CN110330759A - A kind of compositions of thermosetting resin and its application - Google Patents
A kind of compositions of thermosetting resin and its application Download PDFInfo
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- CN110330759A CN110330759A CN201910659226.5A CN201910659226A CN110330759A CN 110330759 A CN110330759 A CN 110330759A CN 201910659226 A CN201910659226 A CN 201910659226A CN 110330759 A CN110330759 A CN 110330759A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The present invention relates to a kind of compositions of thermosetting resin and its application, 30-70 parts of block copolymer rubber, unsaturated diene series rubber 10-50 parts, 5-30 parts of amine copolymer object of N- substituted maleimide, 10-50 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 compositions of thermosetting resin 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 compositions of thermosetting resin.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of compositions of thermosetting resin, 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
Enclose is 2000~200000, wherein preferred range is 5000~50000, is had in resin combination quickly good
Dissolubility, 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
It is 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.
< 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.
Compositions of thermosetting resin of the invention can be used for preparing bonding sheet, metal-clad laminate and printed wire
Plate.
Prepare bonding sheet: compositions of thermosetting resin is coated in reinforcing fiber and forms prepreg in the present invention；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.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.
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.
A kind of compositions of thermosetting resin, the component including following parts by weight content: 30-70 parts of block copolymer rubber,
It is 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
Agent, filler and promotor.
N- substituted maleimide amine copolymer object
< 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 >
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.
It is described containing the block copolymer rubber of larger molecular weight in compositions of thermosetting resin in the embodiment of the present invention
Block copolymer be using styrene as end segment, with polybutadiene, isoprene be intermediate segment linear triblock copolymer
Object, this block copolymer do not have double bond structure usually, have less reactive.The block copolymer rubber has low pole
Property feature, can show dielectric constant and low-dielectric loss extremely low needed for high-frequency high-speed material, but often material is resistance to
It is hot bad, it is lower with the peel strength of metal foil.Use this low polar material and a small amount of polar material such as polyphenylene oxide, cyanogen
The resin combinations such as acid esters, maleimide can obtain good performance balance.Therefore the block copolymer rubber is made
For one of the main component of composition, 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)。
< 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 several, the preferred acrylate modified unsaturated butadiene polymer of maleic anhydride, (methyl)；Wherein, the unsaturation
The number-average molecular weight of diene series rubber is 1000~10000, and it is total that Isosorbide-5-Nitrae-cis-double bonds structure accounts for the unsaturated diene series rubber
The 60~95% of 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, unsaturated diene series rubber is exemplified as polybutadiene, polyisoprene, styrene-butadiene
Copolymer, styrene-isoprene copolymer, divinylbenzene-butadiene copolymer, divinylbenzene-isoprene copolymer
One of object, styrene-butadiene-divinyl benzene copolymer or styrene-isoprene-divinyl benzene copolymer or
It is several.
< small molecule crosslinking agent >
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, wherein fire retardant, filler and promotor are normal
Rule selection.
< 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.
Compositions of thermosetting resin of the invention can be used for preparing bonding sheet, metal-clad laminate and printed wire
Plate.
Prepare bonding sheet
Compositions of thermosetting resin is coated in reinforcing fiber and forms prepreg in the present invention；The reinforcing fiber can
To be that organic fiber or inorfil pass through the enhancing textile fabric being knitted to form, 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 is made of above-mentioned bonding sheet overlapping one side or at least two sides metal foil hot pressing；Metal
The preferred copper foil of foil, further preferably electrolytic copper foil, surface roughness Rz are preferably smaller than 5um, the RTF copper foil that can illustrate, VLP copper
Foil, HVLP copper foil, HVLP2 copper foil can further improve the loss of signal problem of high-frequency high-speed wiring board.
Prepare printed wiring board
Printed wiring board includes at least an above-mentioned bonding sheet or above-mentioned metal-clad laminate.Resin group of the invention
Close object have good mechanical strength and toughness, good glass transition temperature, peel strength and low-dielectric energy, therefore,
It is suitble to prepare the processing of high multilayer printed circuit board.
The preparation method of compositions of thermosetting resin 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 compositions of thermosetting resin 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.
Embodiment 1~13
A kind of compositions of thermosetting resin, the component including following parts by weight content: block copolymer rubber, unsaturation two
Alkene system rubber, N- substituted maleimide amine copolymer object, small molecule crosslinking agent, fire retardant, filler and promotor are each in the present embodiment
As shown in table 1, the content of each component is as shown in table 2 for the source of component and selection.
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 compositions of thermosetting resin, the component including following parts by weight content: block copolymer rubber, unsaturation two
Alkene system rubber, N- substituted maleimide amine copolymer object, small molecule crosslinking agent, fire retardant, filler and promotor, wherein each component
Content it is as shown in table 2.
Wherein, the filler used causes its dielectric loss to increase for high Dk filler (Dk > 10).
Embodiment 12
A kind of compositions of thermosetting resin, the component including following parts by weight content: block copolymer rubber, unsaturation two
Alkene system rubber, N- substituted maleimide amine copolymer object, small molecule crosslinking agent, fire retardant, filler and promotor, wherein each component
Content it is as shown in table 2.
Block copolymer rubber is using styrene as end segment, is the linear of intermediate segment with polybutadiene, isoprene
Triblock copolymer, the number-average molecular weight of block copolymer rubber is 5000, and styrene segment content is 10%；It is unsaturated
Diene series rubber is styrene-isoprene copolymer and divinylbenzene-isoprene copolymer, wherein Isosorbide-5-Nitrae-cis-double bonds
Structure accounts for 60%, number-average molecular weight 1000；The monomer of N- substituted maleimide amine copolymer object is styrene, N- phenyl Malaysia
Acid imide, unsaturated acid anhydride, wherein the molfraction of styrene is 30 parts, and the molfraction of unsaturated acid anhydride is 1 part, and N- replaces
The molfraction of maleimide is 30 parts, small molecule crosslinking agent uses Triallyl isocyanurate, triallyl cyanurate
Ester, front three are for allyl iso cyanurate, front three for allyl cyanurate, the mixture of trihydroxyethyl isocyanuric ester, resistance
Combustion agent is brominated flame-retardant, and filler uses ball-shaped silicon micro powder, is low Dk material, and promotor is the promotor of peroxide.
Embodiment 13
A kind of compositions of thermosetting resin, the component including following parts by weight content: block copolymer rubber, unsaturation two
Alkene system rubber, N- substituted maleimide amine copolymer object, small molecule crosslinking agent, fire retardant, filler and promotor, wherein each component
Content it is as shown in table 2.
Block copolymer rubber is using styrene as end segment, is the linear of intermediate segment with polybutadiene, isoprene
Triblock copolymer, the number-average molecular weight of block copolymer rubber is 15000, and styrene segment content is 50%；Insatiable hunger
It is styrene-isoprene copolymer and divinylbenzene-isoprene copolymer with diene series rubber, wherein Isosorbide-5-Nitrae-is cis- double
Bond structure accounts for 95%, number-average molecular weight 10000；The monomer of N- substituted maleimide amine copolymer object is styrene, N- phenyl
Maleimide, unsaturated acid anhydride, wherein the molfraction of styrene is 60 parts, and the molfraction of unsaturated acid anhydride is 20 parts,
The molfraction of N- substituted maleimide amine is 70 parts, small molecule crosslinking agent uses t-butyl styrene, M-phthalic acid diene
The mixing of propyl diester, diallyl phthalate, trimethylolpropane trimethacrylate or pentaerythritol tetraacrylate
Object, fire retardant are brominated flame-retardant, and filler uses ball-shaped silicon micro powder, are low Dk material, and promotor is the promotion of peroxide
Agent.
Comparative example 1
Comparative example 1 is a kind of resin combination, and raw material composition includes unsaturated diene series rubber, N- substituted maleimide
Amine copolymer object, small molecule crosslinking agent, fire retardant, filler and promotor, the content of specific each component and selection are 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 135 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 is a kind of resin combination, and raw material composition includes block copolymer rubber, unsaturated diene series rubber
Glue, BDM type maleimide, small molecule crosslinking agent, fire retardant, filler and promotor, the content of specific each component and selection are such 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 165 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 is a kind of resin combination, and raw material composition includes block copolymer rubber, unsaturated diene series rubber
Glue, styrene, copolymer-maleic anhydride, 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 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 compositions of thermosetting resin, which is characterized in that the component including following parts by weight content:
2. a kind of compositions of thermosetting resin according to claim 1, which is characterized in that the N- substituted maleimide amine
Copolymer is copolymerized by the monomer of following molar part content: 30-60 parts of styrene monomer, N- substituted maleimide amine 30-70
Part, 1-20 parts of unsaturated acid anhydride.
3. a kind of compositions of thermosetting resin according to claim 2, which is characterized in that the N- substituted maleimide amine
The general molecular formula of copolymer 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 compositions of thermosetting resin according to claim 3, which is characterized in that the R group is methyl, second
Base, isopropyl, cyclohexyl, phenyl, benzyl, phenylethyl, phenyl vinyl, p-hydroxybenzene, xenyl, naphthalene nucleus base.
5. a kind of compositions of thermosetting resin according to claim 1, which is characterized in that the block copolymer rubber is
Using styrene as end segment, with polybutadiene, the linear three block copolymer that isoprene is intermediate segment, number-average molecular weight
5000~150000, and styrene segment accounts for the 10~50% of the block copolymer rubber gross mass.
6. a kind of compositions of thermosetting resin according to claim 1, which is characterized in that the unsaturation diene series rubber
Polymerized monomer include unmodified or one or more of the butadiene containing modified group or isoprene, the modified group
Selected from one or more of epoxy group, maleic anhydride, acrylate, hydroxy or carboxy；Wherein, the number of the diene series rubber
Average 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 compositions of thermosetting resin according to claim 6, which is characterized in that the unsaturation diene series rubber
Selected from polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, divinyl
Base benzene-butadiene copolymer, divinylbenzene-isoprene copolymer, styrene-butadiene-divinyl benzene copolymer or
One or more of styrene-isoprene-divinyl benzene copolymer.
8. a kind of compositions of thermosetting resin according to claim 1, which is characterized in that the small molecule crosslinking agent is selected from
Triallyl isocyanurate, 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.
9. a kind of compositions of thermosetting resin according to claim 1, which is characterized in that further include fire retardant, filler and
Promotor.
10. a kind of compositions of thermosetting resin as described in claim 1 is preparing bonding sheet, metal-clad laminate and print
Application in brush wiring board.
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| WO2023115076A1 (en) * | 2021-12-15 | 2023-06-22 | Stellenbosch University | Terpolymers for lipid nanodisc formation |
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