compound represented by the formula (3): less than 15% of an organic compound represented by the formula (4): 15 to 50%, and the total of compounds represented by formulas (1) to (4): 96% or more, particularly preferably 98% or more, and more preferably 100%.
[ other Components ]
The polyphenylene ether resin composition of the present invention may further contain other components than the above-mentioned components. Examples of the other components include high molecular weight materials, inorganic fillers, flame retardants, additives, curing agents, and reaction initiators.
Specific examples of the high molecular weight material include polybutadiene, butadiene-styrene copolymer, and (meth) acrylic copolymer.
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.
Specific examples of the curing agent include triallyl isocyanurate (TAIC), triallyl isocyanurate (TMAIC), and other triallyl isocyanurate compounds; a polyfunctional methacrylate compound having 2 or more methacryloyl groups in a molecule; a multifunctional acrylate compound having 2 or more acryloyl groups in a molecule; and vinylbenzyl compounds such as styrene and divinylbenzene having a vinylbenzyl group in the molecule.
[ method for producing composition ]
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 organic silicon compound represented by the formula (1) and/or the formula (2) and other components according to a conventional method.
As the solvent, aromatic solvents such as toluene and xylene are preferable; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ether solvents such as tetrahydrofuran, etc., among these, aromatic solvents are more preferable, and toluene and xylene are further preferable.
Examples
The present invention will be described more specifically below with reference to synthetic examples, examples and comparative examples, but the present invention is not limited to these examples.
The viscosity is a measured value at 25 ℃ obtained by an austenitic viscometer, and the area percentage in a gas chromatograph is measured under the following conditions and calculated based on the peak area of each component obtained.
(gas chromatography measurement conditions)
A gas chromatography apparatus: 6890N (Agilent Technologies, Inc.)
Column: HP-5 (5% -phenyl-95% -methylpolysiloxane, manufactured by Agilent Technologies, Inc.)
Column size: a length of 30m, an inner diameter of 0.53mm, and a film thickness of 1.5 μm
Carrier gas: helium
Carrier gas flow: 1 ml/min
Oven temperature: 50-300 DEG C
Temperature rising conditions are as follows: 10 ℃/min
The split ratio is as follows: 100: 1
Detection mode and temperature: flame Ionization Detector (FID) 300 deg.C
Sample injection amount: 1 μ l
[1] Production of (mixture of) organosilicon Compound
[ example 1-1]
Into a 3L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 250g (1.0 mol) of triallyl isocyanurate and a toluene solution of platinum-1, 3-divinyl-1, 1, 3, 3-tetramethyldisiloxane complex (5.0X 10 in terms of platinum atom)-5Mole) and formamide 0.2g (5.0X 10)-3Moles). 122g (1.0 mol) of trimethoxysilane was added dropwise thereto at an internal temperature of 80 to 90 ℃ over 1 hour, followed by stirring at 80 ℃ for 3 hours.
After the stirring was completed, the mixture was concentrated under reduced pressure and filtered to obtain a viscosity of 175mm2A light yellow transparent liquid per second. The area percentage of the product in the gas chromatography was 46% for the organosilicon compound represented by the above formula (1), 24% for the organosilicon compound represented by the above formula (2), 4% for the organosilicon compound represented by the above formula (3), and 26% for the organic compound represented by the above formula (4). This was set as mixture a.
[ examples 1-2]
Into a 3L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 250g (1.0 mol) of triallyl isocyanurate and a toluene solution of platinum-1, 3-divinyl-1, 1, 3, 3-tetramethyldisiloxane complex (5.0X 10 in terms of platinum atom)-5Mole) and formamide 0.2g (5.0X 10)-3Moles). 61g (0.5 mol) of trimethoxysilane was added dropwise thereto at an internal temperature of 80 to 90 ℃ over 0.5 hour, followed by stirring at 80 ℃ for 3 hours.
After the stirring, the mixture was concentrated under reduced pressure and filtered to obtain a viscosity of 135mm2A light yellow transparent liquid per second. The area percentage of the product in the gas chromatography was 43% for the organosilicon compound represented by the above formula (1), 10% for the organosilicon compound represented by the above formula (2), 0% for the organosilicon compound represented by the above formula (3), and 47% for the organic compound represented by the above formula (4). This was designated as mixture B.
