CN108250716B - Polysiloxane-allyl compound modified polyphenyl ether resin composition, and prepreg, laminated board and printed circuit board thereof - Google Patents

Polysiloxane-allyl compound modified polyphenyl ether resin composition, and prepreg, laminated board and printed circuit board thereof Download PDF

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CN108250716B
CN108250716B CN201611241815.4A CN201611241815A CN108250716B CN 108250716 B CN108250716 B CN 108250716B CN 201611241815 A CN201611241815 A CN 201611241815A CN 108250716 B CN108250716 B CN 108250716B
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polysiloxane
ether resin
allyl compound
polyphenylene ether
resin composition
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CN108250716A (en
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黄增彪
成浩冠
丘威平
魏婷
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Shengyi Technology Co Ltd
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
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    • B32B2260/021—Fibrous or filamentary layer
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    • B32—LAYERED PRODUCTS
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    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
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    • B32B2260/023—Two or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • 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
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    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0162—Silicon containing polymer, e.g. silicone

Abstract

The invention provides a polysiloxane-allyl compound modified polyphenyl ether resin composition, a prepreg, a laminated board and a printed circuit board, wherein the polysiloxane-allyl compound modified polyphenyl ether resin composition comprises polyphenyl ether resin and polysiloxane-allyl compound with a structure shown in a formula I, and the content of the polysiloxane-allyl compound in the composition is 15-80 parts by weight relative to 100 parts by weight of the polyphenyl ether resin. According to the invention, the polysiloxane-allyl compound is added into the polyphenyl ether resin composition, the obtained composition has a lower dielectric constant and a lower dielectric loss factor, and is excellent in heat resistance and moisture absorption performance, the application weakness that the composition is poor in bonding performance with a metal foil is solved, the interlayer bonding force of the copper-clad plate is improved, the combustion grade of UL94V-0 can be achieved under the condition that no flame retardant is additionally added, and the halogen-free phosphorus-free flame retardant effect is really achieved.

Description

Polysiloxane-allyl compound modified polyphenyl ether resin composition, and prepreg, laminated board and printed circuit board thereof
Technical Field
The invention belongs to the technical field of copper-clad plate materials, and relates to a polysiloxane-allyl compound modified polyphenyl ether resin composition, and a prepreg, a laminated board and a printed circuit board thereof.
Background
The polyphenylene oxide resin has excellent properties such as higher glass transition temperature, better dimensional stability, lower water absorption rate, smaller linear expansion coefficient, and particularly has very excellent low dielectric constant and low dielectric loss because a molecular structure contains a large amount of benzene ring structures and weakly polar groups. However, the resin is thermoplastic resin and has the defects of high melting point, difficult processing, poor solvent resistance and the like. Nevertheless, polyphenylene ethers still attract great attention and modification in terms of their excellent chemical properties, physical properties, electrical properties, and the like. For example, reactive groups are introduced at the ends or side ends of polyphenylene ether molecules, so that the polyphenylene ether molecules are converted into thermosetting resin. Current modifications have made increasing progress. Meanwhile, the modified resin still needs to be additionally added with a halogen-containing or phosphorus-containing flame retardant, and the cured resin can reach the combustion grade of UL 94V-0.
CN 102161823 discloses the preparation of high frequency circuit board using modified polyphenylene ether, modified polybutadiene or modified butadiene/styrene copolymer resin composition. Although the board has excellent comprehensive performance, the modified polybutadiene or the modified butadiene/styrene copolymer reduces the heat resistance and the interlayer adhesion of the board, and the modified polymer has a polar group, so that the substrate has the problems of increased water absorption and deteriorated dielectric property.
CN 102993683 discloses a method for copolymerizing an organosilicon compound containing unsaturated double bonds and a modified polyphenylene ether resin to prepare a thermosetting resin plate with excellent comprehensive properties such as heat resistance, dimensional stability, low water absorption, dielectric property and the like. However, when the organosilicon compound is used for crosslinking, the bonding capability of the plate and the copper foil is poor, and a flame retardant is required to be additionally added to achieve the combustion grade of UL 94V-0.
CN103709718A discloses a thermosetting resin composition comprising a thermosetting resin and a diallyl compound, wherein the diallyl compound can provide the thermosetting resin composition with excellent dielectric properties, high heat resistance and low water absorption, but the composition also needs to be added with a halogen-based and/or phosphorus-based flame retardant to achieve a desired flame retardant effect.
