CN107090065A - High frequency resin composition and its application in prepreg and metal-clad laminate - Google Patents

High frequency resin composition and its application in prepreg and metal-clad laminate Download PDF

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Publication number
CN107090065A
CN107090065A CN201710482346.3A CN201710482346A CN107090065A CN 107090065 A CN107090065 A CN 107090065A CN 201710482346 A CN201710482346 A CN 201710482346A CN 107090065 A CN107090065 A CN 107090065A
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polybutadiene
high frequency
modified
resin composition
filler
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殷卫峰
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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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/061—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of metal
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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Abstract

High frequency resin composition disclosed by the invention, by mass percentage including following components：45~80wt% of butadiene styrene resin, modified with polar 10~50wt% of polybutadiene, 1~30wt% of styrene, 3~40wt% of crosslinking agent, 1~7wt% of initiator.The invention further relates to application of the resin combination in prepreg and metal-clad laminate.The high frequency resin composition that the present invention is provided, with high-k, low-dielectric loss, bending strength height and the high characteristic of peel strength, can be applied in prepreg and metal-clad laminate.

Description

High frequency resin composition and its application in prepreg and metal-clad laminate
Technical field
The invention belongs to high frequency material technical field, it is related to high frequency resin composition, the invention further relates to the resin combination Application of the thing in prepreg and metal-clad laminate.
Background technology
With the development of the emerging micro-processing technology such as microelectronics, micromechanics, in the tide using high-density installation technology as background In stream, capacitor, integrated circuit, circuit module, antenna rf module etc. constantly develop to miniaturization.Miniaturization, it is interior Putting, multiband, intellectuality are the development trends of mobile terminal miniature antenna, and the size of printed antenna and the relative dielectric of substrate are normal Number is inversely proportional, in order to realize the targets such as its miniaturization, lightweight, it is necessary to copper-clad plate product of the exploitation with high-k.
Patent (the applying date of Application No. 201310023854.7：2013.1.23, publication number：CN103101252A, it is public Open day：2013.5.15 composite-based copper clad plate prepared by a kind of epoxy, hydroxyl extinguishing chemical) is disclosed, although dielectric constant is more than general Logical epoxy substrate, but dielectric loss is high；Patent (the applying date of Application No. 201310307402.1：2013.7.19, bulletin Number：CN103351578B, the day for announcing：2015.8.19 a kind of epoxy, the glass cloth base of high dielectric filler preparation) are disclosed and covers copper Although plate, its dielectric constant increases, but dielectric loss is also high；The Patent No. US5571609A patent (day for announcing： 1996.11.5 a kind of plate prepared using undersaturated polybutadiene, the olefin resin of unsaturationization, filler) is disclosed Material, the sheet material dielectric constant prepared is high, but there is also the dielectric loss of sheet material it is high the problem of.As can be seen here, in the prior art Although dielectric constant can be improved to a certain extent but all there is the problem of dielectric loss is high.
The content of the invention
It is an object of the invention to provide a kind of high frequency resin composition, with high-k, low-dielectric loss, bending Intensity height and the high characteristic of peel strength.
It is another object of the present invention to provide above-mentioned high frequency resin composition in prepreg and metal-clad laminate In application.
First technical scheme of the present invention be：High frequency resin composition, by mass percentage including with the following group Point：45~80wt% of butadiene styrene resin, modified with polar 10~50wt% of polybutadiene, 1~30wt% of styrene, crosslinking 3~40wt% of agent, 1~7wt% of initiator.
The characteristics of first technical scheme of the invention, also resides in,
The percentage by weight that butadiene styrene resin accounts for resin combination is 48~70wt%, further preferred 50~60wt%；Fourth The molecular weight of benzene resin is not more than 11000, and the contents of ethylene of butadiene styrene resin is 60~99%, preferably 70~95wt%, enters one Walk preferably 75~93wt%；The styrene-content of butadiene styrene resin is 30~60wt%, preferably 35~55wt%, further preferred 40 ~50wt%.
The percentage by weight that modified with polar polybutadiene accounts for resin combination is 15~40wt%, further excellent Select 20~30wt%；Modified with polar polybutadiene is selected from epoxide modified polybutadiene, maleic anhydride modified poly- Butadiene resin, acrylic acid modified polybutadiene, hydroxy-end capped polybutadiene, the polybutadiene tree of carboxy blocking Fat, amine be modified polybutadiene in it is a kind of or at least two mixture；Modified with polar polybutadiene Molecular weight be 5000~50000, preferably 8000~40000, further preferred 11000~30000；The poly- fourth of modified with polar The contents of ethylene of diene resin is 60~99wt%, preferably 70~95wt%, further preferred 75~93wt%；Polar group Epoxide group grafting rate on modified polybutadiene molecular resin chain is 5~10.
The percentage by weight that styrene accounts for resin combination is 5~25wt%, further preferred 10~20wt%.
Crosslinking agent is selected from Triallyl isocyanurate, poly- triallyl isocyanurate, TAC, front three Base acrylic acid, diallyl phthalate, divinylbenzene or one kind in polyfunctional acrylate or at least two Mixture.
Initiator is selected from benzoyl peroxide, a, a '-two (isopropylbenzene between tert-butyl hydroperoxide) benzene, peroxidating diisopropyl Double (the tertiary hexyl peroxidating) -3 of benzene, cumyl t-butyl peroxide, 1,1-, 3,5- trimethyl-cyclohexanes, two-(t-butyl peroxy Change isopropyl) benzene, 2,5- dimethyl -2,5- bis- (t-butylperoxy) hex- 3- alkynes, octanoic acid ter-butyl ester, perbenzoic acid uncle A kind of in butyl ester or at least two mixture.
High frequency resin composition also includes filler, and the percentage by weight that filler accounts for resin combination is 30~90wt%, excellent Select 40~85wt%, further preferred 60~80wt%；Angle value is 0.5 μm~20 μm, preferably 1 μm~15 μ in the particle diameter of filler M, further preferred 4 μm~10 μm.
Filler is made up of following two：
Filler 1：Selected from powdered quartz, unformed silica, spherical silica, boron nitride, aluminium nitride, A kind of in carborundum, aluminum oxide or at least two mixture；
Filler 2：Selected from barium titanate, strontium titanates, magnesium titanate, calcium titanate, barium strontium titanate, calcium barium titanate, lead titanates, zirconium metatitanic acid Lead, zirconium lanthanium titanate lead, lanthanium titanate barium, zirconia titanate barium, titanium dioxide, hafnium oxide, lead magnesio-niobate, barium magnesium niobate, lithium niobate, niobium Sour potassium, 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, titanium A kind of in sour copper, lead titanates-lead magnesio-niobate or at least two mixture；
Filler 2 account for the percent by volume of total filler for 30~90vol%, preferably 40~85vol%, further preferred 60~ 80vol%.
Second technical scheme of the present invention be：A kind of prepreg, including glass fabric or non-woven fabrics and The above-mentioned high frequency resin composition on glass fabric or non-woven fabrics is attached to after being dried by impregnation.
3rd technical scheme of the present invention be：
A kind of metal-clad laminate, including at least one above-mentioned prepreg and cover on the prepreg two sides of overlapping On metal foil.
The beneficial effects of the invention are as follows：High frequency resin composition of the present invention, with high-k, low-dielectric loss, curved Qu Qiangdu height and the high characteristic of peel strength, can be applied in prepreg and metal-clad laminate.
Embodiment
With reference to embodiment, the present invention is described in detail.
High frequency resin composition of the present invention, by mass percentage including following components：45~80wt% of butadiene styrene resin, polarity Group modified 10~50wt% of polybutadiene, 1~30wt% of styrene, 3~40wt% of crosslinking agent, initiator 1~ 7wt%.
The percentage by weight that butadiene styrene resin accounts for high frequency resin composition is 45~80wt%, for example：45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 78wt% or 80wt%, preferably 48~70wt%, further preferably For 50~60wt%；The molecular weight of butadiene styrene resin is less than 11000, and the contents of ethylene of butadiene styrene resin is 60~99wt%, for example： 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, 92wt% or 95wt%, preferably 70~ 95wt%, further preferred 75~93wt%；The styrene-content of butadiene styrene resin be 30~60wt%, such as 30wt%, 32wt%, 38wt%, 40wt%, 45wt%, 48wt%, 50wt%, 55wt% or 60wt%, preferably 35~55wt%, enter one Walk preferably 40~50wt%.
The percentage by weight that modified with polar polybutadiene accounts for high frequency resin composition is 10~50wt%, example Such as：10wt%, 15wt%, 20wt%, 25wt%, 28wt%, 30wt%, 33wt%, 35wt%, 40wt%, 43wt%, 35wt% or 50wt%, preferably 15~40wt%, further preferred 20~30wt%；Modified with polar polybutadiene is selected From epoxide modified polybutadiene, maleic anhydride modified polybutadiene, acrylic acid modified polybutadiene, hydroxyl envelope One kind or at least in the polybutadiene that the polybutadiene at end, the polybutadiene of carboxy blocking, amine are modified Two kinds of mixture；The molecular weight of modified with polar polybutadiene is 5000~50000, for example：5000、8000、 10000th, 15000,20000,25000,30000,35000,40000,45000 or 50000, preferably 8000~40000, enter one Step is preferably 11000~30000；If molecular weight is more than 50000, polybutadiene can be caused to be difficult to dissolve in a solvent, follow-up work Skill is poor；If molecular weight be less than 5000, can cause subsequently prepare sheet material during gummosis it is excessive, manufacturability is poor；Polar group changes 60~99wt% of contents of ethylene of property polybutadiene, such as 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, 92wt% or 95wt%, preferably 70~95wt%, more preferably 75~93wt%；Polar group Epoxide group grafting rate on modified polybutadiene molecular resin chain is between 5~10；Modified with polar polybutadiene tree Epoxide group grafting rate on fat strand is between 5~10；If grafting rate is more than 10, the polarity of composite can be caused to increase Greatly, dielectric loss increases；If functional group's grafting rate is less than 5, resin system can be caused too small with the peel strength between copper foil.
Styrene accounts for high frequency resin composition percentage by weight for 1~30wt%, for example：1wt%, 3wt%, 5wt%, 10wt%, 13wt%, 15wt%, 17wt%, 20wt%, 23wt%, 25wt%, 27wt% or 30wt%, preferably 5~ 25wt%, more preferably 10~20wt%；If styrene-content is more than 30wt%, the fragility of prepreg can be caused big, work Skill is poor；If the content of styrene is less than 1wt%, not having improves the effect of sheet material heat resistance.
The percentage by weight that crosslinking agent accounts for high frequency resin composition is 3~40wt%；Crosslinking agent is selected from triallyl isocyanide Urea acid esters, poly- triallyl isocyanurate, TAC, trimethacrylate acid, diallyl phthalate, two A kind of in vinyl benzene or polyfunctional acrylate or at least two mixture.
Initiator accounts for 1~7wt% of percentage by weight of high frequency resin composition, for example：1wt%, 1.3wt%, 1.5wt%, 1.7wt%, 2wt%, 2.3wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 5wt%, 6wt% or 7wt%, preferably 1.5~5wt%, more preferably 2~4wt%；Initiator be selected from benzoyl peroxide (BPO), a, a '- Two (isopropylbenzene between tert-butyl hydroperoxide) benzene, cumyl peroxide (DCP), cumyl t-butyl peroxide, 1,1- it is double (uncle oneself Base peroxidating) -3,3,5- trimethyl-cyclohexanes, two-(t-butylperoxyisopropyl) benzene (BIPB), 2,5- dimethyl -2,5- A kind of in two (t-butylperoxy) hex- 3- alkynes, octanoic acid ter-butyl ester, peroxidized t-butyl perbenzoate or at least two it is mixed Compound.
Also include filler in high frequency resin composition of the present invention, the percentage by weight that filler accounts for high frequency resin composition is 30 ~90wt%, preferably 40~85wt%, more preferably 60~80wt%；Angle value is 0.5 μm~20 μ in the particle diameter of filler M, preferably 1 μm~15 μm, more preferably 4 μm~10 μm.
The filler is made up of following two：
Filler 1：Selected from powdered quartz, unformed silica, spherical silica, boron nitride, aluminium nitride, A kind of in carborundum, aluminum oxide or at least two mixture；
Filler 2：Selected from barium titanate, strontium titanates, magnesium titanate, calcium titanate, barium strontium titanate, calcium barium titanate, lead titanates, zirconium metatitanic acid Lead, zirconium lanthanium titanate lead, lanthanium titanate barium, zirconia titanate barium, titanium dioxide, hafnium oxide, lead magnesio-niobate, barium magnesium niobate, lithium niobate, niobium Sour potassium, 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, titanium A kind of in sour copper, lead titanates-lead magnesio-niobate or at least two mixture；
Filler 2 account for the percent by volume of total filler for 30~90vol%, preferably 40~85vol%, further preferred 60~ 80vol%, remaining is filler 1.
It is used as a kind of application mode of high frequency resin composition of the present invention：Applied to prepreg, the prepreg includes glass Fiber cloth or non-woven fabrics and the high frequency resin composition being attached to by impregnation after dry on glass fabric or non-woven fabrics.
It is used as another application mode of high frequency resin composition of the present invention：Applied to metal-clad laminate, it includes At least one prepreg and the metal foil on the prepreg two sides of overlapping is covered, metal foil is that copper, brass, aluminium, nickel, copper are closed A kind of in gold, brass alloys, aluminium alloy or nickel alloy or at least two composition, the thickness of metal foil is 5 μm~150 μm, for example：15μm、18μm、25μm、30μm、40μm、50μm、60μm、70μm、80μm、90μm、110μm、130μm、140μm.
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：
Four mouthfuls of glass that 4L drying hexamethylenes and 0.05ml~0.48ml tetrahydrofurfuryl alcohols ethylether are added into 4L together are anti- Answer in bottle (through overbaking drying process), and drying nitrogen is passed through as protection, 40 DEG C of constant temperature into four mouthfuls of glass reaction bottles ~60 DEG C, then in 60min simultaneously add following components：25g~200g styrene (S), 30~210g butadiene (B) it is mixed Monomer, 0.4mol/L butyl lithiums 0.02mL~0.1mL are closed, treats that above-mentioned material adds 1.0mL~16.65mL again after the completion of adding dense The cyclohexane solution of the chlorine trimethyl silane for 0.2mol/L is spent, 30min is reacted, addition isopropanol terminating reaction separates out glue Sample, uses acetone extraction 12h after suction filtration, is finally placed in 25 DEG C of baking oven vacuum drying 12h, obtains white solid product.
Different molecular weight, different contents of ethylene, different styrene-content butadiene styrene resin it is as shown in table 1.
The butadiene styrene resin of table 1
According to information in the public domain, different molecular weight, different contents of ethylene, the polybutadiene of different epoxy grafting rates can be prepared Resin, it is as follows：
16L is dried into hexamethylene and 1600g dries butadiene and is added to 4L four mouthfuls of glass reaction bottles together (through overbaking Drying process) in, and it is passed through into four mouthfuls of glass reaction bottles drying nitrogen protection, 40 DEG C~80 DEG C of constant temperature, then to four mouthfuls Following catalytic component is added in glass reaction bottle successively：4ml~9ml tri- [di-(2-ethylhexyl)phosphoric acid] iron (0.4mmol~ Hexane solution, the hexane solution of 16ml~36ml triisobutyl aluminiums (8mmol), 12ml~27ml triphenyl phosphates 0.9mmol) The hexane solution of (1.2mmol~2.7mmol), 17mmol~38mmol tetrahydrofurfuryl alcohol ethylether, PMDETA7mmol~ 17mmol, is warming up to 65 DEG C~90 DEG C, polymerize 1~9 hour；Add ethanol terminating reaction and separate out glue sample, with third after suction filtration Ketone extracts 12~18h；25 DEG C of baking oven vacuum drying 12h are finally putting into, white solid product polybutadiene is obtained.
1000g polybutadiene and 2.5L ethyl acetate are added in 4L four mouthfuls of glass reaction bottles together, 65 DEG C of constant temperature ~75 DEG C, after polybutadiene is completely dissolved, drying nitrogen is passed through into four mouthfuls of glass reaction bottles, 80 DEG C~95 DEG C are warming up to, It is slowly added into system containing 50g~200g formic acid, 5g~42g polyethylene glycol, stirring reaction 2h~4h after completion of dropping, so Afterwards by 30g~215g hydrogen peroxide in being slowly dropped in 30min in four mouthfuls of glass reaction bottles, reactant is slowly warming up to 120 DEG C, continue to react 3h~5h at a constant temperature, after reaction terminates, product is poured out, add absolute ethyl alcohol precipitation, settle one section Suction filtration is carried out after time, with sodium bicarbonate solution and distillation water washing at least 12 times, 25 DEG C of baking ovens vacuum drying are finally putting into 12h, obtains white solid product.
Different molecular weight, different contents of ethylene, different epoxy grafting rate polybutadiene it is as shown in table 2.
The epoxide modified polybutadiene of table 2
Molecular weight Contents of ethylene Epoxy grafting rate
PB-5000 (epoxy) 5000 60% 5
PB-10000 (epoxy) 10000 90% 8
According to information in the public domain, different molecular weight, different contents of ethylene, the poly- fourth of different maleic anhydride grafting ratios can be prepared Diene resin, it is as follows：
16L is dried into hexamethylene and 1600g dries butadiene and is added to 4L four mouthfuls of glass reaction bottles together (through overbaking Drying process) in, and it is passed through into four mouthfuls of glass reaction bottles drying nitrogen protection, 40 DEG C~80 DEG C of constant temperature, then to four mouthfuls Following catalytic component is sequentially added in glass reaction bottle：4ml~9ml tri- [di-(2-ethylhexyl)phosphoric acid] iron (0.4mmol~ Hexane solution, the hexane solution of 16ml~36ml triisobutyl aluminiums (8mmol), 12ml~27ml triphenyl phosphates 0.9mmol) The hexane solution of (1.2mmol~2.7mmol), 17mmol~38mmol tetrahydrofurfuryl alcohol ethylether, PMDETA7mmol~ 17mmol, is warming up to 65 DEG C~90 DEG C, polymerize 1~9 hour；Add ethanol terminating reaction and separate out glue sample, with third after suction filtration Ketone extracts 12~18h；25 DEG C of baking oven vacuum drying 12h are finally placed in, white solid product polybutadiene is obtained.
The above-mentioned polybutadiene of 1000g and 300ml dimethylbenzene are added in 4L four mouthfuls of glass reaction bottles together, constant temperature 65 DEG C~75 DEG C, after polybutadiene is completely dissolved, drying nitrogen is passed through into four mouthfuls of glass reaction bottles, 85 DEG C~95 are warming up to DEG C, the xylene solution containing 165g~370g maleic anhydrides, 48g~110g antifebrins is slowly added into system, is added dropwise After finishing stir 10min~25min, by the xylene solution containing 24g~56gBPO in 30min in be slowly dropped to four mouthfuls In glass reaction bottle, reactant is slowly warming up to 120 DEG C, continues to react 3h~5h at a constant temperature, and after question response terminates, decompression is steamed Evaporate, remove dimethylbenzene and unreacted maleic anhydride, product is poured out, add absolute ethyl alcohol precipitation, sedimentation a period of time is laggard Row suction filtration, then with acetone extraction 12h~18h, be finally placed in 25 DEG C of baking oven vacuum drying 12h, obtain white solid product MA and change Property polybutadiene.
Different molecular weight, different contents of ethylene, difference MA grafting rates butadiene resin it is as shown in table 3.
The MA modified polybutadienes of table 3
Molecular weight Contents of ethylene MA grafting rates
PB-5000(MA) 5000 60% 5
PB-7000(MA) 7000 85% 7
PB-50000(MA) 50000 99% 10
For the present invention is better described, technical scheme is readily appreciated, of the invention is typical but non-limiting Embodiment is as follows：
Embodiment 1
By 80g butadiene styrene resin PBS-1000,10g modified with polar polybutadiene PB-5000 (epoxy), 1g benzene second Alkene, 3g Triallyl isocyanurates, 6gDCP are dissolved in toluene, and adding 30wt% filler, (angle value is in particle diameter Angle value constitutes for 10 μm of strontium titanates in 0.5 μm of silica and 0.379vol% particle diameter), it is mixed to get composition glue Liquid；Above-mentioned glue is impregnated using glass cloth or non-woven fabrics, then baking is cured as B-stage in 5 minutes in 155 DEG C of baking oven, obtains To prepreg；Then, the prepreg of making is placed between copper foil, is laminated and solidifies in 210 DEG C in press, obtain solidfied material Measuring Dielectric Constant Dk, dielectric loss Df, bending strength, peel strength afterwards, measurement result are as shown in table 4.
Embodiment 2
By 45g butadiene styrene resin PBS-5000,10g modified with polar polybutadiene PB-7000 (MA), 4g benzene second The poly- triallyl isocyanurate of alkene, 40g, 1gDCP are dissolved in toluene, and adding 60wt% filler, (angle value is in particle diameter Angle value constitutes for 15 μm of titanium dioxide in 20 μm of aluminum oxide and 0.379vol% particle diameter), it is mixed to get combination composition glue liquid； Above-mentioned glue is impregnated using glass cloth or non-woven fabrics, then baking is cured as B-stage in 5 minutes in 155 DEG C of baking oven, obtains pre- Leaching material；Then, the prepreg of making is placed between copper foil, is laminated and solidifies in 210 DEG C in press, obtain surveying after solidfied material Dielectric constant Dk, dielectric loss Df, bending strength, peel strength are measured, measurement result is as shown in table 4.
Embodiment 3
By 55g butadiene styrene resin PBS-7000,24g modified with polar polybutadiene PB-10000 (epoxy), 10g benzene Ethene, 10g TACs, 1gBIPB are dissolved in toluene, and adding 90wt% filler, (angle value is in particle diameter Angle value constitutes for 20 μm of barium titanate in 15 μm of silica and 0.379vol% particle diameter), it is mixed to get combination composition glue liquid； Above-mentioned glue is impregnated using glass cloth or non-woven fabrics, then baking is cured as B-stage in 5 minutes in 155 DEG C of baking oven, obtains pre- Leaching material；Then, the prepreg of making is placed between copper foil, is laminated and solidifies in 210 DEG C in press, obtain surveying after solidfied material Dielectric constant Dk, dielectric loss Df, bending strength, peel strength are measured, measurement result is as shown in table 4.
Embodiment 4
By 45g butadiene styrene resin PBS-11000,14g modified with polar polybutadiene PB-50000 (MA), 30g benzene Ethene, 9g Triallyl isocyanurates, 2gDCP are dissolved in toluene, add 68.1wt% filler (in particle diameter angle value Silica for 10 μm and angle value is 0.5 μm of titanium dioxide composition in 30.000vol% particle diameter), be mixed to get combination Composition glue liquid；Above-mentioned glue is impregnated using glass cloth or non-woven fabrics, then baking is cured as B ranks in 5 minutes in 155 DEG C of baking oven Section, obtains prepreg；Then, the prepreg of making is placed between copper foil, is laminated and solidifies in 210 DEG C in press, obtain Measuring Dielectric Constant Dk, dielectric loss Df, bending strength, peel strength after solidfied material, measurement result are as shown in table 4.
Embodiment 5
By 45g butadiene styrene resin PBS-11000,50g modified with polar polybutadiene PB-50000 (MA), 1g benzene second Alkene, 3g Triallyl isocyanurates, 1gDCP are dissolved in toluene, and adding 78.8wt% filler, (angle value is in particle diameter Angle value constitutes for 0.5 μm of titanium dioxide in 10 μm of silica and 90.000vol% particle diameter), it is mixed to get composition Glue；Above-mentioned glue is impregnated using glass cloth or non-woven fabrics, then baking is cured as B-stage in 5 minutes in 155 DEG C of baking oven, Obtain prepreg；Then, the prepreg of making is placed between copper foil, is laminated and solidifies in 210 DEG C in press, solidified Measuring Dielectric Constant Dk, dielectric loss Df, bending strength, peel strength after thing, measurement result are as shown in table 4.
Embodiment 6
By 45g butadiene styrene resin PBS-1000,30g modified with polar polybutadiene PB-5000 (epoxy), 1g benzene second Alkene, 17g Triallyl isocyanurates, 7gBPO are dissolved in toluene, add 72.4wt% filler (in particle diameter angle value Boron nitride for 10 μm and angle value is 0.5 μm of titanium dioxide composition in 70.000vol% particle diameter), be mixed to get composition Glue；Above-mentioned glue is impregnated using glass cloth or non-woven fabrics, then baking is cured as B-stage in 5 minutes in 155 DEG C of baking oven, Obtain prepreg；Then, the prepreg of making is placed between copper foil, is laminated and solidifies in 210 DEG C in press, solidified Measuring Dielectric Constant Dk, dielectric loss Df, bending strength, peel strength after thing, measurement result are as shown in table 4.
For technical scheme is better described, the present invention has also done following comparative example：
Comparative example 1
By 80g butadiene styrene resin PBS-1000,10g modified with polar polybutadiene PB-5000 (epoxy), 1g benzene second Alkene, 3g TACs, 6gBPO are dissolved in toluene, add 70wt% filler (in particle diameter angle value be 10 μm Silica composition), be mixed to get combination composition glue liquid；Above-mentioned glue is impregnated using glass cloth or non-woven fabrics, then at 155 DEG C Baking oven in baking be cured as B-stage within 5 minutes, obtain prepreg；Then, the prepreg of making is placed between copper foil, in pressure It is laminated and solidifies in 210 DEG C in machine, obtains Measuring Dielectric Constant Dk after solidfied material, dielectric loss Df, bending strength, stripping by force Degree, measurement result is as shown in table 5.
Comparative example 2
By 80g butadiene styrene resin PBS-1000,10g modified with polar polybutadiene PB-5000 (MA), 1g benzene second Alkene, 3g Triallyl isocyanurates, 6gBIPB are dissolved in toluene, and adding 80wt% filler, (angle value is in particle diameter 0.5 μm of titanium dioxide composition), it is mixed to get combination composition glue liquid；Above-mentioned glue, Ran Hou are impregnated using glass cloth or non-woven fabrics Baking is cured as B-stage in 5 minutes in 155 DEG C of baking oven, obtains prepreg；Then, the prepreg of making is placed between copper foil, It is laminated and solidifies in 210 DEG C in press, obtains Measuring Dielectric Constant Dk after solidfied material, dielectric loss Df, bending strength, stripping Intensity, measurement result is as shown in table 5.
Comparative example 3
By 80g butadiene styrene resin PBS-1000,10g modified with polar polybutadiene PB-5000 (epoxy), 1g benzene second The poly- triallyl isocyanurate of alkene, 3g, 6gBPO are dissolved in toluene, add 10wt% filler (by 5wt% particle diameter moderates Value be 0.5 μm silica and 5wt% particle diameters in angle value be 10 μm titanium dioxide composition), be mixed to get combination composition glue liquid； Above-mentioned glue is impregnated using glass cloth or non-woven fabrics, then baking is cured as B-stage in 5 minutes in 155 DEG C of baking oven, obtains pre- Leaching material；Then, the prepreg of making is placed between copper foil, is laminated and solidifies in 210 DEG C in press, obtain surveying after solidfied material Dielectric constant Dk, dielectric loss Df, bending strength, peel strength are measured, measurement result is as shown in table 5.
Comparative example 4
By 80g butadiene styrene resin PBS-1000,10g modified with polar polybutadiene PB-5000 (epoxy), 0.5g benzene The poly- triallyl isocyanurate of ethene, 3g, 6.5gBPO are dissolved in toluene, add 95wt% filler (by 50wt% particle diameters Middle angle value be 0.5 μm silica and 45wt% particle diameters in angle value be 10 μm titanium dioxide composition), be mixed to get composition Glue；Above-mentioned glue is impregnated using glass cloth or non-woven fabrics, then baking is cured as B-stage in 5 minutes in 155 DEG C of baking oven, Obtain prepreg；Then, the prepreg of making is placed between copper foil, is laminated and solidifies in 210 DEG C in press, it is impossible to prepare Go out qualified sheet material.
Comparative example 5
By 80g butadiene styrene resin PBS-1000,10g modified with polar polybutadiene PB-5000 (epoxy), 1g benzene second Alkene, 3g Triallyl isocyanurates, 6gBIPB are dissolved in toluene, add 64.3wt% filler (in particle diameter angle value Angle value is 0.5 μm of titanium dioxide composition in silica and 95vol% particle diameters for 0.5 μm), it is mixed to get composition glue Liquid；Above-mentioned glue is impregnated using glass cloth or non-woven fabrics, then baking is cured as B-stage in 5 minutes in 155 DEG C of baking oven, obtains To prepreg；Then, the prepreg of making is placed between copper foil, is laminated and solidifies in 210 DEG C in press, obtain solidfied material Measuring Dielectric Constant Dk, dielectric loss Df, bending strength, peel strength afterwards, measurement result are as shown in table 5.
Comparative example 6
By 80g butadiene styrene resin PBS-1000,15.9g modified with polar polybutadiene PB-5000 (epoxy), 1g benzene Ethene, 3g Triallyl isocyanurates, 0.1gDCP are dissolved in toluene, add 30wt% filler (in particle diameter angle value Angle value is 10 μm of strontium titanates composition in silica and 0.379vol% particle diameters for 0.5 μm), it is mixed to get composition glue Liquid；Above-mentioned glue is impregnated using glass cloth or non-woven fabrics, then baking is cured as B-stage in 5 minutes in 155 DEG C of baking oven, obtains To prepreg；Then, the prepreg of making is placed between copper foil, is laminated and solidifies in 210 DEG C in press, it is impossible to prepare Qualified sheet material.
Comparative example 7
By 20g butadiene styrene resin PBS-5000,35g modified with polar polybutadiene PB-7000 (MA), 4g benzene second The poly- triallyl isocyanurate of alkene, 40g, 1gDCP are dissolved in toluene, and adding 60wt% filler, (angle value is in particle diameter Angle value constitutes for 15 μm of titanium dioxide in 20 μm of aluminum oxide and 0.379vol% particle diameters), it is mixed to get combination composition glue liquid；Make Above-mentioned glue is impregnated with glass cloth or non-woven fabrics, then baking is cured as B-stage in 5 minutes in 155 DEG C of baking oven, is presoaked Material；Then, the prepreg of making is placed between copper foil, is laminated and solidifies in 210 DEG C in press, obtain measuring after solidfied material Dielectric constant Dk, dielectric loss Df, bending strength, peel strength, measurement result are as shown in table 6.
Comparative example 8
By 9g butadiene styrene resin PBS-7000,70g modified with polar polybutadiene PB-10000 (epoxy), 10g benzene Ethene, 10g TACs, 1gBIPB are dissolved in toluene, and adding 90wt% filler, (angle value is in particle diameter Angle value constitutes for 20 μm of barium titanate in 15 μm of silica and 0.379vol% particle diameters), it is mixed to get combination composition glue liquid；Make Above-mentioned glue is impregnated with glass cloth or non-woven fabrics, then baking is cured as B-stage in 5 minutes in 155 DEG C of baking oven, is presoaked Material；Then, the prepreg of making is placed between copper foil, is laminated and solidifies in 210 DEG C in press, obtain measuring after solidfied material Dielectric constant Dk, dielectric loss Df, bending strength, peel strength, measurement result are as shown in table 6.
Comparative example 9
By 25g butadiene styrene resin PBS-5000,10g modified with polar polybutadiene PB-7000 (MA), 4g benzene second The poly- triallyl isocyanurate of alkene, 60g, 1gDCP are dissolved in toluene, and adding 60wt% filler, (angle value is in particle diameter Angle value constitutes for 15 μm of titanium dioxide in 20 μm of aluminum oxide and 0.379vol% particle diameters), it is mixed to get combination composition glue liquid；Make Above-mentioned glue is impregnated with glass cloth or non-woven fabrics, then baking is cured as B-stage in 5 minutes in 155 DEG C of baking oven, is presoaked Material；Then, the prepreg of making is placed between copper foil, is laminated and solidifies in 210 DEG C in press, obtain measuring after solidfied material Dielectric constant Dk, dielectric loss Df, bending strength, peel strength, measurement result are as shown in table 6.
Comparative example 10
By 25g butadiene styrene resin PBS-11000,14g modified with polar polybutadiene PB-50000 (MA), 50g benzene Ethene, 9g Triallyl isocyanurates, 2gDCP are dissolved in toluene, add 68.1wt% filler (in particle diameter angle value Angle value is 0.5 μm of titanium dioxide composition in silica and 30.000vol% particle diameters for 10 μm), it is mixed to get composition Glue；Above-mentioned glue is impregnated using glass cloth or non-woven fabrics, then baking is cured as B-stage in 5 minutes in 155 DEG C of baking oven, Obtain prepreg；Then, the prepreg of making is placed between copper foil, is laminated and solidifies in 210 DEG C in press, solidified Measuring Dielectric Constant Dk, dielectric loss Df, bending strength, peel strength after thing, measurement result are as shown in table 6.
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
TAC：Nippon Kasei Chemical Company
Styrene：Xi'an weber power raises chemical industry
BPO：Great river grease Co., Ltd.
BIPB：Great river grease Co., Ltd.
DCP：99% purity, Mike woods Chemical Company
Barium titanate/strontium titanate/barium strontium titanate：Shanghai allusion quotation raises science and technology
Aluminum oxide/boron nitride：Denka electrifications Co., Ltd.
Silica：Jiangsu Lian Rui new materials limited company.
The Example formulations of table 4 and test result
The comparative example formula of table 5 and test result
The comparative example formula of table 6 and test result
The method of testing of above performance is as follows：
1st, bending strength：Method according to IPC-TM-650 2.4.4 defineds is measured.
2nd, peel strength (PS)：According to experiment condition " after thermal stress " in IPC-TM-650 2.4.8 methods, sheet material is tested Peel strength.
3rd, dielectric properties：SPDR (splite post dielectric resonator) method is tested, test condition For A states, 10GHz.
The sheet material that embodiment 1 is prepared to embodiment 6 is can be seen that from embodiment and contrasting for comparative example, its dielectric loss, The combination properties such as peel strength, bending strength are preferable.The silica of filler 1 is used alone in comparative example 1, the dielectric of sheet material is normal The low, peel strength of number is small.The titanium dioxide of filler 2 is used alone in comparative example 2, and the dielectric loss height of sheet material, peel strength are small；Than Weight fraction compared with the filler of example 3 is less than 30%, and the dielectric constant of sheet material is low, bending strength is small；The mass fraction of the filler of comparative example 4 More than 90%, preparation technology is poor, it is impossible to prepare qualified sheet material；The volume fraction that the filler 2 of comparative example 5 accounts for total filler is more than 90%, the dielectric loss height of sheet material, peel strength are small, bending strength is small；In comparative example 6, initiator content is less than 1wt%, system Standby manufacturability is poor, it is impossible to prepare qualified sheet material；In comparative example 7, the content of butadiene styrene resin is less than 45wt%, and the bending of sheet material is strong Degree is small；In comparative example 8, the content of modified with polar polybutadiene is more than 50wt%, and the bending strength of sheet material is small, dielectric Loss is high；In comparative example 9, the content of crosslinking agent is more than 40wt%, and the dielectric loss of sheet material is high；In comparative example 10, styrene Content is more than 30wt%, and the bending strength of sheet material is small.
Comprehensive the above results understand, material of the invention can reach that dielectric constant is low, dielectric loss is small, peel strength is high, The excellent comprehensive performances such as bending strength height, performance has obtained larger improvement, can meet the performance requirement of high dielectric material.

Claims (10)

1. high frequency resin composition, it is characterised in that by mass percentage including following components：45~80wt% of butadiene styrene resin, Modified with polar 10~50wt% of polybutadiene, 1~30wt% of styrene, 3~40wt% of crosslinking agent, initiator 1~ 7wt%.
2. high frequency resin composition as claimed in claim 1, it is characterised in that the butadiene styrene resin accounts for the weight of resin combination Amount percentage is 48~70wt%, further preferred 50~60wt%；The molecular weight of the butadiene styrene resin is not more than 11000, institute The contents of ethylene for stating butadiene styrene resin is 60~99%, preferably 70~95wt%, further preferred 75~93wt%；The butylbenzene The styrene-content of resin is 30~60wt%, preferably 35~55wt%, further preferred 40~50wt%.
3. high frequency resin composition as claimed in claim 1, it is characterised in that the modified with polar polybutadiene The percentage by weight for accounting for resin combination is 15~40wt%, further preferred 20~30wt%；The modified with polar gathers 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 It is a kind of or at least two mixture；The molecular weight of the modified with polar polybutadiene is 5000~50000, excellent Select 8000~40000, further preferred 11000~30000；The contents of ethylene of modified with polar polybutadiene is 60 ~99wt%, preferably 70~95wt%, further preferred 75~93wt%；On modified with polar polybutadiene strand Epoxide group grafting rate be 5~10.
4. high frequency resin composition as claimed in claim 1, it is characterised in that the styrene accounts for the weight of resin combination Percentage is 5~25wt%, further preferred 10~20wt%.
5. high frequency resin composition as claimed in claim 1, it is characterised in that the crosslinking agent is selected from triallyl isocyanide urea Acid esters, poly- triallyl isocyanurate, TAC, trimethacrylate acid, diallyl phthalate, diethyl A kind of in alkenyl benzene or polyfunctional acrylate or at least two mixture.
6. high frequency resin composition as claimed in claim 1, it is characterised in that the initiator be selected from benzoyl peroxide, A, a '-two (isopropylbenzene between tert-butyl hydroperoxide) benzene, cumyl peroxide, cumyl t-butyl peroxide, 1,1- it is double (uncle oneself Base peroxidating) -3,3,5- trimethyl-cyclohexanes, two-(t-butylperoxyisopropyl) benzene, (the tertiary fourth of 2,5- dimethyl -2,5- bis- Base peroxy) hex- 3- alkynes, octanoic acid ter-butyl ester, a kind of in peroxidized t-butyl perbenzoate or at least two mixture.
7. high frequency resin composition as claimed in claim 1, it is characterised in that the high frequency resin composition also includes filling out Material, filler account for the percentage by weight of resin combination for 30~90wt%, preferably 40~85wt%, further preferred 60~ 80wt%；Angle value is 0.5 μm~20 μm, preferably 1 μm~15 μm, further preferred 4 μm~10 μm in the particle diameter of the filler.
8. high frequency resin composition as claimed in claim 7, it is characterised in that the filler is made up of following two：
Filler 1：Selected from powdered quartz, unformed silica, spherical silica, boron nitride, aluminium nitride, carbonization A kind of in silicon, aluminum oxide or at least two mixture；
Filler 2：Selected from 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, hafnium oxide, lead magnesio-niobate, barium magnesium niobate, lithium niobate, niobic acid Potassium, 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, metatitanic acid A kind of in copper, lead titanates-lead magnesio-niobate or at least two mixture；
Filler 2 account for the percent by volume of total filler for 30~90vol%, preferably 40~85vol%, further preferred 60~ 80vol%.
9. a kind of prepreg, it is characterised in that be attached to glass after being dried including glass fabric or non-woven fabrics and by impregnation High frequency resin composition as claimed in claim 8 in glass fiber cloth or non-woven fabrics.
10. a kind of metal-clad laminate, it is characterised in that including at least one prepreg as claimed in claim 9 and Cover the metal foil on the prepreg two sides of overlapping.
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CN111378243A (en) * 2020-04-26 2020-07-07 无锡睿龙新材料科技有限公司 Multifunctional modified resin blended prepreg hydrocarbon composition, application thereof and method for preparing high-frequency high-speed copper-clad plate by using same
CN111378243B (en) * 2020-04-26 2022-09-02 无锡睿龙新材料科技有限公司 Multifunctional modified resin blended prepreg hydrocarbon composition, application thereof and method for preparing high-frequency high-speed copper-clad plate by using same
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CN112552630B (en) * 2020-12-10 2022-03-18 广东生益科技股份有限公司 Resin composition, resin glue solution containing resin composition, prepreg, laminated board, copper-clad plate and printed circuit board
CN112552630A (en) * 2020-12-10 2021-03-26 广东生益科技股份有限公司 Resin composition, resin glue solution containing resin composition, prepreg, laminated board, copper-clad plate and printed circuit board
CN112592554A (en) * 2020-12-15 2021-04-02 广东生益科技股份有限公司 Circuit material and printed circuit board
CN112592554B (en) * 2020-12-15 2022-11-29 广东生益科技股份有限公司 Circuit material and printed circuit board
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
CN114163670A (en) * 2021-11-16 2022-03-11 武汉航威新材料科技有限公司 Energy-saving and environment-friendly epoxy vinyl ester resin prepreg and preparation method and curing method thereof
CN114163670B (en) * 2021-11-16 2023-12-01 武汉航威新材料科技有限公司 Energy-saving environment-friendly epoxy vinyl ester resin prepreg, and preparation method and curing method thereof

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