[ examples 1 to 3]
Into a 3L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 250g (1.0 mol) of triallyl isocyanurate and a toluene solution of platinum-1, 3-divinyl-1, 1, 3, 3-tetramethyldisiloxane complex (5.0X 10 in terms of platinum atom)-5Mole) and formamide 0.2g (5.0X 10)-3Moles). 183g (1.5 mol) of trimethoxysilane was added dropwise thereto at an internal temperature of 80 to 90 ℃ over 1.5 hours, followed by stirring at 80 ℃ for 3 hours.
After the stirring, the mixture was concentrated under reduced pressure and filtered to obtain a viscosity of 285mm2A light yellow transparent liquid per second. The area percentage of the product in the gas chromatography was 38% for the organosilicon compound represented by the above formula (1), 34% for the organosilicon compound represented by the above formula (2), 12% for the organosilicon compound represented by the above formula (3), and 16% for the organic compound represented by the above formula (4). This was set as mixture C.
Synthesis examples 1 to 1
Comprising a stirrer, a reflux condenser, a dropping funnel and a thermometerInto a 3L separable flask was placed 250g (1.0 mol) of triallyl isocyanurate and a toluene solution of platinum-1, 3-divinyl-1, 1, 3, 3-tetramethyldisiloxane complex (5.0X 10 in terms of platinum atom)-5Mole) and formamide 0.2g (5.0X 10)-3Moles). 244g (2.0 mol) of trimethoxysilane was added dropwise thereto at an internal temperature of 80 to 90 ℃ over 2 hours, followed by stirring at 80 ℃ for 3 hours.
After completion of the stirring, the mixture was concentrated under reduced pressure and filtered to obtain a viscosity of 391mm2A light yellow transparent liquid per second. The area percentage of the product in the gas chromatography was 28% for the organosilicon compound represented by the above formula (1), 41% for the organosilicon compound represented by the above formula (2), 19% for the organosilicon compound represented by the above formula (3), and 6% for the organic compound represented by the above formula (4). This was set as mixture D.
Comparative examples 1 to 1
Into a 3L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 250g (1.0 mol) of triallyl isocyanurate and a toluene solution of platinum-1, 3-divinyl-1, 1, 3, 3-tetramethyldisiloxane complex (5.0X 10 in terms of platinum atom)-5Mole) and formamide 0.2g (5.0X 10)-3Moles). 366g (3.0 mol) of trimethoxysilane was added dropwise thereto at an internal temperature of 80 to 90 ℃ over 3 hours, followed by stirring at 80 ℃ for 3 hours.
After the stirring was completed, the mixture was concentrated under reduced pressure and filtered to obtain a viscosity of 305mm2A light yellow transparent liquid per second. The area percentage of the product in the gas chromatography was 0% for the organosilicon compound represented by the above formula (1), 0% for the organosilicon compound represented by the above formula (2), 100% for the organosilicon compound represented by the above formula (3), and 0% for the organic compound represented by the above formula (4). This was set as organosilicon compound E.
Examples 2-1 to 2-4 and comparative examples 2-1 to 2-6
[2] Polyphenylene ether resin composition and production of cured product thereof
(polyphenylene ether)
Modified polyphenylene ether having terminal modified with methacryloyl group (Noryl SA 9000: SABIC Innovative Plastics Co., Ltd., manufactured by Ltd.)
(high molecular weight Material)
High molecular weight material having methacrylic skeleton (ARUFON UP-1080; weight average molecular weight 6000; manufactured by Toyo Seiya Kabushiki Kaisha)
(crosslinking type curing agent)
Triallyl isocyanurate (manufactured by TAIC, Mitsubishi chemical corporation)
(inorganic Filler)
Silica surface-treated with vinylsilane (SC 2300-SVJ: Admatechs Co., Ltd.)
(reaction initiator)
1, 3-bis (tert-butylperoxydiisopropyl) benzene (Perbutyl P manufactured by Nichii oil Co., Ltd.)
[ preparation of resin composition ]
Modified polyphenylene ether (Noryl SA9000) was mixed with toluene, and the mixture was heated to 80 ℃ to dissolve it, thereby obtaining a 50 mass% toluene solution. Then, after adding any one of the high molecular weight material (ARUFON UP-1080), the crosslinking agent (TAIC), the mixtures a to D, and the organic silicon compounds E to I to the obtained toluene solution so as to be in the proportions (parts by mass) described in tables 1 and 2 (comparative example 2-1 did not add an organic silicon 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 thereto, and the mixture was dispersed by a bead mill to obtain a varnish-like resin composition.
