CN106379006A - High frequency copper-clad plate - Google Patents
High frequency copper-clad plate Download PDFInfo
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- CN106379006A CN106379006A CN201610765450.9A CN201610765450A CN106379006A CN 106379006 A CN106379006 A CN 106379006A CN 201610765450 A CN201610765450 A CN 201610765450A CN 106379006 A CN106379006 A CN 106379006A
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- Prior art keywords
- polybutadiene
- resin combination
- clad plate
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- barium
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- 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
Abstract
The invention discloses a high frequency copper-clad plate. The high frequency copper-clad plate comprises an insulating layer and metal foil arranged on single or double surfaces of the insulating layer. A core material layer of the insulating layer comprises at least one a glass cloth or glass fiber paper prepreg prepared from a resin composition I. A surface material layer of the insulating layer comprises a glass cloth or glass fiber paper prepreg prepared from a resin composition II. The resin compositions I and II have the same ingredients comprising butylbenzene resin, polybutadiene resin, a cross-linking agent and an initiator. The high frequency copper-clad plate has excellent integrated performances of good heat resistance, high peel strength and small dielectric loss and satisfies high frequency sheet material performance requirements.
Description
Technical field
The present invention relates to copper-clad plate technical field is and in particular to a kind of high-frequency copper-clad plate.
Background technology
In recent years, step on the development of communication apparatus high performance, multifunction and networking with computer, mobile phone, be
High-speed transfer and process Large Copacity information, operation signal carries out high frequency, needs one kind to be applied to high frequency signal transmission
The high-performance electric insulant of characteristic.
In high-frequency circuit, electric signal transmission loss dielectric loss and conductor losses, radiation loss sum represent, telecommunications
Number more high then dielectric loss of frequency, conductor losses, radiation loss are bigger.Because transmission loss makes the signal of telecommunication decay, destroys telecommunications
Number reliability, this loss simultaneously, from high frequency circuit radiation, is likely to result in electronic failure.Dielectric therefore must be reduced damage
Consumption, conductor losses, radiation loss.It is known that the dielectric loss angle of the insulator of the dielectric loss of the signal of telecommunication and formation circuit
The product of tangent and the signal frequency being used is directly proportional.Therefore as insulator, can be by just selecting dielectric loss angle
Cut little insulant, the increase of suppression dielectric loss.
Application No. CN200810142665.0 (the applying date：2008.7.28, notification number：CN101328277A, the day for announcing：
2010.7.21 Chinese patent) is disclosed one kind and is more than using epoxide modified polybutadiene, maleic anhydride modified molecular weight
50000 butadiene and cinnamic copolymer, this patent does not provide the epoxide modified scope on modified strand, such as
Fruit epoxide group quantity is excessive, the polarity of composite can be led to increase, dielectric constant, dielectric loss increase；If epoxy radicals
Group's quantity is too small, and resin system can be led to too small with the peel strength between Copper Foil.Additionally, the MA modification fourth disclosed in this patent
Diene is more than 50,000 with cinnamic molecular weight of copolymer, is difficult in a solvent dissolve, subsequent technique is poor.
Application No. JP19770061619 (the 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 is not given
MA functional group percent grafting on modified strand, if percent grafting is excessive, can lead to the polarity of composite to increase, dielectric is normal
Number, dielectric loss increase.If functional group's percent grafting is too small, resin system can be led to too small with the peel strength between Copper Foil.
Additionally, not using butadiene styrene resin, the poor heat resistance of sheet material in resin combination in this patent.
Application No. JP19800183423 (the 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
Thing maleic anhydride grafting ratio is too high, leads to the polarity of composite to increase, dielectric constant, dielectric loss increase.Additionally, this patent
Disclosed in MA modified polybutadiene molecular weight be 5 ten thousand to 20 ten thousand, be difficult in a solvent dissolve, subsequent technique is poor.
For problem above, the present invention proposes one kind and has that heat-resist, peel strength is high, dielectric constant is low, dielectric
The little baseplate material waiting excellent comprehensive performance of loss.
Content of the invention
It is an object of the invention to provide a kind of high-frequency copper-clad plate, it has, and heat-resist, peel strength is high, dielectric loss is little
Deng excellent comprehensive performance, the performance requirement of high frequency sheet material can be met.
The technical solution adopted in the present invention is, a kind of high-frequency copper-clad plate, including insulating barrier be arranged at insulating barrier one side
Or two-sided metal forming, glass cloth or glass fiber paper prepreg that the core material layer of insulating barrier is prepared by least resin combination I
Composition, the glass cloth that the precoat of insulating barrier is prepared by resin combination II or glass fiber paper prepreg form.
The feature of the present invention also resides in,
Resin combination I is identical with the component of resin combination II, all includes butadiene styrene resin, polybutadiene, crosslinking
Agent, initiator.
The molecular weight of butadiene styrene resin is less than 11000, and 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%, enters one
Step preferably 40～50%；The percentage by weight 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, enters one
Step preferably 11000～30000；The contents of ethylene 60～99% of polybutadiene, preferably 70～95wt%, further preferred 75～
93wt%；The percentage by weight that polybutadiene accounts for resin combination I is 10～50wt%, preferably 15～40wt%, enters one
Step preferably 20～30wt%.
In resin combination II, polybutadiene is modified with polar polybutadiene, and modified with polar gathers
Butadiene resin is selected from epoxide 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%；Epoxide group percent grafting on modified with polar polybutadiene strand is situated between
Between 5 to 10；The percentage by weight 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 percentage by weight of cross-linking agent is 3～40wt%, and cross-linking 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 percentage by weight of initiator is 1～7wt%, and initiator is selected from a,
Double (the tertiary hexyl of a '-two (isopropylbenzene between tert-butyl hydroperoxide) benzene, cumyl peroxide, cumyl t-butyl peroxide, 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, the coordination compound of single or multiple phenolic compounds, boron trifluoride and its Organic substance,
In phosphoric acid or triphenyl phosphite any one or at least two mixing.
Fire retardant is also included, fire retardant is selected from deca-BDE, ethyl-bis- in resin combination I and resin combination II
(tetrabromo phthalimide), decabromodiphenylethane, three (2,6- 3,5-dimethylphenyl) phosphine, 10- (2,5- dihydroxy phenyl)-
9,10- dihydro-9-oxy -10 phosphine phenanthrene -10- oxide, 2,6- bis- (2,6- 3,5-dimethylphenyl) phosphino- benzene or 10- phenyl -9,10-
In dihydro-9-oxy -10- phosphine phenanthrene -10- oxide any one or at least two mixing.
Filler is also included, filler is selected from powdered quartz, unformed in resin combination I and resin combination II
Silicon dioxide, spherical silica, titanium dioxide, boron nitride, aluminium nitride, carborundum, aluminium oxide, Barium metatitanate., strontium titanates, metatitanic acid
Magnesium, calcium titanate, barium strontium titanate, calcium Barium metatitanate., 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 metaniobate, potassium niobate, tantalic acid aluminum strontium, potassium tantallum niobate (KTH), strontium barium niobate, niobic acid
In barium lead, titanium niobate barium, bismuth tantalate strontium, bismuth titanates, Barium metatitanate. rubidium, copper titanate, lead titanates-lead magnesio-niobate any one or
At least two mixture；
In the particle diameter of filler, angle value is 0.5～20uM, preferably 1～15uM, further preferred 4～10uM；
The percentage by weight of filler is 0～90wt%, preferably 40～85wt%, further preferred 60～80wt%.
Metal forming is copper, pyrite, aluminum, nickel, copper alloy, brass alloys, in aluminium alloy or nickel alloy any one or
At least two combination, the thickness of metal forming is 5～150 μm.
Compared with prior art, the present invention has the advantages that：
High-frequency copper-clad plate of the present invention, it has the excellent comprehensive performances such as heat-resist, peel strength is high, dielectric loss is little,
The performance requirement of high frequency sheet material can be met.
Brief description
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 high-frequency copper-clad plate second embodiment of the present invention.
In figure, 1. core material layer, 2. precoat, 3. metal forming.
Specific embodiment
The present invention is described in detail with reference to the accompanying drawings and detailed description.
High-frequency copper-clad plate of the present invention, as illustrated in fig. 1 and 2, including insulating barrier and the gold being arranged at insulating barrier single or double
Belong to paper tinsel 3, the glass cloth prepared or glass fiber paper prepreg form the core material layer 1 of insulating barrier by least resin combination I, insulation
The glass cloth that the precoat 2 of layer is prepared by resin combination II or glass fiber paper prepreg form.
Resin combination I is identical with the component of resin combination II, all includes butadiene styrene resin, polybutadiene, crosslinking
Agent, initiator.
The molecular weight of butadiene styrene resin is less than 11000, and the contents of ethylene of butadiene styrene resin is 60～99%, such as 60%,
65%th, 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%th, 55% or 60%, preferably 35～55%, further preferred 40～50%；
The percentage by weight of butadiene styrene resin be 45～80wt%, such as 45%, 50%, 55%, 60%, 65%, 70%,
75%th, 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,
15000th, 20000,25000,30000,35000,40000,45000 or 50000, preferably 8000～40000, further preferably
11000～30000；If molecular weight is more than 50,000, polybutadiene can be led to be difficult in a solvent dissolve, subsequent technique is poor.As
Fruit molecular weight is less than 5000, and during leading to subsequently prepare sheet material, gummosis is excessive, and manufacturability is poor.
The contents of ethylene 60～99% of polybutadiene, such as 60%, 65%, 70%, 75%, 80%, 85%, 90%,
92% or 95%, preferably 70～95wt%, further preferred 75～93wt%；
Polybutadiene account for resin combination I percentage by weight be 10～50wt%, such as 10%, 15%, 20%,
25%th, 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 gathers
Butadiene resin is selected from epoxide 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 is more than 50,000, polybutadiene can be led to be difficult in a solvent molten
Solution, subsequent technique is poor.If molecular weight is less than 5000, during leading to subsequently prepare sheet material, gummosis is excessive, and manufacturability is poor.
The contents of ethylene 60～99% of modified with polar polybutadiene, such as 60%, 65%, 70%, 75%,
80%th, 85%, 90%, 92% or 95%, preferably 70～95wt%, further preferred 75～93wt%；Modified with polar gathers
Epoxide group percent grafting on butadiene molecule chain is between 5 to 10；If percent grafting is more than 10, composite can be led to
Polarity increases, and dielectric loss increases；If functional group's percent grafting is less than 5, resin system can be led to strong with the stripping between Copper Foil
Spend little.The percentage by weight that modified with polar polybutadiene accounts for resin combination II is 10～50wt%, for example
10%th, 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 percentage by weight of cross-linking agent is 3～40wt%, and cross-linking 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 percentage by weight of initiator is 1～7wt%, such as 1%,
1.3%th, 1.5%, 1.7%, 2%, 2.3%, 2.5%, 3%, 3.5%, 4%, 5%, 6% or 7%, preferably 1.5～5%, enter
One step preferably 2～4wt%.Initiator is selected from a, a '-two (isopropylbenzene between tert-butyl hydroperoxide) benzene, cumyl peroxide, uncle
Double (the tertiary hexyl peroxidating) -3 of 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
Compound, 2,4,6- tri- (dimethylamino methylamine) phenol, benzyl dimethylamine, imidazoles, three amylic phenol acid amides, single or multiple phenolate are closed
In the coordination compound of thing, boron trifluoride and its Organic substance, phosphoric acid or triphenyl phosphite any one or at least two mixed
Close.
Fire retardant is also included, fire retardant is selected from deca-BDE, ethyl-bis- in resin combination I and resin combination II
(tetrabromo phthalimide), decabromodiphenylethane, three (2,6- 3,5-dimethylphenyl) phosphine, 10- (2,5- dihydroxy phenyl)-
9,10- dihydro-9-oxy -10 phosphine phenanthrene -10- oxide, 2,6- bis- (2,6- 3,5-dimethylphenyl) phosphino- benzene or 10- phenyl -9,10-
In dihydro-9-oxy -10- phosphine phenanthrene -10- oxide any one or at least two mixing.
Filler is also included, filler is selected from powdered quartz, unformed in resin combination I and resin combination II
Silicon dioxide, spherical silica, titanium dioxide, boron nitride, aluminium nitride, carborundum, aluminium oxide, Barium metatitanate., strontium titanates, metatitanic acid
Magnesium, calcium titanate, barium strontium titanate, calcium Barium metatitanate., 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 metaniobate, potassium niobate, tantalic acid aluminum strontium, potassium tantallum niobate (KTH), strontium barium niobate, niobic acid
In barium lead, titanium niobate barium, bismuth tantalate strontium, bismuth titanates, Barium metatitanate. rubidium, copper titanate, lead titanates-lead magnesio-niobate any one or
At least two mixture；
In the particle diameter of filler, angle value is 0.5～20uM, such as 0.5,1.0,2.0,4.0,6.0,10,12,15,20,25,28
Or 30, preferably 1～15uM, further preferred 4～10uM；
The percentage by weight of filler be 0～90wt%, such as 0%, 25%, 35%, 45%, 55%, 65%, 70%,
75%th, 78%, 80%, 85% or 90%, preferably 40～85wt%, further preferred 60～80wt%.
Metal forming is copper, pyrite, aluminum, nickel, copper alloy, brass alloys, in aluminium alloy or nickel alloy any one or
At least two combination, the thickness of metal forming is 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：
16L is dried hexamethylene, 1600g is dried butadiene and puts 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 add following catalytic component：4ml～9ml tri-
The hexane solution of [di-(2-ethylhexyl)phosphoric acid] ferrum (0.4mmol～0.9mmol), 16ml～36ml triisobutyl aluminium
(8mmol) hexane solution, the hexane solution of 12ml～27ml triphenyl phosphate (1.2mmol～2.7mmol), 17mmol～
The tetrahydrofurfuryl alcohol ethylether of 38mmol, PMDETA 7mmol～17mmol, are warming up to 65 DEG C～90 DEG C, are polymerized 1～9 hour.So
After add ethanol terminating reaction and separate out glue sample, sucking filtration, with acetone extraction 12～18h, put into 25 DEG C of baking ovens vacuum drying 12h,
Obtain white solid product polybutadiene.
Different molecular weight, different contents of ethylene, different molecular weight butadiene resin as shown in table 1.
Table 1 polybutadiene
| 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, different molecular weight, different contents of ethylene, the polybutadiene of different epoxy percent grafting can be prepared
Resin, as follows：
16L is dried hexamethylene, 1600g is dried butadiene and puts 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 add following catalytic component：4ml～9ml tri-
The hexane solution of [di-(2-ethylhexyl)phosphoric acid] ferrum (0.4mmol～0.9mmol), 16ml～36ml triisobutyl aluminium
(8mmol) hexane solution, the hexane solution of 12ml～27ml triphenyl phosphate (1.2mmol～2.7mmol), 17mmol～
The tetrahydrofurfuryl alcohol ethylether of 38mmol, PMDETA 7mmol～17mmol, are warming up to 65 DEG C～90 DEG C, are polymerized 1～9 hour.So
After add ethanol terminating reaction and separate out glue sample, sucking filtration, with acetone extraction 12～18h, put into 25 DEG C of baking ovens vacuum drying 12h,
Obtain white solid product polybutadiene.
By 1000g polybutadiene, 2.5L ethyl acetate is put in four mouthfuls of glass reaction bottles of 4L, 65 DEG C～75 DEG C of constant temperature,
After polybutadiene is completely dissolved, be passed through drying nitrogen, be warming up to 80 DEG C～95 DEG C, be slowly added to in system containing 50g～
200g formic acid, 5g～42g Polyethylene Glycol, stirring reaction 2～4 hours after completion of dropping, then by the hydrogen peroxide of 30g～215g
Interior in 30min be slowly dropped in four-hole bottle, reactant is slowly warmed up to 120 DEG C, continues reaction 3～5 hours at a constant temperature,
After reaction terminates, product is poured out, add dehydrated alcohol precipitation, sedimentation a period of time, sucking filtration, with sodium bicarbonate solution and distillation
Water washing at least 12 times, puts into 25 DEG C of baking oven vacuum drying 12h, obtains white solid product.
Different molecular weight, different contents of ethylene, different epoxy percent grafting polybutadiene as shown in table 2.
The epoxide modified polybutadiene of table 2
| Molecular weight | Contents of ethylene | Epoxy percent grafting | |
| 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, different molecular weight, different contents of ethylene, the poly- fourth of different maleic anhydride grafting ratio can be prepared
Diene resin, as follows：
16L is dried hexamethylene, 1600g is dried butadiene and puts 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 add following catalytic component：4ml～9ml tri-
The hexane solution of [di-(2-ethylhexyl)phosphoric acid] ferrum (0.4mmol～0.9mmol), 16ml～36ml triisobutyl aluminium
(8mmol) hexane solution, the hexane solution of 12ml27ml triphenyl phosphate (1.2mmol～2.7mmol), 17mmol～
The tetrahydrofurfuryl alcohol ethylether of 38mmol, PMDETA 7mmol～17mmol, are warming up to 65 DEG C～90 DEG C, are polymerized 1～9 hour.So
After add ethanol terminating reaction and separate out glue sample, sucking filtration, with acetone extraction 12～18h, put into 25 DEG C of baking ovens vacuum drying 12h,
Obtain white solid product polybutadiene.
By above-mentioned for 1000g polybutadiene, 300ml dimethylbenzene is put in four mouthfuls of glass reaction bottles of 4L, constant temperature 65 DEG C～75
DEG C, after polybutadiene is completely dissolved, be passed through drying nitrogen, be warming up to 85 DEG C～95 DEG C, be slowly added to in system containing
165g～370g maleic anhydride, the xylene solution of 48g～110g acetanilide, stir 10min～25min after completion of dropping,
It is slowly dropped to interior in 30min for the xylene solution containing 24g～56g BPO in four-hole bottle, reactant is slowly warmed up to
120 DEG C, continue reaction 3～5 hours at a constant temperature, after reaction terminates, blood pressure lowering is distilled, and removes dimethylbenzene and unreacted maleic acid
Acid anhydride, product is poured out, and adds dehydrated alcohol precipitation, sedimentation a period of time, sucking filtration, with acetone extraction 12h～18h, puts into 25 DEG C
Baking oven is vacuum dried 12h, obtains white solid product MA modified polybutadiene.
Different molecular weight, different contents of ethylene, different MA percent grafting butadiene resin as shown in table 3.
Table 3 MA modified polybutadiene
| Molecular weight | Contents of ethylene | MA percent grafting | |
| 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, specific as follows.
4L is dried hexamethylene, 0.05ml～0.48ml tetrahydrofurfuryl alcohol ethylether, puts into four mouthfuls of glass reaction bottle (warps of 4L
Overbaking dried) in, it is passed through drying nitrogen protection, 40 DEG C～60 DEG C of constant temperature, be then simultaneously introduced 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～
0.1mL, is subsequently adding the cyclohexane solution of the 0.2mol/L mono- chlorine trimethyl silane of 1.0mL～16.65mL, reacts 30min, plus
Enter isopropanol terminating reaction and separate out glue sample, sucking filtration, use acetone extraction 12h, put into 25 DEG C of baking oven vacuum drying 12h, obtain white
Solid product.
Different molecular weight, different contents of ethylene, different styrene-content butadiene styrene resin as shown in table 4.
Table 4 butadiene styrene resin
For the present invention is better described, readily appreciate technical scheme, the present invention's is typical but non-limiting
Embodiment is as follows：
Embodiment
Embodiment 1-8 and the manufacture method of comparative example 1-4 copper-clad laminate：Design parameter is as shown in table 5 and table 6.
Butadiene styrene resin, maleic anhydride modified polybutadiene, cross-linking agent, initiator are dissolved in toluene, after fully dissolving,
Add angle value, the filler of different quality containing in different-grain diameter, be then mixed to get glue at room temperature.Impregnated using glass cloth
Above-mentioned glue, then in 155 DEG C of baking oven, baking is cured as B-stage for 5 minutes, and control obtains prepreg.
Then, the prepreg of making is placed between Copper Foil, is laminated and solidifies in 210 DEG C in press, obtain solidfied material
Measuring Dielectric Constant afterwards, Tg, peel strength, DK, Df.Specific performance test result is shown in Table 5, table 6.
In above-described embodiment and comparative example, used material is specific as follows：
Triallyl isocyanurate：Nippon Kasei Chemical Company TAIC M-60
Poly- triallyl isocyanurate：Nippon Kasei Chemical Company
Triallyl cyanurate：Nippon Kasei Chemical Company
BPO：Great river oils and fatss Co., Ltd.
BIPB：Great river oils and fatss Co., Ltd.
DCP：Shanghai Fang Rui reaches chemical industry
Barium titanate/strontium titanate/barium strontium titanate：Shanghai allusion quotation raises science and technology
Lead titanates：Hubei Prunus persica f. compressa culminant star electronics.
Table 5 embodiment 1～8 formula and test result
Table 6 comparative example 1～4 formula and test result
The method of testing of above characteristic is as follows：：
1st, glass transition temperature (Tg)：DMA method according to IPC-TM-650 2.4.24 defined is measured.
2nd, peel strength (PS)：According to " after thermal stress " experiment condition in IPC-TM-650 2.4.8 method, test sheet material
Peel strength.
3rd, dielectric properties：SPDR (splite post dielectric resonator) method is tested, test condition
For A state, 10GHz.
From table 5 and table 6, can be seen that what embodiment 1 was prepared to embodiment 8 from the contrast of embodiment and comparative example
Sheet material, the combination property such as its dielectric loss, dielectric constant, peel strength, glass transition temperature preferably, uses in comparative example 1
Unmodified polybutadiene, the dielectric loss ratio of sheet material is relatively low, and the peel strength of sheet material is low；Using high percent grafting in comparative example 2
Polybutadiene, the peel strength of sheet material is high, but dielectric loss is high；Comparative example 3 uses the little butadiene styrene resin of styrene-content,
The Tg of sheet material is low；Comparative example 4 uses the little butadiene styrene resin of contents of ethylene, butadiene resin, and the Tg of sheet material is low.
Comprehensive the above results understand, the material of the present invention can reach that heat-resist, peel strength is high, dielectric constant is low, be situated between
Electrical loss is little to wait excellent comprehensive performance, and performance has obtained larger improvement, can meet the performance requirement of high frequency material.
Above example, not imposes any restrictions to the content of the compositionss of the present invention, every technology according to the present invention
Any trickle amendment, equivalent variations and modification that essence or compositionss composition or content are made to above example, all still fall within
In the range of technical solution of the present invention.
Applicant states, the present invention illustrates the detailed composition of the present invention by above-described embodiment, but the present invention not office
It is limited to above-mentioned detailed composition, that is, do not mean that the present invention has to rely on above-mentioned detailed composition and could implement.Art
Technical staff is it will be clearly understood that any improvement in the present invention, the equivalence replacement to each raw material of product of the present invention and auxiliary element
Interpolation, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (10)
1. a kind of high-frequency copper-clad plate, including insulating barrier and the metal forming (3) being arranged at insulating barrier single or double, its feature exists
In, by least resin combination I, the glass cloth prepared or glass fiber paper prepreg form the core material layer (1) of described insulating barrier,
The glass cloth that the precoat (2) of described insulating barrier is prepared by resin combination II or glass fiber paper prepreg form.
2. high-frequency copper-clad plate according to claim 1 is it is characterised in that described resin combination I and resin combination II
Component identical, all include butadiene styrene resin, polybutadiene, cross-linking agent, initiator.
3. high-frequency copper-clad plate according to claim 2 it is characterised in that described butadiene styrene resin molecular weight be less than 11000,
The contents of ethylene of described butadiene styrene resin is 60～99%, preferably 70～95wt%, further preferred 75～93wt%；Described fourth
The styrene-content of benzene resin is 30～60%, preferably 35～55%, further preferred 40～50%；The weight of described butadiene styrene resin
Amount percentage ratio is 45～80wt%, preferably 48～70wt%, further preferred 50～60wt%.
4. high-frequency copper-clad plate according to claim 2 is it is characterised in that in described resin combination I, polybutadiene
Molecular weight be 5000～50000, preferably 8000～40000, further preferred 11000～30000；The vinyl of polybutadiene
Content 60～99%, preferably 70～95wt%, further preferred 75～93wt%；Polybutadiene accounts for resin combination I's
Percentage by weight is 10～50wt%, preferably 15～40wt%, further preferred 20～30wt%.
5. high-frequency copper-clad plate according to claim 2 is it is characterised in that in described resin combination II, polybutadiene tree
Fat is modified with polar polybutadiene, and modified with polar polybutadiene is selected from epoxide modified polybutadiene tree
Fat, maleic anhydride modified polybutadiene, acrylic acid modified polybutadiene, hydroxy-end capped polybutadiene, carboxylic
In the modified polybutadiene of the polybutadiene of base end-blocking, amine any one or at least two mixing.
6. high-frequency copper-clad plate according to claim 5 is it is characterised in that in described resin combination II, polar group changes
Property polybutadiene molecular weight be 5000～50000, preferably 8000～40000, further preferred 11000～30000；Polar group
The contents of ethylene 60～99% of group's modified polybutadiene, preferably 70～95wt%, further preferred 75～93wt%；Polar group
Epoxide group percent grafting on group's modified polybutadiene strand is between 5 to 10；Modified with polar polybutadiene
The percentage by weight accounting for resin combination II is 10～50wt%, preferably 15～40wt%, further preferred 20～30wt%.
7. high-frequency copper-clad plate according to claim 2 is it is characterised in that described resin combination I and resin combination II
In, the percentage by weight of cross-linking agent is 3～40wt%, and cross-linking agent is selected from triallyl isocyanurate, poly- isocyanuric acid three allyl
Ester, triallyl cyanurate, trimethacrylate acid, diallyl phthalate, divinylbenzene or polyfunctional third
In olefin(e) acid ester any one or at least two mixing.
8. high-frequency copper-clad plate according to claim 2 is it is characterised in that described resin combination I and resin combination II
In, the percentage by weight of initiator is 1～7wt%, and initiator is selected from a, a '-two (isopropylbenzene between tert-butyl hydroperoxide) benzene, mistake
Oxidation diisopropylbenzene (DIPB), cumyl t-butyl peroxide, double (the tertiary hexyl peroxidating) -3 of 1,1-, 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
Salt, level Four amine salt compound, 2,4,6- tri- (dimethylamino methylamine) phenol, benzyl dimethylamine, imidazoles, three amyl group phenolic acid
In amine, the coordination compound of single or multiple phenolic compounds, boron trifluoride and its Organic substance, phosphoric acid or triphenyl phosphite any one or
The mixing of person at least two.
9. high-frequency copper-clad plate according to claim 2 is it is characterised in that described resin combination I and resin combination II
In also include fire retardant, fire retardant be selected from deca-BDE, ethyl-bis- (tetrabromo phthalimide), decabrominated dipheny base second
Alkane, three (2,6- 3,5-dimethylphenyl) phosphine, 10- (2,5- dihydroxy phenyl) -9,10- dihydro-9-oxy -10 phosphine phenanthrene -10- oxidation
In thing, 2,6- bis- (2,6- 3,5-dimethylphenyl) phosphino- benzene or 10- phenyl -9,10- dihydro-9-oxy -10- phosphine phenanthrene -10- oxide
Any one or at least two mixing.
10. high-frequency copper-clad plate according to claim 2 is it is characterised in that described resin combination I and resin combination II
In also include filler, filler be selected from powdered quartz, unformed silicon dioxide, spherical silica, titanium dioxide, nitrogen
Change boron, aluminium nitride, carborundum, aluminium oxide, Barium metatitanate., strontium titanates, magnesium titanate, calcium titanate, barium strontium titanate, calcium Barium metatitanate., metatitanic acid
Lead, lead zirconate titanate, zirconium lanthanium titanate lead, lanthanium titanate barium, zirconia titanate barium, titanium dioxide, hafnium oxide, lead magnesio-niobate, barium magnesium niobate,
Lithium metaniobate, potassium niobate, tantalic acid aluminum strontium, potassium tantallum niobate (KTH), strontium barium niobate, lead bariun niobate, titanium niobate barium, bismuth tantalate strontium, bismuth titanates, titanium
In sour barium rubidium, copper titanate, lead titanates-lead magnesio-niobate any one or at least two mixture；
In the particle diameter of filler, angle value is 0.5～20uM, preferably 1～15uM, further preferred 4～10uM；
The percentage by weight of filler is 0～90wt%, preferably 40～85wt%, further preferred 60～80wt%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN110461891A (en) * | 2017-03-30 | 2019-11-15 | 日铁化学材料株式会社 | Soluble polyfunctional vinyl aromatic co-polymer, its manufacturing method and curable resin composition and its hardening thing |
| CN111372372A (en) * | 2020-03-30 | 2020-07-03 | 广东生益科技股份有限公司 | Circuit material and circuit board comprising same |
| 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 |
| CN115302869A (en) * | 2022-07-05 | 2022-11-08 | 广东生益科技股份有限公司 | High-frequency copper-clad plate and printed circuit board comprising same |
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| CN102161823A (en) * | 2010-07-14 | 2011-08-24 | 广东生益科技股份有限公司 | Composite material, high-frequency circuit substrate therefrom and manufacture method thereof |
| 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 |
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| CN110461891A (en) * | 2017-03-30 | 2019-11-15 | 日铁化学材料株式会社 | Soluble polyfunctional vinyl aromatic co-polymer, its manufacturing method and curable resin composition and its hardening thing |
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| 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 |
| CN111372372A (en) * | 2020-03-30 | 2020-07-03 | 广东生益科技股份有限公司 | Circuit material and circuit board comprising same |
| 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 |
| 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 |
| CN115302869A (en) * | 2022-07-05 | 2022-11-08 | 广东生益科技股份有限公司 | High-frequency copper-clad plate and printed circuit board comprising same |
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