CN106280179B - A kind of high frequency resin composition and its application - Google Patents

A kind of high frequency resin composition and its application Download PDF

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CN106280179B
CN106280179B CN201610769622.XA CN201610769622A CN106280179B CN 106280179 B CN106280179 B CN 106280179B CN 201610769622 A CN201610769622 A CN 201610769622A CN 106280179 B CN106280179 B CN 106280179B
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high frequency
resin composition
composition according
polybutadiene
modified
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CN106280179A (en
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殷卫峰
张记明
曾耀德
李莎
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SHAANXI SHENGYI SCI TECH Co Ltd
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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
    • C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/10—Copolymers of styrene with conjugated dienes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

The invention discloses a kind of high frequency resin compositions, including butadiene styrene resin, the unsaturated polybutadiene of modified with polar, crosslinking agent, initiator.The invention also discloses application of the high frequency resin composition in prepreg, laminate, copper-clad laminate, printed circuit board.High frequency resin composition of the present invention has the excellent comprehensive performances such as heat-resist, peel strength is high, dielectric loss is small, can satisfy the performance requirement of high frequency plate.

Description

A kind of high frequency resin composition and its application
Technical field
The present invention relates to high frequency material technical fields, and in particular to a kind of high frequency resin composition, the invention further relates to this The application of high frequency resin composition.
Background technique
In recent years, as computer, mobile phone step on communication apparatus high performance, multifunction and the development of networking, it is High-speed transfer and processing large capacity information, operation signal are carrying out high frequency, need a kind of to be suitable for high frequency signal transmission The high-performance electric insulating materials of characteristic.
In high-frequency circuit, electric signal transmission loss dielectric loss is indicated with the sum of conductor losses, radiation loss, telecommunications Number more high then dielectric loss of frequency, conductor losses, radiation loss are bigger.Since transmission loss makes electric signal decaying, destruction telecommunications Number reliability, while the loss may cause electronic failure from high frequency circuit radiation.Therefore it must reduce dielectric damage Consumption, conductor losses, radiation loss.It is well known that the dielectric loss angle of the insulator of the dielectric loss of electric signal and formation circuit The product of tangent and used signal frequency is directly proportional.Therefore it is used as insulator, it can be by selection dielectric loss angle just Small insulating materials is cut, the increase of dielectric loss is inhibited.
Application No. is US19980132869 (applying date: 1998.8.12, notification number: US6048807A, the day for announcing: 2000.4.11 patent) discloses a kind of high frequency of the olefin resin using unsaturated polybutadiene+cyclisation+filler preparation The plate loss of copper-clad plate, preparation is small, tack-free, but without using butadiene styrene resin, plate in resin combination in this patent Poor heat resistance.
Application No. is JP19770101034 (applying date: 1977.8.25, notification number: JP54036380A, the day for announcing: 1979.3.17 patent) discloses a kind of height of 1/2 polybutadiene using molecular weight 5 ten thousand to 20 ten thousand+crystallization filler preparation The plate loss of frequency copper-clad plate, preparation is small, tack-free.But without using butadiene styrene resin, plate in resin combination in this patent The poor heat resistance of material.In addition, polybutadiene molecular weight disclosed in this patent is 5 ten thousand to 20 ten thousand, it is difficult to dissolve in a solvent, after Continuous craftsmanship is poor.
Application No. is JP19800183423 (applying date: 1980.12.24, notification number: JP57105347A, the day for announcing: 182.6.30 patent) discloses a kind of high-frequency copper-clad plate using maleic anhydride modified polybutadiene, but modified combination Object maleic anhydride grafting ratio is excessively high, causes the polarity of composite material to increase, dielectric constant, dielectric loss increase.In addition, this patent Disclosed in MA modified polybutadiene molecular weight be 5 ten thousand to 20 ten thousand, be difficult to dissolve in a solvent, subsequent technique is poor.
In view of the above problems, having the invention proposes one kind, heat-resist, peel strength is high, dielectric loss is small, preparation The tack-free equal excellent comprehensive performances of prepreg baseplate material.
Summary of the invention
The object of the present invention is to provide a kind of high frequency resin compositions, with heat-resist, peel strength is high, dielectric damage Small Deng excellent comprehensive performances are consumed, can satisfy the performance requirement of high frequency plate.
It is a further object to provide above-mentioned high frequency resin compositions in prepreg, laminate, copper foil covered pressure Application in plate, printed circuit board.
The technical scheme adopted by the invention is that a kind of high frequency resin composition, including butadiene styrene resin, modified with polar Unsaturated polybutadiene, crosslinking agent, initiator.
The features of the present invention also characterized in that
The molecular weight 12000~50000 of butadiene styrene resin, preferably 13000~40000, further preferred 15000~30000； The contents of ethylene of butadiene styrene resin is 60~99%, preferably 70~95wt%, further preferred 75~93wt%；Butadiene styrene resin Styrene-content is 30~60%, preferably 35~55%, further preferred 40~50%.
Butadiene styrene resin accounts for the weight percent of resin combination for 40~80%, preferably 42~70wt%, further preferably 45~60wt%.
The unsaturated polybutadiene of modified with polar is selected from epoxy-modified polybutadiene, maleic anhydride modified Polybutadiene, acrylic acid modified polybutadiene, hydroxy-end capped polybutadiene, carboxy blocking polybutadiene In the modified polybutadiene of resin, amine any one or at least two mixing.
The molecular weight of the unsaturated polybutadiene of modified with polar be 5000~50000, preferably 8000~ 40000, further preferred 11000~30000；The contents of ethylene 60 of the unsaturated polybutadiene of modified with polar~ 99%, preferably 70~95wt%, further preferred 75~93wt%；The unsaturated polybutadiene molecule of modified with polar Polar group grafting rate on chain is between 5 to 10；The unsaturated polybutadiene of modified with polar accounts for resin combination The weight percent of object is 10~40wt%, preferably 15~35wt%, further preferred 20~30wt%.
The weight percent that crosslinking agent accounts for resin combination is 3~40wt%；Crosslinking agent be selected from triallyl isocyanurate, Poly- triallyl isocyanurate, triallyl cyanurate, trimethacrylate acid, diallyl phthalate, divinyl In base benzene or polyfunctional acrylate any one or at least two mixing.
The weight percent that initiator accounts for resin combination is 1~7wt%；Initiator is selected from a, (t-butyl peroxy of a '-two Isopropylbenzene between change) benzene, cumyl peroxide, cumyl t-butyl peroxide, bis- (the tert-hexyl peroxide) -3,3,5- three of 1,1- Hexahydrotoluene, 2,5- dimethyl -2,5- bis- (t-butylperoxy) hex- 3- alkynes, octanoic acid ter-butyl ester, the tertiary fourth of perbenzoic acid In ester any one or at least two mixing.
The high frequency resin composition further includes fire retardant, and fire retardant is selected from deca-BDE, bis- (the tetrabromo-benzene neighbours two of ethyl- Carboximide), decabromodiphenylethane, three (2,6- 3,5-dimethylphenyl) phosphines, 10- (2,5- dihydroxy phenyl) -9,10- dihydro - 9- aoxidizes -10 phosphine phenanthrene -10- oxides, (2,6- 3,5-dimethylphenyl) the phosphino- benzene of 2,6- bis- or 10- phenyl -9,10- dihydro-9-oxy In change -10- phosphine phenanthrene -10- oxide any one or at least two mixing.
The high frequency resin composition further includes filler, and filler is selected from crystalline sillica, unformed silica, ball Type silica, titanium dioxide, boron nitride, aluminium nitride, silicon carbide, aluminium oxide, barium titanate, strontium titanates, magnesium titanate, calcium titanate, Barium strontium titanate, calcium barium titanate, lead titanates, lead zirconate titanate, zirconium lanthanium titanate lead, lanthanium titanate barium, zirconia titanate barium, titanium dioxide, dioxy Change hafnium, lead magnesio-niobate, barium magnesium niobate, lithium niobate, potassium niobate, tantalic acid aluminium strontium, potassium tantallum niobate (KTH), strontium barium niobate, lead bariun niobate, niobic acid Titanium barium, bismuth tantalate strontium, bismuth titanates, barium titanate rubidium, copper titanate, in lead titanates-lead magnesio-niobate any one or at least two Mixture；
Angle value is 0.5~20uM, preferably 1~15uM, further preferred 4~10uM in the partial size of filler；
Filler account for resin combination weight percent be 0~90wt%, preferably 40~85wt%, further preferred 60~ 80wt%.
Second technical solution of the present invention be, above-mentioned resin combination is in prepreg, laminate, copper foil covered Application in pressing plate, printed circuit board.
Compared with prior art, the invention has the following beneficial effects:
High frequency resin composition of the present invention, with the excellent combinations such as heat-resist, peel strength is high, dielectric loss is small Can, it can satisfy the performance requirement of high frequency plate.
Specific embodiment
The present invention is described in detail With reference to embodiment.
High frequency resin composition of the present invention, including butadiene styrene resin, the unsaturated polybutadiene of modified with polar, friendship Join agent, initiator.
The molecular weight 12000~50000 of butadiene styrene resin, for example, 12000,15000,20000,25000,30000,35000, 40000,45000 or 50000, preferably 13000~40000, further preferred 15000~30000；
The contents of ethylene of butadiene styrene resin be 60~99%, such as 60%, 65%, 70%, 75%, 80%, 85%, 90%, 92% or 95%, preferably 70~95wt%, further preferred 75~93wt%；
The styrene-content of butadiene styrene resin be 30~60%, such as 30%, 32%, 38%, 40%, 45%, 48%, 50%, 55% or 60%, preferably 35~55%, further preferred 40~50%.
Butadiene styrene resin accounts for the weight percent 40~80% of resin combination, for example, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 78% or 80%, preferably 42~70wt%, further preferred 45~60wt%.
The unsaturated polybutadiene of modified with polar is selected from epoxy-modified polybutadiene, maleic anhydride modified Polybutadiene, acrylic acid modified polybutadiene, hydroxy-end capped polybutadiene, carboxy blocking polybutadiene In the modified polybutadiene of resin, amine any one or at least two mixing.
The molecular weight of the unsaturated polybutadiene of modified with polar be 5000~50000, such as 5000,8000, 10000,15000,20000,25000,30000,35000,40000,45000 or 50000, preferably 8000~40000, into one Step preferably 11000~30000；If molecular weight is greater than 50,000, it will lead to polybutadiene and be difficult to dissolve in a solvent, subsequent technique Property is poor.If molecular weight less than 5000, will lead to, subsequent gummosis during preparing plate is excessive, and craftsmanship is poor.
The contents of ethylene 60~99% of the unsaturated polybutadiene of modified with polar, for example, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 92% or 95%, preferably 70~95wt%, further preferred 75~93wt%；
Polar group grafting rate on the unsaturated polybutadiene strand of modified with polar between 5 to 10 it Between；If grafting rate is greater than 10, the polarity that will lead to composite material increases, and dielectric loss increases；If functional group's grafting rate is small In 5, it is too small with the peel strength between copper foil to will lead to resin system.
The weight percent that the unsaturated polybutadiene of modified with polar accounts for resin combination is 10~40wt%, Such as 10%, 15%, 20%, 25%, 28%, 30%, 33%, 35%, 38% or 40%, preferably 15~35wt%, further It is preferred that 20~30wt%.
The weight percent that crosslinking agent accounts for resin combination is 3~40wt%；Crosslinking agent be selected from triallyl isocyanurate, Poly- triallyl isocyanurate, triallyl cyanurate, trimethacrylate acid, diallyl phthalate, divinyl In base benzene or polyfunctional acrylate any one or at least two mixing.
Initiator account for resin combination weight percent be 1~7wt%, such as 1%, 1.3%, 1.5%, 1.7%, 2%, 2.3%, 2.5%, 3%, 3.5%, 4%, 5%, 6% or 7%, preferably 1.5~5%, further preferred 2~4wt%； Initiator be selected from a, a '-two (isopropylbenzene between tert-butyl hydroperoxide) benzene, cumyl peroxide, cumyl t-butyl peroxide, 1,1- bis- (tert-hexyl peroxide) -3,3,5- trimethyl-cyclohexanes, (t-butylperoxy) hex- of 2,5- dimethyl -2,5- bis- 3- Alkynes, octanoic acid ter-butyl ester, in peroxidized t-butyl perbenzoate any one or at least two mixing.
The high frequency resin composition further includes fire retardant, and fire retardant is selected from deca-BDE, bis- (the tetrabromo-benzene neighbours two of ethyl- Carboximide), decabromodiphenylethane, three (2,6- 3,5-dimethylphenyl) phosphines, 10- (2,5- dihydroxy phenyl) -9,10- dihydro - 9- aoxidizes -10 phosphine phenanthrene -10- oxides, (2,6- 3,5-dimethylphenyl) the phosphino- benzene of 2,6- bis- or 10- phenyl -9,10- dihydro-9-oxy In change -10- phosphine phenanthrene -10- oxide any one or at least two mixing.
The high frequency resin composition further includes filler, and filler is selected from crystalline sillica, unformed silica, ball Type silica, titanium dioxide, boron nitride, aluminium nitride, silicon carbide, aluminium oxide, barium titanate, strontium titanates, magnesium titanate, calcium titanate, Barium strontium titanate, calcium barium titanate, lead titanates, lead zirconate titanate, zirconium lanthanium titanate lead, lanthanium titanate barium, zirconia titanate barium, titanium dioxide, dioxy Change hafnium, lead magnesio-niobate, barium magnesium niobate, lithium niobate, potassium niobate, tantalic acid aluminium strontium, potassium tantallum niobate (KTH), strontium barium niobate, lead bariun niobate, niobic acid Titanium barium, bismuth tantalate strontium, bismuth titanates, barium titanate rubidium, copper titanate, in lead titanates-lead magnesio-niobate any one or at least two Mixture；
Angle value is 0.5~20uM in the partial size of filler, such as 0.5,1.0,2.0,4.0,6.0,10,12,15,20,25,28 Or 30, preferably 1~15uM, further preferred 4~10uM；
Filler account for resin combination weight percent be 0~90wt%, such as 0%, 25%, 35%, 45%, 55%, 65%, 70%, 75%, 78%, 80%, 85% or 90%, preferably 40~85wt%, further preferred 60~80wt%.
According to information in the public domain, the polybutadiene of different molecular weight, different contents of ethylene, different epoxy grafting rates can be prepared Resin, it is as follows.
By the dry hexamethylene of 16L, the dry butadiene of 1600g is put into four mouthfuls of glass reaction bottles of 4L (at overbaking drying Reason) in, it is passed through drying nitrogen protection, 40 DEG C~80 DEG C of constant temperature, then sequentially adds following catalytic component: 4ml~9ml tri- The hexane solution, 16ml~36ml triisobutyl aluminium of [di-(2-ethylhexyl)phosphoric acid] iron (0.4mmol~0.9mmol) The hexane solution of (8mmol), the hexane solution of 12ml~27ml triphenyl phosphate (1.2mmol~2.7mmol), 17mmol~ Tetrahydrofurfuryl alcohol ethylether, the PMDETA 7mmol~17mmol of 38mmol is warming up to 65 DEG C~90 DEG C, polymerize 1~9 hour.So After add ethyl alcohol and terminate reaction glue sample is precipitated, filter, with 12~18h of acetone extraction, be put into 25 DEG C of baking ovens vacuum drying 12h, Obtain white solid product polybutadiene.
By 1000g polybutadiene, 2.5L ethyl acetate is put into four mouthfuls of glass reaction bottles of 4L, and 65 DEG C~75 DEG C of constant temperature, After polybutadiene is completely dissolved, it is passed through drying nitrogen, is warming up to 80 DEG C~95 DEG C, be slowly added into system containing 50g~ 200g formic acid, 5g~42g polyethylene glycol are stirred to react 2~4 hours, then by the hydrogen peroxide of 30g~215g after being added dropwise It being slowly dropped in four-hole bottle in 30min, reactant is slowly warming up to 120 DEG C, and the reaction was continued at a constant temperature 3~5 hours, After reaction, product is poured out, dehydrated alcohol precipitating is added, sedimentation a period of time, filters, with sodium bicarbonate solution and distillation Water washing at least 12 times, 25 DEG C of baking oven vacuum drying 12h are put into, white solid product is obtained.
Different molecular weight, different contents of ethylene, the polybutadiene of different epoxy grafting rates are as shown in table 1.
The epoxy-modified polybutadiene of table 1
Molecular weight Contents of ethylene Epoxy grafting rate
PB-5000 (epoxy) 5000 60% 5
PB-10000 (epoxy)) 10000 90% 8
PB-5000-02 (epoxy)) 5000 60% 2
PB-5000-30 (epoxy) 5000 30% 5
According to information in the public domain, the poly- fourth of different molecular weight, different contents of ethylene, different maleic anhydride grafting ratios can be prepared Diene resin, it is as follows.
By the dry hexamethylene of 16L, the dry butadiene of 1600g is put into four mouthfuls of glass reaction bottles of 4L (at overbaking drying Reason) in, it is passed through drying nitrogen protection, 40 DEG C~80 DEG C of constant temperature, then sequentially adds following catalytic component: 4ml~9ml tri- The hexane solution, 16ml~36ml triisobutyl aluminium of [di-(2-ethylhexyl)phosphoric acid] iron (0.4mmol~0.9mmol) The hexane solution of (8mmol), the hexane solution of 12ml~27ml triphenyl phosphate (1.2mmol~2.7mmol), 17mmol~ Tetrahydrofurfuryl alcohol ethylether, the PMDETA 7mmol~17mmol of 38mmol is warming up to 65 DEG C~90 DEG C, polymerize 1~9 hour.So After add ethyl alcohol and terminate reaction glue sample is precipitated, filter, with 12~18h of acetone extraction, be put into 25 DEG C of baking ovens vacuum drying 12h, Obtain white solid product polybutadiene.
By the above-mentioned polybutadiene of 1000g, 300ml dimethylbenzene is put into four mouthfuls of glass reaction bottles of 4L, constant temperature 65 DEG C~75 DEG C, after polybutadiene is completely dissolved, be passed through drying nitrogen, be warming up to 85 DEG C~95 DEG C, be slowly added into system containing 165g~370g maleic anhydride, the xylene solution of 48g~110g antifebrin stir 10min~25min after being added dropwise, By the xylene solution containing 24g~56g BPO in 30min in be slowly dropped in four-hole bottle, reactant is slowly warming up to 120 DEG C, the reaction was continued at a constant temperature 3~5 hours, and after reaction, decompression distillation removes dimethylbenzene and unreacted maleic acid Acid anhydride pours out product, and dehydrated alcohol precipitating is added, sedimentation a period of time, filters, with acetone extraction 12h~18h, is put into 25 DEG C Baking oven is dried in vacuo 12h, obtains white solid product MA modified polybutadiene.
Different molecular weight, different contents of ethylene, the butadiene resin of difference MA grafting rate are as shown in table 2.
Table 2MA modified polybutadiene
Molecular weight Contents of ethylene Epoxy grafting rate
PB-7000(MA) 7000 85% 7
PB-50000(MA) 50000 99% 10
PB-5000-15(MA) 5000 60% 15
According to information in the public domain, the butadiene styrene resin of different molecular weight, different contents of ethylene can be prepared, it is specific as follows.
By 4L dry hexamethylene, 0.05ml~0.48ml tetrahydrofurfuryl alcohol ethylether, it is put into four mouthfuls of glass reaction bottles (warp of 4L Overbaking is dried) in, it is passed through drying nitrogen protection, 40 DEG C~60 DEG C of constant temperature, is then added simultaneously with the following group in 60min Point: 25g~200g styrene (S), the mix monomer of 30~210g butadiene (B), 0.4mol/L butyl lithium 0.02mL~ Then the cyclohexane solution of the mono- chlorine trimethyl silane of 0.2mol/L of 1.0mL~16.65mL is added in 0.1mL, react 30min, add Enter isopropanol and terminate reaction precipitation glue sample, filter, with acetone extraction 12h, is put into 25 DEG C of baking ovens vacuum drying 12h, obtains white Solid product.
Different molecular weight, different contents of ethylene, the butadiene styrene resin of different styrene-contents are as shown in table 3.
3 butadiene styrene resin of table
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, of the invention is typical but non-limiting Embodiment is as follows:
Embodiment
The production method of embodiment 1-8 and comparative example 1-4 copper-clad laminate: design parameter is as shown in table 4 and table 5.
Butadiene styrene resin, maleic anhydride modified polybutadiene, crosslinking agent, initiator are dissolved in toluene, after completely dissolution, The filler of angle value, different quality containing in different-grain diameter is added, is then mixed to get glue at room temperature.It is impregnated using glass cloth Then above-mentioned glue toasts in 155 DEG C of baking oven and is cured as within 5 minutes B-stage, control obtains prepreg.
Then, the prepreg of production is placed between copper foil, is laminated and solidifies in 210 DEG C in press, obtains solidfied material Measuring Dielectric Constant afterwards, Tg, peel strength, DK, Df.Specific performance test result is shown in Table 4, table 5.
Used material is specific as follows in above-described embodiment and comparative example:
Triallyl isocyanurate: Nippon Kasei Chemical Company TAIC M-60
Poly- triallyl isocyanurate: Nippon Kasei Chemical Company
Triallyl cyanurate: Nippon Kasei Chemical Company
BPO: great river grease Co., Ltd.
BIPB: great river grease Co., Ltd.
DCP: Shanghai Fang Rui reaches chemical industry
Barium titanate/strontium titanate/barium strontium titanate: Shanghai allusion quotation raises science and technology
Lead titanates: Hubei flat peach culminant star electronics.
4 Examples 1 to 8 formula of table and test result
5 comparative example 1~4 of table formula and test result
The test method of the above characteristic is as follows::
1, it glass transition temperature (Tg): is measured according to the DMA method of IPC-TM-650 2.4.24 defined.
2, peel strength (PS): according to experiment condition " after thermal stress " in IPC-TM-650 2.4.8 method, plate is tested Peel strength.
3, dielectric properties: SPDR (splite post dielectric resonator) method is tested, test condition For A state, 10GHz.
By table 4 and table 5 it is found that being prepared to embodiment 8 from embodiment 1 it can be seen from the comparison of embodiment and comparative example Plate, the comprehensive performances such as dielectric loss, dielectric constant, peel strength, glass transition temperature are preferable, use in comparative example 1 The dielectric loss of the polybutadiene of low grafting rate, plate is relatively low, but peel strength is small；High grafting rate is used in comparative example 2 Polybutadiene, the peel strength of plate is high, but dielectric loss is high；The butadiene styrene resin small using styrene-content of comparative example 3, The Tg of plate is low；Butadiene styrene resin of the comparative example 4 using molecular weight 500, the too viscous hand of prepreg, technique can not operate.Comparative example 5 makes With the small butadiene styrene resin of contents of ethylene, butadiene resin, the Tg of plate is low.
Heat-resist, peel strength is high, dielectric constant is low it is found that material of the invention can achieve for comprehensive the above results, is situated between The small equal excellent comprehensive performances of electrical loss, performance have obtained biggish improvement, can satisfy the performance requirement of high dielectric material.
Above embodiments not impose any restrictions the content of composition of the invention, all technologies according to the present invention Essence or composition composition or content any subtle modifications, equivalent variations and modifications to the above embodiments, still fall within In the range of technical solution of the present invention.
The Applicant declares that the present invention is explained by the above embodiments detailed composition of the invention, but the present invention not office It is limited to above-mentioned detailed composition, that is, does not mean that the present invention must rely on above-mentioned detailed composition and could implement.Technical field Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.

Claims (26)

1. a kind of high frequency resin composition, which is characterized in that the unsaturated polybutadiene including butadiene styrene resin, modified with polar Resin, crosslinking agent, initiator；
The molecular weight 12000~50000 of the butadiene styrene resin；The contents of ethylene of the butadiene styrene resin is 60~99wt%；Institute The styrene-content for stating butadiene styrene resin is 30~60wt%；
The weight percent that the butadiene styrene resin accounts for resin combination is 40~80%.
2. high frequency resin composition according to claim 1, which is characterized in that the molecular weight 13000 of the butadiene styrene resin ~40000.
3. high frequency resin composition according to claim 2, which is characterized in that the molecular weight 15000 of the butadiene styrene resin ~30000.
4. high frequency resin composition according to claim 1, which is characterized in that the contents of ethylene of the butadiene styrene resin is 70~95wt%.
5. high frequency resin composition according to claim 4, which is characterized in that the contents of ethylene of the butadiene styrene resin is 75~93wt%.
6. high frequency resin composition according to claim 1, which is characterized in that the styrene-content of the butadiene styrene resin is 35~55wt%.
7. high frequency resin composition according to claim 6, which is characterized in that the styrene-content of the butadiene styrene resin is 40~50wt%.
8. high frequency resin composition according to claim 1, which is characterized in that the butadiene styrene resin accounts for resin combination Weight percent is 42~70wt%.
9. high frequency resin composition according to claim 8, which is characterized in that the butadiene styrene resin accounts for resin combination Weight percent is 45~60wt%.
10. high frequency resin composition according to claim 1, which is characterized in that the unsaturation of the modified with polar Polybutadiene is selected from epoxy-modified polybutadiene, maleic anhydride modified polybutadiene, acrylic acid modified poly- fourth In the modified polybutadiene of diene resin, hydroxy-end capped polybutadiene, the polybutadiene of carboxy blocking, amine Any one or at least two mixing.
11. high frequency resin composition according to claim 1, which is characterized in that the unsaturation of the modified with polar The molecular weight of polybutadiene is 5000~50000；The ethylene of the unsaturated polybutadiene of the modified with polar 60~99wt% of base content；Polar group grafting rate on the unsaturated polybutadiene strand of the modified with polar Between 5 to 10；The weight percent that the unsaturated polybutadiene of the modified with polar accounts for resin combination is 10~40wt%.
12. high frequency resin composition according to claim 11, which is characterized in that the unsaturation of the modified with polar The molecular weight of polybutadiene is 8000~40000.
13. high frequency resin composition according to claim 12, which is characterized in that the unsaturation of the modified with polar The molecular weight of polybutadiene is 11000~30000.
14. high frequency resin composition according to claim 11, which is characterized in that the unsaturation of the modified with polar 70~95wt% of contents of ethylene of polybutadiene.
15. high frequency resin composition according to claim 14, which is characterized in that the unsaturation of the modified with polar 75~93wt% of contents of ethylene of polybutadiene.
16. high frequency resin composition according to claim 11, which is characterized in that the unsaturation of the modified with polar The weight percent that polybutadiene accounts for resin combination is 15~35wt%.
17. high frequency resin composition according to claim 16, which is characterized in that the unsaturation of the modified with polar The weight percent that polybutadiene accounts for resin combination is 20~30wt%.
18. high frequency resin composition according to claim 1, which is characterized in that the crosslinking agent accounts for resin combination Weight percent is 3~40wt%；The crosslinking agent is selected from triallyl isocyanurate, poly- triallyl isocyanurate, triolefin In propyl ester cyanurate, diallyl phthalate, divinylbenzene or polyfunctional acrylate any one or The mixing of person at least two.
19. high frequency resin composition according to claim 1, which is characterized in that the initiator accounts for resin combination Weight percent is 1~7wt%；The initiator is selected from a, and a '-two (isopropylbenzene between tert-butyl hydroperoxide) benzene, peroxidating two are different Bis- (tert-hexyl peroxide) -3 propyl benzene, cumyl t-butyl peroxide, 1,1-, 3,5- trimethyl-cyclohexanes, dimethyl -2 2,5-, In 5- bis- (t-butylperoxy) hex- 3- alkynes, peroxidized t-butyl perbenzoate any one or at least two mixing.
20. high frequency resin composition according to claim 1, which is characterized in that the high frequency resin composition further includes resistance Agent is fired, the fire retardant is selected from deca-BDE, ethyl-bis- (tetrabromo phthalimides), decabromodiphenylethane, three (2,6- 3,5-dimethylphenyl) phosphine, -10 phosphine phenanthrene -10- oxide of 10- (2,5- dihydroxy phenyl) -9,10- dihydro-9-oxy, 2,6- It is any in two (2,6- 3,5-dimethylphenyl) phosphino- benzene or 10- phenyl -9,10- dihydro-9-oxy -10- phosphine phenanthrene -10- oxide It is a kind of or at least two mixing.
21. high frequency resin composition according to claim 1, which is characterized in that the high frequency resin composition further includes filling out Material, the filler be selected from crystalline sillica, unformed silica, spherical silica, titanium dioxide, boron nitride, Aluminium nitride, silicon carbide, aluminium oxide, barium titanate, strontium titanates, magnesium titanate, calcium titanate, barium strontium titanate, calcium barium titanate, lead titanates, zirconium Lead titanates, zirconium lanthanium titanate lead, lanthanium titanate barium, zirconia titanate barium, hafnium oxide, lead magnesio-niobate, barium magnesium niobate, lithium niobate, potassium niobate, Tantalic acid aluminium strontium, potassium tantallum niobate (KTH), strontium barium niobate, lead bariun niobate, titanium niobate barium, bismuth tantalate strontium, bismuth titanates, barium titanate rubidium, copper titanate, In lead titanates-lead magnesio-niobate any one or at least two mixture；
Angle value is 0.5~20uM in the partial size of the filler；
The weight percent that the filler accounts for resin combination is 0~90wt%.
22. high frequency resin composition according to claim 21, which is characterized in that angle value is 1 in the partial size of the filler ~15uM.
23. high frequency resin composition according to claim 22, which is characterized in that angle value is 4 in the partial size of the filler ~10uM.
24. high frequency resin composition according to claim 21, which is characterized in that the filler accounts for the weight of resin combination Amount percentage is 40~85wt%.
25. high frequency resin composition according to claim 24, which is characterized in that the filler accounts for the weight of resin combination Amount percentage is 60~80wt%.
26. any high frequency resin composition is in prepreg, copper-clad laminate, printing electricity according to claim 1~25 Application in the plate of road.
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CN101328277A (en) * 2008-07-28 2008-12-24 广东生益科技股份有限公司 Composite material, high-frequency circuit board made thereof and making method
CN102161823A (en) * 2010-07-14 2011-08-24 广东生益科技股份有限公司 Composite material, high-frequency circuit substrate therefrom and manufacture method thereof

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US6333384B1 (en) * 1998-11-02 2001-12-25 Gil Technologies Vinyl-terminated polybutadiene and butadiene-styrene copolymers containing urethane and/or ester residues, and the electrical laminates obtained therefrom

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CN101328277A (en) * 2008-07-28 2008-12-24 广东生益科技股份有限公司 Composite material, high-frequency circuit board made thereof and making method
CN102161823A (en) * 2010-07-14 2011-08-24 广东生益科技股份有限公司 Composite material, high-frequency circuit substrate therefrom and manufacture method thereof

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