[ production of prepreg ]
Using the above varnishes, prepregs were produced for the subsequent evaluation.
In the production of the prepreg, a #1078 type, WEA1078 glass cloth manufactured by ritonavir textile corporation was used as a 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 became 60 μm, and was dried by heating at 120 ℃ for 3 minutes until the material became a semi-cured state, to obtain a prepreg.
[ production of laminated sheet ]
Each of the prepregs 1 prepared as described above was pressed with copper foils (GT-MP manufactured by Kogaku electric industries Co., Ltd.) having a thickness of 12 μm disposed on both surfaces thereof, and the pressed product was subjected to vacuum processing at a temperature of 220 ℃ and a pressure of 40kgf/cm2The test piece was heated and pressed for 90 minutes under the conditions described above, to obtain an evaluation laminate sheet 1 having a thickness of 84 μm, in which copper foils were bonded to both sides.
Further, 12 sheets of the above prepreg were stacked, copper foils were disposed on the uppermost and lowermost surfaces, and heat-molded by the same method as described above to obtain a copper-clad laminate, and then the copper foils were peeled off and removed to obtain an evaluation laminate 2 having a thickness of 720 μm.
Using the evaluation laminates 1 and 2 produced as described above, the adhesion of the copper foil and the dielectric characteristics were evaluated by the following methods. The results are shown in tables 1 and 2.
(1) Copper foil adhesion
In the evaluation of the laminated sheet 1, the thickness was measured in accordance with JIS C6481: 1996, measured the peel strength of the copper foil from the insulation layer. A pattern having a width of 10mm and a length of 100mm was formed, and the pattern was peeled off at a speed of 50 mm/min using a tensile tester, and the peel strength (peel strength) at this time was measured, and the obtained peel strength was defined as a copper foil adhesive force (adhesion force). The measurement unit is kN/m.
(2) Dielectric Properties (relative permittivity and dielectric loss tangent)
The relative dielectric constant and the dielectric loss tangent of the evaluation substrate at 10GHz were measured by the cavity resonator perturbation method. As the evaluation substrate, the above-described evaluation laminated plate 2 was used.
Specifically, the relative dielectric constant (DK) and the dielectric loss tangent (Df) of the evaluation substrate at 10GHz were measured using a Network Analyzer (N5230A: Agilent Technologies, Inc.).
[ TABLE 1]
Figure BDA0002651091290000141
[ TABLE 2]
Figure BDA0002651091290000151
Onium 1 organosilicon compound F: vinyltrimethoxysilane (KBM-1003, manufactured by shin-Etsu chemical Co., Ltd.)
Onium 2 organosilicon compound G: 3-methacryloxypropyltrimethoxysilane (KBM-503, manufactured by shin-Etsu chemical Co., Ltd.)
Onium 3 organosilicon compound H: japanese patent laid-open publication No. 2018-16709, organosilicon Compound 1 of example 1-1
Onium 4 organosilicon compounds I: japanese patent laid-open publication No. 2019-77761, organosilicon Compound 1 of example 1-1
As shown in table 1, the cured product of the polyphenylene ether resin composition containing the organic silicon compound of the present invention showed excellent dielectric characteristics and adhesion to a copper foil. On the other hand, as shown in table 2, the polyphenylene ether resin composition containing no organic silicon compound of the present invention had poor adhesion to the copper foil.

Claims (3)

1. A polyphenylene ether resin composition characterized by comprising: at least one of a polyphenylene ether resin and an organosilicon compound represented by the following structural formulae (1) and (2),
[ CHEM 1]
Figure FDA0002651091280000011
In the formula, R1Each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R2Each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and each m independently represents an integer of 1 to 3.
2. The polyphenylene ether resin composition according to claim 1, comprising at least an organosilicon compound represented by the structural formula (1).
3. A mixture of compounds in which the ratio determined by the area percentage method of gas chromatography is
An organosilicon compound represented by the following structural formula (1): 35 to 75 percent,
An organosilicon compound represented by the following structural formula (2): 10 to 50 percent,
An organosilicon compound represented by the following structural formula (3): less than 15 percent,
An organic compound represented by the following structural formula (4): 15 to 50%, and
the total of compounds represented by the following structural formulae (1) to (4): more than 96 percent of the total weight of the composition,
[ CHEM 2]
Figure FDA0002651091280000021
In the formula, R1Each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R2Each 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.
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