CN108250716A - Polyphenyl ether resin composition and its prepreg, the laminate and printed circuit board of a kind of polysiloxanes-allyl compound modification - Google Patents
Polyphenyl ether resin composition and its prepreg, the laminate and printed circuit board of a kind of polysiloxanes-allyl compound modification Download PDFInfo
- Publication number
- CN108250716A CN108250716A CN201611241815.4A CN201611241815A CN108250716A CN 108250716 A CN108250716 A CN 108250716A CN 201611241815 A CN201611241815 A CN 201611241815A CN 108250716 A CN108250716 A CN 108250716A
- Authority
- CN
- China
- Prior art keywords
- substituted
- unsubstituted
- polysiloxanes
- allyl compound
- tert
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
- B32B17/061—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 of metal
-
- 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
-
- 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
- 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
-
- 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
- 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
- B32B5/22—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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes 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
-
- 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
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
- B32B2260/021—Fibrous or filamentary layer
-
- 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
- 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
- B32B2260/021—Fibrous or filamentary layer
- B32B2260/023—Two or more layers
-
- 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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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 present invention provides polyphenyl ether resin composition and its prepreg, the laminate and printed circuit board that a kind of polysiloxanes allyl compound is modified, the polyphenyl ether resin composition that the polysiloxanes allyl compound is modified includes polyphenylene oxide resin and the polysiloxanes allyl compound with structure shown in Formulas I, relative to 100 parts by weight of polyphenyleneoxide resins, the content of polysiloxanes allyl compound is 15 80 parts by weight in the composition.The present invention adds in polysiloxanes allyl compound in polyphenyl ether resin composition, obtained composition has relatively low dielectric constant and relatively low dielectric loss factor, heat resistance and moisture pick-up properties are excellent, solves the application weakness of composition and metal foil bond properties difference simultaneously, improve the interlayer adhesion of copper-clad plate, the burning grade of UL94V 0 can also be reached under conditions of without in addition addition fire retardant, be truly realized the effect of halogen-free phosphorus-free inflaming retarding.
Description
Technical field
The invention belongs to copper-clad plate field of material technology, are related to the polyphenyl that a kind of polysiloxanes-allyl compound is modified
Ether resin composition and its prepreg, laminate and printed circuit board.
Background technology
Group of the polyphenylene oxide resin due to containing a large amount of benzene ring structure and low pole in molecular structure, thus with excellent
Performance, such as higher glass transition temperature, preferable dimensional stability, relatively low water absorption rate, smaller linear expansion
Coefficient especially has very outstanding low-k and low-dielectric loss.But the resinoid is thermoplastic resin, there are molten
The shortcomings of point is high, processing difficulties, solvent resistant energy force difference.Even so, the outstanding chemical property of polyphenylene oxide, physical property, electrically
It can wait and still attract greatly concern and be modified.Reactive group such as is introduced in polyphenylene oxide molecular chain-end or side, makes it
Converted into thermoset resin.Current modification has been achieved for the progress increased.In addition resin modified simultaneously still needs
Containing halogen or phosphorous fire retardant, resin cured matter can be only achieved the burning grade of UL94V-0 for addition.
It is disclosed in CN 102161823 using Noryl, the polybutadiene of modification or the butadiene of modification/benzene second
Alkene copolymer resin combination is prepared for high-frequency circuit board.Although the comprehensive performance of the plank is outstanding, modified polybutadiene
Alkene or the butadiene/styrene copolymers of modification reduce the heat resistance and interlayer adhesion of plank, and modified poly
With polar group on object, substrate is caused to there are problems that water absorption rate increase, dielectric properties deteriorate.
It is disclosed in CN 102993683 and uses organo-silicon compound and modified polyphenylene ether resin containing unsaturated double-bond
The method of copolymerization is prepared for the very excellent heat of the comprehensive performances such as heat resistance, dimensional stability, low water absorption and dielectric properties
Thermosetting resin plank.But it is crosslinked using organo-silicon compound, the adhesive force of the plank and copper foil is poor, while needs in addition to add
Enter the burning grade that fire retardant can be only achieved UL94V-0.
CN103709718A discloses a kind of compositions of thermosetting resin, which includes thermosetting property tree
Fat and diallyl compound, although the diallyl compound can assign compositions of thermosetting resin excellent dielectricity
Energy, high-fire resistance, low water absorbable, but in the composition also need addition halogen system and/or phosphorus flame retardant can be only achieved
Ideal flame retardant effect.
Therefore, in this field, it is expected to obtain one kind under the premise of other flame retardant constituents are not added both with good resistance
Combustion property, and copper-clad plate heat-resistant stability, dielectricity, hygroscopicity and the resin combination with the adhesive property of metal foil can be improved
Object.
Invention content
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of polysiloxanes-allyl compounds to be modified
Polyphenyl ether resin composition and its prepreg, laminate and printed circuit board, the composition have relatively low dielectric constant and
Relatively low dielectric loss factor, heat resistance and moisture pick-up properties are excellent, while solve composition and metal foil bond properties is poor
Application weakness, in the case where in addition not adding fire retardant, can Halogen, it is without phosphorus under the conditions of reach the burning of UL94V-0
Grade is really achieved the effect of halogen-free phosphorus-free inflaming retarding.
For this purpose, the present invention uses following technical scheme:
On the one hand, the present invention provides the polyphenyl ether resin composition that a kind of polysiloxanes-allyl compound is modified, described
Composition includes polyphenylene oxide resin and polysiloxanes-allyl compound, relative to 100 parts by weight of polyphenyleneoxide resins, described group
The content for closing polysiloxanes-allyl compound in object is 15-80 parts by weight, and the polysiloxanes-allyl compound has
Structure shown in Formulas I:
Wherein, R1And R2It independently is substituted or unsubstituted C1-C4 straight chained alkyls, substituted or unsubstituted C1-C4 branches
Any one in alkyl, substituted or unsubstituted C4-C10 cycloalkyl or substituted or unsubstituted phenyl;R3For substitution or
Unsubstituted C1-C4 straight chained alkyls, substituted or unsubstituted C1-C4 branched alkyls, substituted or unsubstituted C4-C10 cycloalkyl,
Substituted or unsubstituted phenyl orIn any one, wherein R be substituted or unsubstituted C1-C4 straight chains alkane
Base, substituted or unsubstituted C1-C4 branched alkyls, substituted or unsubstituted C4-C10 cycloalkyl or substituted or unsubstituted benzene
Any one in base, m are the integer of 1-6;R4For substituted or unsubstituted C1-C4 straight chained alkyls, substituted or unsubstituted C1-
C4 branched alkyls, hydroxyl orIn any one;R5For substituted or unsubstituted C1-C4 straight chained alkyls, substitution or not
Any one in substituted C1-C4 branched alkyls ,-O- or-S-;N is the integer of 4-50.
Relative to 100 parts by weight of polyphenyleneoxide resins, the content of polysiloxanes-allyl compound is in the composition
15-80 parts by weight, such as 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 weight
Part, 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.
In the present invention, since the polysiloxanes-allyl compound is non-halogen non-phosphate compound, in the present invention
Described in group substituent group in do not contain halogen and phosphorus atoms.
In the present invention, R1、R2、R3、R4Or in the restriction of R, the substituted or unsubstituted C1-C4 straight chained alkyls can be with
To replace or being C1, C2, C3 or C4 straight chained alkyl of substitution, such as-CH3、-CH2CH3Or-CH2CH2CH3Deng preferably-CH3;Institute
Stating substituted or unsubstituted C1-C4 branched alkyls can be to replace or be C1, C2, C3 or C4 branched alkyl of substitution, such asThe substituted or unsubstituted C4-C10 cycloalkyl can be substituted or unsubstituted C4, C5, C6, C7, C8,
C9 or C10 cycloalkyl, such as can beDeng;The substituted or unsubstituted phenyl
Can beDeng.
In the present invention, in R5Restriction in, the substituted or unsubstituted C1-C4 straight chained alkyls can with for substitution or
For substituted C1, C2, C3 or C4 straight chained alkyl, such as-CH2-、-CH2CH2-、-CH2CH2CH2Or-CH2CH2CH2CH2-;It is described
Substituted or unsubstituted C1-C4 branched alkyls can be substitution or be substitution C1, C2, C3 or C4 branched alkyl, preferably-C
(CH3)2Or-CH (CH3)-。
Preferably, R1And R2It independently is methyl or phenyl.
Preferably, R3Selected from methyl, phenyl orIn any one.
Preferably, R4Selected from methyl, hydroxyl orIn any one.
Preferably, R5Selected from-C (CH3)2-、-CH(CH3)-、-CH2, any one in-O- or-S-.
In the present invention, m is the integer of 1-6, such as m can be 1,2,3,4,5 or 6.
In the present invention, n be 4-50 integer, such as n can be 4,5,6,7,8,9,10,12,15,18,20,22,24,
26th, 28,30,33,35,38,40,42,44,46,48 or 50.
Preferably, the polysiloxanes-allyl compound is with appointing in the compound of structure as shown in following formula a-e
It anticipates a kind of or at least two combinations:
Wherein n is the integer of 4-50.
Preferably, the preparation method of polysiloxanes-allyl compound of the present invention is:Diallyl shown in Formula II
Compound occurs hydrosilylation with hydrogen containing siloxane shown in formula III and obtains polysiloxanes shown in Formulas I-pi-allyl chemical combination
Object, reaction equation are as follows:
Wherein R1、R2、R3、R4And R5And the restriction of n is as described above.
Preferably, diallyl compound shown in Formula II is selected from diallyl bisphenol diglycidyl ether, 2,2'- diene
It is any one in propyl bisphenol-A, 2,2'- diallyl bis-phenol E, 2,2'- diallyl Bisphenol Fs or 2,2'- diallyl bisphenol Ss
Kind or at least two combination, preferably diallyl bisphenol diglycidyl ether, further preferred 2,2'- diallyl bisphenols
Diglycidyl ether.
Preferably, the weight percentage for the hydrogen being connected directly in hydrogen containing siloxane shown in formula III with silicon is 0.05-
0.46%, for example, 0.06%, 0.08%, 0.1%, 0.13%, 0.15%, 0.18%, 0.2%, 0.25%, 0.28%,
0.3%th, 0.35%, 0.38%, 0.4%, 0.43% or 0.45%.
Preferably, diallyl compound medium vinyl shown in Formula II and si-h bond in hydrogen containing siloxane shown in formula III
Molar ratio be (2.4-2):1, such as 2.4:1、2.3:1、2.2:1、2.1:1 or 2:1.
Preferably, the hydrosilylation carries out in the presence of a catalyst, and the catalyst is catalyst made from platonic;
Preferably, the catalyst made from platonic is Speier catalyst and/or Karsted catalyst;
Preferably, the catalyst made from platonic is chloroplatinic acid (H2PtCl6) and/or the platiniferous shown in molecular structural formula is urged as follows
Agent:Its molecular formula is represented by Pt2[(CH2=
CHSiMe2)2O]3(write a Chinese character in simplified form into Pt2(dvs)3).Pt is electronically formed covalently with the double bond on siloxanes in structural formula as described above
With reference to forming the catalyst made from platonic.
Preferably, the dosage of the catalyst is the 5-25ppm of hydrogen containing siloxane quality shown in formula III, and (ppm is represented
Hundred a ten thousandths, therefore 5-25ppm can also write 0.0005%-0.0025% herein), for example, 5ppm, 8ppm, 10ppm,
13ppm, 15ppm, 18ppm, 20ppm, 22ppm or 25ppm.
Preferably, the hydrosilylation carries out in organic solvent, and the organic solvent is toluene, dimethylbenzene, four
In hydrogen furans or DMF any one or at least two combination, preferred toluene.
Preferably, the temperature of the hydrosilylation be 55-85 DEG C, such as 56 DEG C, 58 DEG C, 60 DEG C, 63 DEG C, 65 DEG C,
68 DEG C, 70 DEG C, 73 DEG C, 75 DEG C, 78 DEG C, 80 DEG C, 82 DEG C or 84 DEG C.
Preferably, hydrogen containing siloxane shown in formula III is added in a manner of being added dropwise dropwise in the hydrosilylation
Into the reaction system containing diallyl compound shown in Formula II.
Preferably, the hydrosilylation carries out in the presence of protective gas, the preferred nitrogen of protective gas.
Preferably, the hydrosilylation carries out under stiring.
Preferably, after the reaction was complete after hydrogen containing siloxane shown in formula III, stop reaction.
Judge that the method whether the reaction was complete of hydrogen containing siloxane shown in formula III is in the present invention:Utilize infrared spectrum
The signal peak of Si-H in reaction solution is detected, if signal peak disappearance or extremely faint, hydrogen containing siloxane is anti-shown in formula III
Should be complete, otherwise unreacted is complete, needs to continue to react.
Preferably, the polyphenylene oxide resin for any one in the modified polyphenylene ether resin with structure shown in formula IV or
At least two combination:
Wherein, X is selected from the group containing vinyl;A is selected fromM be selected from covalent bond ,-
CH2-、-C(CH3)2-、-CH(CH3)-、-O-、-SO2,-S- or carbonyl;R11、R21、R31And R41Independently selected from hydrogen, substitution or
It is arbitrary in unsubstituted C1-C4 straight chained alkyls, substituted or unsubstituted C1-C4 branched alkyls or substituted or unsubstituted phenyl
It is a kind of;R12、R22、R32And R42Independently selected from substituted or unsubstituted C1-C4 straight chained alkyls, substituted or unsubstituted C1-C4 branch
Any one in alkyl group or substituted or unsubstituted phenyl;A and b independently is the integer of 1-100.
Preferably, X is selected from
In any one.
In the present invention, in R11、R21、R31And R41Restriction in, the substituted or unsubstituted C1-C4 straight chained alkyls can
Think substitution or C1, C2, C3 or C4 straight chained alkyl for substitution, such as-CH2-、-CH2CH2-、-CH2CH2CH2Or-
CH2CH2CH2CH2-;The substituted or unsubstituted C1-C4 branched alkyls can be substitution or be C1, C2, C3 or the C4 replaced
Branched alkyl, preferably-C (CH3)2Or-CH (CH3)-;The substituted or unsubstituted phenyl can beDeng.
In the present invention, a and b can independently be 1,3,5,8,10,12,15,18,20,30,40,50,60,70,80,90
Or the specific integer value between 100 and above-mentioned numerical value, as space is limited and for it is concise the considerations of, the present invention no longer limit arrange
Lift the specific point value that the range includes.
Preferably, the polyphenyl ether resin composition that polysiloxanes of the present invention-allyl compound is modified further includes solid
Change accelerating agent.
Preferably, relative to 100 parts by weight of polyphenyleneoxide resins, the content of curing accelerator is 0.3-3 in the composition
Parts by weight, such as 0.3 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 parts by weight, 1.3 parts by weight, 1.5 parts by weight, 1.8 weight
Part, 2 parts by weight, 2.3 parts by weight, 2.5 parts by weight, 2.8 parts by weight or 3 parts by weight.
Preferably, the curing accelerator is the peroxide for causing radical reaction;
Preferably, the curing accelerator is di-tert-butyl peroxide, dilauroyl peroxide, diphenyl peroxide first
Acyl, cumyl peroxyneodecanoate, new peroxide tert-butyl caprate, peroxidating pivalic acid spy pentyl ester, peroxidating pivalic acid uncle
Butyl ester, tert-butyl hydroperoxide isobutyrate, tert-butyl hydroperoxide -3,5,5 Trimethylhexanoic acid ester, peroxide acetic acid butyl ester, mistake
Aoxidize t-butyl perbenzoate, 1,1- di-tert-butyl peroxide -3,5,5- trimethyl-cyclohexanes, 1,1- di-tert-butyl peroxide hexamethylenes
Alkane, 2,2- bis- (tert-butyl hydroperoxide) butane, bis- (4- tert-butylcyclohexyls) peroxy dicarbonates, peroxy dicarbonate ten
Six esters, 14 ester of peroxy dicarbonate, two special penta own peroxide, dicumyl peroxide, bis- (tert-butyl hydroperoxide is different
Propyl) benzene, 2,5- dimethyl -2,5- di-t-butyl hexane peroxides, 2,5- dimethyl -2,5- di-tert-butyl peroxides hexin,
Diisopropylbenzene hydroperoxide, isopropyl benzene hydroperoxide, tertiary amyl hydrogen peroxide, tert-butyl hydroperoxide, tert-butyl hydroperoxide are different
Propyl benzene, diisopropylbenzene hydroperoxide, peroxycarbonates -2 ethyl hexanoic acid tert-butyl ester, tert-butyl hydroperoxide carbonic acid -2- ethyl hexyls
In ester, 4,4- bis- (tert-butyl hydroperoxide) n-butyl pentanoate, methyl ethyl ketone peroxide or cyclohexane peroxide any one or extremely
Mixture two kinds few.
Preferably, the composition further includes inorganic filler.
Preferably, relative to 100 parts by weight of polyphenyleneoxide resins, the content of inorganic filler is 0-350 weights in the composition
It measures part and does not include 0, such as 1 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 weight
Part, 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 weight
Part, 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.
Preferably, the inorganic filler is selected from powdered quartz, amorphous silica, preparing spherical SiO 2, melts
Melt appointing in silica, titanium dioxide, silicon carbide, glass fibre, aluminium oxide, aluminium nitride, boron nitride, barium titanate or strontium titanates
It anticipates a kind of or at least two mixtures.
On the other hand, the present invention provides a kind of resin adhesive liquid, the resin adhesive liquid be by polysiloxanes of the present invention-
The polyphenyl ether resin composition that allyl compound is modified, which is dissolved or dispersed in solvent, to be obtained.
Preferably, the solvent is one kind or at least two in ketone, hydro carbons, ethers, esters or aprotic solvent
Combination, preferably acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), toluene, dimethylbenzene, methanol, ethyl alcohol, primary alconol, ethylene glycol list first
Ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, ethyl acetate, N,N-dimethylformamide or N, N- diethylformamide
In it is a kind of or at least two mixture.The solvent can be used alone, and can also be used in mixed way.The additive amount of solvent can be by
Those skilled in the art determine according to the viscosity of selected resin, so as to get the modest viscosity of resin adhesive liquid, convenient for curing, this
Invention is not construed as limiting this.
On the other hand, the present invention provides a kind of cover film, and the cover film is prepared by resin adhesive liquid as described above.
On the other hand, the present invention provides a kind of prepreg, and the prepreg includes reinforcing material and by being impregnated with drying
Adhere to the polyphenyl ether resin composition that polysiloxanes as described above-allyl compound thereon is modified afterwards.
Preferably, the total weight for the polyphenyl ether resin composition being modified using the polysiloxanes-allyl compound is 100
Parts by weight meter, the dosage of reinforcing material is 50~230 parts by weight in the prepreg, such as 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.
In the present invention, the reinforcing material is selected from carbon fiber, glass fabric, aramid fibre or non-woven fabrics,
Preferably glass fabric.
On the other hand, the present invention provides a kind of insulation board, and the insulation board includes an at least prepreg as described above.
On the other hand, the present invention provides a kind of laminate, and the laminate includes an at least prepreg as described above.
On the other hand, the present invention provides a kind of metal-clad laminate, and the metal-clad laminate is including one or extremely
The prepreg as described above of few two overlappings and the metal foil of the one or both sides of the prepreg after overlapping.
On the other hand, the present invention provides a kind of printed circuit board, and the printed circuit board includes one or at least two and folds
The prepreg as described above closed.
Relative to the prior art, the invention has the advantages that:
The present invention adds in polysiloxanes-allyl compound in polyphenyl ether resin composition, and obtained composition has
Relatively low dielectric constant and relatively low dielectric loss factor, heat resistance and moisture pick-up properties are excellent, at the same solve composition with
The application weakness of metal foil bond properties difference improves the interlayer adhesion of copper-clad plate, in the condition without in addition adding fire retardant
Under can also reach the burning grade of UL 94V-0, be truly realized the effect of halogen-free phosphorus-free inflaming retarding.
Description of the drawings
Fig. 1 is the infrared spectrum characterization result of polysiloxanes-allyl compound that the embodiment of the present invention 1 is prepared
Figure.
Specific embodiment
The technical solution further illustrated the present invention below by specific embodiment.Those skilled in the art should be bright
, the embodiment be only to aid in understand the present invention, be not construed as to the present invention concrete restriction.
The material used in following embodiment and comparative example is as shown in table 1.
Table 1
Embodiment 1
In the present embodiment, Si―H addition reaction system is passed through by 2,2'- diallyl bisphenols and hydrogen containing siloxane HWG17606
Polysiloxanes-allyl compound shown in standby Formulas I, preparation method are as follows:
Diallyl bisphenol and catalyst chloroplatinic acid are completely dissolved with suitable toluene, mixes, is previously heated to 60
DEG C, the hydrogen containing siloxane of metered amount, sustained response, until reaction mixing is molten are added dropwise under being kept stirring in nitrogen atmosphere
Signal peak (near 2145cm-1) disappearance or very faint of Si -- H bond in the infrared spectrum of liquid, and pi-allyl signal peak
(near 1635cm-1) still maintains relatively strong, stops heating, and decompression removal solvent obtains polysiloxanes-allyl compound,
Structure is as shown in formula d.
The results are shown in Figure 1 for the infrared spectrum characterization of polysiloxanes-allyl compound being prepared, can from Fig. 1
To find out, the signal peak (2146.03cm-1) of Si -- H bond is very faint, and pi-allyl signal peak (1632.38cm-1) is very strong.
MX9000 and the formula d compounds of above-mentioned preparation are dissolved with suitable solvent, add in the curing agent dissolved in advance
DCP, inorganic filler is fully dispersed, obtains the resin adhesive liquid composition.
The composition is impregnated on glass fabric, 2-20min is heated under 110-200 DEG C of baking oven, institute is made
State prepreg.Two sides is descended several Prepreg Lays and on it to be covered with copper foil, then as in vacuum hotpressing machine, in 170-
1.5-3h is suppressed under the pressure of 210 DEG C of additional 1-2kg, obtains laminate or copper-clad plate prepared by the composition.Described group
Close object proportioning and with its preparation laminate or copper-clad plate performance such as table 2.
Embodiment 2
In the present embodiment, by 3,3'- diallyl -4,4 ' hexichol phenolic ether diglycidyl ethers and hydrogen containing siloxane
HWG17606 is as follows by polysiloxanes-allyl compound, preparation method shown in Si―H addition reaction formula I:
The Karstd of 3,3'- diallyls -4,4 ' hexichol phenolic ether diglycidyl ether and 10ppm is urged with suitable toluene
Agent is completely dissolved, and mixing is previously heated to 70 DEG C, and the hydrogeneous poly- of metered amount is added dropwise under being kept stirring in nitrogen atmosphere
Siloxanes, sustained response, until the signal peak (2145cm of Si -- H bond in the infrared spectrum of reaction mixture-1Near) disappear or
Person is very faint, and pi-allyl signal peak (1635cm-1Near) still maintain relatively strong, stop heating, decompression removal solvent obtains
Polysiloxanes-allyl compound, structure is as shown in formula a.
MX9000 and the formula a compounds of above-mentioned preparation are dissolved with suitable solvent, add in the curing agent dissolved in advance
DCP, inorganic filler is fully dispersed, obtains the resin adhesive liquid composition.
The composition is impregnated on glass fabric, 2-20min is heated under 110-200 DEG C of baking oven, institute is made
State prepreg.Two sides is descended several Prepreg Lays and on it to be covered with copper foil, then as in vacuum hotpressing machine, in 170-
1.5-3h is suppressed under the pressure of 210 DEG C of additional 1-2kg, obtains laminate or copper-clad plate prepared by the composition.Described group
Close object proportioning and with its preparation laminate or copper-clad plate performance such as table 2.
Embodiment 3
In the present embodiment, by (3,3'- diallyl -4, the 4 ' dimethylbenzene) methane of 1,1- bis- and hydrogen containing siloxane
HWG17606 is as follows by polysiloxanes-allyl compound, preparation method shown in Si―H addition reaction formula I:
The Karstd of (3,3'- diallyls -4,4 ' dimethylbenzene) methane of 1,1- bis- and 10ppm are catalyzed with suitable toluene
Agent is completely dissolved, and mixing is previously heated to 85 DEG C, the hydrogeneous poly- silicon of metered amount is added dropwise under being kept stirring in nitrogen atmosphere
Oxygen alkane, sustained response, until in the infrared spectrum of reaction mixture Si -- H bond signal peak (near 2145cm-1) disappear or
Person is very faint, and pi-allyl signal peak still maintains relatively strong (near 1635cm-1), stops heating, and decompression removal solvent obtains
To polysiloxanes-allyl compound, structure is as shown in formula b.
MX9000 and the formula b compounds of above-mentioned preparation are dissolved with suitable solvent, add in the curing agent dissolved in advance
DCP, inorganic filler is fully dispersed, obtains the resin adhesive liquid composition.
