CN106280179A - A kind of high frequency resin composition and application thereof - Google Patents

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

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Publication number
CN106280179A
CN106280179A CN201610769622.XA CN201610769622A CN106280179A CN 106280179 A CN106280179 A CN 106280179A CN 201610769622 A CN201610769622 A CN 201610769622A CN 106280179 A CN106280179 A CN 106280179A
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high frequency
resin
resin composition
modified
barium
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CN106280179B (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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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)
  • Medicinal Chemistry (AREA)
  • 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 composition, including butadiene styrene resin, the unsaturated polyester butadiene resin of modified with polar, cross-linking agent, initiator.The invention also discloses the application in prepreg, laminate, copper-clad laminate, printed circuit board of this high frequency resin composition.High frequency resin composition of the present invention, has the excellent comprehensive performances such as heat-resist, peel strength is high, dielectric loss is little, can meet the performance requirement of high frequency sheet material.

Description

A kind of high frequency resin composition and application thereof
Technical field
The present invention relates to high frequency material technical field, be specifically related to a kind of high frequency resin composition, the invention still further relates to this The application of high frequency resin composition.
Background technology
In recent years, along with the development of communication apparatus high performance, multifunction and networking stepped on by computer, mobile phone, for High-speed transfer and process Large Copacity information, operation signal is carrying out high frequency, needs one to be applicable to high frequency signal transmission The high-performance electric insulant of characteristic.
In high-frequency circuit, signal of telecommunication transmission loss dielectric loss represents with conductor losses, radiation loss sum, telecommunications Number the highest then dielectric loss of frequency, conductor losses, radiation loss are the biggest.Owing to transmission loss makes signal of telecommunication decay, destroys telecommunications Number reliability, this loss is from high frequency circuit radiation simultaneously, is likely to result in electronic failure.Therefore must reduce dielectric to damage Consumption, conductor losses, radiation loss.It is known that the dielectric loss angle of the insulator of the dielectric loss of the signal of telecommunication and formation circuit Tangent and the product of signal frequency used are directly proportional.Therefore as insulator, can be by just selecting dielectric loss angle Cut little insulant, the increase of suppression dielectric loss.
Application No. US19980132869 (applying date: 1998.8.12, notification number: US6048807A, the day for announcing: 2000.4.11) patent discloses high frequency prepared by a kind of olefin resin+filler using undersaturated polybutadiene+cyclisation Copper-clad plate, the sheet material loss of preparation is little, tack-free, but does not use butadiene styrene resin, sheet material in this patent in resin combination Poor heat resistance.
Application No. JP19770101034 (applying date: 1977.8.25, notification number: JP54036380A, the day for announcing: 1979.3.17) patent discloses height prepared by a kind of 1/2 polybutadiene+crystallization filler using molecular weight 5 ten thousand to 20 ten thousand Frequently copper-clad plate, the sheet material loss of preparation is little, tack-free.But this patent does not use in resin combination butadiene styrene resin, plate The poor heat resistance of material.Additionally, the polybutadiene molecular weight disclosed in this patent is 5 ten thousand to 20 ten thousand, it is difficult in a solvent dissolve, after Continuous manufacturability is poor.
Application No. 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 Thing maleic anhydride grafting ratio is too high, causes the polarity of composite to increase, and dielectric constant, dielectric loss increase.Additionally, this patent Disclosed in MA modified polybutadiene molecular weight be 5 ten thousand to 20 ten thousand, be difficult in a solvent dissolve, subsequent technique is poor.
For problem above, the present invention propose one have heat-resist, peel strength is high, dielectric loss is little, preparation Prepreg tack-free wait excellent comprehensive performance baseplate material.
Summary of the invention
It is an object of the invention to provide a kind of high frequency resin composition, its have heat-resist, peel strength is high, dielectric is damaged Consume little excellent comprehensive performance of Denging, the performance requirement of high frequency sheet material can be met.
It is a further object to provide above-mentioned high frequency resin composition in prepreg, laminate, copper foil covered pressure Application in plate, printed circuit board.
The technical solution adopted in the present invention is, a kind of high frequency resin composition, including butadiene styrene resin, modified with polar Unsaturated polyester butadiene resin, cross-linking agent, initiator.
The feature of the present invention also resides in,
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%.
It is 40～80% that butadiene styrene resin accounts for the percentage by weight of resin combination, preferably 42～70wt%, further preferably 45～60wt%.
The unsaturated polyester butadiene resin of modified with polar is selected from epoxide modified polybutadiene, maleic anhydride modified Polybutadiene, acrylic acid modified polybutadiene, hydroxy-end capped polybutadiene, the polybutadiene of carboxy blocking Any one or the mixing of at least two in the polybutadiene that resin, amine are modified.
The molecular weight of the unsaturated polyester butadiene resin of modified with polar is 5000～50000, preferably 8000～ 40000, further preferred 11000～30000；The contents of ethylene 60 of the unsaturated polyester butadiene resin of modified with polar～ 99%, preferably 70～95wt%, further preferred 75～93wt%；The unsaturated polyester butadiene resin molecule of modified with polar Polar group percent grafting on chain is between 5 to 10；The unsaturated polyester butadiene resin of modified with polar accounts for resin combination The percentage by weight of thing is 10～40wt%, preferably 15～35wt%, further preferred 20～30wt%.
It is 3～40wt% that cross-linking agent accounts for the percentage by weight of resin combination；Cross-linking agent selected from triallyl isocyanurate, Poly-triallyl isocyanurate, triallyl cyanurate, trimethacrylate acid, diallyl phthalate, divinyl Any one or the mixing of at least two in base benzene or polyfunctional acrylate.
It is 1～7wt% that initiator accounts for the percentage by weight of resin combination；Initiator is selected from a, a '-two (t-butyl peroxy Isopropylbenzene between change) benzene, cumyl peroxide, cumyl t-butyl peroxide, double (tertiary hexyl the peroxidating)-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 Any one or the mixing of at least two in ester.
This high frequency resin composition also includes fire retardant, and fire retardant is selected from deca-BDE, ethyl-bis-(tetrabromo-benzene neighbour two Carboximide), decabromodiphenylethane, three (2,6-3,5-dimethylphenyl) phosphine, 10-(2,5-dihydroxy phenyl)-9,10-dihydro- 9-oxidation-10 phosphine phenanthrene-10-oxides, 2,6-bis-(2,6-3,5-dimethylphenyl) phosphino-benzene or 10-phenyl-9,10-dihydro-9-oxy Change any one or the mixing of at least two in-10-phosphine phenanthrene-10-oxide.
This high frequency resin composition also includes filler, and filler is selected from powdered quartz, unformed silicon dioxide, ball Type silicon dioxide, titanium dioxide, boron nitride, aluminium nitride, carborundum, aluminium oxide, Barium metatitanate., strontium titanates, magnesium titanate, calcium titanate, Barium strontium titanate, calcium Barium metatitanate., 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 metaniobate, potassium niobate, tantalic acid aluminum strontium, potassium tantallum niobate (KTH), strontium barium niobate, lead bariun niobate, niobic acid Any one or at least two in titanium barium, bismuth tantalate strontium, bismuth titanates, Barium metatitanate. rubidium, copper titanate, lead titanates-lead magnesio-niobate Mixture；
In the particle diameter of filler, angle value is 0.5～20uM, preferably 1～15uM, further preferred 4～10uM；
It is 0～90wt% that filler accounts for the percentage by weight of resin combination, preferably 40～85wt%, further preferred 60～ 80wt%.
Second technical scheme of the present invention is, above-mentioned resin combination is at prepreg, laminate, copper foil covered Application in pressing plate, printed circuit board.
Compared with prior art, there is advantages that
High frequency resin composition of the present invention, it has the excellent combination such as heat-resist, peel strength is high, dielectric loss is little Can, the performance requirement of high frequency sheet material can be met.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is described in detail.
High frequency resin composition of the present invention, including butadiene styrene resin, the unsaturated polyester butadiene resin of modified with polar, friendship Connection agent, initiator.
The molecular weight 12000～50000, such as 12000 of butadiene styrene resin, 15000,20000,25000,30000,35000, 40000,45000 or 50000, preferably 13000～40000, further preferred 15000～30000；
The contents of ethylene of butadiene styrene resin is 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 is 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 percentage by weight 40～80% of resin combination, such as 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 78% or 80%, preferably 42～70wt%, further preferred 45～60wt%.
The unsaturated polyester butadiene resin of modified with polar is selected from epoxide modified polybutadiene, maleic anhydride modified Polybutadiene, acrylic acid modified polybutadiene, hydroxy-end capped polybutadiene, the polybutadiene of carboxy blocking Any one or the mixing of at least two in the polybutadiene that resin, amine are modified.
The molecular weight of the unsaturated polyester butadiene resin of modified with polar is 5000～50000, such as 5000,8000, 10000,15000,20000,25000,30000,35000,40000,45000 or 50000, preferably 8000～40000, enter one Step preferably 11000～30000；If molecular weight is more than 50,000, polybutadiene can be caused to be difficult in a solvent dissolve, subsequent technique Property is poor.If molecular weight less than 5000, can cause follow-up prepare sheet material during gummosis excessive, manufacturability is poor.
The contents of ethylene 60～99% of the unsaturated polyester butadiene resin of modified with polar, such as 60%, 65%, 70%, 75%, 80%, 85%, 90%, 92% or 95%, preferably 70～95wt%, further preferred 75～93wt%；
Polar group percent grafting on the unsaturated polyester butadiene resin strand of modified with polar between 5 to 10 it Between；If percent grafting is more than 10, the polarity of composite can be caused to increase, dielectric loss increases；If functional group's percent grafting is little In 5, resin system can be caused too small with the peel strength between Copper Foil.
It is 10～40wt% that the unsaturated polyester butadiene resin of modified with polar accounts for the percentage by weight of resin combination, Such as 10%, 15%, 20%, 25%, 28%, 30%, 33%, 35%, 38% or 40%, preferably 15～35wt%, further Preferably 20～30wt%.
It is 3～40wt% that cross-linking agent accounts for the percentage by weight of resin combination；Cross-linking agent selected from triallyl isocyanurate, Poly-triallyl isocyanurate, triallyl cyanurate, trimethacrylate acid, diallyl phthalate, divinyl Any one or the mixing of at least two in base benzene or polyfunctional acrylate.
It is 1～7wt% that initiator accounts for the percentage by weight of resin combination, 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 selected from a, a '-two (isopropylbenzene between tert-butyl hydroperoxide) benzene, cumyl peroxide, cumyl t-butyl peroxide, 1,1-double (tertiary hexyl peroxidating)-3,3,5-trimethyl-cyclohexanes, 2,5-dimethyl-2,5-bis-(t-butylperoxy) hex-3- Any one or the mixing of at least two in alkynes, octanoic acid ter-butyl ester, peroxidized t-butyl perbenzoate.
This high frequency resin composition also includes fire retardant, and fire retardant is selected from deca-BDE, ethyl-bis-(tetrabromo-benzene neighbour two Carboximide), decabromodiphenylethane, three (2,6-3,5-dimethylphenyl) phosphine, 10-(2,5-dihydroxy phenyl)-9,10-dihydro- 9-oxidation-10 phosphine phenanthrene-10-oxides, 2,6-bis-(2,6-3,5-dimethylphenyl) phosphino-benzene or 10-phenyl-9,10-dihydro-9-oxy Change any one or the mixing of at least two in-10-phosphine phenanthrene-10-oxide.
This high frequency resin composition also includes filler, and filler is selected from powdered quartz, unformed silicon dioxide, ball Type silicon dioxide, titanium dioxide, boron nitride, aluminium nitride, carborundum, aluminium oxide, Barium metatitanate., strontium titanates, magnesium titanate, calcium titanate, Barium strontium titanate, calcium Barium metatitanate., 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 metaniobate, potassium niobate, tantalic acid aluminum strontium, potassium tantallum niobate (KTH), strontium barium niobate, lead bariun niobate, niobic acid Any one or at least two in titanium barium, bismuth tantalate strontium, bismuth titanates, Barium metatitanate. rubidium, copper titanate, lead titanates-lead magnesio-niobate Mixture；
In the particle diameter of filler, angle value is 0.5～20uM, 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；
It is 0～90wt% that filler accounts for the percentage by weight of resin combination, 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, different molecular weight, different contents of ethylene, the polybutadiene of different epoxy percent grafting can be prepared Resin, as follows.
16L is dried hexamethylene, and 1600g is dried butadiene and puts into four mouthfuls of glass reaction bottles of 4L and (be dried place through overbaking Reason) in, it is passed through drying nitrogen protection, constant temperature 40 DEG C～80 DEG C, is then sequentially added into following catalytic component: 4ml～9ml tri- The hexane solution of [di-(2-ethylhexyl)phosphoric acid] ferrum (0.4mmol～0.9mmol), 16ml～36ml triisobutyl aluminium (8mmol) hexane solution, the hexane solution of 12ml～27ml triphenyl phosphate (1.2mmol～2.7mmol), 17mmol～ The tetrahydrofurfuryl alcohol ethylether of 38mmol, PMDETA 7mmol～17mmol, be warming up to 65 DEG C～90 DEG C, is polymerized 1～9 hour.So After add ethanol and terminate reaction and separate out glue sample, sucking filtration, with acetone extraction 12～18h, 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 in 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 80 DEG C～95 DEG C, be slowly added in system containing 50g～ 200g formic acid, 5g～42g Polyethylene Glycol, stirring reaction 2～4 hours after dropping, then by the hydrogen peroxide of 30g～215g Being slowly dropped in 30min in four-hole bottle, reactant is slowly warmed up to 120 DEG C, continues reaction 3～5 hours at a constant temperature, After reaction terminates, being poured out by product, add dehydrated alcohol precipitation, settle a period of time, sucking filtration, with sodium bicarbonate solution and distillation Water washs at least 12 times, puts into 25 DEG C of baking oven vacuum drying 12h, obtains white solid product.
Different molecular weight, different contents of ethylene, different epoxy percent grafting polybutadiene as shown in table 1.
The epoxide modified polybutadiene of table 1
Molecular weight Contents of ethylene Epoxy percent grafting
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, different molecular weight, different contents of ethylene, the poly-fourth of different maleic anhydride grafting ratio can be prepared Diene resin, as follows.
16L is dried hexamethylene, and 1600g is dried butadiene and puts into four mouthfuls of glass reaction bottles of 4L and (be dried place through overbaking Reason) in, it is passed through drying nitrogen protection, constant temperature 40 DEG C～80 DEG C, is then sequentially added into following catalytic component: 4ml～9ml tri- The hexane solution of [di-(2-ethylhexyl)phosphoric acid] ferrum (0.4mmol～0.9mmol), 16ml～36ml triisobutyl aluminium (8mmol) hexane solution, the hexane solution of 12ml～27ml triphenyl phosphate (1.2mmol～2.7mmol), 17mmol～ The tetrahydrofurfuryl alcohol ethylether of 38mmol, PMDETA 7mmol～17mmol, be warming up to 65 DEG C～90 DEG C, is polymerized 1～9 hour.So After add ethanol and terminate reaction and separate out glue sample, sucking filtration, with acetone extraction 12～18h, put into 25 DEG C of baking ovens vacuum drying 12h, Obtain white solid product polybutadiene.
By above-mentioned for 1000g polybutadiene, 300ml dimethylbenzene is put in 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 in system containing 165g～370g maleic anhydride, the xylene solution of 48g～110g acetanilide, stir 10min～25min after dropping, By the xylene solution containing 24g～56g BPO in 30min in be slowly dropped in four-hole bottle, reactant is slowly warmed up to 120 DEG C, continuing reaction 3～5 hours at a constant temperature, after reaction terminates, blood pressure lowering is distilled, and removes dimethylbenzene and unreacted maleic acid Acid anhydride, pours out product, adds dehydrated alcohol precipitation, settles a period of time, sucking filtration, with acetone extraction 12h～18h, put into 25 DEG C Baking oven vacuum drying 12h, obtains white solid product MA modified polybutadiene.
Different molecular weight, different contents of ethylene, different MA percent grafting butadiene resin as shown in table 2.
Table 2MA modified polybutadiene
Molecular weight Contents of ethylene Epoxy percent grafting
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, specific as follows.
4L is dried hexamethylene, 0.05ml～0.48ml tetrahydrofurfuryl alcohol ethylether, puts into four mouthfuls of glass reaction bottle (warps of 4L Overbaking dried) in, it is passed through drying nitrogen protection, constant temperature 40 DEG C～60 DEG C, then in 60min, is simultaneously introduced following group Point: 25g～200g styrene (S), 30～the mix monomer of 210g butadiene (B), 0.4mol/L butyl lithium 0.02mL～ 0.1mL, is subsequently adding the cyclohexane solution of the 0.2mol/L mono-chlorine trimethyl silane of 1.0mL～16.65mL, reacts 30min, adds Enter isopropanol and terminate reaction precipitation glue sample, sucking filtration, use acetone extraction 12h, put into 25 DEG C of baking ovens vacuum drying 12h, obtain white Solid product.
Different molecular weight, different contents of ethylene, different styrene-content butadiene styrene resin as shown in table 3.
Table 3 butadiene styrene resin
For the present invention is better described, it is simple to understand technical scheme, the present invention's is typical but non-limiting Embodiment is as follows:
Embodiment
Embodiment 1-8 and the manufacture method of 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, cross-linking agent, initiator are dissolved in toluene, after fully dissolving, Add angle value, the filler of different quality mark in different-grain diameter, be the most at room temperature mixed to get glue.Use glass cloth impregnates Above-mentioned glue, then in the baking oven of 155 DEG C, baking is cured as B-stage for 5 minutes, and control obtains prepreg.
Then, the prepreg of making is placed between Copper Foil, is laminated in 210 DEG C and solidifies in press, obtaining solidfied material Rear Measuring Dielectric Constant, Tg, peel strength, DK, Df.Specific performance test result is shown in Table 4, table 5.
Material used in above-described embodiment and comparative example is specific as follows:
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 oils and fats Co., Ltd.
BIPB: great river oils and fats 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 Prunus persica f. compressa culminant star electronics.
Table 4 embodiment 1～8 formula and test result
Table 5 comparative example 1～4 formula and test result
The method of testing of above characteristic is as follows::
1, glass transition temperature (Tg): be measured according to the DMA method of IPC-TM-650 2.4.24 defined.
2, peel strength (PS): according to " after thermal stress " experiment condition in IPC-TM-650 2.4.8 method, tests sheet material Peel strength.
3, dielectric properties: SPDR (splite post dielectric resonator) method is tested, test condition For A state, 10GHz.
From table 4 and table 5, from the contrast of embodiment and comparative example it can be seen that what embodiment 1 was prepared to embodiment 8 Sheet material, the combination property such as its dielectric loss, dielectric constant, peel strength, glass transition temperature is preferable, uses in comparative example 1 The polybutadiene of low percent grafting, the dielectric loss ratio of sheet material is relatively low, but peel strength is little；Comparative example 2 uses high percent grafting Polybutadiene, the peel strength of sheet material is high, but dielectric loss is high；Comparative example 3 uses the butadiene styrene resin that styrene-content is little, The Tg of sheet material is low；Comparative example 4 uses the butadiene styrene resin of molecular weight 500, the most viscous hands of prepreg, and technique cannot operate.Comparative example 5 makes With the little butadiene styrene resin of contents of ethylene, butadiene resin, the Tg of sheet material is low.
Combining the above results to understand, the material of the present invention can reach heat-resist, peel strength is high, dielectric constant is low, Jie Electrical loss is little waits excellent comprehensive performance, and performance has obtained bigger improvement, can meet the performance requirement of high dielectric material.
Above example, not imposes any restrictions the content of the compositions of the present invention, every technology according to the present invention Any trickle amendment, equivalent variations and the modification that above example is made by essence or compositions composition or content, all still falls within In the range of technical solution of the present invention.
Applicant states, by above-described embodiment, the present invention illustrates that the detailed of the present invention forms, but the present invention not office It is limited to above-mentioned detailed composition, does not i.e. mean that the present invention has to rely on above-mentioned detailed composition and could implement.Art Technical staff is it will be clearly understood that any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and auxiliary element Interpolation, concrete way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.

Claims (10)

1. a high frequency resin composition, it is characterised in that include the unsaturated polyester butadiene of butadiene styrene resin, modified with polar Resin, cross-linking agent, initiator.
High frequency resin composition the most according to claim 1, it is characterised in that the molecular weight 12000 of described butadiene styrene resin ～50000, preferably 13000～40000, further preferred 15000～30000；The contents of ethylene of described butadiene styrene resin is 60 ～99%, preferably 70～95wt%, further preferred 75～93wt%；The styrene-content of described butadiene styrene resin be 30～ 60%, preferably 35～55%, further preferred 40～50%.
High frequency resin composition the most according to claim 1 and 2, it is characterised in that described butadiene styrene resin accounts for resin combination The percentage by weight of thing is 40～80%, preferably 42～70wt%, further preferred 45～60wt%.
High frequency resin composition the most according to claim 1, it is characterised in that the unsaturated polyester of described modified with polar Butadiene resin is selected from epoxide modified polybutadiene, maleic anhydride modified polybutadiene, acrylic acid modified polybutadiene In the polybutadiene that olefine resin, hydroxy-end capped polybutadiene, the polybutadiene of carboxy blocking, amine are modified Any one or the mixing of at least two.
5. according to the high frequency resin composition described in claim 1 or 4, it is characterised in that the insatiable hunger of described modified with polar It is 5000～50000 with the molecular weight of polybutadiene, preferably 8000～40000, further preferred 11000～30000；Institute State the contents of ethylene 60～99% of the unsaturated polyester butadiene resin of modified with polar, preferably 70～95wt%, further Preferably 75～93wt%；Polar group percent grafting on the unsaturated polyester butadiene resin strand of described modified with polar is situated between Between 5 to 10；It is 10 that the unsaturated polyester butadiene resin of described modified with polar accounts for the percentage by weight of resin combination ～40wt%, preferably 15～35wt%, further preferred 20～30wt%.
High frequency resin composition the most according to claim 1, it is characterised in that described cross-linking agent accounts for the weight of resin combination Amount percentage ratio is 3～40wt%；Described cross-linking agent is selected from triallyl isocyanurate, poly-triallyl isocyanurate, three allyls In the acid of ester cyanurate, trimethacrylate, diallyl phthalate, divinylbenzene or polyfunctional acrylate Any one or the mixing of at least two.
High frequency resin composition the most according to claim 1, it is characterised in that described initiator accounts for the weight of resin combination Amount percentage ratio is 1～7wt%；Described initiator is selected from a, a '-two (isopropylbenzene between tert-butyl hydroperoxide) benzene, peroxidating diisopropyl Benzene, cumyl t-butyl peroxide, 1, double (the tertiary hexyl peroxidating)-3 of 1-, 3,5-trimethyl-cyclohexanes, 2,5-dimethyl-2,5- Any one or at least two in two (t-butylperoxy) hex-3-alkynes, octanoic acid ter-butyl ester, peroxidized t-butyl perbenzoate Mixing.
High frequency resin composition the most according to claim 1, it is characterised in that this high frequency resin composition also includes fire-retardant Agent, described fire retardant selected from deca-BDE, ethyl-bis-(tetrabromo phthalimide), decabromodiphenylethane, three (2, 6-3,5-dimethylphenyl) phosphine, 10-(2,5-dihydroxy phenyl)-9,10-dihydro-9-oxy-10 phosphine phenanthrene-10-oxide, 2,6-bis- Any one in (2,6-3,5-dimethylphenyl) phosphino-benzene or 10-phenyl-9,10-dihydro-9-oxy-10-phosphine phenanthrene-10-oxide Plant or the mixing of at least two.
High frequency resin composition the most according to claim 1, it is characterised in that this high frequency resin composition also includes filling out Material, described filler selected from powdered quartz, unformed silicon dioxide, spherical silica, titanium dioxide, boron nitride, Aluminium nitride, carborundum, aluminium oxide, Barium metatitanate., strontium titanates, magnesium titanate, calcium titanate, barium strontium titanate, calcium Barium metatitanate., lead titanates, zirconium Lead titanates, zirconium lanthanium titanate lead, lanthanium titanate barium, zirconia titanate barium, titanium dioxide, hafnium oxide, lead magnesio-niobate, barium magnesium niobate, niobic acid Lithium, potassium niobate, tantalic acid aluminum strontium, potassium tantallum niobate (KTH), strontium barium niobate, lead bariun niobate, titanium niobate barium, bismuth tantalate strontium, bismuth titanates, Barium metatitanate. Any one or the mixture of at least two in rubidium, copper titanate, lead titanates-lead magnesio-niobate；
In the particle diameter of described filler, angle value is 0.5～20uM, preferably 1～15uM, further preferred 4～10uM；
It is 0～90wt% that described filler accounts for the percentage by weight of resin combination, preferably 40～85wt%, further preferred 60～ 80wt%.
10. according to the arbitrary described high frequency resin composition of claim 1～9 prepreg, laminate, copper-clad laminate, Application in printed circuit board.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109438960A (en) * 2018-11-09 2019-03-08 陕西生益科技有限公司 A kind of high frequency resin composition and application
CN109467862A (en) * 2018-11-09 2019-03-15 陕西生益科技有限公司 A kind of high frequency resin composition and its application
CN110922705A (en) * 2019-12-13 2020-03-27 陕西易莱德新材料科技有限公司 High-heat-resistance conductive composite material and preparation method thereof
CN113150457A (en) * 2021-01-05 2021-07-23 广州辰东新材料有限公司 Modified hydrocarbon-modified syndiotactic polystyrene composite material, copper-clad plate containing modified hydrocarbon-modified syndiotactic polystyrene composite material and preparation method of copper-clad plate

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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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US20020040104A1 (en) * 1998-11-02 2002-04-04 Gil Technologies Vinyl-terminated polybutadiene and butadiene-styrene copolymers containing urethane and/or ester residues, and the electrical laminates obtained therefrom
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

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109438960A (en) * 2018-11-09 2019-03-08 陕西生益科技有限公司 A kind of high frequency resin composition and application
CN109467862A (en) * 2018-11-09 2019-03-15 陕西生益科技有限公司 A kind of high frequency resin composition and its application
CN110922705A (en) * 2019-12-13 2020-03-27 陕西易莱德新材料科技有限公司 High-heat-resistance conductive composite material and preparation method thereof
CN113150457A (en) * 2021-01-05 2021-07-23 广州辰东新材料有限公司 Modified hydrocarbon-modified syndiotactic polystyrene composite material, copper-clad plate containing modified hydrocarbon-modified syndiotactic polystyrene composite material and preparation method of copper-clad plate

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