CN106379006B - A kind of high-frequency copper-clad plate - Google Patents
A kind of high-frequency copper-clad plate Download PDFInfo
- Publication number
- CN106379006B CN106379006B CN201610765450.9A CN201610765450A CN106379006B CN 106379006 B CN106379006 B CN 106379006B CN 201610765450 A CN201610765450 A CN 201610765450A CN 106379006 B CN106379006 B CN 106379006B
- Authority
- CN
- China
- Prior art keywords
- resin combination
- polybutadiene
- clad plate
- plate according
- frequency copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- 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
- 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
- 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
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a kind of high-frequency copper-clad plates, including insulating layer and the metal foil for being set to insulating layer single or double, the core material layer of insulating layer is made of at least resin combination I glass cloth prepared or glass fiber paper prepreg, and the precoat of insulating layer is made of the resin combination II glass cloth prepared or glass fiber paper prepreg；Resin combination I is identical with the component of resin combination II, includes butadiene styrene resin, polybutadiene, crosslinking agent, initiator.High-frequency copper-clad plate of the present invention can satisfy the performance requirement of high frequency plate with the excellent comprehensive performances such as heat-resist, peel strength is high, dielectric loss is small.
Description
Technical field
The present invention relates to technical field of copper clad laminate, and in particular to a kind of high-frequency copper-clad plate.
Background technique
In recent years, as computer, mobile phone step on communication apparatus high performance, multifunction and the development of networking, it is
High-speed transfer and processing large capacity information, operation signal are carrying out high frequency, need a kind of to be suitable for high frequency signal transmission
The high-performance electric insulating materials of characteristic.
In high-frequency circuit, electric signal transmission loss dielectric loss is indicated with the sum of conductor losses, radiation loss, telecommunications
Number more high then dielectric loss of frequency, conductor losses, radiation loss are bigger.Since transmission loss makes electric signal decaying, destruction telecommunications
Number reliability, while the loss may cause electronic failure from high frequency circuit radiation.Therefore it must reduce dielectric damage
Consumption, conductor losses, radiation loss.It is well known that the dielectric loss angle of the insulator of the dielectric loss of electric signal and formation circuit
The product of tangent and used signal frequency is directly proportional.Therefore it is used as insulator, it can be by selection dielectric loss angle just
Small insulating materials is cut, the increase of dielectric loss is inhibited.
Application No. is CN200810142665.0 (applying date: 2008.7.28, notification number: CN101328277A, the day for announcing:
2010.7.21 Chinese patent) discloses a kind of epoxy-modified polybutadiene of use, maleic anhydride modified molecular weight is greater than
50000 butadiene and the copolymer of styrene, this patent do not provide the epoxy-modified range on modified strand, such as
Fruit epoxide group quantity is excessive, and the polarity that will lead to composite material increases, and dielectric constant, dielectric loss increase；If epoxy group
Group's quantity is too small, and it is too small with the peel strength between copper foil to will lead to resin system.In addition, MA disclosed in this patent is modified fourth
The molecular weight of copolymer of diene and styrene is greater than 50,000, is difficult to dissolve in a solvent, subsequent technique is poor.
Application No. is JP19770061619 (applying date: 1977.5.26, notification number: JP53145891A, the day for announcing:
1978.12.19 patent) discloses a kind of high-frequency copper-clad plate using maleic anhydride modified polybutadiene, but does not provide
MA functional group grafting rate on modified strand, if grafting rate is excessive, the polarity that will lead to composite material increases, and dielectric is normal
Number, dielectric loss increase.If functional group's grafting rate is too small, it is too small with the peel strength between copper foil to will lead to resin system.
In addition, without using butadiene styrene resin, the poor heat resistance of plate in resin combination in this patent.
Application No. is JP19800183423 (applying date: 1980.12.24, notification number: JP57105347A, the day for announcing:
1982.6.30 patent) discloses a kind of high-frequency copper-clad plate using maleic anhydride modified polybutadiene, but modified post-polymerization
Object maleic anhydride grafting ratio is excessively high, causes the polarity of composite material to increase, dielectric constant, dielectric loss increase.In addition, this patent
Disclosed in MA modified polybutadiene molecular weight be 5 ten thousand to 20 ten thousand, be difficult to dissolve in a solvent, subsequent technique is poor.
In view of the above problems, having the invention proposes one kind, heat-resist, peel strength is high, dielectric constant is low, dielectric
The baseplate material of small equal excellent comprehensive performances is lost.
Summary of the invention
The object of the present invention is to provide a kind of high-frequency copper-clad plates, with heat-resist, peel strength is high, dielectric loss is small
Equal excellent comprehensive performances, can satisfy the performance requirement of high frequency plate.
The technical scheme adopted by the invention is that a kind of high-frequency copper-clad plate, including insulating layer and it is set to insulating layer single side
Or two-sided metal foil, the glass cloth or glass fiber paper prepreg that the core material layer of insulating layer is prepared by an at least resin combination I
Composition, the precoat of insulating layer are made of the resin combination II glass cloth prepared or glass fiber paper prepreg.