Therefore, in the field, a resin composition which has good flame retardancy without adding other flame retardant components and can improve the heat resistance stability, dielectric property, moisture absorption and adhesive property with a metal foil of a copper-clad plate is desired.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a polysiloxane-allyl compound modified polyphenyl ether resin composition, a prepreg thereof, a laminated board and a printed circuit board, wherein the composition has a lower dielectric constant and a lower dielectric loss factor, has excellent heat resistance and moisture absorption performance, simultaneously solves the application weakness of poor adhesion performance of the composition and a metal foil, can achieve the combustion grade of UL94V-0 under the conditions of no halogen and no phosphorus without adding a flame retardant, and really achieves the effects of no halogen and no phosphorus.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides a polysiloxane-allyl compound modified polyphenylene ether resin composition, the composition comprising a polyphenylene ether resin and a polysiloxane-allyl compound, the content of the polysiloxane-allyl compound in the composition being 15 to 80 parts by weight relative to 100 parts by weight of the polyphenylene ether resin, the polysiloxane-allyl compound having a structure represented by formula I:
Figure BDA0001196329650000021
Figure BDA0001196329650000031
wherein R is1And R2Independently is any one of substituted or unsubstituted C1-C4 linear alkyl, substituted or unsubstituted C1-C4 branched alkyl, substituted or unsubstituted C4-C10 naphthenic base or substituted or unsubstituted phenyl; r3Is substituted or unsubstituted C1-C4 linear alkyl, substituted or unsubstituted C1-C4 branched alkyl, substituted or unsubstituted C4-C10 cycloalkyl, substituted or unsubstituted phenyl or
Figure BDA0001196329650000032
Wherein R is any one of substituted or unsubstituted C1-C4 straight-chain alkyl, substituted or unsubstituted C1-C4 branched-chain alkyl, substituted or unsubstituted C4-C10 naphthenic base or substituted or unsubstituted phenyl, and m is an integer of 1-6; r4Is substituted or unsubstituted C1-C4 straight chain alkyl, substituted or unsubstituted C1-C4 branched chain alkyl, hydroxyl or
Figure BDA0001196329650000033
Any one of the above; r5Is any one of substituted or unsubstituted C1-C4 straight-chain alkyl, substituted or unsubstituted C1-C4 branched-chain alkyl, -O-or-S-; n is an integer of 4 to 50.
The content of the polysiloxane-allyl compound in the composition is 15 to 80 parts by weight, for example, 15 parts by weight, 18 parts by weight, 20 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, or 80 parts by weight, relative to 100 parts by weight of the polyphenylene ether resin.
In the present invention, since the polysiloxane-allyl compound is a halogen-free and phosphorus-free compound, the substituent of the group in the present invention does not contain a halogen and a phosphorus atom.
In the present invention, R1、R2、R3、R4Or R, the substituted or unsubstituted C1-C4 linear alkyl can be substituted or substituted C1, C2, C3 or C4 linear alkylAlkyl radicals, e.g. -CH3、-CH2CH3or-CH2CH2CH3Etc., preferably-CH3(ii) a The substituted or unsubstituted C1-C4 branched alkyl group can be a substituted or substituted C1, C2, C3, or C4 branched alkyl group, e.g.
Figure BDA0001196329650000034
The substituted or unsubstituted C4-C10 cycloalkyl group may be a substituted or unsubstituted C4, C5, C6, C7, C8, C9, or C10 cycloalkyl group, and may be, for example, a substituted or unsubstituted C4, C5, C7, C9, or C10 cycloalkyl group
Figure BDA0001196329650000041
Etc.; the substituted or unsubstituted phenyl group may be
Figure BDA0001196329650000042
And the like.
In the present invention, at R5The substituted or unsubstituted C1-C4 linear alkyl group can be a substituted or substituted C1, C2, C3 or C4 linear alkyl group, such as-CH2-、-CH2CH2-、-CH2CH2CH2-or-CH2CH2CH2CH2-; the substituted or unsubstituted C1-C4 branched alkyl group can be substituted or substituted C1, C2, C3 or C4 branched alkyl, and is preferably-C (CH)3)2-or-CH (CH)3)-。
Preferably, R1And R2Independently methyl or phenyl.
Preferably, R3Selected from methyl, phenyl or
Figure BDA0001196329650000043
Any one of them.
Preferably, R4Selected from methyl, hydroxy or
Figure BDA0001196329650000044
Any one of them.
Preferably, R5Is selected from-C (CH)3)2-、-CH(CH3)-、-CH2Any one of-O-or-S-.
In the present invention, m is an integer of 1 to 6, for example m may be 1, 2, 3, 4, 5 or 6.
In the present invention, n is an integer of 4 to 50, for example, n may be 4, 5, 6, 7, 8, 9, 10, 12, 15, 18, 20, 22, 24, 26, 28, 30, 33, 35, 38, 40, 42, 44, 46, 48 or 50.
Preferably, the polysiloxane-allyl compound is any one of or a combination of at least two of the compounds having the structure shown in the following formulas a-e:
Figure BDA0001196329650000045
Figure BDA0001196329650000051
wherein n is an integer from 4 to 50.
Preferably, the preparation method of the polysiloxane-allyl compound comprises the following steps: the diallyl compound shown in the formula II and hydrogenous polysiloxane shown in the formula III are subjected to hydrosilylation reaction to obtain polysiloxane-allyl compound shown in the formula I, wherein the reaction formula is as follows:
Figure BDA0001196329650000061
wherein R is1、R2、R3、R4And R5And n is as defined above.
Preferably, the diallyl compound represented by the formula II is selected from any one or a combination of at least two of diallyl bisphenol a diglycidyl ether, 2' -diallyl bisphenol a, 2' -diallyl bisphenol E, 2' -diallyl bisphenol F and 2,2' -diallyl bisphenol S, preferably diallyl bisphenol a diglycidyl ether, and more preferably 2,2' -diallyl bisphenol a diglycidyl ether.
Preferably, the hydrogenpolysiloxanes of formula III contain 0.05 to 0.46% by weight of hydrogen directly attached to silicon, for example 0.06%, 0.08%, 0.1%, 0.13%, 0.15%, 0.18%, 0.2%, 0.25%, 0.28%, 0.3%, 0.35%, 0.38%, 0.4%, 0.43% or 0.45%.
Preferably, the molar ratio of vinyl groups in the diallyl compound of formula II to silicon-hydrogen bonds in the hydrogenpolysiloxane of formula III is (2.4-2): 1, e.g. 2.4:1, 2.3:1, 2.2:1, 2.1:1 or 2: 1.
Preferably, the hydrosilylation reaction is carried out in the presence of a catalyst, the catalyst being a platinum-containing catalyst;
preferably, the platinum-containing catalyst is a Speier catalyst and/or a Karsted catalyst;
preferably, the platinum-containing catalyst is chloroplatinic acid (H)2PtCl6) And/or a platinum-containing catalyst represented by the following molecular structural formula:
Figure BDA0001196329650000071
the molecular formula of which can be expressed as Pt2[(CH2＝CHSiMe2)2O]3(abbreviated as Pt)2(dvs)3). In the formula described above, Pt forms a covalent bond with the double bond electrons on the siloxane to form the platinum-containing catalyst.
Preferably, the catalyst is used in an amount of 5 to 25ppm (ppm means parts per million, so that 5 to 25ppm may be written herein as 0.0005% to 0.0025%) based on the mass of the hydrogenpolysiloxane of formula III, for example 5ppm, 8ppm, 10ppm, 13ppm, 15ppm, 18ppm, 20ppm, 22ppm or 25 ppm.
Preferably, the hydrosilylation reaction is carried out in an organic solvent, which is any one or a combination of at least two of toluene, xylene, tetrahydrofuran, or DMF, preferably toluene.
Preferably, the temperature of the hydrosilylation reaction is 55-85 ℃, such as 56 ℃, 58 ℃, 60 ℃, 63 ℃, 65 ℃, 68 ℃, 70 ℃, 73 ℃, 75 ℃, 78 ℃, 80 ℃, 82 ℃ or 84 ℃.
Preferably, the hydrogenpolysiloxane of formula III in the hydrosilylation reaction is added dropwise to the reaction system containing the diallyl compound of formula II.
Preferably, the hydrosilylation reaction is carried out in the presence of a protective gas, preferably nitrogen.
Preferably, the hydrosilylation reaction is carried out with stirring.
Preferably, the reaction is stopped after the completion of the reaction of the hydrogenpolysiloxane of formula III.
The method for judging whether the hydrogenpolysiloxane shown in the formula III completely reacts or not in the invention comprises the following steps: and detecting a signal peak of Si-H in the reaction liquid by utilizing infrared spectroscopy, wherein if the signal peak disappears or is extremely weak, the hydrogenpolysiloxane shown in the formula III completely reacts, otherwise, the hydrogenpolysiloxane does not completely react, and the reaction needs to be continued.
Preferably, the polyphenylene ether resin is any one or a combination of at least two of modified polyphenylene ether resins having a structure represented by formula IV:
Figure BDA0001196329650000081
wherein X is selected from a vinyl-containing group; a is selected from
Figure BDA0001196329650000082
M is selected from the group consisting of a covalent bond, -CH2-、-C(CH3)2-、-CH(CH3)-、-O-、-SO2-, -S-or carbonyl; r11、R21、R31And R41Independently selected from any one of hydrogen, substituted or unsubstituted C1-C4 straight chain alkyl, substituted or unsubstituted C1-C4 branched chain alkyl or substituted or unsubstituted phenyl; r12、R22、R32And R42Independently selected from any one of substituted or unsubstituted C1-C4 linear alkyl, substituted or unsubstituted C1-C4 branched alkyl or substituted or unsubstituted phenyl; a and b are independently integers from 1 to 100.
Preferably, X is selected from
Figure BDA0001196329650000083
Any one of them.
In the present invention, at R11、R21、R31And R41The substituted or unsubstituted C1-C4 linear alkyl group may be a substituted or substituted C1, C2, C3 or C4 linear alkyl group, e.g., -CH2-、-CH2CH2-、-CH2CH2CH2-or-CH2CH2CH2CH2-; the substituted or unsubstituted C1-C4 branched alkyl group can be substituted or substituted C1, C2, C3 or C4 branched alkyl, and is preferably-C (CH)3)2-or-CH (CH)3) -; the substituted or unsubstituted phenyl group may be
Figure BDA0001196329650000091
And the like.
In the present invention, a and b may be independently 1, 3,5, 8, 10, 12, 15, 18, 20, 30, 40, 50, 60, 70, 80, 90 or 100, and specific integer values therebetween, which are not intended to be exhaustive or to be included in the range for brevity.
Preferably, the polysiloxane-allyl compound-modified polyphenylene ether resin composition of the present invention further comprises a curing accelerator.
Preferably, the curing accelerator is contained in the composition in an amount of 0.3 to 3 parts by weight, for example, 0.3 part by weight, 0.5 part by weight, 0.8 part by weight, 1 part by weight, 1.3 parts by weight, 1.5 parts by weight, 1.8 parts by weight, 2 parts by weight, 2.3 parts by weight, 2.5 parts by weight, 2.8 parts by weight or 3 parts by weight, relative to 100 parts by weight of the polyphenylene ether resin.
Preferably, the curing accelerator is a peroxide that initiates a free radical reaction;
preferably, the curing accelerator is di-tert-butyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, cumyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-3, 5, 5-trimethylhexanoate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, 1-di-tert-butyl peroxy-3, 5, 5-trimethylcyclohexane, 1-di-tert-butyl peroxycyclohexane, 2-di (tert-butyl peroxy) butane, bis (4-tert-butylcyclohexyl) peroxydicarbonate, hexadecyl peroxydicarbonate, tetradecyl peroxydicarbonate, dipentyl hexylperoxide, dicumyl peroxide, di-n-butyl peroxy-butyrate, di-tert-butyl peroxy-butyl peroxydicarbonate, any one or a mixture of at least two of bis (t-butylperoxyisopropyl) benzene, 2, 5-dimethyl-2, 5-di-t-butylperoxyhexane, 2, 5-dimethyl-2, 5-di-t-butylperoxyhexyne, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-amyl hydroperoxide, t-butyl cumyl peroxide, diisopropylbenzene hydroperoxide, tert-butyl peroxycarbonate-2-ethyl hexanoate, t-butyl peroxy2-ethylhexyl carbonate, n-butyl 4, 4-di (t-butylperoxy) valerate, methyl ethyl ketone peroxide or cyclohexane peroxide.
Preferably, the composition further comprises an inorganic filler.
Preferably, the content of the inorganic filler in the composition is 0 to 350 parts by weight excluding 0, for example, 1 part by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, 100 parts by weight, 130 parts by weight, 150 parts by weight, 180 parts by weight, 200 parts by weight, 250 parts by weight, 280 parts by weight, 300 parts by weight, or 350 parts by weight, with respect to 100 parts by weight of the polyphenylene ether resin.
Preferably, the inorganic filler is selected from any one or a mixture of at least two of crystalline silica, amorphous silica, spherical silica, fused silica, titanium dioxide, silicon carbide, glass fiber, alumina, aluminum nitride, boron nitride, barium titanate or strontium titanate.
In another aspect, the present invention provides a resin cement obtained by dissolving or dispersing the polysiloxane-allyl compound-modified polyphenylene ether resin composition of the present invention in a solvent.
Preferably, the solvent is one or a combination of at least two of ketones, hydrocarbons, ethers, esters or aprotic solvents, preferably one or a mixture of at least two of acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, methanol, ethanol, primary alcohols, ethylene glycol monomethyl ether, propylene glycol methyl ether acetate, ethyl acetate, N-dimethylformamide or N, N-diethylformamide. The solvents can be used alone or in combination. The addition amount of the solvent can be determined by those skilled in the art according to the viscosity of the selected resin, so that the viscosity of the resin glue solution is moderate, and the curing is convenient, and the invention is not limited to this.
In another aspect, the present invention provides a cover film prepared from the resin glue solution as described above.
In another aspect, the present invention provides a prepreg comprising a reinforcing material and attached thereto by impregnation drying a polysiloxane-allyl compound-modified polyphenylene ether resin composition as described above.
Preferably, the reinforcing material is used in an amount of 50 to 230 parts by weight, for example, 60 parts by weight, 80 parts by weight, 100 parts by weight, 120 parts by weight, 140 parts by weight, 160 parts by weight, 180 parts by weight, 200 parts by weight or 220 parts by weight, based on 100 parts by weight of the total polysiloxane-allyl compound-modified polyphenylene ether resin composition.
In the present invention, the reinforcing material is selected from carbon fibers, glass fiber cloth, aramid fibers or non-woven fabric, preferably glass fiber cloth.
In another aspect, the present invention provides an insulating panel comprising at least one sheet of prepreg as described above.
In another aspect, the present invention provides a laminate comprising at least one prepreg as described above.
In another aspect, the present invention provides a metal-clad laminate comprising one or at least two stacked prepregs as described above, and a metal foil on one or both sides of the stacked prepregs.
In another aspect, the present invention provides a printed circuit board comprising one or at least two superimposed prepregs as described above.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the polysiloxane-allyl compound is added into the polyphenyl ether resin composition, so that the obtained composition has a lower dielectric constant, a lower dielectric loss factor and excellent heat resistance and moisture absorption performance, the application weakness of poor bonding performance between the composition and a metal foil is solved, the interlayer bonding force of the copper-clad plate is improved, the UL94V-0 combustion grade can be achieved under the condition of not adding a flame retardant, and the effect of really halogen-free phosphorus-free flame retardation is achieved.
Drawings
FIG. 1 is a graph showing the results of IR spectroscopy characterization of a polysiloxane-allyl compound prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The materials used in the following examples and comparative examples are shown in table 1.
TABLE 1
Figure BDA0001196329650000121
Example 1
In this example, a polysiloxane-allyl compound of formula I was prepared from 2,2' -diallylbisphenol A and hydrogenpolysiloxane HWG17606 by hydrosilylation as follows:
completely dissolving diallyl bisphenol A and a catalyst chloroplatinic acid by using a proper amount of toluene, mixing, heating to 60 ℃ in advance, dropwise adding hydrogen-containing polysiloxane with a metered amount under stirring in a nitrogen atmosphere, continuously reacting until a signal peak (about 2145cm < -1 >) of an Si-H bond in an infrared spectrum of a reaction mixed solution disappears or is very weak and a signal peak (about 1635cm < -1 >) of allyl remains strong, stopping heating, and removing the solvent under reduced pressure to obtain the polysiloxane-allyl compound, wherein the structure of the polysiloxane-allyl compound is shown as a formula d.
The infrared spectrum of the polysiloxane-allyl compound obtained is characterized as shown in FIG. 1. from FIG. 1, it can be seen that the signal peak of Si-H bond (2146.03cm-1) is very weak, while the signal peak of allyl group (1632.38cm-1) is very strong.
And (3) dissolving MX9000 and the compound of the formula d prepared by using a proper amount of solvent, adding curing agent DCP and inorganic filler which are dissolved in advance, and fully dispersing to obtain the resin glue solution composition.
And (3) soaking the composition on glass fiber cloth, and heating for 2-20min in an oven at the temperature of 110-200 ℃ to prepare the prepreg. And (3) overlapping and combining a plurality of prepregs, covering copper foils on the upper surface and the lower surface of the prepregs, and then placing the prepregs into a vacuum hot press to press for 1.5 to 3 hours at the temperature of 170-210 ℃ and under the pressure of 1 to 2kg to obtain the laminated board or the copper-clad plate prepared from the composition. The mixture ratio of the composition and the performance of the laminated board or the copper-clad board prepared by the composition are shown in a table 2.
Example 2
In this example, a polysiloxane-allyl compound of formula I was prepared from 3,3 '-diallyl-4, 4' diphenol ether diglycidyl ether and hydrogenpolysiloxane HWG17606 by hydrosilylation as follows:
dissolving 3,3 '-diallyl-4, 4' -biphenol ether diglycidyl ether and 10ppm Karstd catalyst completely with appropriate amount of toluene, mixing, preheating to 70 deg.C, adding hydrogen-containing polysiloxane dropwise under stirring in nitrogen atmosphere, and reacting until the signal peak of Si-H bond (2145 cm) in infrared spectrum of the reaction mixture solution-1Nearby) disappeared or was very faint, while the allyl signal peak (1635 cm)-1Nearby), stopping heating, and removing the solvent under reduced pressure to obtain the polysiloxane-allyl compound with the structure shown in the formula a.
And (3) dissolving MX9000 and the compound of the formula a prepared by using a proper amount of solvent, adding curing agent DCP and inorganic filler which are dissolved in advance, and fully dispersing to obtain the resin glue solution composition.
And (3) soaking the composition on glass fiber cloth, and heating for 2-20min in an oven at the temperature of 110-200 ℃ to prepare the prepreg. And (3) overlapping and combining a plurality of prepregs, covering copper foils on the upper surface and the lower surface of the prepregs, and then placing the prepregs into a vacuum hot press to press for 1.5 to 3 hours at the temperature of 170-210 ℃ and under the pressure of 1 to 2kg to obtain the laminated board or the copper-clad plate prepared from the composition. The mixture ratio of the composition and the performance of the laminated board or the copper-clad board prepared by the composition are shown in a table 2.
Example 3
In this example, polysiloxane-allyl compounds of formula I were prepared from 1, 1-bis (3,3 '-diallyl-4, 4' xylene) methane and hydrogenpolysiloxane HWG17606 by hydrosilylation as follows:
completely dissolving 1, 1-bis (3,3 '-diallyl-4, 4' -xylene) methane and 10ppm Karstd catalyst by using a proper amount of toluene, mixing, heating to 85 ℃ in advance, dropwise adding a metered amount of hydrogenpolysiloxane under stirring in a nitrogen atmosphere, continuously reacting until a signal peak (around 2145cm < -1 >) of an Si-H bond in an infrared spectrum of a reaction mixed solution disappears or is very weak and an allyl signal peak (around 1635cm < -1 >) is still strong, stopping heating, and removing the solvent under reduced pressure to obtain the polysiloxane-allyl compound, wherein the structure of the polysiloxane-allyl compound is shown in a formula b.
And (3) dissolving MX9000 and the compound of the formula b prepared by using a proper amount of solvent, adding curing agent DCP and inorganic filler which are dissolved in advance, and fully dispersing to obtain the resin glue solution composition.
And (3) soaking the composition on glass fiber cloth, and heating for 2-20min in an oven at the temperature of 110-200 ℃ to prepare the prepreg. And (3) overlapping and combining a plurality of prepregs, covering copper foils on the upper surface and the lower surface of the prepregs, and then placing the prepregs into a vacuum hot press to press for 1.5 to 3 hours at the temperature of 170-210 ℃ and under the pressure of 1 to 2kg to obtain the laminated board or the copper-clad plate prepared from the composition. The mixture ratio of the composition and the performance of the laminated board or the copper-clad board prepared by the composition are shown in a table 2.
Examples 4 to 7
The composition differences of the compositions of the embodiments 4-5 and the embodiment 2 are that the types of the polyphenyl ether resin are different, and the compositions of other materials, the preparation of glue solution, the preparation of prepreg and the preparation method of the copper-clad plate are the same as those of the embodiment 2. The difference between the embodiment 6 and the embodiment 1 is that the type and the addition amount of the curing agent are different, and the preparation methods of other materials, glue solution preparation, prepreg preparation and copper-clad plate are the same as the embodiment 1. The difference between the embodiment 7 and the embodiment 1 is that the composition in the embodiment 7 is not added with inorganic filler, and the preparation methods of other materials, glue solution preparation, prepreg preparation and copper-clad plate are the same as the embodiment 1. The mixture ratio of the composition and the performance of the laminated board or the copper-clad board prepared by the composition are shown in a table 2.
Comparative examples 1 to 2
The specific preparation method of comparative examples 1-2 was the same as that of example 1, except that the ratio of the polysiloxane-allyl compound in the polyphenylene ether resin composition was different from that of the corresponding examples. The mixture ratio of the composition and the performance of the laminated board or the copper-clad board prepared by the composition are shown in a table 2.
Comparative example 3
In this example, a resin composition was obtained by dispersing 3,3 '-diallyl-4, 4' -biphenol ether diglycidyl ether, polyphenylene ether, and the like in a suitable amount of a methyl ethyl ketone/toluene mixed solvent without adding hydrogen-containing polysiloxane, and adding a previously dissolved curing accelerator and an inorganic filler.
The composition is impregnated on glass fiber cloth and heated for 2-20min in an oven at the temperature of 110-200 ℃ to prepare the prepreg. A plurality of prepregs are overlapped and coated with copper foils on the upper surface and the lower surface, and then the prepregs are put into a vacuum hot press and pressed for 1.5 to 3 hours at the temperature of 170-210 ℃ and under the pressure of 1 to 2kg, so as to obtain the laminated board or the copper-clad plate prepared by the composition. The mixture ratio of the composition and the performance of the laminated board or the copper-clad board prepared by the composition are shown in a table 2.
Comparative example 4
A resin composition was obtained by dispersing a hydrogen-containing polysiloxane, an allyl compound, a platinum-containing catalyst, a polyphenylene ether resin, etc. in a suitable amount of a methyl ethyl ketone/toluene mixed solvent, and adding a previously dissolved curing accelerator and an inorganic filler in the respective material ratios of example 1.
The composition is impregnated on glass fiber cloth and heated for 2-20min in an oven at the temperature of 110-200 ℃ to prepare the prepreg. A plurality of prepregs are overlapped and coated with copper foils on the upper surface and the lower surface, and then the prepregs are put into a vacuum hot press and pressed for 1.5 to 3 hours at the temperature of 170-210 ℃ and under the pressure of 1 to 2kg, so as to obtain the laminated board or the copper-clad plate prepared by the composition. The mixture ratio of the composition and the performance of the laminated board or the copper-clad board prepared by the composition are shown in a table 2.
TABLE 2
Figure BDA0001196329650000161
The above performance test method is as follows:
peel Strength (PS): IPC-TM-6502.4.8 was used for the test
Combustibility: UL94 vertical burn test
Dielectric constant and dielectric loss tangent: IPC-TM-650SPDR method
As can be seen from the performance characterization result data in Table 2, the copper-clad plate prepared under the halogen-free and phosphorus-free conditions has excellent flame retardant property which can reach UL94V-0 grade and the peel strength of 0.83N-cm by adding the polysiloxane-allyl compound into the composition-1The dielectric constant can be less than 3.79, the dielectric loss tangent can be less than 0.008, and the composite material has good dielectric property and adhesive property. When the polysiloxane-allyl compound is not used and is changed into diallyl bisphenol A diglycidyl ether (comparative example 3), the flame retardance of the copper clad laminate can only reach UL94V-2 grade; when the amount of the polysiloxane-allyl compound used is too small relative to 100 parts by weight of the polyphenylene ether resin (comparative example 1), the copper clad laminate has flame retardancy only up to UL94V-1 rating, and when the amount of the polysiloxane-allyl compound used is too large relative to 100 parts by weight of the polyphenylene ether resin (comparative example 2), the copper clad laminate has flame retardancy up to UL94V-0 rating, but the copper clad laminate has peeling propertyThe strength is only 0.46N cm-1The normal use of the copper-clad plate is influenced; when the raw materials are physically blended without hydrosilylation (comparative example 4), the burning grade is V-2, the dielectric property is relatively worst, and the peeling strength is very low due to the existence of the single polysiloxane component, so that the application of the raw materials on a copper-clad plate is not facilitated.
The applicant states that the above embodiments are only preferred embodiments of the present invention, and the present invention is not limited to the above embodiments, i.e. it does not mean that the present invention must rely on the above embodiments to be implemented. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.

Claims (39)

1. A polysiloxane-allyl compound modified polyphenylene ether resin composition for preparing a copper clad laminate with a dielectric constant of 3.79 or less, which comprises a polyphenylene ether resin and a polysiloxane-allyl compound, wherein the content of the polysiloxane-allyl compound in the composition is 15-80 parts by weight relative to 100 parts by weight of the polyphenylene ether resin, and the polysiloxane-allyl compound has a structure shown in a formula I:
Figure DEST_PATH_IMAGE002
formula I;
wherein R is1And R2Independently is any one of substituted or unsubstituted C1-C4 linear alkyl, substituted or unsubstituted C1-C4 branched alkyl, substituted or unsubstituted C4-C10 naphthenic base or substituted or unsubstituted phenyl; r3Is substituted or unsubstituted C1-C4 linear alkyl, substituted or unsubstituted C1-C4 branched alkyl, substituted or unsubstituted C4-C10 cycloalkyl, substituted or unsubstituted phenyl or
Figure DEST_PATH_IMAGE004
Wherein R is any one of substituted or unsubstituted C1-C4 straight-chain alkyl, substituted or unsubstituted C1-C4 branched-chain alkyl, substituted or unsubstituted C4-C10 naphthenic base or substituted or unsubstituted phenyl, and m is an integer of 1-6; r4Is substituted or unsubstituted C1-C4 straight chain alkyl, substituted or unsubstituted C1-C4 branched chain alkyl, hydroxyl or
Figure DEST_PATH_IMAGE006
Any one of the above; r5Is any one of substituted or unsubstituted C1-C4 straight-chain alkyl, substituted or unsubstituted C1-C4 branched-chain alkyl, -O-or-S-; n is an integer of 12 to 50;
the polyphenylene ether resin is any one or combination of at least two of modified polyphenylene ether resins with a structure shown in a formula IV:
Figure DEST_PATH_IMAGE008
formula IV
Wherein X is selected from a vinyl-containing group; a is selected from
Figure DEST_PATH_IMAGE010
M is selected from the group consisting of a covalent bond, -CH2-、-C(CH3)2-、-CH(CH3)-、-O-、-SO2-, -S-or carbonyl; r11、R21、R31And R41Independently selected from any one of hydrogen, substituted or unsubstituted C1-C4 straight chain alkyl, substituted or unsubstituted C1-C4 branched chain alkyl or substituted or unsubstituted phenyl; r12、R22、R32And R42Independently selected from any one of substituted or unsubstituted C1-C4 linear alkyl, substituted or unsubstituted C1-C4 branched alkyl or substituted or unsubstituted phenyl; a and b are independently integers from 1 to 100.
2. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 1,characterized in that R is1And R2Independently methyl or phenyl.
3. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 1, wherein R is R3Selected from methyl, phenyl or
Figure DEST_PATH_IMAGE012
Any one of them.
4. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 1, wherein R is R4Selected from methyl, hydroxy or
Figure DEST_PATH_IMAGE013
Any one of them.
5. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 1, wherein R is R5Is selected from-C (CH)3)2-、-CH(CH3)-、-CH2Any one of-O-or-S-.
6. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 1, wherein the polysiloxane-allyl compound is any one of compounds having a structure represented by the following formulae a to e or a combination of at least two of them:
Figure DEST_PATH_IMAGE015
formula a;
Figure DEST_PATH_IMAGE017
formula b;
Figure DEST_PATH_IMAGE019
formula c;
Figure DEST_PATH_IMAGE021
formula d;
Figure DEST_PATH_IMAGE023
formula e;
wherein n is an integer from 12 to 50.
7. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 1, wherein the polysiloxane-allyl compound is prepared by: the diallyl compound shown in the formula II and hydrogenous polysiloxane shown in the formula III are subjected to hydrosilylation reaction to obtain polysiloxane-allyl compound shown in the formula I, wherein the reaction formula is as follows:
Figure DEST_PATH_IMAGE025
，
wherein n is an integer of 12 to 50.
8. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 7, wherein the diallyl compound represented by formula II is selected from any one or a combination of at least two of diallyl bisphenol A diglycidyl ether, 2 '-diallyl bisphenol A, 2' -diallyl bisphenol E, 2 '-diallyl bisphenol F, and 2,2' -diallyl bisphenol S.
9. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 7, wherein the diallyl compound represented by formula II is selected from diallyl bisphenol A diglycidyl ether.
10. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 7, wherein the diallyl compound represented by formula II is selected from 2,2' -diallyl bisphenol A diglycidyl ether.
11. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 7, wherein the hydrogenpolysiloxane represented by the formula III has a content of hydrogen directly bonded to silicon of 0.05 to 0.46% by weight.
12. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 7, wherein the molar ratio of vinyl groups in the diallyl compound represented by formula II to silicon-hydrogen bonds in the hydrogenpolysiloxane represented by formula III is (2.4-2): 1.
13. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 7, wherein the hydrosilylation reaction is carried out in the presence of a catalyst, and the catalyst is a platinum-containing catalyst.
14. The polysiloxane-allyl compound-modified polyphenylene ether resin composition of claim 13, wherein the platinum-containing catalyst is a Speier catalyst and/or a Karsted catalyst.
15. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 13, wherein the platinum-containing catalyst is chloroplatinic acid and/or a platinum-containing catalyst represented by the following molecular structural formula:
Figure DEST_PATH_IMAGE027
。
16. the polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 13, wherein the catalyst is used in an amount of 5 to 25ppm based on the mass of the hydrogenpolysiloxane represented by formula III.
17. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 13, wherein the hydrosilylation reaction is carried out in an organic solvent which is any one of toluene, xylene, tetrahydrofuran or DMF or a combination of at least two thereof.
18. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 17, wherein the organic solvent is toluene.
19. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 7, wherein the temperature of the hydrosilylation reaction is 55 to 85 ℃.
20. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 7, wherein the hydrogenpolysiloxane of formula III in the hydrosilylation reaction is added dropwise to the reaction system containing the diallyl compound of formula II.
21. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 7, wherein the hydrosilylation reaction is carried out in the presence of a protective gas.
22. The polysiloxane-allyl compound-modified polyphenylene ether resin composition of claim 21, wherein the protective gas is nitrogen.
23. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 7, wherein the hydrosilylation reaction is performed with stirring.
24. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 7, wherein the reaction is stopped after the completion of the reaction of the hydrogenpolysiloxane represented by formula III.
25. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 1, wherein X is selected from the group consisting of
Figure DEST_PATH_IMAGE029
、
Figure DEST_PATH_IMAGE031
、
Figure DEST_PATH_IMAGE033
Or
Figure DEST_PATH_IMAGE035
Any one of them.
26. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 1, wherein the polysiloxane-allyl compound-modified polyphenylene ether resin composition further comprises a curing accelerator.
27. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 26, wherein the content of the curing accelerator in the composition is 0.3 to 3 parts by weight relative to 100 parts by weight of the polyphenylene ether resin.
28. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 26, wherein the curing accelerator is a peroxide that initiates a radical reaction.
29. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 26, wherein the curing accelerator is di-t-butyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, cumyl peroxyneodecanoate, t-butyl peroxyneodecanoate, pivaloyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxy-3, 5, 5-trimethylhexanoate, t-butyl peroxyacetate, t-butyl peroxybenzoate, 1-di-t-butyl peroxy-3, 5, 5-trimethylcyclohexane, 1-di-t-butyl peroxycyclohexane, 2-di (t-butylperoxy) butane, bis (4-t-butylcyclohexyl) peroxydicarbonate, bis (t-butylperoxy) peroxydicarbonate, and the like, Dicetyl peroxydicarbonate, tetradecyl peroxydicarbonate, ditert-amyl-hexyl peroxide, dicumyl peroxide, bis (t-butylperoxyisopropyl) benzene, 2, 5-dimethyl-2, 5-di-t-butylperoxyhexane, 2, 5-dimethyl-2, 5-di-t-butylperoxyhexyne, cumene hydroperoxide, tert-amyl hydroperoxide, tert-butyl cumyl peroxide, tert-butyl peroxycarbonate-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexyl carbonate, n-butyl 4, 4-di (t-butylperoxy) valerate, methyl ethyl ketone peroxide or cyclohexane peroxide, or a mixture of at least two thereof.
30. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 1, wherein the composition further comprises an inorganic filler.
31. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 30, wherein the content of the inorganic filler in the composition is 0 to 350 parts by weight excluding 0, relative to 100 parts by weight of the polyphenylene ether resin.
32. The polysiloxane-allyl compound-modified polyphenylene ether resin composition according to claim 30, wherein the inorganic filler is selected from any one or a mixture of at least two of crystalline silica, amorphous silica, spherical silica, fused silica, titanium dioxide, silicon carbide, glass fiber, alumina, aluminum nitride, boron nitride, barium titanate or strontium titanate.
33. A resin cement obtained by dissolving or dispersing the polysiloxane-allyl compound-modified polyphenylene ether resin composition according to any one of claims 1 to 32 in a solvent.
34. A cover film prepared from the resin dope according to claim 33.
35. A prepreg comprising a reinforcing material and attached thereto by impregnation drying the polysiloxane-allyl compound-modified polyphenylene ether resin composition according to any one of claims 1 to 32.
36. An insulating board comprising at least one sheet of prepreg according to claim 35.
37. A laminate comprising at least one prepreg according to claim 35.
38. A metal-clad laminate comprising one or at least two stacked prepregs according to claim 35, and a metal foil on one or both sides of the stacked prepregs.
39. A printed circuit board comprising one or at least two superimposed prepregs according to claim 35.
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