The composition is impregnated on glass fabric, 2-20min is heated under 110-200 DEG C of baking oven, institute is made
State prepreg.Two sides is descended several Prepreg Lays and on it to be covered with copper foil, then as in vacuum hotpressing machine, in 170-
1.5-3h is suppressed under the pressure of 210 DEG C of additional 1-2kg, obtains laminate or copper-clad plate prepared by the composition.Described group
Close object proportioning and with its preparation laminate or copper-clad plate performance such as table 2.
Embodiment 4-7
The composition composition of embodiment 4-5 and embodiment 2 the difference is that different, other objects of polyphenylene oxide resin type
Material composition, glue are prepared, prepared by prepreg, the preparation method of copper-clad plate is same as Example 2.Embodiment 6 and embodiment 1
The difference is that curing agent type and additive amount are different, unclassified stores composition, glue are prepared, prepared by prepreg, the system of copper-clad plate
Preparation Method is same as Example 1.Embodiment 7 is with embodiment 1 the difference is that without adding in inorganic fill out in 7 composition of embodiment
Material, unclassified stores composition, glue are prepared, prepared by prepreg, the preparation method of copper-clad plate is same as Example 1.The combination
The proportioning of object and with its preparation laminate or copper-clad plate performance such as table 2.
Comparative example 1-2
The specific preparation method of comparative example 1-2 is identical with the operation of embodiment 1, only difference is that polyphenylene oxide resin combines
The ratio of polysiloxanes-allyl compound and corresponding embodiment are different in object.The proportioning of the composition and use it
The laminate of preparation or the performance of copper-clad plate such as table 2.
Comparative example 3
This example is added without hydrogen containing siloxane, by 3,3'- diallyl -4,4 ' hexichol phenolic ether diglycidyl ethers, polyphenyl
Ether etc. is scattered with suitable butanone/toluene Mixed Solvent, adds in the curing accelerator dissolved in advance, inorganic filler tree
Oil/fat composition.
The composition is impregnated on glass fabric, 2-20min is heated under 110-200 DEG C of baking oven, is made pre-
Leaching material.Two sides is descended several Prepreg Lays and on it to be covered with copper foil, then as in vacuum hotpressing machine, at 170-210 DEG C
1.5-3h is suppressed under the pressure of additional 1-2kg, obtains laminate or the copper-clad plate of composition preparation.The proportioning of the composition
And with its preparation laminate or copper-clad plate performance such as table 2.
Comparative example 4
According to the various material ratios of embodiment 1, by hydrogen containing siloxane, allyl compound, catalyst made from platonic, polyphenyl
Ether resin etc. is scattered with suitable butanone/toluene Mixed Solvent, adds in the curing accelerator dissolved in advance, and inorganic filler obtains
To resin combination.
The composition is impregnated on glass fabric, 2-20min is heated under 110-200 DEG C of baking oven, is made pre-
Leaching material.Two sides is descended several Prepreg Lays and on it to be covered with copper foil, then as in vacuum hotpressing machine, at 170-210 DEG C
1.5-3h is suppressed under the pressure of additional 1-2kg, obtains laminate or the copper-clad plate of composition preparation.The proportioning of the composition
And with its preparation laminate or copper-clad plate performance such as table 2.
Table 2
More than performance test methods are as follows:
Peel strength (PS):Test uses IPC-TM-650 2.4.8
Flammability:94 testing vertical flammabilities of UL
Dielectric constant and dielectric loss tangent:IPC-TM-650SPDR methods
It can be seen from the performance characterization result data of table 2 with the present invention polysiloxanes-allyl compound add in
In composition, the excellent fireproof performance of the copper-clad plate prepared under the conditions of non-halogen non-phosphate can reach UL94V-0 grades, stripping
Intensity can be reached for 0.83Ncm-1More than, dielectric constant can reach 3.79 hereinafter, dielectric loss tangent can reach
0.008 hereinafter, have preferable dielectric properties and adhesive property.When without using polysiloxanes-allylation of the present invention
When closing object, and being changed into diallyl bisphenol diglycidyl ether (comparative example 3), the anti-flammability of copper-clad plate is only capable of reaching
UL94V-2 grades;When the polysiloxanes-allyl compound is very few relative to the dosage of the polyphenylene oxide resin of 100 parts by weight
When (comparative example 1), the anti-flammability of copper-clad plate is only capable of reaching UL94V-1 grades, when the polysiloxanes-allyl compound phase
For the dosage of the polyphenylene oxide resin of 100 parts by weight it is excessive when (comparative example 2), although the anti-flammability of copper-clad plate can reach
UL94V-0 grades, but its peel strength is only 0.46Ncm-1Influence the normal use of copper-clad plate;The raw material is not advance
Si―H addition reaction is carried out during physical blending (comparative example 4), burning grade is V-2, and dielectric properties are relatively worst, peel strength because
Presence for individual polysiloxane ingredient shows very low, is unfavorable for its application in copper-clad plate.
Applicant states that above-described embodiment is only presently preferred embodiments of the present invention, and the invention is not limited in above-mentioned implementations
Example, that is, do not mean that the present invention has to rely on above-described embodiment and could implement.Person of ordinary skill in the field it will be clearly understood that
Any improvement in the present invention, the addition of equivalence replacement and auxiliary element to raw material selected by the present invention, the choosing of concrete mode
It selects, all falls within protection scope of the present invention and the open scope.
Claims (10)
1. the polyphenyl ether resin composition that a kind of polysiloxanes-allyl compound is modified, which is characterized in that the composition packet
Polyphenylene oxide resin and polysiloxanes-allyl compound are included, relative to 100 parts by weight of polyphenyleneoxide resins, is gathered in the composition
The content of siloxanes-allyl compound is 15-80 parts by weight, and the polysiloxanes-allyl compound has to be tied shown in Formulas I
Structure:
Wherein, R1And R2It independently is substituted or unsubstituted C1-C4 straight chained alkyls, substituted or unsubstituted C1-C4 branched alkanes
Any one in base, substituted or unsubstituted C4-C10 cycloalkyl or substituted or unsubstituted phenyl;R3For substitution or not
Substituted C1-C4 straight chained alkyls, substituted or unsubstituted C4-C10 cycloalkyl, take substituted or unsubstituted C1-C4 branched alkyls
Generation or unsubstituted phenyl orIn any one, wherein R for substituted or unsubstituted C1-C4 straight chained alkyls,
Substituted or unsubstituted C1-C4 branched alkyls, substituted or unsubstituted C4-C10 cycloalkyl or substituted or unsubstituted phenyl
In any one, m be 1-6 integer;R4For substituted or unsubstituted C1-C4 straight chained alkyls, substituted or unsubstituted C1-C4
Branched alkyl, hydroxyl orIn any one;R5It does not take for substituted or unsubstituted C1-C4 straight chained alkyls, substitution or
Any one in the C1-C4 branched alkyls in generation ,-O- or-S-;N is the integer of 4-50.
2. the polyphenyl ether resin composition that polysiloxanes according to claim 1-allyl compound is modified, feature exist
In R1And R2It independently is methyl or phenyl;
Preferably, R3Selected from methyl, phenyl orIn any one;
Preferably, R4Selected from methyl, hydroxyl orIn any one;
Preferably, R5Selected from-C (CH3)2-、-CH(CH3)-、-CH2, any one in-O- or-S-;
Preferably, the polysiloxanes-allyl compound is with any one in the compound of structure as shown in following formula a-e
Kind or at least two combination:
Wherein n is the integer of 4-50;
Preferably, the preparation method of the polysiloxanes-allyl compound is:Diallyl compound shown in Formula II and formula
Hydrogen containing siloxane shown in III occurs hydrosilylation and obtains polysiloxanes-allyl compound shown in Formulas I, and reaction equation is such as
Under:
Preferably, diallyl compound shown in Formula II is selected from diallyl bisphenol diglycidyl ether, 2,2'- diallyls
In bisphenol-A, 2,2'- diallyl bis-phenol E, 2,2'- diallyl Bisphenol Fs or 2,2'- diallyl bisphenol Ss any one or
At least two combination, preferably diallyl bisphenol diglycidyl ether, further preferred 2,2'- diallyl bisphenols two contract
Water glycerin ether;
Preferably, the weight percentage for the hydrogen being connected directly in hydrogen containing siloxane shown in formula III with silicon is 0.05-
0.46%;
Preferably, diallyl compound medium vinyl shown in Formula II rubs with si-h bond in hydrogen containing siloxane shown in formula III
You are than being (2.4-2):1;
Preferably, the hydrosilylation carries out in the presence of a catalyst, and the catalyst is catalyst made from platonic;
Preferably, the catalyst made from platonic is Speier catalyst and/or Karsted catalyst;
Preferably, the catalyst made from platonic is the catalyst made from platonic shown in chloroplatinic acid and/or following molecular structural formula:
Preferably, the dosage of the catalyst is the 5-25ppm of hydrogen containing siloxane quality shown in formula III;
Preferably, the hydrosilylation carries out in organic solvent, and the organic solvent is toluene, dimethylbenzene, tetrahydrochysene furan
Mutter or DMF in any one or at least two combination, preferred toluene;
Preferably, the temperature of the hydrosilylation is 55-85 DEG C;
Preferably, hydrogen containing siloxane shown in formula III is to be added in a manner of being added dropwise dropwise to containing in the hydrosilylation
In the reaction system for having diallyl compound shown in Formula II;
Preferably, the hydrosilylation carries out in the presence of protective gas, the preferred nitrogen of protective gas;
Preferably, the hydrosilylation carries out under stiring;
Preferably, after the reaction was complete after hydrogen containing siloxane shown in formula III, stop reaction.
3. the polyphenyl ether resin composition that polysiloxanes according to claim 1 or 2-allyl compound is modified, special
Sign is that the polyphenylene oxide resin is any one or at least two in the modified polyphenylene ether resin with structure shown in formula IV
Combination:
Wherein, X is selected from the group containing vinyl;A is selected fromM is selected from covalent bond ,-CH2-、-C
(CH3)2-、-CH(CH3)-、-O-、-SO2,-S- or carbonyl;R11、R21、R31And R41Independently selected from hydrogen, substituted or unsubstituted
Any one in C1-C4 straight chained alkyls, substituted or unsubstituted C1-C4 branched alkyls or substituted or unsubstituted phenyl;R12、
R22、R32And R42Independently selected from substituted or unsubstituted C1-C4 straight chained alkyls, substituted or unsubstituted C1-C4 branched alkyls or
Any one in substituted or unsubstituted phenyl;A and b independently is the integer of 1-100;
Preferably, X is selected fromIn
Any one;
Preferably, the polyphenyl ether resin composition that the polysiloxanes-allyl compound is modified further includes curing accelerator;
Preferably, relative to 100 parts by weight of polyphenyleneoxide resins, the content of curing accelerator is 0.3-3 weight in the composition
Part;
Preferably, the curing accelerator is the peroxide for causing radical reaction;
Preferably, the curing accelerator is di-tert-butyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, mistake
Aoxidize neodecanoic acid isopropyl phenyl ester, new peroxide tert-butyl caprate, peroxidating pivalic acid spy pentyl ester, the peroxidating pivalic acid tert-butyl ester,
Tert-butyl hydroperoxide isobutyrate, tert-butyl hydroperoxide -3,5,5 Trimethylhexanoic acid ester, peroxide acetic acid butyl ester, peroxidating
T-butyl perbenzoate, 1,1- di-tert-butyl peroxide -3,5,5- trimethyl-cyclohexanes, 1,1- cyclohexane di-tert-butyl peroxides,
2,2- bis- (tert-butyl hydroperoxide) butane, bis- (4- tert-butylcyclohexyls) peroxy dicarbonates, peroxy dicarbonate 16
Ester, 14 ester of peroxy dicarbonate, two special penta own peroxide, dicumyl peroxide, bis- (tert-butyl hydroperoxide isopropyls
Base) benzene, 2,5- dimethyl -2,5- di-t-butyl hexane peroxides, 2,5- dimethyl -2,5- di-tert-butyl peroxides hexin, two
Isopropyl benzene hydroperoxide, isopropyl benzene hydroperoxide, tertiary amyl hydrogen peroxide, tert-butyl hydroperoxide, tert-butyl hydroperoxide isopropyl
Benzene, diisopropylbenzene hydroperoxide, peroxycarbonates -2 ethyl hexanoic acid tert-butyl ester, tert-butyl hydroperoxide carbonic acid -2- ethyl hexyls
In ester, 4,4- bis- (tert-butyl hydroperoxide) n-butyl pentanoate, methyl ethyl ketone peroxide or cyclohexane peroxide any one or extremely
Mixture two kinds few;
Preferably, the composition further includes inorganic filler;
Preferably, relative to 100 parts by weight of polyphenyleneoxide resins, the content of inorganic filler is 0-350 parts by weight in the composition
And do not include 0;
Preferably, the inorganic filler is selected from powdered quartz, amorphous silica, preparing spherical SiO 2, melting two
It is any one in silica, titanium dioxide, silicon carbide, glass fibre, aluminium oxide, aluminium nitride, boron nitride, barium titanate or strontium titanates
Kind or at least two mixture.
4. a kind of resin adhesive liquid, which is characterized in that the resin adhesive liquid is by the poly- silicon as described in any one of claim 1-3
The polyphenyl ether resin composition that oxygen alkane-allyl compound is modified, which is dissolved or dispersed in solvent, to be obtained.
5. a kind of cover film, which is characterized in that the cover film is prepared by resin adhesive liquid as claimed in claim 4.
6. a kind of prepreg, which is characterized in that the prepreg includes reinforcing material and by adhering to thereon after being impregnated with drying
The polyphenyl ether resin composition that is modified of the polysiloxanes as described in any one of claim 1-3-allyl compound.
7. a kind of insulation board, which is characterized in that the insulation board includes an at least prepreg as claimed in claim 6.
8. a kind of laminate, which is characterized in that the laminate includes an at least prepreg as claimed in claim 6.
9. a kind of metal-clad laminate, which is characterized in that the metal-clad laminate includes one or at least two overlapping
Prepreg as claimed in claim 6 and the prepreg after overlapping one or both sides metal foil.
10. a kind of printed circuit board, which is characterized in that the printed circuit board include one or at least two overlapping such as right
It is required that the prepreg described in 6.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611241815.4A CN108250716B (en) | 2016-12-29 | 2016-12-29 | Polysiloxane-allyl compound modified polyphenyl ether resin composition, and prepreg, laminated board and printed circuit board thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611241815.4A CN108250716B (en) | 2016-12-29 | 2016-12-29 | Polysiloxane-allyl compound modified polyphenyl ether resin composition, and prepreg, laminated board and printed circuit board thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108250716A true CN108250716A (en) | 2018-07-06 |
CN108250716B CN108250716B (en) | 2021-07-06 |
Family
ID=62719640
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201611241815.4A Active CN108250716B (en) | 2016-12-29 | 2016-12-29 | Polysiloxane-allyl compound modified polyphenyl ether resin composition, and prepreg, laminated board and printed circuit board thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108250716B (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110845853A (en) * | 2019-12-09 | 2020-02-28 | 苏州生益科技有限公司 | Resin composition, and prepreg, laminated board, insulating board, circuit board and coverlay film comprising same |
CN110922764A (en) * | 2019-12-09 | 2020-03-27 | 苏州生益科技有限公司 | Silicon-containing resin composition and prepreg and laminated board manufactured by using same |
CN110950901A (en) * | 2019-12-09 | 2020-04-03 | 苏州生益科技有限公司 | Silicone resin and preparation method thereof, resin composition, prepreg, laminated board, insulating board, circuit substrate and covering film |
CN113801462A (en) * | 2021-09-28 | 2021-12-17 | 浙江华正新材料股份有限公司 | Resin composition, prepreg, circuit board and printed circuit board |
CN114573975A (en) * | 2022-01-25 | 2022-06-03 | 南亚新材料科技股份有限公司 | Metal foil-clad laminated board containing filler particle clusters and preparation method thereof |
US20220193992A1 (en) * | 2020-12-22 | 2022-06-23 | Lawrence Livermore National Security, Llc | Refractive index matching base resin for extremely fine three-dimensional ceramic structures |
WO2023089982A1 (en) * | 2021-11-17 | 2023-05-25 | 本州化学工業株式会社 | Curable resin composition, varnish, prepreg, and cured product |
CN117511233A (en) * | 2024-01-08 | 2024-02-06 | 乌镇实验室 | Polyphenyl ether modified hydrocarbon resin composition and application thereof in copper-clad plate |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5169887A (en) * | 1991-02-25 | 1992-12-08 | General Electric Company | Method for enhancing the flame retardance of polyphenylene ethers |
CN1192452A (en) * | 1997-03-03 | 1998-09-09 | 通用电气公司 | Novel flame retardance additives for aromatic-based polymers, and related polymer compositions |
US20010014723A1 (en) * | 1999-12-15 | 2001-08-16 | Satoru Moritomi | Thermoplastic resin, process for producing same and theroplastic resin composition |
JP2007119649A (en) * | 2005-10-31 | 2007-05-17 | Kaneka Corp | Flame retardant and flame-retardant resin composition |
CN101333327A (en) * | 2008-07-02 | 2008-12-31 | 中国科学院广州化学研究所 | Composite modified polyphenylene oxide/epoxy material for printing circuit coller clad plate and method for preparing same |
JP2010209266A (en) * | 2009-03-12 | 2010-09-24 | Shin-Etsu Chemical Co Ltd | Liquid epoxy resin composition for sealing semiconductor, and flip-chip semiconductor device sealed with the same as underfill material |
JP2014122275A (en) * | 2012-12-21 | 2014-07-03 | Shin Etsu Chem Co Ltd | Silicone skeleton-containing polymer compound, negative resist material, photocurable dry film, pattern formation method and coating for protection of electric/electronic component |
CN105960426A (en) * | 2014-01-23 | 2016-09-21 | 信越化学工业株式会社 | Resin composition, resin film, and semiconductor device and method for manufacturing same |
-
2016
- 2016-12-29 CN CN201611241815.4A patent/CN108250716B/en active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5169887A (en) * | 1991-02-25 | 1992-12-08 | General Electric Company | Method for enhancing the flame retardance of polyphenylene ethers |
CN1192452A (en) * | 1997-03-03 | 1998-09-09 | 通用电气公司 | Novel flame retardance additives for aromatic-based polymers, and related polymer compositions |
US20010014723A1 (en) * | 1999-12-15 | 2001-08-16 | Satoru Moritomi | Thermoplastic resin, process for producing same and theroplastic resin composition |
JP2007119649A (en) * | 2005-10-31 | 2007-05-17 | Kaneka Corp | Flame retardant and flame-retardant resin composition |
CN101333327A (en) * | 2008-07-02 | 2008-12-31 | 中国科学院广州化学研究所 | Composite modified polyphenylene oxide/epoxy material for printing circuit coller clad plate and method for preparing same |
JP2010209266A (en) * | 2009-03-12 | 2010-09-24 | Shin-Etsu Chemical Co Ltd | Liquid epoxy resin composition for sealing semiconductor, and flip-chip semiconductor device sealed with the same as underfill material |
JP2014122275A (en) * | 2012-12-21 | 2014-07-03 | Shin Etsu Chem Co Ltd | Silicone skeleton-containing polymer compound, negative resist material, photocurable dry film, pattern formation method and coating for protection of electric/electronic component |
CN105960426A (en) * | 2014-01-23 | 2016-09-21 | 信越化学工业株式会社 | Resin composition, resin film, and semiconductor device and method for manufacturing same |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110950901B (en) * | 2019-12-09 | 2023-07-07 | 苏州生益科技有限公司 | Silicone resin, method for producing the same, resin composition, prepreg, laminated board, insulating board, circuit board, and coverlay film |
CN110845853A (en) * | 2019-12-09 | 2020-02-28 | 苏州生益科技有限公司 | Resin composition, and prepreg, laminated board, insulating board, circuit board and coverlay film comprising same |
CN110950901A (en) * | 2019-12-09 | 2020-04-03 | 苏州生益科技有限公司 | Silicone resin and preparation method thereof, resin composition, prepreg, laminated board, insulating board, circuit substrate and covering film |
CN110922764B (en) * | 2019-12-09 | 2021-10-08 | 苏州生益科技有限公司 | Silicon-containing resin composition and prepreg and laminated board manufactured by using same |
CN110845853B (en) * | 2019-12-09 | 2021-11-26 | 苏州生益科技有限公司 | Resin composition, and prepreg, laminated board, insulating board, circuit board and coverlay film comprising same |
CN110922764A (en) * | 2019-12-09 | 2020-03-27 | 苏州生益科技有限公司 | Silicon-containing resin composition and prepreg and laminated board manufactured by using same |
US20220193992A1 (en) * | 2020-12-22 | 2022-06-23 | Lawrence Livermore National Security, Llc | Refractive index matching base resin for extremely fine three-dimensional ceramic structures |
CN113801462A (en) * | 2021-09-28 | 2021-12-17 | 浙江华正新材料股份有限公司 | Resin composition, prepreg, circuit board and printed circuit board |
CN113801462B (en) * | 2021-09-28 | 2024-01-09 | 浙江华正新材料股份有限公司 | Resin composition, prepreg, circuit board and printed circuit board |
WO2023089982A1 (en) * | 2021-11-17 | 2023-05-25 | 本州化学工業株式会社 | Curable resin composition, varnish, prepreg, and cured product |
CN114573975B (en) * | 2022-01-25 | 2023-08-04 | 南亚新材料科技股份有限公司 | Metal foil-clad laminated board containing filler particle clusters and preparation method thereof |
CN114573975A (en) * | 2022-01-25 | 2022-06-03 | 南亚新材料科技股份有限公司 | Metal foil-clad laminated board containing filler particle clusters and preparation method thereof |
CN117511233A (en) * | 2024-01-08 | 2024-02-06 | 乌镇实验室 | Polyphenyl ether modified hydrocarbon resin composition and application thereof in copper-clad plate |
CN117511233B (en) * | 2024-01-08 | 2024-04-12 | 乌镇实验室 | Polyphenyl ether modified hydrocarbon resin composition and application thereof in copper-clad plate |
Also Published As
Publication number | Publication date |
---|---|
CN108250716B (en) | 2021-07-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108250716A (en) | Polyphenyl ether resin composition and its prepreg, the laminate and printed circuit board of a kind of polysiloxanes-allyl compound modification | |
CN104725828B (en) | A kind of resin combination and use its prepreg and laminate | |
CN104725857B (en) | A kind of resin combination and use its prepreg and laminate | |
CN104845363B (en) | A kind of halogen-free resin composition and application thereof | |
CN104774476B (en) | Phosphor-containing flame-proof composition and use its phosphorous polyphenyl ether resin composition, prepreg and laminate | |
CN105086417B (en) | A kind of resin combination and its application in high-frequency circuit board | |
CN106609031B (en) | A kind of polyphenyl ether resin composition and prepreg, laminate and printed circuit board containing it | |
CN108250443A (en) | A kind of polysiloxanes-allyl compound fire retardant and its preparation method and application | |
CN108250746A (en) | Bismaleimide amine composition and its prepreg, the laminate and printed circuit board of a kind of polysiloxanes-allyl compound modification | |
CN106609032B (en) | A kind of polyphenyl ether resin composition and prepreg, laminate and printed circuit board containing it | |
CN106700424B (en) | A kind of low-loss resin combination, prepreg and laminate | |
CN106916418A (en) | A kind of compositions of thermosetting resin, prepreg, metal-clad laminate and printed circuit board | |
CN103467982A (en) | Cyanate ester composition and method used for preparing copper-clad plates by cyanate ester composition | |
JP2021505723A (en) | Phosphorus-containing polysiloxane compound additives for thermosetting resins, flame retardant compositions containing them, and articles manufactured from them. | |
JP2023052699A (en) | Prepreg, metal-clad laminate, and wiring board | |
CN103102795A (en) | Modified unsaturated polyesterimide solvent-free impregnating varnish for oil proof motor | |
CN102936449A (en) | Halogen-free flame retardant heat conduction insulation warmish and preparation method thereof | |
CN108623890A (en) | A kind of high heat-resistant insulation material and preparation method thereof and cable protection pipe obtained | |
CN108148196B (en) | Styryl siloxy polyphenylene oxide resin and preparation method and application thereof | |
CN113337098A (en) | Thermosetting resin composition and application thereof | |
CN106280387B (en) | There is halogen fire-proof resin composition and uses its manufactured resin, laminate | |
CN106349643B (en) | A kind of compositions of thermosetting resin and prepreg and laminate using its making | |
CN108148162B (en) | A kind of styryl siloxy phenolic resin and its preparation method and application | |
CN108250605A (en) | Polybutadiene composition and its prepreg, the laminate and printed circuit board of a kind of polysiloxanes-allyl compound modification | |
CN108148202A (en) | A kind of poly- silicon phenylene ether resins of styryl and its preparation method and application |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |