CN110317445A - A kind of high frequency resin composition and its application - Google Patents
A kind of high frequency resin composition and its application Download PDFInfo
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- CN110317445A CN110317445A CN201910659227.XA CN201910659227A CN110317445A CN 110317445 A CN110317445 A CN 110317445A CN 201910659227 A CN201910659227 A CN 201910659227A CN 110317445 A CN110317445 A CN 110317445A
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- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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Abstract
The present invention relates to a kind of high frequency resin composition and its applications, 25-50 parts of modified polyphenylene ether resin, 15-40 parts of block copolymer rubber, unsaturated diene series rubber 10-50 parts, 5-30 parts of amine copolymer object of N- substituted maleimide, 10-30 parts of small molecule crosslinking agent, fire retardant, filler and promotor.Compared with prior art, the present invention introduces N- substituted maleimide amine copolymer object in rubbery system and can significantly improve material glass transition temperature and peel strength while have many advantages, such as that dielectric loss is small, heat-resist.
Description
Technical field
The present invention relates to high-frequency high-speed technical fields, more particularly, to a kind of high frequency resin composition and its application.
Background technique
With the arrival in 5G epoch, the continuous improvement of terminal applies and network speed, the message transmission rate of equipment room is
It is promoted from several hundred Mbps to 20Gbps, the industrial technology of PCB is regardless of soft board and hardboard be all toward high frequency, high speed and highly dense at present
Spend the method development of structure dress, corresponding product is light, it is thin, can carry, the development trend of multifunction, for material and preparation method
Demand can be more and more harsh, under high-frequency high-speed and miniature requirement, high-frequency transmission and low-loss material will substitute biography comprehensively
Defeated line, most important one material property demand are exactly ultralow dielectric properties, high-fire resistance, good anti-flammability.
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.It is passed as a result, as high-frequency signal
Defeated insulator, can be by the small insulating materials of selection dielectric loss angle tangent, to inhibit the increase of dielectric loss.
Currently, the insulating materials as high frequency signal transmission usually passes through polytetrafluoroethylene material or hydrocarbon resin material system
Standby, due to polytetrafluoroethylene material processing difficulties, hydrocarbon material is used widely in terms of high frequency.Pass through block copolymer rubber
Glue or the hydrocarbon resin of the olefin resin and filler of unsaturationization preparation, that there are peel strengths is low, heat resistance is bad, bending is strong
Small disadvantage is spent, and the bonding sheet prepared is likely to occur viscous problem due to rubber material, influences the production of bonding sheet, protects
It deposits and transports.Therefore, it is necessary to develop a kind of high-fire resistance, high-peeling strength, low-dielectric loss, low-expansion high frequency base
Plate material.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind to be with hydrocarbon resin
Main high frequency resin composition.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of high frequency resin composition, the component including following parts by weight content:
< N- substituted maleimide amine copolymer object >
N- substituted maleimide amine copolymer object is copolymerized by the monomer of following molar part content: styrene monomer 30-60
Part, 30-70 parts of N- substituted maleimide amine, 1-20 parts of unsaturated acid anhydride；Styrene, N- substituted maleimide amine, maleic anhydride
The molecular formula of copolymer is as follows:
In formula, x, y, z is respectively the molar ratio of styrene monomer, N- substituted maleimide amine, unsaturated acid anhydride, x:y:z
=0.3~0.6:0.3~0.7:0.01~0.2.
R group is methyl, ethyl, isopropyl, cyclohexyl, benzene in above-mentioned N- substituted maleimide amine copolymer object molecular formula
Base, benzyl, phenylethyl, phenyl vinyl, p-hydroxybenzene, xenyl, naphthalene nucleus base；Wherein preferred methyl, phenyl, phenyl second
Alkenyl, molecular formula difference are as follows:
A) N- methylmaleimido copolymer:
B) N-phenylmaleimide copolymer:
C) N- phenyl vinyl maleimide copolymer:
The N- substituted maleimide amine copolymer object that the present invention uses is styrene, N- substituted maleimide amine, maleic anhydride
Copolymer (SMI), the compatibility being able to ascend between polarity and non-polar resin, styrene segment and rubber type of material are by good
Compatibility, and maleimide and maleic anhydride segment can have good compatibility with polar resin, while be able to ascend boundary
Surface intensity improves the binding force with the peel strength of metal foil and with glass beam.N- substituted maleimide amine copolymer object has
Good heat resistance, outstanding thermal stability (350 DEG C are not decomposed), when being used in mixed way with hydrocarbon resin, as hydrocarbon material
Heat-proof modifier improves the glass transition temperature and heat resistance of plate.
Wherein, the content of N- substituted maleimide amine copolymer object is preferably 5-30 parts, if the N- of addition replaces Malaysia acyl
Imine copolymer is very few, and to the improved heat resistance of material than relatively limited, and peel strength is lower；If the N- of addition replaces horse
It is excessive to carry out imide copolymer, then its dielectric properties is risen, and water absorption rate can also obviously increase.
The molecular weight of N- substituted maleimide amine copolymer object is not particularly limited, the preferable model of usual number-average molecular weight
It encloses for 2000-200000, wherein preferred range is 5000-50000, is had in resin combination quickly good molten
Xie Xing, while also can guarantee the reliable heat resistance of material and thermal stability.
< block copolymer rubber >
The block copolymer rubber is using styrene as end segment, is intermediate segment with polybutadiene, isoprene
Linear three block copolymer, number-average molecular weight is 5000~150000, and styrene segment accounts for the block copolymer rubber
The 10~50% of glue gross mass.
Containing the block copolymer rubber of larger molecular weight in compositions of thermosetting resin, the block copolymer be with
Styrene is end segment, with polybutadiene, the linear three block copolymer that isoprene is intermediate segment, this block copolymer
Do not have double bond structure usually, there is less reactive.The block copolymer rubber has low polar character, can show
Extremely low dielectric constant and low-dielectric loss needed for high-frequency high-speed material, but the heat resistance of often material is bad, with metal foil
Peel strength it is lower.Use this low polar material and a small amount of polar material such as polyphenylene oxide, cyanate, maleimide etc.
Resin combination can obtain good performance balance.Therefore the block copolymer rubber as composition it is main at
/ mono-, the ratio selection of styrene segment and butadiene segment is particularly important.
Above-mentioned block copolymer rubber optimization styrene-butadiene-styrene (SBS), styrene-isoprene-benzene second
Alkene (SIS), styrene-butadiene/isoprene styrene (SBIS), the s-B-S (HSBS) of hydrogenation,
The styrene-isoprene-phenylethene (HSIS) of hydrogenation, styrene-butadiene/isoprene styrene of hydrogenation
(HSBIS)。
The preferred 5000-150000 of its number-average molecular weight of the block copolymer rubber, when molecular weight of copolymer is less than
When 5000, material itself is excessively soft, apparent humidification cannot be played to resin base material, and prepreg is easy to happen
Viscous problem；When molecular weight of copolymer is greater than 150000, block copolymer amount is excessively high, and dissolubility is not in a solvent for resin
It is good, and viscosity is excessively high, does not have good processing condition, and prepreg does not have good mobility in pressing,
It is unfavorable for the production of substrate and the filling of wiring board and flows into the patterned features of adjacent layer.
The ratio that styrene segment accounts for the block copolymer rubber gross mass is preferably 10~50%, styrene segment ratio
When example is less than 10%, the glass transition temperature of material is too low；When styrene segment is greater than 50%, substrate and metal foil removing are strong
It spends lower.Styrene segment account for block copolymer mass ratio be 10-50% when, material properties such as dielectric properties, glass
Changing transition temperature, peel strength, heat resistance etc. has preferable harmony.
< unsaturation diene series rubber >
The polymerized monomer of the unsaturation diene series rubber includes unmodified or butadiene or isoamyl two containing modified group
One or more of alkene, the modified group are selected from one of epoxy group, maleic anhydride, acrylate, hydroxy or carboxy
Or it is several；Wherein, the number-average molecular weight of the diene series rubber is 500~20000, and unsaturated double-bond structure accounts for the diene series
The 60~99% of rubber backbone quality.
Specifically, diene series rubber is polybutadiene, the polyisoprene for containing double bond structure containing side chain or main chain；It is excellent
Select 1,2- polybutadiene, cis- Isosorbide-5-Nitrae polybutadiene, 1,2- polyisoprene, cis- Isosorbide-5-Nitrae polyisoprene.
More specifically, the unsaturation diene series rubber is selected from polybutadiene, polyisoprene, styrene-fourth two
Alkene copolymer, styrene-isoprene copolymer, divinylbenzene-butadiene copolymer, divinylbenzene-isoprene are total
One of polymers, styrene-butadiene-divinyl benzene copolymer or styrene-isoprene-divinyl benzene copolymer
Or it is several.
The number-average molecular weight of unsaturated diene rubber selected by the present invention is 500-20000, further preferred molecular weight
For 1000-10000.When the molecular weight of unsaturated macromolecule resin is less than 500, it is not improved to dielectric properties are reduced, when
When the molecular weight of unsaturated macromolecule resin is greater than 20000, the glass transition temperature and peel strength of resin system can be deteriorated；
Unsaturated double-bond structure accounts for the 60~99% of the diene series rubber main chain quality, unsaturated double bond mistake in diene series rubber
When low, crosslink that the group reacted is less, and peel strength is low, and glass transition temperature is lower with other thermosetting resins, and
Mechanical strength is bad.
Wherein, unsaturated diene series rubber modified group is selected from epoxy group, maleic anhydride, (methyl) acrylate, hydroxyl
Or one or more of carboxyl；The acrylate modified unsaturated butadiene polymer of further preferred maleic anhydride, (methyl)
Close object.Modified unsaturation diene series rubber is conducive to further increase the peel strength of resin and metal foil, resin boundary surface interlayer
Adhesion strength.
< modified polyphenylene ether resin >
The modified polyphenylene ether resin is that the end group of polyphenylene oxide resin is used vinyl or methacrylate
Modification is prepared, the preferred 500-10000 of number-average molecular weight.
Diene series rubber with unsaturated double-bond structure arranges in pairs or groups with modified polyphenylene ether resin, can further decrease material
Expect dielectric constant and dielectric loss, while improving the adhesion strength of resin and copper foil, promote resin boundary surface and metal interlevel can
By property.
Noryl number-average molecular weight preferred 500-10000, further preferably 1000-5000 are preferred.Work as molecular weight
When less than 500, reaction-ity ethylene base is excessive, is not easy to obtain lower dielectric properties, and reaction speed is too fast, is difficult to control；When
When molecular weight is greater than 10000, polyphenylene oxide resin melt viscosity is excessively high, and the compatibility poor with other resins, the material of preparation
Easily cause bad order.
The Noryl is the polyphenylene oxide that vinyl modified or methacrylate end block, and can be illustrated such as
Sabic SA-9000, the modified polyphenylene ether resin blocked with methacrylate；It can also illustrate such as Mitsubishi Chemical OPE-2ST,
The modified polyphenylene ether resin blocked with phenyl vinyl.
< small molecule crosslinking agent >
Also contain small molecule crosslinking agent in resin combination, is mainly used for improving block copolymer rubber, unsaturated diene
It is the crosslink density of rubber and N- substituted maleimide amine copolymer object, increases cross-linked network compactness, improves material glass and turn
Temperature and heat resistance.
It is different that small molecule crosslinking agent preferably is selected from Triallyl isocyanurate, triallylcyanurate, three methylallyls
Cyanurate, front three are for allyl cyanurate, trihydroxyethyl isocyanuric ester, t-butyl styrene, M-phthalic acid diene
One in propyl diester, diallyl phthalate, trimethylolpropane trimethacrylate or pentaerythritol tetraacrylate
Kind is several；
In addition, the invention patent further includes fire retardant, filler and promotor.
< fire retardant >
The fire retardant that the present invention uses preferably is selected from the mixture of one of brominated flame-retardant or phosphonium flame retardant or both,
Wherein, in order to adapt to low dielectric resin system, preferred brominated flame-retardant or phosphonium flame retardant are not dissolved in resin system, are led to
Often selected from polyphenylene oxide resin and other resins without reactive and the addition type bromine system of heat resistance and dielectric property will not be reduced
Fire retardant or phosphorus flame retardant.
Addition type brominated flame-retardant preferably is selected from deca-BDE, decabromodiphenylethane, brominated styrene or ten in the present invention
One or more of double tetrabromo phthalimides of dibromodiphenyl ether, ethylene；Addition type phosphonium flame retardant is selected from three (2,6- bis-
Aminomethyl phenyl) phosphorus, the miscellaneous -10- phosphorus phenanthrene -10- oxide of 10- (2,5- dihydroxy phenyl) -9,10- dihydro-9-oxy, 2,6- bis- (2,
6- 3,5-dimethylphenyl) one of phosphorus base benzene or the miscellaneous -10- phosphorus phenanthrene -10- oxide of 10- phenyl -9,10- dihydro-9-oxy or several
Kind.
< filler >
Filler used in the present invention is not particularly limited, can selected from aluminium nitride, aluminium borate, magnesia, magnesium carbonate,
Boron nitride, crystalline silica, synthetic silica, hollow silica, preparing spherical SiO 2, fused silica, talcum
One of powder, aluminium oxide, barium sulfate, barium titanate, strontium titanates, calcium carbonate or titanium dioxide are a variety of.
< promotor >
In order to promote resin combination react, enhances crosslink density, improves glass transition temperature and heat resistance,
Promotor (initiator) can be used to further speed up reaction.
Promotor used in the present invention is preferably organic peroxide radical initiator, is selected from di-tert-butyl peroxide
Object, dilauroyl peroxide, dibenzoyl peroxide, cumyl peroxyneodecanoate, new peroxide tert-butyl caprate, peroxide
Change the pivalic acid tert-butyl ester, tert-butyl hydroperoxide isobutyrate, tert-butyl hydroperoxide -3,5,5 Trimethylhexanoic acid ester, peroxidating second
Tert-butyl acrylate, peroxidized t-butyl perbenzoate, 1,1- di-tert-butyl peroxide -3,5,5- trimethyl-cyclohexane, the tertiary fourth of 1,1- bis-
Base cyclohexane peroxide, 2,2- bis- (tert-butyl hydroperoxide) butane, bis- (4- tert-butylcyclohexyl) peroxy dicarbonates, peroxide
Change two carbonic ester hexadecyl esters, 14 ester of peroxy dicarbonate, two special penta own peroxide, dicumyl peroxide, bis- (uncles
Butyl peroxy isopropyl) benzene, 2,5- dimethyl -2,5- di-t-butyl hexane peroxide, 2,5- dimethyl -2,5- di-t-butyl
Peroxidating hexin, diisopropylbenzene hydroperoxide, isopropyl benzene hydroperoxide, tertiary amyl hydrogen peroxide, tert-butyl hydroperoxide, tertiary fourth
Base dicumyl peroxide, diisopropylbenzene hydroperoxide, peroxycarbonates -2 ethyl hexanoic acid tert-butyl ester, tert-butyl hydroperoxide carbon
One in acid -2- ethylhexyl, 4,4- bis- (tert-butyl hydroperoxide) n-butyl pentanoate, methyl ethyl ketone peroxide or cyclohexane peroxide
Kind is several.
High frequency resin composition of the invention can be used for preparing bonding sheet, metal-clad laminate and printed wire
Plate.
Prepare bonding sheet: medium-high frequency resin combination of the present invention is coated in reinforcing fiber and forms prepreg；Described
Reinforcing fiber can be organic fiber or inorfil passes through the enhancing textile fabric being knitted to form, preferably fiberglass braided fibre
Wei Bu, including E-glass, T-glass, NE-glass, L-glass and Q-glass.
Prepare metal-clad laminate: the metal-clad laminate overlaps one side or at least two sides using above-mentioned bonding sheet
Metal foil hot pressing is made；The preferred copper foil of metal foil, further preferably electrolytic copper foil, surface roughness Rz are preferably smaller than 5um,
Can illustrate RTF copper foil, VLP copper foil, HVLP copper foil, HVLP2 copper foil, can further improve the signal damage of high-frequency high-speed wiring board
Mistake problem.
Prepare printed wiring board: printed wiring board includes at least an above-mentioned bonding sheet or above-mentioned clad with metal foil is laminated
Plate.Resin combination of the invention have good mechanical strength and toughness, good glass transition temperature, peel strength and
Therefore low-dielectric energy is suitble to prepare the processing of high multilayer printed circuit board.
Use N- substituted maleimide copolymer as the heat resistance modified of rubber in the present invention, in resin combination
Agent and compatilizer contain N- substituted maleimide amine structure and maleic anhydride structure in the triblock copolymer, and N- is replaced
Resin base material of the based copolymer for the block copolymer rubber containing vinyl and unsaturated diene series rubber
In, the heat resistance of vinyl segment is improved using maleimide structure, enhances the heat resistance of resin base material, in addition horse
Carry out acid anhydride structure and also improves the polarity of vinyl segment.
Compared with prior art, the invention has the following advantages that
(1) N- substituted maleimide copolymer is used, the heat resistance of resin base material is improved, improves and inorganic material
The compatibility of material and fire retardant, and the interface peel intensity of high resin substrate and metal foil is improved, with resin of the invention
Composition has good dielectric properties and mechanical performance as insulator；
(2) selection for optimizing the unsaturated diene series rubber in resin base material, using high-content unsaturated double-bond structure
Liquid polybutadiene, further improve electrical insulating property, peel strength and the glass transition temperature of resin combination；
(3) it is added to modified polyphenylene ether resin in resin base material, further improves the heat resistance of high frequency resin composition
And peel strength of copper foil.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
The component including following parts by weight content: a kind of high frequency resin composition 15-40 parts of block copolymer rubber, changes
25-50 parts of polyphenylene oxide resin, unsaturated diene series rubber 10-50 parts, 5-30 parts of amine copolymer object of N- substituted maleimide, small point of property
Sub- crosslinking agent 10-50 parts, fire retardant, filler and promotor.
< N- substituted maleimide amine copolymer object >
N- substituted maleimide amine copolymer object is copolymerized by the monomer of following molar part content: styrene monomer 30-60
Part, 30-70 parts of N- substituted maleimide amine, 1-20 parts of unsaturated acid anhydride；Styrene, N- substituted maleimide amine, maleic anhydride
The molecular formula of copolymer is as follows:
In formula, x, y, z is respectively the molar ratio of styrene monomer, N- substituted maleimide amine, unsaturated acid anhydride, x:y:z
=0.3~0.6:0.3~0.7:0.01~0.2.
R group is methyl, ethyl, isopropyl, cyclohexyl, benzene in above-mentioned N- substituted maleimide amine copolymer object molecular formula
Base, benzyl, phenylethyl, phenyl vinyl, p-hydroxybenzene, xenyl, naphthalene nucleus base；Wherein preferred methyl, phenyl, phenyl second
Alkenyl, molecular formula difference are as follows:
A) N- methylmaleimido copolymer:
B) N-phenylmaleimide copolymer:
C) N- phenyl vinyl maleimide copolymer:
< block copolymer rubber >
Containing the block copolymer rubber of larger molecular weight in high frequency resin composition, the block copolymer is with benzene
Ethylene is end segment, and with polybutadiene, the linear three block copolymer that isoprene is intermediate segment, number-average molecular weight exists
5000~150000, and styrene segment accounts for the 10~50% of the block copolymer rubber gross mass.This block copolymerization
Object does not have double bond structure usually, has less reactive.Block copolymer rubber optimization styrene-in the embodiment of the present invention
Butadiene-styrene (SBS), styrene-isoprene-phenylethene (SIS), styrene-butadiene/isoprene styrene
(SBIS), the s-B-S (HSBS) of hydrogenation, the styrene-isoprene-phenylethene (HSIS) of hydrogenation, hydrogen
Styrene-butadiene/isoprene styrene (HSBIS) of change.
< unsaturation diene series rubber >
The polymerized monomer of unsaturated diene series rubber includes butadiene unmodified or containing modified group in resin combination
Or one or more of isoprene, diene series rubber are the polybutadiene for containing double bond structure containing side chain or main chain, gather
Isoprene；It is preferred that 1,2- polybutadiene, cis- Isosorbide-5-Nitrae polybutadiene, 1,2- polyisoprene, cis- Isosorbide-5-Nitrae polyisoprene.
Wherein, unsaturated diene series rubber modified group is selected from epoxy group, maleic anhydride, (methyl) acrylate, hydroxyl
Or one or more of carboxyl；The acrylate modified unsaturated butadiene polymer of further preferred maleic anhydride, (methyl)
Close object.Modified unsaturation diene series rubber is conducive to further increase the peel strength of resin and metal foil, resin boundary surface interlayer
Adhesion strength.
The selection of unsaturated diene series rubber is exemplified as polybutadiene, polyisoprene, styrene butadiene copolymers
Object, styrene-isoprene copolymer, divinylbenzene-butadiene copolymer, divinylbenzene-isoprene copolymer, benzene
One or more of ethylene-butylene-divinyl benzene copolymer or styrene-isoprene-divinyl benzene copolymer.
< modified polyphenylene ether resin >
Modified polyphenylene ether resin is to change the end group of polyphenylene oxide resin using vinyl or methyl methacrylate base
Property is prepared, and it is 500~10000 that molecular weight, which can choose,.
< small molecule crosslinking agent >
The selection of small molecule crosslinking agent is exemplified as Triallyl isocyanurate, triallylcyanurate, front three for alkene
Propyl isocyanuric acid ester, front three are for allyl cyanurate, trihydroxyethyl isocyanuric ester, t-butyl styrene, isophthalic diformazan
Diene acid propyl diester, diallyl phthalate, trimethylolpropane trimethacrylate or pentaerythritol tetraacrylate
One or more of；
In addition, the present embodiment patent further includes fire retardant, filler and promotor.
< fire retardant >
The fire retardant that the present embodiment uses preferably is selected from the mixing of one of brominated flame-retardant or phosphonium flame retardant or both
Object, wherein in order to adapt to low dielectric resin system, preferred brominated flame-retardant or phosphonium flame retardant do not dissolve in resin system
In, it is generally selected from polyphenylene oxide resin and other resins without reactivity and will not reduce the addition type of heat resistance and dielectric property
Bromide fire retardant or phosphorus flame retardant.
In the present embodiment addition type brominated flame-retardant preferably be selected from deca-BDE, decabromodiphenylethane, brominated styrene or
One or more of double tetrabromo phthalimides of deca-BDE, ethylene；Addition type phosphonium flame retardant is selected from three (2,6-
3,5-dimethylphenyl) phosphorus, the miscellaneous -10- phosphorus phenanthrene -10- oxide of 10- (2,5- dihydroxy phenyl) -9,10- dihydro-9-oxy, 2,6- bis-
One of (2,6- 3,5-dimethylphenyl) phosphorus base benzene or the miscellaneous -10- phosphorus phenanthrene -10- oxide of 10- phenyl -9,10- dihydro-9-oxy or
It is several.
< filler >
Filler used in the present embodiment is not particularly limited, and can be selected from aluminium nitride, aluminium borate, magnesia, carbonic acid
Magnesium, boron nitride, crystalline silica, synthetic silica, hollow silica, preparing spherical SiO 2, fused silica, cunning
One of mountain flour, aluminium oxide, barium sulfate, barium titanate, strontium titanates, calcium carbonate or titanium dioxide are a variety of.
< promotor >
In order to promote resin combination react, enhances crosslink density, improves glass transition temperature and heat resistance,
Promotor (initiator) can be used to further speed up reaction.
Promotor used in the present embodiment is preferably organic peroxide radical initiator, is selected from di-t-butyl peroxide
Compound, dilauroyl peroxide, dibenzoyl peroxide, cumyl peroxyneodecanoate, new peroxide tert-butyl caprate, mistake
Aoxidize the pivalic acid tert-butyl ester, tert-butyl hydroperoxide isobutyrate, tert-butyl hydroperoxide -3,5,5 Trimethylhexanoic acid ester, peroxidating
Tert-butyl acetate, peroxidized t-butyl perbenzoate, 1,1- di-tert-butyl peroxide -3,5,5- trimethyl-cyclohexane, 1,1-, bis- uncle
Butyl peroxy hexamethylene, 2,2- bis- (tert-butyl hydroperoxide) butane, bis- (4- tert-butylcyclohexyl) peroxy dicarbonates, mistake
Aoxidize two carbonic ester hexadecyl esters, 14 ester of peroxy dicarbonate, two special penta own peroxide, dicumyl peroxide, double
(t-butylperoxyisopropyl) benzene, 2,5- dimethyl -2,5- di-t-butyl hexane peroxide, two uncle of 2,5- dimethyl -2,5-
Butyl peroxy hexin, diisopropylbenzene hydroperoxide, isopropyl benzene hydroperoxide, tertiary amyl hydrogen peroxide, tert-butyl hydroperoxide,
Cumyl t-butyl peroxide, diisopropylbenzene hydroperoxide, peroxycarbonates -2 ethyl hexanoic acid tert-butyl ester, t-butyl peroxy
Change in carbonic acid -2- ethylhexyl, 4,4- bis- (tert-butyl hydroperoxide) n-butyl pentanoate, methyl ethyl ketone peroxide or cyclohexane peroxide
One or more.
High frequency resin composition of the invention can be used for preparing bonding sheet, metal-clad laminate and printed wire
Plate.
Prepare bonding sheet: the present embodiment medium-high frequency resin combination is coated in reinforcing fiber and forms prepreg；It is described
Reinforcing fiber can be organic fiber or inorfil and pass through the enhancing textile fabric being knitted to form, it is preferably fiberglass braided
Fiber cloth, including E-glass, T-glass, NE-glass, L-glass and Q-glass.
Prepare metal-clad laminate: the metal-clad laminate overlaps one side or at least two sides using above-mentioned bonding sheet
Metal foil hot pressing is made；The preferred copper foil of metal foil, further preferably electrolytic copper foil, surface roughness Rz are preferably smaller than 5um,
Can illustrate RTF copper foil, VLP copper foil, HVLP copper foil, HVLP2 copper foil, can further improve the signal damage of high-frequency high-speed wiring board
Mistake problem.
Prepare printed wiring board: printed wiring board includes at least an above-mentioned bonding sheet or above-mentioned clad with metal foil is laminated
Plate.The resin combination of the present embodiment has good mechanical strength and toughness, good glass transition temperature, peel strength
Therefore it is suitble to prepare the processing of high multilayer printed circuit board with low-dielectric energy.
The preparation method of high frequency resin composition in this implementation, comprising the following steps:
(1) it stocks up by formula；
(2) block copolymer rubber, unsaturated diene series rubber and N- substituted maleimide amine copolymer are dissolved in solvent,
Crosslinking agent is added, obtains high frequency resin composition after decentralized processing.
Further, if containing fire retardant, inorganic filler and promotor in composite formula, step (2) is by block
Copolymer rubber, unsaturated diene series rubber and N- substituted maleimide amine copolymer are dissolved in solvent, and fire retardant is added, inorganic fills out
Material and promotor, stir evenly, low dielectric resin composition are obtained after decentralized processing.
The copper-clad plate being prepared is tested for the property, test method are as follows:
Glass transition temperature (Tg): DMA instrument test is used, according to the DMA of IPC-TM-650 2.4.24.4 defined
Test method is measured.
Z axis thermal expansion coefficient (CTE): using TMA instrument test, surveys according to the TMA of IPC-TM-650 2.4.24 defined
Method for testing measurement.
Peel strength of copper foil (PS): being tested using Shimadzu puller system, according to the test of IPC-TM-650 2.4.8 defined
Method measurement.
Dielectric constant (Dk) and dielectric loss factor (Df): dielectric constant and dielectric loss factor test method are according to IPC-
The test method of TM-650 2.5.5.9 defined measures.
Pressure cooker gluten substitute (PCT): laminate is in 120 DEG C of progress thermophilic digestion experiments, according to IPC-TM-650
2.6.16 the test method of defined measures.
288 DEG C of separation times (T288): TMA instrument test is used, according to the survey of IPC-TM-650 2.4.24.1 defined
Method for testing measurement.
Anti-flammability: test grading is carried out according to the material combustion method of UL-94 defined.
Water absorption rate: it is measured according to the laminate water absorption rate test method of IPC-TM-650 2.6.2.1 defined.
Resin Flow: being measured Resin Flow by Shimadzu capillary rheometer, and 2g resin-oatmeal briquetting is with one
Constant-pressure squeezes out resin from aperture, is assessed according to the stroke that resin flows out in rheometer.It is longer to flow out stroke, tree
Membranous lipid fluidity is better.
Heat resistance: refer to that substance is still able to maintain the property of its excellent physical mechanical property under conditions of heated.
Resin system compatibility: substrate cross section is taken to observe the microscopic uniformity of solidified resin in the secure execution mode (sem, if there is tree
Rouge agglomeration, as resin are incompatible.
The following are specific implementation situations of the invention.
A kind of high frequency resin composition, the component including following parts by weight content: modified polyphenylene ether resin, block copolymer
Rubber, unsaturated diene series rubber, N- substituted maleimide amine copolymer object, small molecule crosslinking agent, fire retardant, filler and promotion
Agent, as shown in table 1, the content of each component is as shown in table 2 for the source of each component and selection in the present embodiment.
The source of raw material components in 1 embodiment 1~13 of table and comparative example 1~3
The component proportion data of table 2 embodiment 1~13 and comparative example 1~3
The component proportion data (continued) of 2 embodiment 1~13 of table and comparative example 1~3
The component proportion data (continued) of 3 embodiment 1~13 of table and comparative example 1~3
The component proportion data (continued) of 4 embodiment 1~13 of table and comparative example 1~3
Embodiment 11
A kind of high frequency resin composition, the component including following parts by weight content: modified polyphenylene ether resin, block copolymer
Rubber, unsaturated diene series rubber, N- substituted maleimide amine copolymer object, small molecule crosslinking agent, fire retardant, filler and promotion
Agent, wherein the content of each component is as shown in table 2.
Wherein, the filler used causes its dielectric loss higher for high Dk filler (Dk > 10).
Embodiment 12
A kind of high frequency resin composition, the component including following parts by weight content: modified polyphenylene ether resin, block copolymer
Rubber, unsaturated diene series rubber, N- substituted maleimide amine copolymer object, small molecule crosslinking agent, fire retardant, filler and promotion
Agent, wherein the content of each component is as shown in table 2.
Modified polyphenylene ether resin is that the end group of polyphenylene oxide resin is prepared using vinyl modified；Block copolymerization
Object rubber is using styrene as end segment, with polybutadiene, the linear three block copolymer that isoprene is intermediate segment, block
The number-average molecular weight of copolymer rubber is 5000, and styrene segment content is 10%；Unsaturated diene series rubber is benzene second
Alkene-isoprene copolymer and divinylbenzene-isoprene copolymer, wherein Isosorbide-5-Nitrae-cis-double bonds structure accounts for 60%, number
Average molecular weight is 1000；The monomer of N- substituted maleimide amine copolymer object is styrene, N-phenylmaleimide, unsaturated acids
Acid anhydride, wherein the molfraction of styrene is 30 parts, and the molfraction of unsaturated acid anhydride is 1 part, and N- substituted maleimide amine rubs
Your number is 30 parts, small molecule crosslinking agent uses Triallyl isocyanurate, triallylcyanurate, three methylallyls
For allyl cyanurate, the mixture of trihydroxyethyl isocyanuric ester, fire retardant is brominated fire-retardant for isocyanuric acid ester, front three
Agent, filler use ball-shaped silicon micro powder, are low Dk material, and promotor is the promotor of peroxide.
Embodiment 13
A kind of high frequency resin composition, the component including following parts by weight content: block copolymer rubber, unsaturated diene
It is rubber, N- substituted maleimide amine copolymer object, small molecule crosslinking agent, fire retardant, filler and promotor, wherein each component
Content is as shown in table 2.
Modified polyphenylene ether resin is that the end group of polyphenylene oxide resin is prepared using vinyl modified；Block copolymerization
Object rubber is using styrene as end segment, with polybutadiene, the linear three block copolymer that isoprene is intermediate segment, block
The number-average molecular weight of copolymer rubber is 15000, and styrene segment content is 50%；Unsaturated diene series rubber is benzene second
Alkene-isoprene copolymer and divinylbenzene-isoprene copolymer, wherein Isosorbide-5-Nitrae-cis-double bonds structure accounts for 95%, number
Average molecular weight is 10000；The monomer of N- substituted maleimide amine copolymer object is styrene, N-phenylmaleimide, unsaturation
Acid anhydrides, wherein the molfraction of styrene is 60 parts, and the molfraction of unsaturated acid anhydride is 20 parts, N- substituted maleimide amine
Molfraction is 70 parts, small molecule crosslinking agent uses t-butyl styrene, properties of diallyl isophathalate, phthalic acid two
The mixture of allyl ester, trimethylolpropane trimethacrylate or pentaerythritol tetraacrylate, fire retardant are brominated fire-retardant
Agent, filler use ball-shaped silicon micro powder, are low Dk material, and promotor is the promotor of peroxide.
Comparative example 1
Comparative example 1 is a kind of resin combination, and raw material composition includes modified polyphenylene ether resin, unsaturated diene series rubber
Glue, N- substituted maleimide amine copolymer object, small molecule crosslinking agent, fire retardant, filler and promotor, the content of specific each component and
Selection is as shown in table 2.
Comparative example 1 and the main distinction of embodiment are, without addition block copolymer rubber in comparative example, from table 1
As can be seen that the glass transformation temperature of the resin combination in comparative example 1 is 185 DEG C, well below the present invention in detection data
The glass transformation temperature of resin combination in middle any embodiment shows its mechanicalness in addition, its peel strength of copper foil is lower
Can be bad, 288 DEG C of lower leaf times are shorter, show that its thermal stability is poor.Therefore, block copolymer rubber is added in resin base material
Glue is conducive to the heat resistance and peel strength that improve resin combination.
Comparative example 2
Comparative example 2 be a kind of resin combination, raw material composition include modified polyphenylene ether resin, block copolymer rubber,
Unsaturated diene series rubber, BDM type maleimide, small molecule crosslinking agent, fire retardant, filler and promotor, specific each component
Content and selection it is as shown in table 2.
Comparative example 2 and the main distinction of embodiment are, replace N- substituted maleimide amine total with BDM type maleimide
Polymers, the glass transformation temperature from the resin combination that can be seen that in comparative example 2 in the detection data of table 1 is 205 DEG C, low
The glass transformation temperature of resin combination in the present invention in any embodiment, and its dielectric loss is higher, and energy consumption is high, tree
Membranous lipid fluidity is poor, and heat resistance is bad, shows that the resistance to of resin combination can be reduced by adding N- substituted maleimide amine copolymer object
Hot and peel strength.
Comparative example 3
Comparative example 3 be a kind of resin combination, raw material composition include modified polyphenylene ether resin, block copolymer rubber,
Unsaturated diene series rubber, styrene, copolymer-maleic anhydride, small molecule crosslinking agent, fire retardant, filler and promotor, specifically
The content of each component and selection are as shown in table 2.
Comparative example 3 and the main distinction of embodiment are, replace N- to replace Malaysia acyl with styrene, copolymer-maleic anhydride
Imine copolymer, it is poor from the resin combination compatibility that can be seen that in the detection data of table 1 in comparative example 3, in addition, should
The peel strength of resin combination is extremely low, and 288 DEG C of lower leaf times are very short, and therefore, N- substituted maleimide amine copolymer object adds
Add particularly significant, the synergistic effect between maleimide structure and maleic anhydride structure therein and resin base material is conducive to change
The mechanical performance and dielectric properties of kind resin combination.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (10)
1. a kind of high frequency resin composition, which is characterized in that the component including following parts by weight content:
2. a kind of high frequency resin composition according to claim 1, which is characterized in that the N- substituted maleimide amine is total
Polymers is copolymerized by the monomer of following molar part content: 30-70 parts of N- substituted maleimide amine, 30-60 parts of vinyl monomer,
1-10 parts of unsaturated acid anhydride.
3. a kind of high frequency resin composition according to claim 2, which is characterized in that the N- substituted maleimide amine is total
The general molecular formula of polymers are as follows:
In formula, x, y, z is respectively the molar ratio of styrene monomer, N- substituted maleimide amine, unsaturated acid anhydride, x:y:z=0.3
~0.6:0.3~0.7:0.01~0.2.
4. a kind of high frequency resin composition according to claim 3, which is characterized in that the R group be methyl, ethyl,
Isopropyl, cyclohexyl, phenyl, benzyl, phenylethyl, phenyl vinyl, p-hydroxybenzene, xenyl, naphthalene nucleus base.
5. a kind of high frequency resin composition according to claim 1, which is characterized in that the block copolymer rubber be with
Styrene is end segment, and with polybutadiene, the linear three block copolymer that isoprene is intermediate segment, number-average molecular weight exists
5000~150000, and styrene segment accounts for the 10~50% of the block copolymer rubber gross mass.
6. a kind of high frequency resin composition according to claim 1, which is characterized in that the unsaturation diene series rubber
Polymerized monomer includes unmodified or one or more of the butadiene containing modified group or isoprene, the modified group choosing
From one or more of epoxy group, maleic anhydride, acrylate, hydroxy or carboxy；Wherein, the number of the diene series rubber is equal
Molecular weight is 500~20000, and unsaturated double-bond structure accounts for the 60~99% of the diene series rubber main chain quality.
7. a kind of high frequency resin composition according to claim 6, which is characterized in that the unsaturation diene series rubber choosing
From polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, divinyl
Benzene-butadiene copolymer, divinylbenzene-isoprene copolymer, styrene-butadiene-divinyl benzene copolymer or benzene
One or more of ethylene-isoprene-divinylbenzene copolymer.
8. a kind of high frequency resin composition according to claim 1, which is characterized in that the modified polyphenylene ether resin is will
The end group of polyphenylene oxide resin is prepared using vinyl or methacrylate modification, number-average molecular weight 500
~10000.
9. a kind of high frequency resin composition according to claim 1, which is characterized in that the small molecule crosslinking agent is selected from three
Allyl iso cyanurate, triallylcyanurate, front three are for allyl iso cyanurate, front three for allyl cyanurate
Ester, trihydroxyethyl isocyanuric ester, t-butyl styrene, properties of diallyl isophathalate, diallyl phthalate,
One or more of trimethylolpropane trimethacrylate or pentaerythritol tetraacrylate.
10. a kind of high frequency resin composition according to claim 1, which is characterized in that further include fire retardant, filler and rush
Into agent.
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| JP2021528890A JP7170136B2 (en) | 2019-07-22 | 2019-12-30 | High frequency resin composition and use thereof |
| PCT/CN2019/129924 WO2021012619A1 (en) | 2019-07-22 | 2019-12-30 | High-frequency resin composition and use thereof |
| KR1020217017023A KR102523921B1 (en) | 2019-07-22 | 2019-12-30 | High-frequency resin composition and its application |
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| 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 |
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| 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 |
| CN114085525A (en) * | 2021-12-13 | 2022-02-25 | 南亚新材料科技股份有限公司 | Low-thermal expansion coefficient resin composition and application thereof |
| CN114656893A (en) * | 2022-02-24 | 2022-06-24 | 上海安缔诺科技有限公司 | Low dielectric adhesive film material based on maleic anhydride functionalized styrene-butadiene rubber and application thereof |
| CN116003687A (en) * | 2023-01-09 | 2023-04-25 | 南亚新材料科技股份有限公司 | Maleimide resin prepolymer, preparation method thereof, resin composition and application |
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| JP7170136B2 (en) | 2022-11-11 |
| KR20210090653A (en) | 2021-07-20 |
| KR102523921B1 (en) | 2023-04-19 |
| JP2022508173A (en) | 2022-01-19 |
| WO2021012619A1 (en) | 2021-01-28 |
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