CN109438960A - A kind of high frequency resin composition and application - Google Patents
A kind of high frequency resin composition and application Download PDFInfo
- Publication number
- CN109438960A CN109438960A CN201811331092.6A CN201811331092A CN109438960A CN 109438960 A CN109438960 A CN 109438960A CN 201811331092 A CN201811331092 A CN 201811331092A CN 109438960 A CN109438960 A CN 109438960A
- Authority
- CN
- China
- Prior art keywords
- high frequency
- formula
- resin composition
- initiator
- frequency resin
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2309/06—Copolymers with styrene
-
- 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
- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2409/06—Copolymers with styrene
-
- 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
- C08J2447/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Derivatives of such polymers
-
- 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
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2471/12—Polyphenylene oxides
Abstract
The present invention provides a kind of high frequency resin composition and application.The raw material for preparing of the high frequency resin composition includes: unsaturated polyphenylene oxide resin, butadiene styrene resin, unsaturated polybutadiene, bismaleimide and initiator.There are the excellent comprehensive performances such as dielectric loss is small, dielectric constant is low, peel strength is high and bending strength is high according to the high frequency resin composition of above-mentioned material preparation, this can not only meet the transmission of high-frequency signal, also meet the performance requirements such as machining, the mechanical support of plate of high frequency resin composition preparation.
Description
Technical field
The present invention relates to high frequency technique field more particularly to a kind of high frequency resin composition and applications.
Background technique
In recent years, with the high performance-based such as computer and network, the development of multifunction, it is desirable that computer etc. can be located
It manages large capacity information and realizes the high-speed transfer of large capacity information.For the processing and high-speed transfer for realizing large capacity information, behaviour
Make signal gradually high frequency, forms high-frequency signal.For the transmission for realizing high-frequency signal, need a kind of suitable for high frequency signal transmission
The high-performance electric insulating materials of characteristic.
In the circuit of high frequency signal transmission, electric signal transmission loss passes through dielectric loss, conductor losses and radiation loss
The sum of indicate.Signal frequency is higher, then dielectric loss, conductor losses, radiation loss are bigger.Since electric signal transmission loss is easy
There is electric signal decaying, destroy the problem of electric signal reliability, meanwhile, electric signal transmission loss is issued from high-frequency circuit to be radiated,
The radiation may cause electronic failure.Therefore, it is necessary to reduce dielectric loss, conductor losses, radiation loss.It is well known that
The dielectric loss of electric signal and the dielectric loss angle tangent of insulator and multiplying for used signal frequency for forming circuit
Product is directly proportional.As a result, as the insulator of high frequency signal transmission, insulation material that can be small by selection dielectric loss angle tangent
Material, to inhibit the increase of dielectric loss.
Currently, the insulator as high frequency signal transmission generally passes through polybutadiene, polyisoprene and thermoplastic elastic
Body preparation, or prepared by unsaturated polybutadiene, the olefin resin of unsaturationization and filler, or by unsaturated
Polybutadiene, cyclic olefin resin and filler preparation.Although the insulator of above-mentioned material preparation has tack-free characteristic, system
A large amount of filler is used during standby, peel strength is low, energy consumption is high and bending strength is small so that the insulator of preparation has
Disadvantage.
Summary of the invention
The present invention provides a kind of high frequency resin composition and application, has to solve the insulator of existing high frequency signal transmission
The problem that peel strength is low, energy consumption is high and bending strength is small.
The application provides a kind of high frequency resin composition, the composition prepare raw material include: unsaturated polyphenylene oxide resin,
Butadiene styrene resin, unsaturated polybutadiene, bismaleimide and initiator.It is following specifically describe respectively it is provided by the present application
High frequency resin composition prepares raw material.
Unsaturated polyphenylene oxide resin be number-average molecular weight be 500-5000, molecular end have unsaturated double-bond polyphenylene oxide
(PPO, Polyphenylene Oxide) resin.In this application, shown in the structural formula of unsaturated polyphenylene oxide resin such as formula (1),
Wherein, in formula (1), a, b are respectively the integer of 1-30, shown in Z such as formula (2) or formula (3) ,-(- O-Y-)-such as formula (4)
Shown ,-(- O-X-O-)-is as shown in formula (5).Formula (2)-formula (5) structural formula is as follows:
In formula (3), A is selected from the alkylidene that arylene, carbonyl or carbon atom number are 1-10；M is the integer of 0-10；R1-R3
It is respectively selected from hydrogen or carbon atom number is 10 alkyl below；R1-R3It is identical or different.
In formula (4), R4And R6Being respectively selected from hydrogen atom, halogen atom, phenyl or carbon atom number is 8 alkyl below；R5With
R7Being respectively selected from halogen atom, phenyl or carbon atom number is 8 alkyl below；R4With R6It is identical or different, R5With R7It is identical or not
Together.
In formula (5), R8-R15Being respectively selected from hydrogen atom, halogen atom, phenyl or carbon atom number is 8 alkyl below；B choosing
It is 20 alkylene below from carbon atom number；N is 0 or 1；R8-R15It is identical or different.
Butadiene styrene resin is using styrene, butadiene as monomer, using lithium alkylide as initiator, using anionic solution polymerization skill
A kind of thermoplastic macromolecule material of block structure high styrenic percentage of art synthesis.In the application, the molecular weight of butadiene styrene resin
For 1000-11000, the contents of ethylene in butadiene styrene resin is 60-99%, and the styrene-content in butadiene styrene resin is 30-60%.
More preferably, the contents of ethylene in butadiene styrene resin is 70-95%, and the styrene-content in butadiene styrene resin is 35-55%.More
For preferably, the contents of ethylene in butadiene styrene resin is 75-93%, the styrene-content in butadiene styrene resin is 40-50%.
In the application, different molecular weight, different contents of ethylene, different styrene-content butadiene styrene resin preparation process
Are as follows:
By 4L dry hexamethylene, 0.05-0.48ml tetrahydrofurfuryl alcohol ethylether, four mouthfuls of glass reaction bottles for being put into 4L (are passed through
Baking is dried) in, it is passed through drying nitrogen protection, 40-60 DEG C of constant temperature, following components then is added simultaneously in 60min: 25-
200g styrene (S), the mix monomer of 30-210g butadiene (B), 0.4mol/L butyl lithium 0.02-0.1mL, are then added
The cyclohexane solution of the mono- chlorine trimethyl silane of 0.2mol/L of 1.0-16.65mL reacts 30min, and isopropanol is added and terminates reaction
Glue sample is precipitated, filters, with acetone extraction 12h, is put into 25 DEG C of baking oven vacuum drying 12h, obtains white solid product.The white is solid
The molecular weight of body product, contents of ethylene and styrene-content are as shown in table 1, wherein the type of butadiene styrene resin is with molecular weight area
Point.
Table 1: different molecular weight, different contents of ethylene, different styrene-content butadiene styrene resin
Polar group grafting rate on the modified with polar polybutadiene strand of unsaturated polybutadiene is between 5
To between 15, wherein the polar group can be maleic anhydride (MAH, Maleic anhydride).In this application, insatiable hunger
Molecular weight with polybutadiene is 1000-50000, wherein the contents of ethylene in unsaturated polybutadiene is 60-
99%.Unsaturated polybutadiene is selected from epoxy-modified polybutadiene, maleic anhydride modified polybutadiene, propylene
What sour modified polybutadiene resin, hydroxy-end capped polybutadiene, the polybutadiene of carboxy blocking and amine were modified
At least one of polybutadiene.
It is following to be described by taking the preparation of maleic anhydride modified polybutadiene as an example, to prepare different molecular weight, no
The unsaturated polybutadiene of same contents of ethylene, difference MAH grafting rate.
Specifically, by volume be 16L drying hexamethylene and quality be 1600g drying butadiene to be put into volume be 4L's
In four mouthfuls of glass reaction bottles, which is dried.Dry nitrogen is passed through into four mouthfuls of glass reaction bottles
Gas shielded, and constant temperature is in 40-80 DEG C.Then, following components successively is added into four mouthfuls of glass reaction bottles: volume 4-9ml, object
The amount of matter is the hexane solution of three [di-(2-ethylhexyl)phosphoric acid] iron of 0.4-0.9mmol, volume 16-36ml, substance
Amount be 8mmol triisobutyl aluminium hexane solution, volume 12-27ml, substance amount be 1.2-2.7mmol phosphoric acid triphen
The hexane solution of ester, the amount of substance are the tetrahydrofurfuryl alcohol ethylether of 17-38mmol, and the amount of substance is the PMDETA of 7-17mmol
(pentamethyl-diethylenetriamine).It is warming up to 65-90 DEG C, polymerization reaction 1-9h.After polymerization reaction, ethyl alcohol is added and terminates reaction
Glue sample is precipitated, filters, with acetone extraction 12-18h, is put into 25 DEG C of baking oven vacuum drying 12h, obtains white solid product polybutadiene
Alkene (PB, polybutadiene).
By the above-mentioned polybutadiene of 1000g, 300ml dimethylbenzene is put into four mouthfuls of glass reaction bottles of 4L, and 65-75 DEG C of constant temperature,
After polybutadiene is completely dissolved, it is passed through drying nitrogen, is warming up to 85-95 DEG C, is slowly added into system containing 165-370g
Maleic anhydride, the xylene solution of 48-110g antifebrin stir 10-25min after being added dropwise, and will contain 24-56g BPO
Xylene solution in 30min in be slowly dropped in four-hole bottle, reactant is slowly warming up to 120 DEG C, continues at a constant temperature
Reaction 3-5 hours, after reaction, decompression distillation removes dimethylbenzene and unreacted maleic anhydride, product is poured out, is added
Dehydrated alcohol precipitating, filters sedimentation a period of time, with acetone extraction 12-18h, is put into 25 DEG C of baking oven vacuum drying 12h, obtains
White solid product MAH modified polybutadiene, concrete outcome are as shown in table 2, wherein the type of MAH modified polybutadiene is to divide
Son amount is distinguished.
Table 2: the unsaturated polybutadiene of different molecular weight, different contents of ethylene, difference MAH grafting rate
| Type | Molecular weight | Contents of ethylene | MA grafting rate |
| PB-5000(MAH) | 5000 | 60% | 5 |
| PB-7000(MAH) | 7000 | 85% | 7 |
| PB-50000(MAH) | 50000 | 99% | 10 |
| PB-5000-15(MAH) | 5000 | 60% | 15 |
Bismaleimide is the bifunctional compound using maleimide as active end group, with shown in formula (6)
Structural formula.
In formula (6), R1For the fatty group or aromatic series base of m valence；XaAnd XbSelected from hydrogen atom, halogen atom and fatty group
In identical or different monovalent atom or organic group, the integer that m is 1 or more.
Initiator comes to cause to cause unsaturated polyphenylene oxide resin, butadiene styrene resin, unsaturated polybutadiene and span
The substance of imide reaction.In this application, initiator includes the first initiator and/or the second initiator, wherein first causes
The 1min half life temperature of agent is 50-160 DEG C, and the 1min half life temperature of the second initiator is 160-300 DEG C.
Specifically, the first initiator is selected from a, a '-two (isopropylbenzene between tert-butyl hydroperoxide) benzene, cumyl peroxide
(DCP, Dicumyl peroxide), cumyl t-butyl peroxide, bis- (tert-hexyl peroxide) -3 1,1-, 3,5- front three basic rings
In hexane, 2,5- dimethyl -2,5- bis- (t-butylperoxy) hex- 3- alkynes, octanoic acid ter-butyl ester and peroxidized t-butyl perbenzoate
At least one.
Second initiator is selected from a, a '-two (isopropylbenzene between tert-butyl hydroperoxide) benzene, benzoyl peroxide (BPO, Benzoyl
Peroxide), bis- (the tert-hexyl peroxide) -3,3,5- trimethyls of cumyl peroxide, cumyl t-butyl peroxide, 1,1-
Hexamethylene, 2,5- dimethyl -2,5- bis- (t-butylperoxy) hex- 3- alkynes, octanoic acid ter-butyl ester and peroxidized t-butyl perbenzoate
At least one of.
Further, the high frequency resin composition in the application further includes crosslinking agent and fire retardant.Crosslinking agent is for enhancing height
The bond strength of frequency resin combination.Fire retardant is used to improve the burning point of high frequency resin composition, and then prevents high frequency resin group
Close object burning.In this application, crosslinking agent is selected from triallyl isocyanurate, poly- triallyl isocyanurate, triallyl three
At least one of polycyanate ester, diallyl phthalate, divinylbenzene and polyfunctional acrylate.Fire retardant choosing
From deca-BDE, ethyl-bis- (tetrabromo phthalimides), decabromodiphenylethane, three (2,6- 3,5-dimethylphenyl) phosphines,
- 10 phosphine phenanthrene -10- oxide of 10- (2,5- dihydroxy phenyl) -9,10- dihydro-9-oxy, 2,6- bis- (2,6- 3,5-dimethylphenyl)
At least one of phosphino- benzene and 10- phenyl -9,10- dihydro-9-oxy -10- phosphine phenanthrene -10- oxide.
Further, the high frequency resin composition in the application further includes filler, and angle value is 0.5-20 μ in the partial size of filler
m.More preferably, angle value is 1-15 μm in the partial size of filler.It is further preferable that angle value is 4-10 μm in the partial size of filler.This
In application, filler is selected from silica, titanium dioxide, boron nitride, aluminium nitride, silicon carbide, aluminium oxide, barium titanate, strontium titanates, titanium
Sour magnesium, calcium titanate, barium strontium titanate, calcium barium titanate, lead titanates, lead zirconate titanate, zirconium lanthanium titanate lead, lanthanium titanate barium, zirconia titanate barium, two
Hafnium oxide, lead magnesio-niobate, barium magnesium niobate, lithium niobate, potassium niobate, tantalic acid aluminium strontium, potassium tantallum niobate (KTH), strontium barium niobate, lead bariun niobate, niobium
At least one of sour titanium barium, bismuth tantalate strontium, bismuth titanates, barium titanate rubidium, copper titanate and lead titanates-lead magnesio-niobate.
In the above-mentioned raw material for preparing high frequency resin composition, in parts by weight, the preparation of high frequency resin composition
Raw material includes: unsaturated polyphenylene oxide resin 40-80 parts, 45-80 parts of butadiene styrene resin, unsaturated 10-50 parts of polybutadiene, double
3-40 parts and initiator 1-7 parts of maleimide.More preferably, the raw material for preparing of high frequency resin composition includes: unsaturation
42-70 parts of polyphenylene oxide resin, 48-70 parts of butadiene styrene resin, unsaturated 15-35 parts of polybutadiene, bismaleimide 5-30
Part and initiator 1.5-6 parts.It is further preferable that the raw material for preparing of high frequency resin composition includes: unsaturated polyphenylene oxide resin 45-
60 parts, 50-60 parts of butadiene styrene resin, unsaturated 20-30 parts of polybutadiene, 10-20 parts of bismaleimide and initiator 2-5
Part.
The application also provides a kind of prepreg, which includes reinforcing material and the above-mentioned high frequency resin referred to
Composition, and high frequency resin composition is attached on reinforcing material.Wherein, reinforcing material includes glass-fiber-fabric, paper and composite wood
Material etc..
The application also provides a kind of laminate, which includes at least one layer of above-mentioned prepreg.
The application also provides a kind of copper-clad plate, which includes at least one layer of above-mentioned prepreg and be attached to half admittedly
Change the metal foil of piece unilateral side or two sides.When copper-clad plate includes multilayer prepreg, superimposed prepreg unilateral side or
Two sides adhesion metal foil.
The application also provides a kind of printed circuit board, which includes above-mentioned laminate or copper-clad plate.
Prepreg, laminate, copper-clad plate and printed circuit board provided by the present application are prepared according to existing preparation method
It forms.
The technical solution that the embodiment of the present invention provides can include the following benefits:
The present invention provides a kind of high frequency resin composition and application.The raw material for preparing of the high frequency resin composition includes: not
It is saturated polyphenylene oxide resin, butadiene styrene resin, unsaturated polybutadiene, bismaleimide and initiator.According to above-mentioned material
It is excellent that the high frequency resin composition of preparation has that dielectric loss is small, dielectric constant is low, peel strength is high and bending strength is high etc.
Comprehensive performance, this can not only meet the transmission of high-frequency signal, and the machinery for also meeting the plate of high frequency resin composition preparation adds
The performance requirements such as work, mechanical support.
It should be understood that above general description and following detailed description be only it is exemplary and explanatory, not
It can the limitation present invention.
Specific embodiment
Embodiment 1
The embodiment of the present application provides a kind of high frequency resin composition, which prepares raw material according to weight
Number includes: 40 parts of unsaturated polyphenylene oxide resin, 45 parts of butadiene styrene resin, unsaturated 10 parts of polybutadiene, bismaleimide
3 parts and 1 part of initiator of amine.
The structural formula of unsaturated polyphenylene oxide resin is
In above-mentioned formula, the structural formula of Z isThe structural formula of (- O-Y-)-is
The structural formula of (- O-X-O-)-isA, b is respectively 1.Wherein, R4For hydrogen
Atom, R5For halogen atom, R6For phenyl, R7For propyl, R8For hydrogen atom, R9For halogen atom, R10For phenyl, R11For first
Base, R12For ethyl, R13For pentyl, R14For isoamyl alkyl, R15For butane group, B is the alkylene that carbon atom number is 10, n 1.
The structural formula of bismaleimide isWherein, R1For divalent fatty group, XaFor hydrogen original
Son, XbFor halogen atom.
Unsaturated polybutadiene is maleic anhydride modified polybutadiene, and initiator is cumyl peroxide.
Embodiment 2
The embodiment of the present application provides a kind of high frequency resin composition, which prepares raw material according to weight
Number includes: 80 parts of unsaturated polyphenylene oxide resin, 80 parts of butadiene styrene resin, unsaturated 50 parts of polybutadiene, bismaleimide
40 parts and 7 parts of initiator of amine.
The structural formula of unsaturated polyphenylene oxide resin isOn
It states in formula, the structural formula of Z isThe structural formula of (- O-Y-)-is-(-
O-X-O-)-structural formula beA, b is respectively 2.Wherein, A is sub- fragrance
Base, m 1, R1For hydrogen atom, R2For methyl, R3For propyl.R4For halogen atom, R5For phenyl, R6For halogen atom, R7For benzene
Base, R8For halogen atom, R9For halogen atom, R10For phenyl, R11For phenyl, R12For ethyl, R13For pentyl, R14For isoamyl
Alkyl, R15For butane group, n 0.
The structural formula of bismaleimide isWherein, R1For trivalent aromatic series base, XaFor halogen original
Son, XbFor the monovalent atom in fatty group.
Unsaturated polybutadiene is epoxy-modified polybutadiene, and initiator is octanoic acid ter-butyl ester.
Embodiment 3
The embodiment of the present application provides a kind of high frequency resin composition, which prepares raw material according to weight
Number includes: 60 parts of unsaturated polyphenylene oxide resin, 55 parts of butadiene styrene resin, unsaturated 25 parts of polybutadiene, bismaleimide
15 parts and 3 parts of initiator of amine.
The structural formula of unsaturated polyphenylene oxide resin is
In above-mentioned formula, the structural formula of Z isThe structural formula of (- O-Y-)-is
The structural formula of (- O-X-O-)-isA is 15, b 30.Wherein, A is Asia
Aromatic radical, m 6, R1For hydrogen atom, R2For methyl, R3For propyl.R4For heptane atom, R5For phenyl, R6For halogen atom, R7
For phenyl, R8For halogen atom, R9For hydrogen atom, R10For phenyl, R11For phenyl, R12For ethyl, R13For methyl, R14For heptane
Base, R15For butane group, n 0.
The structural formula of bismaleimide isWherein, R1For 5 valence aromatic series bases, XaFor halogen original
Son, XbFor the monovalent organic group in fatty group.
Unsaturated polybutadiene is hydroxy-end capped polybutadiene, and initiator is butyl peroxy isopropylbenzene.
Above-described embodiment 1-3 is only several high frequency resin compositions that the embodiment of the present application is enumerated.Due to high frequency resin group
Every kind of conjunction object prepares raw material, and there are many washabilitys respectively, thus the type of high frequency resin composition is more, does not arrange one by one herein
It lifts, but this does not limit the application to the protection scope of high frequency resin composition.
The embodiment of the present application also provides a kind of prepreg, which includes reinforcing material and the above-mentioned height referred to
Frequency resin combination, and high frequency resin composition is attached on reinforcing material.Wherein, reinforcing material include glass-fiber-fabric, paper and
Composite material etc..
The embodiment of the present application also provides a kind of laminate, which includes at least one layer of above-mentioned prepreg.
The embodiment of the present application also provides a kind of copper-clad plate, which includes at least one layer of above-mentioned prepreg and attachment
Metal foil in prepreg unilateral side or two sides.When copper-clad plate includes multilayer prepreg, in superimposed prepreg
Unilateral or two sides adhesion metal foil.
The embodiment of the present application also provides a kind of printed circuit board, which includes above-mentioned laminate or copper-clad plate.
There is peel strength height, bending strength height, dielectric to verify high frequency resin composition provided by the embodiments of the present application
The excellent comprehensive performances such as small, dielectric constant is low are lost, the embodiment of the present application also carries out dielectric properties, bending to the copper-clad plate of preparation
Intensity and peel strength are tested.
Specifically, butadiene styrene resin, polybutadiene, bismaleimide and initiator are dissolved in dimethylbenzene, then
Filler is added, is then mixed to get high frequency resin composition at room temperature.Above-mentioned high frequency resin combination is impregnated using reinforcing material
Object toasts 5 minutes in 155 DEG C of baking oven and is cured as B-stage, obtains prepreg.Prepreg is placed between copper foil,
It is laminated and solidifies in 210 DEG C in press, obtain copper-clad plate.The copper-clad plate being prepared is advised according to IPC-TM-650 2.4.24
Fixed DMA (Dynamic thermomechanical analysis, dynamic thermomechanical analysis) method measures bending strength.Root
According to the dielectric properties of SPDR (splite post dielectric resonator) method test copper-clad plate, wherein test condition
For A state, frequency 10GHz.Using the peel strength of peeling strength test machine copper-clad plate.Above-mentioned high frequency resin composition preparation
Raw material and dielectric properties, bending strength, the test result of peel strength please refer to table 3, and the selection for preparing raw material is only typical case
And non-limiting a example.
Table 3: the raw material and the dielectric properties of copper-clad plate of high frequency resin composition preparation, bending strength, peel strength
Test result
By the data in table 3 it is found that copper-clad plate in embodiment 1-5 has a stable dielectric properties, and dielectric constant and
Dielectric loss is smaller.The bending strength of copper-clad plate in embodiment 1-5 is all larger than 290MPa, bending strength with higher.Separately
Outside, the peel strength of the copper-clad plate in embodiment 1-5 is higher.Comparative example 1-5 is as it can be seen that the copper-clad plate in embodiment 1 has
Minimum dielectric constant, the smallest dielectric loss, highest bending strength and higher peel strength, as a result, in embodiment 1
Copper-clad plate be by optimal performance high frequency resin composition prepare copper-clad plate.
Known to comparative example 1-5 and embodiment 6-13:
Compared with Example 1, the additional amount of the PPO resin in embodiment 6 is less than the additional amount of PPO resin in embodiment 1,
And the peel strength of the copper-clad plate in embodiment 6 is much smaller than the peel strength of copper-clad plate in embodiment 1.Thus illustrate, copper-clad plate
Peel strength it is related with the additional amount of PPO resin.
Compared with Example 1, the additional amount of the PPO resin in embodiment 7 is greater than the additional amount of PPO resin in embodiment 1,
And the dielectric loss of the copper-clad plate in embodiment 7 is greater than the dielectric loss of copper-clad plate in embodiment 1.Thus illustrate, copper-clad plate
Dielectric loss is related with the additional amount of PPO resin.
Compared with Example 1, the additional amount of the bismaleimide in embodiment 8 is less than bismaleimide in embodiment 1
The additional amount of amine, and the bending strength of the copper-clad plate in embodiment 8 is much smaller than the bending strength of copper-clad plate in embodiment 1.This master
If causing the mechanical strength of copper-clad plate inadequate since crosslink density is insufficient, and then cause bending strength smaller.
Compared with Example 3, the additional amount of the bismaleimide in embodiment 9 is greater than bismaleimide in embodiment 3
The additional amount of amine, and the bending strength of the copper-clad plate in embodiment 9 is less than the bending strength of copper-clad plate in embodiment 3.This is main
It is to cause the brittleness of copper-clad plate larger since crosslink density is excessive, and then cause bending strength smaller.
Compared with Example 1, the additional amount of the butadiene styrene resin in embodiment 10 is less than the addition of butadiene styrene resin in embodiment 1
Amount, and the bending strength of the copper-clad plate in embodiment 10 is much smaller than the bending strength of copper-clad plate in embodiment 1.This is mainly due to
Rigid radical is less and cause the mechanical strength of copper-clad plate inadequate in high frequency resin composition, and then causes bending strength smaller.
Compared with Example 3, the additional amount of the butadiene styrene resin in embodiment 11 is greater than the addition of butadiene styrene resin in embodiment 1
Amount, and the bending strength of the copper-clad plate in embodiment 11 is less than the bending strength of copper-clad plate in embodiment 3.This is mainly due to height
Rigid radical excessively causes the brittleness of copper-clad plate larger in frequency resin combination, and then causes bending strength smaller.
Compared with Example 1, the additional amount of the polybutadiene in embodiment 12 is less than polybutadiene tree in embodiment 1
The additional amount of rouge, and the bending strength of the copper-clad plate in embodiment 12 is less than the bending strength of copper-clad plate in embodiment 1.This is main
It is to cause the mechanical strength of copper-clad plate inadequate since crosslink density is insufficient, and then cause bending strength smaller.
Compared with Example 3, the additional amount of the polybutadiene in embodiment 13 is greater than polybutadiene tree in embodiment 3
The additional amount of rouge, and the bending strength of the copper-clad plate in embodiment 13 is less than the bending strength of copper-clad plate in embodiment 3.This is main
It is to cause the brittleness of copper-clad plate larger since crosslink density is excessive, and then cause bending strength smaller.
From the analysis above, we can see that high frequency resin composition provided by the embodiments of the present application enables to do the semi-solid preparation prepared
Piece, laminate, copper-clad plate and printed circuit board have lower dielectric constant, lesser dielectric loss and higher removing
Intensity, bending strength, and then the transmission of high-frequency signal can not only be met, also meet the plate of high frequency resin composition preparation
The performance requirements such as machining, mechanical support.
Those skilled in the art will readily occur to of the invention its after considering specification and the disclosure invented here of practice
Its embodiment.This application is intended to cover any variations, uses, or adaptations of the invention, these modifications, purposes or
Person's adaptive change follows general principle of the invention and including the undocumented common knowledge in the art of the present invention
Or conventional techniques.The description and examples are only to be considered as illustrative, and true scope and spirit of the invention are by following
Claim is pointed out.
It should be understood that the relational terms of such as " first " and " second " or the like be used merely to an entity or
Operation is distinguished with another entity or operation, and without necessarily requiring or implying between these entities or operation, there are any
This actual relationship or sequence.The invention is not limited to the precision architectures being described above, and can not take off
It carry out various modifications and changes from its range.The scope of the present invention is limited only by the attached claims.
Claims (10)
1. a kind of high frequency resin composition, which is characterized in that the raw material for preparing of the composition includes: unsaturated polyphenylene oxide tree
Rouge, butadiene styrene resin, unsaturated polybutadiene, bismaleimide and initiator.
2. high frequency resin composition according to claim 1, which is characterized in that the composition prepares raw material according to weight
Amount number includes: unsaturated polyphenylene oxide resin 40-80 part, 10-50 parts 45-80 parts of butadiene styrene resin, unsaturation of polybutadiene,
3-40 parts and initiator 1-7 parts of bismaleimide.
3. high frequency resin composition according to claim 1, which is characterized in that the structure of the unsaturation polyphenylene oxide resin
Shown in formula such as formula (1),
In formula (1), a, b are respectively the integer of 1-30, shown in Z such as formula (2) or formula (3) ,-(- O-Y-)-as shown in formula (4) ,-(-
O-X-O-)-as shown in formula (5),
In formula (3), A is selected from the alkylidene that arylene, carbonyl or carbon atom number are 1-10；M is the integer of 0-10；R1-R3Respectively
It is 10 alkyl below selected from hydrogen or carbon atom number；R1-R3It is identical or different；
In formula (4), R4And R6Being respectively selected from hydrogen atom, halogen atom, phenyl or carbon atom number is 8 alkyl below；R5And R7Point
Not Xuan Zi halogen atom, phenyl or carbon atom number be 8 alkyl below；R4With R6It is identical or different, R5With R7It is identical or different；
In formula (5), R8-R15Being respectively selected from hydrogen atom, halogen atom, phenyl or carbon atom number is 8 alkyl below；B is selected from carbon
Atomicity is 20 alkylene below；N is 0 or 1；R8-R15It is identical or different.
4. high frequency resin composition according to claim 1, which is characterized in that the structural formula of the bismaleimide is such as
Shown in formula (6),
In formula (6), R1For the fatty group or aromatic series base of m valence；XaAnd XbThe phase in hydrogen atom, halogen atom and fatty group
Same or different monovalent atom or organic group, the integer that m is 1 or more.
5. high frequency resin composition according to claim 1, which is characterized in that the initiator includes the first initiator
And/or second initiator, the 1min half life temperature of first initiator are 50-160 DEG C, the 1min of second initiator
Half life temperature is 160-300 DEG C.
6. high frequency resin composition according to claim 1, which is characterized in that the high frequency resin composition further includes handing over
Join agent and fire retardant.
7. a kind of prepreg, which is characterized in that including reinforced resin and be attached on the reinforcing material as right is wanted
Seek high frequency resin composition described in any one of 1-6.
8. a kind of laminate, which is characterized in that including at least one layer of prepreg as claimed in claim 7.
9. a kind of copper-clad plate, which is characterized in that including at least one layer of prepreg as claimed in claim 7 and be attached to described
The metal foil of prepreg unilateral side or two sides.
10. a kind of printed circuit board, which is characterized in that including laminate according to any one of claims 8 or as claimed in claim 9 cover
Copper sheet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811331092.6A CN109438960A (en) | 2018-11-09 | 2018-11-09 | A kind of high frequency resin composition and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811331092.6A CN109438960A (en) | 2018-11-09 | 2018-11-09 | A kind of high frequency resin composition and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109438960A true CN109438960A (en) | 2019-03-08 |
Family
ID=65551514
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811331092.6A Pending CN109438960A (en) | 2018-11-09 | 2018-11-09 | A kind of high frequency resin composition and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109438960A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111154197A (en) * | 2020-01-15 | 2020-05-15 | 上海材料研究所 | Hydrocarbon resin composition and preparation method and application thereof |
| CN111253888A (en) * | 2020-03-30 | 2020-06-09 | 广东生益科技股份有限公司 | Circuit material and circuit board comprising same |
| CN111253702A (en) * | 2020-03-30 | 2020-06-09 | 广东生益科技股份有限公司 | Resin composition, and prepreg and circuit material using same |
| CN111372372A (en) * | 2020-03-30 | 2020-07-03 | 广东生益科技股份有限公司 | Circuit material and circuit board comprising same |
| CN111393724A (en) * | 2020-03-30 | 2020-07-10 | 广东生益科技股份有限公司 | Resin composition, and prepreg and circuit material using same |
| WO2021012619A1 (en) * | 2019-07-22 | 2021-01-28 | 南亚新材料科技股份有限公司 | High-frequency resin composition and use thereof |
| US11008456B2 (en) | 2019-03-12 | 2021-05-18 | Taiwan Union Technology Corporation | Resin composition and uses of the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090026663A1 (en) * | 2007-07-25 | 2009-01-29 | Sabic Innovative Plastics Ip Bv | Thermoformable polycarbonate/polyester compositions and uses |
| CN103965606A (en) * | 2013-02-04 | 2014-08-06 | 联茂电子股份有限公司 | Low dielectric material |
| CN104725828A (en) * | 2015-03-04 | 2015-06-24 | 广东生益科技股份有限公司 | Resin composition, prepreg using resin composition and laminate |
| CN106280179A (en) * | 2016-08-29 | 2017-01-04 | 陕西生益科技有限公司 | A kind of high frequency resin composition and application thereof |
-
2018
- 2018-11-09 CN CN201811331092.6A patent/CN109438960A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090026663A1 (en) * | 2007-07-25 | 2009-01-29 | Sabic Innovative Plastics Ip Bv | Thermoformable polycarbonate/polyester compositions and uses |
| CN103965606A (en) * | 2013-02-04 | 2014-08-06 | 联茂电子股份有限公司 | Low dielectric material |
| CN104725828A (en) * | 2015-03-04 | 2015-06-24 | 广东生益科技股份有限公司 | Resin composition, prepreg using resin composition and laminate |
| CN106280179A (en) * | 2016-08-29 | 2017-01-04 | 陕西生益科技有限公司 | A kind of high frequency resin composition and application thereof |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI794445B (en) * | 2019-03-12 | 2023-03-01 | 台燿科技股份有限公司 | Resin composition and uses of the same |
| US11008456B2 (en) | 2019-03-12 | 2021-05-18 | Taiwan Union Technology Corporation | Resin composition and uses of the same |
| JP2022508173A (en) * | 2019-07-22 | 2022-01-19 | 南亜新材料科技股▲ふん▼有限公司 | High frequency resin composition and its use |
| KR102523921B1 (en) * | 2019-07-22 | 2023-04-19 | 난야 뉴 머티리얼 테크놀로지 컴퍼니 리미티드 | High-frequency resin composition and its application |
| JP7170136B2 (en) | 2019-07-22 | 2022-11-11 | 南亜新材料科技股▲ふん▼有限公司 | High frequency resin composition and use thereof |
| WO2021012619A1 (en) * | 2019-07-22 | 2021-01-28 | 南亚新材料科技股份有限公司 | High-frequency resin composition and use thereof |
| KR20210090653A (en) * | 2019-07-22 | 2021-07-20 | 난야 뉴 머티리얼 테크놀로지 컴퍼니 리미티드 | High frequency resin composition and its application |
| CN111154197A (en) * | 2020-01-15 | 2020-05-15 | 上海材料研究所 | Hydrocarbon resin composition and preparation method and application thereof |
| CN111393724A (en) * | 2020-03-30 | 2020-07-10 | 广东生益科技股份有限公司 | Resin composition, and prepreg and circuit material using same |
| US20210307164A1 (en) * | 2020-03-30 | 2021-09-30 | Shengyi Technology Co., Ltd. | Circuit material and circuit board containing the same |
| CN111372372A (en) * | 2020-03-30 | 2020-07-03 | 广东生益科技股份有限公司 | Circuit material and circuit board comprising same |
| US11584851B2 (en) | 2020-03-30 | 2023-02-21 | Shengyi Technology Co., Ltd. | Resin composition, and prepreg and circuit material using the same |
| CN111253702A (en) * | 2020-03-30 | 2020-06-09 | 广东生益科技股份有限公司 | Resin composition, and prepreg and circuit material using same |
| CN111253888A (en) * | 2020-03-30 | 2020-06-09 | 广东生益科技股份有限公司 | Circuit material and circuit board comprising same |
| CN111253702B (en) * | 2020-03-30 | 2023-06-06 | 广东生益科技股份有限公司 | Resin composition, prepreg and circuit material using same |
| CN111372372B (en) * | 2020-03-30 | 2023-12-22 | 广东生益科技股份有限公司 | Circuit material and circuit board comprising same |
| US11930595B2 (en) * | 2020-03-30 | 2024-03-12 | Shengyi Technology Co., Ltd. | Circuit material and circuit board containing the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109438960A (en) | A kind of high frequency resin composition and application | |
| TWI541288B (en) | A resin composition and a prepreg and laminate using the same | |
| US10584222B2 (en) | Resin composition and pre-preg and laminate using the composition | |
| JP3771160B2 (en) | Curable polyphenylene ether resin, composition thereof, and method for producing the resin | |
| CN104774476A (en) | Phosphorus-containing flame retardant composition, and phosphorus-containing polyphenyl ether resin composition, prepreg and laminated board using the same | |
| KR20080093920A (en) | Prepreg, multilayer wiring board and electronic parts using same | |
| CN113614172A (en) | Resin composition and use thereof | |
| CN106379006B (en) | A kind of high-frequency copper-clad plate | |
| CN108081709B (en) | Low-dielectric-loss and low-dielectric-loss glass fiber copper-clad plate and preparation method thereof | |
| CN111253888A (en) | Circuit material and circuit board comprising same | |
| CN106280199B (en) | A kind of compositions of thermosetting resin and its application | |
| CN106280178B (en) | A kind of resin combination and its application | |
| CN111372372A (en) | Circuit material and circuit board comprising same | |
| CN111703150A (en) | Method for reducing dielectric loss of polyolefin composite substrate material | |
| CN109467862A (en) | A kind of high frequency resin composition and its application | |
| JP2017502109A (en) | Vinyl-capped poly (phenylene) ether and styrene butadiene copolymer blends for curable compositions | |
| CN106380715B (en) | A kind of resin combination | |
| WO2020027189A1 (en) | Metal-clad laminate, printed circuit board, and method of manufacturing same | |
| JP7294834B2 (en) | Curable compositions, dry films, cured products, laminates and electronic components | |
| CN108250605B (en) | Polysiloxane-allyl compound modified polybutadiene resin composition, and prepreg, laminated board and printed circuit board thereof | |
| US5009949A (en) | Resin composition and electrical laminate obtained therefrom | |
| JPS62121758A (en) | Polyphenylene oxide resin composition and sheet composed of said resin composition | |
| JPH01115917A (en) | Thermosetting resin | |
| JPS6242787B2 (en) | ||
| JPH0311301B2 (en) |
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 |