The features of the present invention also characterized in that
Resin combination I is identical with the component of resin combination II, includes butadiene styrene resin, polybutadiene, crosslinking
Agent, initiator.
The molecular weight of butadiene styrene resin less than 11000, the contents of ethylene of butadiene styrene resin is 60~99%, preferably 70~
95wt%, further preferred 75~93wt%；The styrene-content of butadiene styrene resin is 30~60%, preferably 35~55%, into one
Step preferably 40~50%；The weight percent of butadiene styrene resin be 45~80wt%, preferably 48~70wt%, further preferred 50~
60wt%.
In resin combination I, the molecular weight of polybutadiene is 5000~50000, preferably 8000~40000, into one
Step preferably 11000~30000；The contents of ethylene 60~99% of polybutadiene, preferably 70~95wt%, further preferred 75~
93wt%；The weight percent that polybutadiene accounts for resin combination I is 10~50wt%, preferably 15~40wt%, into one
Walk preferably 20~30wt%.
In resin combination II, polybutadiene is modified with polar polybutadiene, and modified with polar is poly-
Butadiene resin is selected from epoxy-modified polybutadiene, maleic anhydride modified polybutadiene, acrylic acid modified polybutadiene
In the modified polybutadiene of olefine resin, hydroxy-end capped polybutadiene, the polybutadiene of carboxy blocking, amine
Any one or at least two mixing.
In resin combination II, the molecular weight of modified with polar polybutadiene is 5000~50000, preferably 8000~
40000, further preferred 11000~30000；The contents of ethylene 60~99% of modified with polar polybutadiene, preferably 70
~95wt%, further preferred 75~93wt%；Epoxy group grafting rate on modified with polar polybutadiene strand is situated between
Between 5 to 10；The weight percent that modified with polar polybutadiene accounts for resin combination II is 10~50wt%, excellent
Select 15~40wt%, further preferred 20~30wt%.
In resin combination I and resin combination II, the weight percent of crosslinking agent is 3~40wt%, and crosslinking agent is selected from
Triallyl isocyanurate, poly- triallyl isocyanurate, triallyl cyanurate, trimethacrylate acid, O-phthalic
In diallyl phthalate, divinylbenzene or polyfunctional acrylate any one or at least two mixing.
In resin combination I and resin combination II, the weight percent of initiator is 1~7wt%, and initiator is selected from a,
A '-two (isopropylbenzene between tert-butyl hydroperoxide) benzene, cumyl peroxide, cumyl t-butyl peroxide, bis- (the tertiary hexyls of 1,1-
Peroxidating) -3,3,5- trimethyl-cyclohexanes, 2,5- dimethyl -2,5- bis- (t-butylperoxy) hex- 3- alkynes, octanoic acid ter-butyl ester,
Peroxidized t-butyl perbenzoate, three second class amine and its esters, level Four amine salt compound, 2,4,6- tri- (dimethylamino methylamine) benzene
Phenol, benzyl dimethylamine, imidazoles, three amylic phenol acid amides, single or multiple phenolic compounds, boron trifluoride and its organic matter complex,
In phosphoric acid or triphenyl phosphite any one or at least two mixing.
It further include fire retardant in resin combination I and resin combination II, it is bis- that fire retardant is selected from deca-BDE, ethyl-
(tetrabromo phthalimide), decabromodiphenylethane, three (2,6- 3,5-dimethylphenyl) phosphines, 10- (2,5- dihydroxy phenyl)-
- 10 phosphine phenanthrene -10- oxide of 9,10- dihydro-9-oxy, (2,6- 3,5-dimethylphenyl) the phosphino- benzene of 2,6- bis- or 10- phenyl -9,10-
In dihydro-9-oxy -10- phosphine phenanthrene -10- oxide any one or at least two mixing.
It further include filler in resin combination I and resin combination II, filler is selected from crystalline sillica, unformed
Silica, spherical silica, titanium dioxide, boron nitride, aluminium nitride, silicon carbide, aluminium oxide, barium titanate, strontium titanates, metatitanic acid
Magnesium, calcium titanate, barium strontium titanate, calcium barium titanate, lead titanates, lead zirconate titanate, zirconium lanthanium titanate lead, lanthanium titanate barium, zirconia titanate barium, dioxy
Change titanium, hafnium oxide, lead magnesio-niobate, barium magnesium niobate, lithium niobate, potassium niobate, tantalic acid aluminium strontium, potassium tantallum niobate (KTH), strontium barium niobate, niobic acid
Barium lead, titanium niobate barium, bismuth tantalate strontium, bismuth titanates, barium titanate rubidium, copper titanate, in lead titanates-lead magnesio-niobate any one or
At least two mixture；
Angle value is 0.5~20uM, preferably 1~15uM, further preferred 4~10uM in the partial size of filler；
The weight percent of filler is 0~90wt%, preferably 40~85wt%, further preferred 60~80wt%.
Metal foil be copper, brass, aluminium, nickel, copper alloy, brass alloys, aluminium alloy or nickel alloy in any one or
At least two combination, metal foil with a thickness of 5~150 μm.
Compared with prior art, the invention has the following beneficial effects:
High-frequency copper-clad plate of the present invention, with the excellent comprehensive performances such as heat-resist, peel strength is high, dielectric loss is small,
It can satisfy the performance requirement of high frequency plate.
Detailed description of the invention
Fig. 1 is the structure chart of the first embodiment of high-frequency copper-clad plate of the present invention；
Fig. 2 is the structure chart of second of embodiment of high-frequency copper-clad plate of the present invention.
In figure, 1. core material layers, 2. precoats, 3. metal foils.
Specific embodiment
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
High-frequency copper-clad plate of the present invention, as illustrated in fig. 1 and 2, including insulating layer and the gold for being set to insulating layer single or double
Belong to foil 3, the core material layer 1 of insulating layer is made of at least resin combination I glass cloth prepared or glass fiber paper prepreg, insulate
The precoat 2 of layer is made of the resin combination II glass cloth prepared or glass fiber paper prepreg.
Resin combination I is identical with the component of resin combination II, includes butadiene styrene resin, polybutadiene, crosslinking
Agent, initiator.
The molecular weight of butadiene styrene resin less than 11000, 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 be 30~60%, such as 30%, 32%, 38%, 40%, 45%, 48%,
50%, 55% or 60%, preferably 35~55%, further preferred 40~50%；
The weight percent of butadiene styrene resin be 45~80wt%, such as 45%, 50%, 55%, 60%, 65%, 70%,
75%, 78% or 80%, preferably 48~70wt%, further preferred 50~60wt%.
In resin combination I, the molecular weight of polybutadiene is 5000~50000, such as 5000,8000,10000,
15000,20000,25000,30000,35000,40000,45000 or 50000, preferably 8000~40000, further preferably
11000~30000；If molecular weight is greater than 50,000, it will lead to polybutadiene and be difficult to dissolve in a solvent, subsequent technique is poor.Such as
Fruit molecular weight less than 5000, will lead to it is subsequent prepare plate during gummosis it is excessive, craftsmanship is poor.
The contents of ethylene 60~99% of polybutadiene, for example, 60%, 65%, 70%, 75%, 80%, 85%, 90%,
92% or 95%, preferably 70~95wt%, further preferred 75~93wt%；
Polybutadiene account for resin combination I weight percent be 10~50wt%, such as 10%, 15%, 20%,
25%, 28%, 30%, 33%, 35%, 40%, 43%, 35% or 50%, preferably 15~40wt%, further preferred 20~
30wt%.
In resin combination II, polybutadiene is modified with polar polybutadiene, and modified with polar is poly-
Butadiene resin is selected from epoxy-modified polybutadiene, maleic anhydride modified polybutadiene, acrylic acid modified polybutadiene
In the modified polybutadiene of olefine resin, hydroxy-end capped polybutadiene, the polybutadiene of carboxy blocking, amine
Any one or at least two mixing.
In resin combination II, the molecular weight of modified with polar polybutadiene is 5000~50000, preferably 8000~
40000, further preferred 11000~30000；If molecular weight be greater than 50,000, will lead to polybutadiene be difficult in a solvent it is molten
Solution, subsequent technique are poor.If molecular weight less than 5000, will lead to, subsequent gummosis during preparing plate is excessive, and craftsmanship is poor.
The contents of ethylene 60~99% of modified with polar polybutadiene, for example, 60%, 65%, 70%, 75%,
80%, 85%, 90%, 92% or 95%, preferably 70~95wt%, further preferred 75~93wt%；Modified with polar is poly-
Epoxy group grafting rate on butadiene molecule chain is between 5 to 10；If grafting rate is greater than 10, composite material will lead to
Polarity increases, and dielectric loss increases；If less than 5, it is strong with the removing between copper foil to will lead to resin system for functional group's grafting rate
It spends small.The weight percent that modified with polar polybutadiene accounts for resin combination II is 10~50wt%, such as
10%, 15%, 20%, 25%, 28%, 30%, 33%, 35%, 40%, 43%, 35% or 50%, preferably 15~40wt%,
Further preferred 20~30wt%.
In resin combination I and resin combination II, the weight percent of crosslinking agent is 3~40wt%, and crosslinking agent is selected from
Triallyl isocyanurate, poly- triallyl isocyanurate, triallyl cyanurate, trimethacrylate acid, O-phthalic
In diallyl phthalate, divinylbenzene or polyfunctional acrylate any one or at least two mixing.
In resin combination I and resin combination II, the weight percent of initiator is 1~7wt%, such as 1%,
1.3%, 1.5%, 1.7%, 2%, 2.3%, 2.5%, 3%, 3.5%, 4%, 5%, 6% or 7%, preferably 1.5~5%, into
One step preferably 2~4wt%.Initiator is selected from a, a '-two (isopropylbenzene between tert-butyl hydroperoxide) benzene, cumyl peroxide, uncle
Bis- (tert-hexyl peroxide) -3 butyl peroxy isopropylbenzene, 1,1-, 3,5- trimethyl-cyclohexanes, 2,5- dimethyl -2,5-, bis- (uncle
Butyl peroxy) hex- 3- alkynes, octanoic acid ter-butyl ester, peroxidized t-butyl perbenzoate, three second class amine and its esters, quaternary ammonium compound salinization
Object, 2 are closed, 4,6- tri- (dimethylamino methylamine) phenol, benzyl dimethylamine, imidazoles, three amylic phenol acid amides, single or multiple phenolate are closed
In object, the complex of boron trifluoride and its organic matter, phosphoric acid or triphenyl phosphite any one or at least two it is mixed
It closes.
It further include fire retardant in resin combination I and resin combination II, it is bis- that fire retardant is selected from deca-BDE, ethyl-
(tetrabromo phthalimide), decabromodiphenylethane, three (2,6- 3,5-dimethylphenyl) phosphines, 10- (2,5- dihydroxy phenyl)-
- 10 phosphine phenanthrene -10- oxide of 9,10- dihydro-9-oxy, (2,6- 3,5-dimethylphenyl) the phosphino- benzene of 2,6- bis- or 10- phenyl -9,10-
In dihydro-9-oxy -10- phosphine phenanthrene -10- oxide any one or at least two mixing.
It further include filler in resin combination I and resin combination II, filler is selected from crystalline sillica, unformed
Silica, spherical silica, titanium dioxide, boron nitride, aluminium nitride, silicon carbide, aluminium oxide, barium titanate, strontium titanates, metatitanic acid
Magnesium, calcium titanate, barium strontium titanate, calcium barium titanate, lead titanates, lead zirconate titanate, zirconium lanthanium titanate lead, lanthanium titanate barium, zirconia titanate barium, dioxy
Change titanium, hafnium oxide, lead magnesio-niobate, barium magnesium niobate, lithium niobate, potassium niobate, tantalic acid aluminium strontium, potassium tantallum niobate (KTH), strontium barium niobate, niobic acid
Barium lead, titanium niobate barium, bismuth tantalate strontium, bismuth titanates, barium titanate rubidium, copper titanate, in lead titanates-lead magnesio-niobate any one or
At least two mixture；
Angle value is 0.5~20uM in the partial size of filler, such as 0.5,1.0,2.0,4.0,6.0,10,12,15,20,25,28
Or 30, preferably 1~15uM, further preferred 4~10uM；
The weight percent of filler be 0~90wt%, such as 0%, 25%, 35%, 45%, 55%, 65%, 70%,
75%, 78%, 80%, 85% or 90%, preferably 40~85wt%, further preferred 60~80wt%.
Metal foil be copper, brass, aluminium, nickel, copper alloy, brass alloys, aluminium alloy or nickel alloy in any one or
At least two combination, metal foil with a thickness of 5~150 μm, such as 15 μm, 18 μm, 25 μm, 30 μm, 40 μm, 50 μm, 60 μm,
70μm、80μm、90μm、110μm、130μm、140μm。
According to information in the public domain, the polybutadiene of different molecular weight, different contents of ethylene can be prepared, as follows:
By the dry hexamethylene of 16L, the dry butadiene of 1600g is put into four mouthfuls of glass reaction bottles of 4L (at overbaking drying
Reason) in, it is passed through drying nitrogen protection, 40 DEG C~80 DEG C of constant temperature, then sequentially adds following catalytic component: 4ml~9ml tri-
The hexane solution, 16ml~36ml triisobutyl aluminium of [di-(2-ethylhexyl)phosphoric acid] iron (0.4mmol~0.9mmol)
The hexane solution of (8mmol), the hexane solution of 12ml~27ml triphenyl phosphate (1.2mmol~2.7mmol), 17mmol~
Tetrahydrofurfuryl alcohol ethylether, the PMDETA 7mmol~17mmol of 38mmol is warming up to 65 DEG C~90 DEG C, polymerize 1~9 hour.So
After add ethyl alcohol and terminate reaction glue sample is precipitated, filter, with 12~18h of acetone extraction, be put into 25 DEG C of baking ovens vacuum drying 12h,
Obtain white solid product polybutadiene.
Different molecular weight, different contents of ethylene, the butadiene resin of different molecular weight are as shown in table 1.
1 polybutadiene of table
| Molecular weight | Contents of ethylene | |
| P-5000 | 5000 | 60% |
| P-7000 | 7000 | 85% |
| P-10000 | 10000 | 90% |
| P-50000 | 50000 | 99% |
| P-5000-30 | 5000 | 30% |
According to information in the public domain, the polybutadiene of different molecular weight, different contents of ethylene, different epoxy grafting rates can be prepared
Resin, as follows:
By the dry hexamethylene of 16L, the dry butadiene of 1600g is put into four mouthfuls of glass reaction bottles of 4L (at overbaking drying
Reason) in, it is passed through drying nitrogen protection, 40 DEG C~80 DEG C of constant temperature, then sequentially adds following catalytic component: 4ml~9ml tri-
The hexane solution, 16ml~36ml triisobutyl aluminium of [di-(2-ethylhexyl)phosphoric acid] iron (0.4mmol~0.9mmol)
The hexane solution of (8mmol), the hexane solution of 12ml~27ml triphenyl phosphate (1.2mmol~2.7mmol), 17mmol~
Tetrahydrofurfuryl alcohol ethylether, the PMDETA 7mmol~17mmol of 38mmol is warming up to 65 DEG C~90 DEG C, polymerize 1~9 hour.So
After add ethyl alcohol and terminate reaction glue sample is precipitated, filter, with 12~18h of acetone extraction, be put into 25 DEG C of baking ovens vacuum drying 12h,
Obtain white solid product polybutadiene.
By 1000g polybutadiene, 2.5L ethyl acetate is put into four mouthfuls of glass reaction bottles of 4L, and 65 DEG C~75 DEG C of constant temperature,
After polybutadiene is completely dissolved, it is passed through drying nitrogen, is warming up to 80 DEG C~95 DEG C, be slowly added into system containing 50g~
200g formic acid, 5g~42g polyethylene glycol are stirred to react 2~4 hours, then by the hydrogen peroxide of 30g~215g after being added dropwise
It being slowly dropped in four-hole bottle in 30min, reactant is slowly warming up to 120 DEG C, and the reaction was continued at a constant temperature 3~5 hours,
After reaction, product is poured out, dehydrated alcohol precipitating is added, sedimentation a period of time, filters, with sodium bicarbonate solution and distillation
Water washing at least 12 times, 25 DEG C of baking oven vacuum drying 12h are put into, white solid product is obtained.
Different molecular weight, different contents of ethylene, the polybutadiene of different epoxy grafting rates are as shown in table 2.
The epoxy-modified polybutadiene of table 2
| Molecular weight | Contents of ethylene | Epoxy grafting rate | |
| PB-5000 (epoxy) | 5000 | 60% | 5 |
| PB-7000 (epoxy) | 7000 | 85% | 7 |
| PB-10000 (epoxy) | 10000 | 90% | 8 |
| PB-50000 (epoxy) | 50000 | 99% | 10 |
| PB-5000-30 (epoxy) | 5000 | 30% | 5 |
According to information in the public domain, the poly- fourth of different molecular weight, different contents of ethylene, different maleic anhydride grafting ratios can be prepared
Diene resin, as follows:
By the dry hexamethylene of 16L, the dry butadiene of 1600g is put into four mouthfuls of glass reaction bottles of 4L (at overbaking drying
Reason) in, it is passed through drying nitrogen protection, 40 DEG C~80 DEG C of constant temperature, then sequentially adds following catalytic component: 4ml~9ml tri-
The hexane solution, 16ml~36ml triisobutyl aluminium of [di-(2-ethylhexyl)phosphoric acid] iron (0.4mmol~0.9mmol)
The hexane solution of (8mmol), the hexane solution of 12ml27ml triphenyl phosphate (1.2mmol~2.7mmol), 17mmol~
Tetrahydrofurfuryl alcohol ethylether, the PMDETA 7mmol~17mmol of 38mmol is warming up to 65 DEG C~90 DEG C, polymerize 1~9 hour.So
After add ethyl alcohol and terminate reaction glue sample is precipitated, filter, with 12~18h of acetone extraction, be put into 25 DEG C of baking ovens vacuum drying 12h,
Obtain white solid product polybutadiene.
By the above-mentioned polybutadiene of 1000g, 300ml dimethylbenzene is put into four mouthfuls of glass reaction bottles of 4L, constant temperature 65 DEG C~75
DEG C, after polybutadiene is completely dissolved, be passed through drying nitrogen, be warming up to 85 DEG C~95 DEG C, be slowly added into system containing
165g~370g maleic anhydride, the xylene solution of 48g~110g antifebrin stir 10min~25min after being added dropwise,
By the xylene solution containing 24g~56g BPO in 30min in be slowly dropped in four-hole bottle, reactant is slowly warming up to
120 DEG C, the reaction was continued at a constant temperature 3~5 hours, and after reaction, decompression distillation removes dimethylbenzene and unreacted maleic acid
Acid anhydride pours out product, and dehydrated alcohol precipitating is added, sedimentation a period of time, filters, with acetone extraction 12h~18h, is put into 25 DEG C
Baking oven is dried in vacuo 12h, obtains white solid product MA modified polybutadiene.
Different molecular weight, different contents of ethylene, the butadiene resin of difference MA grafting rate are as shown in table 3.
3 MA modified polybutadiene of table
| Molecular weight | Contents of ethylene | MA grafting rate | |
| PB-5000(MA) | 5000 | 60% | 5 |
| PB-7000(MA) | 7000 | 85% | 7 |
| PB-10000(MA) | 10000 | 90% | 8 |
| PB-50000(MA) | 50000 | 99% | 10 |
| PB-5000-15(MA) | 5000 | 60% | 15 |
According to information in the public domain, the butadiene styrene resin of different molecular weight, different contents of ethylene can be prepared, it is specific as follows.
By 4L dry hexamethylene, 0.05ml~0.48ml tetrahydrofurfuryl alcohol ethylether, it is put into four mouthfuls of glass reaction bottles (warp of 4L
Overbaking is dried) in, it is passed through drying nitrogen protection, 40 DEG C~60 DEG C of constant temperature, is then added simultaneously with the following group in 60min
Point: 25g~200g styrene (S), the mix monomer of 30~210g butadiene (B), 0.4mol/L butyl lithium 0.02mL~
Then the cyclohexane solution of the mono- chlorine trimethyl silane of 0.2mol/L of 1.0mL~16.65mL is added in 0.1mL, react 30min, add
Enter isopropanol and terminate reaction precipitation glue sample, filter, with acetone extraction 12h, is put into 25 DEG C of baking ovens vacuum drying 12h, obtains white
Solid product.
Different molecular weight, different contents of ethylene, the butadiene styrene resin of different styrene-contents are as shown in table 4.
4 butadiene styrene resin of table
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, of the invention is typical but non-limiting
Embodiment is as follows:
Embodiment
The production method of embodiment 1-8 and comparative example 1-4 copper-clad laminate: design parameter is as shown in table 5 and table 6.
Butadiene styrene resin, maleic anhydride modified polybutadiene, crosslinking agent, initiator are dissolved in toluene, after completely dissolution,
The filler of angle value, different quality containing in different-grain diameter is added, is then mixed to get glue at room temperature.It is impregnated using glass cloth
Then above-mentioned glue toasts in 155 DEG C of baking oven and is cured as within 5 minutes B-stage, control obtains prepreg.
Then, the prepreg of production is placed between copper foil, is laminated and solidifies in 210 DEG C in press, obtains solidfied material
Measuring Dielectric Constant afterwards, Tg, peel strength, DK, Df.Specific performance test result is shown in Table 5, 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
Triallyl cyanurate: Nippon Kasei Chemical Company
BPO: great river grease Co., Ltd.
BIPB: great river grease Co., Ltd.
DCP: Shanghai Fang Rui reaches chemical industry
Barium titanate/strontium titanate/barium strontium titanate: Shanghai allusion quotation raises science and technology
Lead titanates: Hubei flat peach culminant star electronics.
5 Examples 1 to 8 formula of table and test result
6 comparative example 1~4 of table formula and test result
The test method of the above characteristic is as follows::
1, it glass transition temperature (Tg): is measured according to the DMA method of IPC-TM-650 2.4.24 defined.
2, peel strength (PS): according to experiment condition " after thermal stress " in IPC-TM-650 2.4.8 method, plate is tested
Peel strength.
3, dielectric properties: SPDR (splite post dielectric resonator) method is tested, test condition
For A state, 10GHz.
By table 5 and table 6 it is found that being prepared to embodiment 8 from embodiment 1 it can be seen from the comparison of embodiment and comparative example
Plate, the comprehensive performances such as dielectric loss, dielectric constant, peel strength, glass transition temperature are preferable, use in comparative example 1
The dielectric loss of unmodified polybutadiene, plate is relatively low, and the peel strength of plate is low；High grafting rate is used in comparative example 2
Polybutadiene, the peel strength of plate is high, but dielectric loss is high；The butadiene styrene resin small using styrene-content of comparative example 3,
The Tg of plate is low；For comparative example 4 using the small butadiene styrene resin of contents of ethylene, butadiene resin, the Tg of plate is low.
Heat-resist, peel strength is high, dielectric constant is low it is found that material of the invention can achieve for comprehensive the above results, is situated between
The small equal excellent comprehensive performances of electrical loss, performance have obtained biggish improvement, can satisfy the performance requirement of high frequency material.
Above embodiments not impose any restrictions the content of composition of the invention, all technologies according to the present invention
Essence or composition composition or content any subtle modifications, equivalent variations and modifications to the above embodiments, still fall within
In the range of technical solution of the present invention.
The Applicant declares that the present invention is explained by the above embodiments detailed composition of the invention, but the present invention not office
It is limited to above-mentioned detailed composition, that is, does not mean that the present invention must rely on above-mentioned detailed composition and could implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (26)
1. a kind of high-frequency copper-clad plate, including insulating layer and the metal foil (3) for being set to insulating layer single or double, feature exists
In, the core material layer (1) of the insulating layer is made of at least resin combination I glass cloth prepared or glass fiber paper prepreg,
The precoat (2) of the insulating layer is made of the resin combination II glass cloth prepared or glass fiber paper prepreg；
The resin combination I and resin combination II includes butadiene styrene resin, polybutadiene, crosslinking agent, initiator；
In the resin combination I, the molecular weight of polybutadiene is 5000~50000；The contents of ethylene of polybutadiene
For 60~99wt%；The weight percent that polybutadiene accounts for resin combination I is 10~50wt%；
In the resin combination II, polybutadiene is modified with polar polybutadiene, and modified with polar is poly-
Butadiene resin is selected from epoxy-modified polybutadiene, maleic anhydride modified polybutadiene, acrylic acid modified polybutadiene
In the modified polybutadiene of olefine resin, hydroxy-end capped polybutadiene, the polybutadiene of carboxy blocking, amine
Any one or at least two mixing；
In the resin combination II, the molecular weight of modified with polar polybutadiene is 11000~30000；Polar group changes
60~99wt% of contents of ethylene of property polybutadiene；Epoxy group grafting rate on modified with polar polybutadiene strand
Between 5 to 10；The weight percent that modified with polar polybutadiene accounts for resin combination II is 10~50wt%.
2. high-frequency copper-clad plate according to claim 1, which is characterized in that in the resin combination I, polybutadiene
Molecular weight be 8000~40000.
3. high-frequency copper-clad plate according to claim 1, which is characterized in that in the resin combination I, polybutadiene
Molecular weight be 11000~30000.
4. high-frequency copper-clad plate according to claim 1, which is characterized in that in the resin combination I, the second of polybutadiene
Amount vinyl content is 70~95wt%.
5. high-frequency copper-clad plate according to claim 1, which is characterized in that in the resin combination I, the second of polybutadiene
Amount vinyl content is 75~93wt%.
6. high-frequency copper-clad plate according to claim 1, which is characterized in that the polybutadiene accounts for resin combination I
Weight percent be 15~40wt%.
7. high-frequency copper-clad plate according to claim 1, which is characterized in that the polybutadiene accounts for resin combination I
Weight percent be 20~30wt%.
8. high-frequency copper-clad plate according to claim 1, which is characterized in that in the resin combination II, polar group changes
Property polybutadiene contents of ethylene be 70~95wt%.
9. high-frequency copper-clad plate according to claim 1, which is characterized in that in the resin combination II, polar group changes
Property polybutadiene contents of ethylene be 75~93wt%.
10. high-frequency copper-clad plate according to claim 1, which is characterized in that the modified with polar polybutadiene
The weight percent for accounting for resin combination II is 15~40wt%.
11. high-frequency copper-clad plate according to claim 1, which is characterized in that the modified with polar polybutadiene
The weight percent for accounting for resin combination II is 20~30wt%.
12. high-frequency copper-clad plate according to claim 1, which is characterized in that the molecular weight of the butadiene styrene resin is less than
11000, the contents of ethylene of the butadiene styrene resin is 60~99wt%；The styrene-content of the butadiene styrene resin be 30~
60wt%；It is 45~80wt% that the butadiene styrene resin, which accounts for resin combination I and the weight percent of resin combination II,.
13. high-frequency copper-clad plate according to claim 12, which is characterized in that the contents of ethylene of the butadiene styrene resin is 70
~95wt%.
14. high-frequency copper-clad plate according to claim 12, which is characterized in that the contents of ethylene of the butadiene styrene resin is 75
~93wt%.
15. high-frequency copper-clad plate according to claim 12, which is characterized in that the styrene-content of the butadiene styrene resin is 35
~55wt%.
16. high-frequency copper-clad plate according to claim 12, which is characterized in that the styrene-content of the butadiene styrene resin is 40
~50wt%.
17. high-frequency copper-clad plate according to claim 12, which is characterized in that the butadiene styrene resin account for resin combination I and
The weight percent of resin combination II is 48~70wt%.
18. high-frequency copper-clad plate according to claim 12, which is characterized in that the butadiene styrene resin account for resin combination I and
The weight percent of resin combination II is 50~60wt%.
19. high-frequency copper-clad plate according to claim 1, which is characterized in that the resin combination I and resin combination II
In, the weight percent of crosslinking agent is 3~40wt%, and crosslinking agent is selected from triallyl isocyanurate, triallyl cyanuric acid
Any one in ester, diallyl phthalate, divinylbenzene or polyfunctional acrylate or at least two
Mixing.
20. high-frequency copper-clad plate according to claim 1, which is characterized in that the resin combination I and resin combination II
In, the weight percent of initiator is 1~7wt%, and initiator is selected from a, a '-two (isopropylbenzene between tert-butyl hydroperoxide) benzene, mistake
Aoxidize diisopropylbenzene (DIPB), cumyl t-butyl peroxide, bis- (tert-hexyl peroxide) -3 1,1-, 3,5- trimethyl-cyclohexanes, 2,5-
Dimethyl -2,5- bis- (t-butylperoxy) hex- 3- alkynes, peroxidized t-butyl perbenzoate, imidazoles, in any one or
At least two mixing.
21. high-frequency copper-clad plate according to claim 1, which is characterized in that the resin combination I and resin combination II
In further include fire retardant, fire retardant is selected from deca-BDE, ethylene-bis- (tetrabromo phthalimides), decabrominated dipheny base second
Alkane, three (2,6- Dimethoxyphenyl) phosphorus, the miscellaneous -10- phosphine phenanthrene -10- oxygen of 10- (2,5- dihydroxy phenyl) -9,10- dihydro-9-oxy
Compound.
22. high-frequency copper-clad plate according to claim 1, which is characterized in that the resin combination I and resin combination II
In further include filler, filler is selected from crystalline sillica, unformed silica, spherical silica, titanium dioxide, nitrogen
Change boron, aluminium nitride, silicon carbide, aluminium oxide, barium titanate, strontium titanates, magnesium titanate, calcium titanate, barium strontium titanate, barium titanate calcium, metatitanic acid
Lead, lead zirconate titanate, zirconium lanthanium titanate lead, lanthanium titanate barium, zirconia titanate barium, hafnium oxide, lead magnesio-niobate, barium magnesium niobate, lithium niobate, niobium
Sour potassium, potassium tantallum niobate (KTH), strontium barium niobate, lead bariun niobate, bismuth tantalate strontium, bismuth titanates, in lead magnesio-niobate lead titanates any one or
The mixture of person at least two；
Angle value is 0.5~20uM in the partial size of filler；
The weight percent of filler is 0~90wt%.
23. high-frequency copper-clad plate according to claim 22, which is characterized in that in the partial size of the filler angle value be 1~
15uM。
24. high-frequency copper-clad plate according to claim 22, which is characterized in that in the partial size of the filler angle value be 4~
10uM。
25. high-frequency copper-clad plate according to claim 22, which is characterized in that the weight percent of the filler be 40~
85wt%.
26. high-frequency copper-clad plate according to claim 22, which is characterized in that the weight percent of the filler be 60~
80wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610765450.9A CN106379006B (en) | 2016-08-29 | 2016-08-29 | A kind of high-frequency copper-clad plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610765450.9A CN106379006B (en) | 2016-08-29 | 2016-08-29 | A kind of high-frequency copper-clad plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106379006A CN106379006A (en) | 2017-02-08 |
| CN106379006B true CN106379006B (en) | 2019-09-27 |
Family
ID=57937847
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610765450.9A Active CN106379006B (en) | 2016-08-29 | 2016-08-29 | A kind of high-frequency copper-clad plate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106379006B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7126493B2 (en) * | 2017-03-30 | 2022-08-26 | 日鉄ケミカル＆マテリアル株式会社 | Soluble polyfunctional vinyl aromatic copolymer, production method thereof, curable resin composition and cured product thereof |
| CN107090065A (en) * | 2017-06-22 | 2017-08-25 | 陕西生益科技有限公司 | High frequency resin composition and its application in prepreg and metal-clad laminate |
| CN110103477A (en) * | 2019-05-09 | 2019-08-09 | 河源广工大协同创新研究院 | A kind of preparation method of high-frequency copper-clad plate |
| CN111372372B (en) * | 2020-03-30 | 2023-12-22 | 广东生益科技股份有限公司 | Circuit material and circuit board comprising 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 |
| CN115302869B (en) * | 2022-07-05 | 2024-05-24 | 广东生益科技股份有限公司 | High-frequency copper-clad plate and printed circuit board comprising same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3952560B2 (en) * | 1997-10-31 | 2007-08-01 | 日本ゼオン株式会社 | Composite film |
| CN101328277B (en) * | 2008-07-28 | 2010-07-21 | 广东生益科技股份有限公司 | Composite material, high-frequency circuit board made thereof and making method |
| CN102161823B (en) * | 2010-07-14 | 2012-09-26 | 广东生益科技股份有限公司 | Composite material, high-frequency circuit substrate therefrom and manufacture method thereof |
| CN103865431A (en) * | 2012-12-11 | 2014-06-18 | 江西中用覆铜板有限公司 | Conducting resin composite material, preparation method of conducting resin composite material and printed circuit board containing conducting resin composite material |
-
2016
- 2016-08-29 CN CN201610765450.9A patent/CN106379006B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106379006A (en) | 2017-02-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106379006B (en) | A kind of high-frequency copper-clad plate | |
| CN106280179B (en) | A kind of high frequency resin composition and its application | |
| CN107109182B (en) | Laminated body containing low dielectric adhesive layer | |
| CN106280199B (en) | A kind of compositions of thermosetting resin and its application | |
| CN106280178B (en) | A kind of resin combination and its application | |
| TWI541288B (en) | A resin composition and a prepreg and laminate using the same | |
| US10023707B2 (en) | Thermosetting resin composition and prepreg as well as hardened product using the same | |
| JP4325337B2 (en) | Resin composition, prepreg, laminate and multilayer printed wiring board using the same | |
| US10584222B2 (en) | Resin composition and pre-preg and laminate using the composition | |
| AU2010345325B2 (en) | Composite material, high-frequency circuit substrate made therefrom and making method thereof | |
| TWI780176B (en) | Copper clad laminate and print circuit board comprising the same | |
| CN103937156A (en) | Thermosetting resin composition and method for manufacturing prepreg and laminated board by using thermosetting resin composition | |
| JP2007099893A (en) | Resin varnish having low dielectric loss tangent, excellent in stability and circuit board material using the same | |
| CN107090065A (en) | High frequency resin composition and its application in prepreg and metal-clad laminate | |
| TW200846398A (en) | Prepreg, multilayer printed wiring board and electronic parts using same | |
| CN103173012B (en) | bismaleimide-triazine resin composite material, organic substrate and preparation method thereof | |
| TW201008987A (en) | Prepreg comprising thin layer quartz glass cloth, and wiring plate using the same | |
| CN103709718B (en) | A kind of compositions of thermosetting resin and application thereof | |
| CN109438960A (en) | A kind of high frequency resin composition and application | |
| EP3733594A1 (en) | Boron nitride agglomerate, thermosetting resin composition containing same, and use thereof | |
| CN109476124A (en) | Laminated body containing low dielectric adhesive layer | |
| CN106366477B (en) | A kind of high frequency resin composition | |
| CN107417862A (en) | Oligomer, the composition and composite for including it | |
| CN106380715B (en) | A kind of resin combination | |
| CN111253888A (en) | Circuit material and circuit board comprising same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |