CN109203602A - A kind of high frequency double face copper and the preparation method and application thereof - Google Patents
A kind of high frequency double face copper and the preparation method and application thereof Download PDFInfo
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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
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
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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
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
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- Engineering & Computer Science (AREA)
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- Microelectronics & Electronic Packaging (AREA)
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Abstract
The invention discloses a kind of high frequency double face coppers, it from top to bottom successively include copper foil, polyimide layer, thermoplastic high frequency glue-line, polyimide layer, copper foil, the polyimide layer is to be coated on copper foil surface by the polymeric composition of the low DK and DF to be formed by heating high temperature cyclization, and the thermoplastic high frequency glue-line is to be coated on polyimides layer surface by the low dielectric polymeric composite composition of the thermoplastic to be formed by heating high temperature cyclization.The invention also discloses a kind of circuit boards made of the high frequency double face copper.The high frequency double face copper of the application is suitable for 5G or more product, and raw material uses diamines and dicarboxylic anhydride, can effectively reduce DF.
Description
Technical field
The invention belongs to technical field of electronic materials, specifically, being related to a kind of high frequency double face copper and its preparation side
Method and application.
Background technique
With the continuous improvement of terminal applies and network speed, the message transmission rate of equipment room is promoted from several hundred Mbps
To 20Gbps, the industrial technology of PCB is regardless of soft board and hardboard sent out toward the method for high frequency, high speed and high density structure dress at present
Exhibition, corresponding product is light, it is thin, can carry, the development trend of multifunction, can be increasingly for the demand of material and preparation method
It is harsh, under data-interface high speed trend, the application pair such as terminal antenna, high-speed interface transmission line, server internal transmission line
The substitutive demand of high-frequency high-speed soft board increasingly increases, and constitutes the substitution logic to conventional transmission line, and high-frequency high-speed and miniaturization need
It asks down, high-frequency transmission and low-loss material will substitute transmission line comprehensively, and most important one material property demand is exactly LOW DK/
DF, peel strength.
In the prior art, using commercially available high frequency film (PI and LCP), high-frequency copper-clad plate is made using high-temperature laminating legal system.
But because technology and cost all rest in supplier on hand, therefore develop coating pressing method equally up to commercially available same level, together
Sample can be applied in the material of high-speed high frequency.
Summary of the invention
The object of the present invention is to provide a kind of high frequency double face coppers.
It is a further object to provide a kind of preparation methods of high frequency double face copper.
It is also another object of the present invention to provide one kind circuit boards made of the high frequency double face copper.
To achieve the goals above, The technical solution adopted by the invention is as follows:
The first aspect of the invention provides a kind of high frequency double face copper, from top to bottom successively includes copper foil, polyamides
Imine layer, thermoplastic high frequency glue-line, polyimide layer, copper foil, the polyimide layer are by the high score subgroup of the low DK and DF
Conjunction object is coated on copper foil surface and is formed by heating high temperature cyclization, and the thermoplastic high frequency glue-line is by the low dielectric high score of the thermoplastic
Sub- composite is coated on polyimides layer surface and is formed by heating high temperature cyclization.
The polyimide layer with a thickness of 9-50um.
The copper foil with a thickness of 12-18um.
The thermoplastic high frequency glue-line with a thickness of 8-21um.
Described BHFX-92F-HA-V2-12 μm of copper foil model, RZ=0.45 (day mine).
The polymeric composition (high frequency PI composition) of the low DK and DF, is made of the component of following parts by weight:
20~60 parts of dicarboxylic anhydride containing ester groups；
1~25 part of diamine monomer containing pyrimidine group；
100~180 parts of solvent.
The dicarboxylic anhydride containing ester groups is aromatic tetracarboxylic dianhydride, the preferably bis- trihemellitic acids of p-phenylene-
Ester dianhydride (TAHQ), 3,3', 4,4'- biphenyltetracarboxylic dianhydrides (BPDA), Bisphenol A Type Diether Dianhydride (BPADA), specific structure is such as
Shown in lower:
The diamine monomer containing pyrimidine group is aromatic diamine, preferably 3,5- diaminostilbene, 2,4- triazoles
(DTZ), 1,4- phenylene bis- (4-aminobenzoic acid ester) (ABHQ), two p-aminophenyl ester (BPTP) of terephthalic acid (TPA), to amino
Benzoic acid p-aminophenyl ester (APAB), 4,4 '-diaminodiphenyl ethers (ODA), bis- (4- aminophenyl) terephthalates
(BPBT), specific structure is as follows:
The diamine monomer containing pyrimidine group is 3,5- diaminostilbene, 2,4- triazole (DTZ), p-aminobenzoic acid
The mixture of p-aminophenyl ester (APAB), 4,4 '-diaminodiphenyl ethers (ODA).
The solvent is N-Methyl pyrrolidone (NMP), DMAC N,N' dimethyl acetamide, butyrolactone, N.N- dimethyl formyl
Amine, dimethyl sulfoxide.
The solid content of the polymeric composition of the low DK and DF is 30wt% (low DK and DF polyamic acid solution), is glued
Degree is 30000~60000CPs.
The low dielectric polymeric composite composition (thermoplastic high frequency glue) of the thermoplastic, is by the component system of following parts by weight
At:
The dicarboxylic anhydride is 3,3', 4,4'- biphenyltetracarboxylic dianhydrides (BPDA), Bisphenol A Type Diether Dianhydride (BPADA), tool
Body structure is as follows:
The diamine monomer is 2,2'- bis- [4- (4- aminophenoxy phenyl)] propane (BAPP), (the 4- amino of 4,4'- bis-
Phenoxy group) biphenyl (BAPB), bis- (3- amino-benzene oxygen) biphenyl (43BAPOB) of 4,4'-, the bis- [4- (4- amino-benzene oxygen) of 2,2-
Phenyl] -1, bis- (4'- amino-benzene oxygen) benzene (TPE-R) of 1,1,3,3,3- hexafluoropropane (HFBAPP), 1,3-, specific structure is such as
Shown in lower:
The solvent is N-Methyl pyrrolidone (NMP), DMAC N,N' dimethyl acetamide, butyrolactone, N.N- dimethyl formyl
Amine, dimethyl sulfoxide, dimethylbenzene.
The filler (Filler) is FS06 of the silicon than section (Shanghai) mining industry Co., Ltd, FS06:Fused silica
(vitreous silica), specifications and models: FS06ARA；The EA-2000 of Asahi Kasei Corporation, EA-2000:PTPE POWER (Teflon powder
End), specifications and models: EA-2000.
The second aspect of the invention provides a kind of preparation method of high frequency double face copper, including following step
It is rapid:
The polymeric composition of low DK and DF is formed into low DK by high temperature cyclization on copper foil via coating process coating
With the polyimide layer of DF, then via the low dielectric polymer composite group of coating process coating thermoplastic on polyimide layer
It closes object (thermoplastic high frequency glue), forms thermoplastic high frequency glue-line by high temperature cyclization, single-side coated copper plate is obtained, then by two above-mentioned lists
Face copper-clad plate coats cated one side and places with respect to lamination, high frequency double face copper is obtained by pressing, specifically such as Fig. 3 institute
Show, Fig. 3 is the flow diagram of the preparation method of high frequency double face copper of the invention.
The coating process condition are as follows: temperature is 140 DEG C of holding 10min.
The high temperature cyclization condition are as follows: at room temperature, be warming up to 150 DEG C through 15min, keep the temperature 5min, be warming up to through 10min
200 DEG C, 5min is kept the temperature, 250 DEG C is warming up to through 10min, keeps the temperature 5min, is cooled to 200 DEG C through 10min, keeps the temperature 20min, warp
10min is warming up to 250 DEG C, keeps the temperature 20min, is then down to room temperature through 60min.
The temperature of the pressing is 350-400 DEG C.
The preparation method of the polymeric composition of the low DK and DF, comprising the following steps:
The dicarboxylic anhydride containing ester groups, the diamine monomer containing pyrimidine group are dissolved in solvent by the proportion, stirred
Mix the polymeric composition that dissolution obtains the low DK and DF.
The preparation method of the low dielectric polymeric composite composition (thermoplastic high frequency glue) of the thermoplastic, including following step
It is rapid:
Dicarboxylic anhydride, diamine monomer are dissolved in solvent by the proportion, stirring and dissolving is added filler (Filler) and stirs
It mixes, adds solvent and be heated to reflux, obtain the low dielectric polymeric composite composition of the thermoplastic (thermoplastic high frequency glue).
The third aspect of the invention provides a kind of circuit board made of the high frequency double face copper.
The principle of the present invention part is as follows:
The method for reducing dielectric constant:
Claslius-Mosotti equation:
Wherein Pm: the Moore polarizability of atomic group, Vm: the Moore volume of atomic group.
Pm can be reduced by introducing esters functional group, coplanar increase Vm that macoradical destroys phenyl ring can also be introduced.
Therefore the method for reducing dielectric constant mainly has introduction esters functional group, close structure arrangement, blending low Df material.
General PI is because of structurally flexible (CH2,-O- etc.) structure is easy rotation, be easy to produce gap in storehouse, lead to storehouse not
Dk and Df is closely made to increase, therefore the structure that ester-introduced class formation (C=CO) makes with introducing macoradical in structure is not easy to rotate,
Close structure causes Dk and Df to decline after storehouse again.
The storehouse gap of the prior art is as follows:
Dk=3.2
Df=0.008.
The storehouse of the application is close, specific as follows:
For conductor copper foil, path is shorter when the more smooth electric current of conductive surface flows through, the more coarse electric current of conductive surface
Path is longer when flowing through, as shown in Figure 1, Fig. 1 is schematic diagram when conductor copper foil surface current flows through.Selection has low roughness
Copper foil can have the characteristic of excellent LOW DK and DF, but when copper foil roughness is lower, will cause polyimide layer and copper
The low defect of tackness between foil.Therefore the composition to copper Bonding strength can be promoted on Molecular Design.In the composition
Using the diamine monomer containing pyrimidine group, wherein pyrimidine group can will enhance polyimides and copper foil with the coordination of copper
Bond strength.As shown in Fig. 2, the material that Fig. 2 is the prior art and the application is attached to the schematic diagram on copper foil.In the prior art
Peel strength be 0.5kgf/cm, the application and copper generate coordination, peel strength 0.9kgf/cm.
Due to the adoption of the above technical scheme, the present invention has the following advantages and beneficial effects:
In order to solve the problems, such as that DK&DF is excessively high, The inventive process provides with LOW DK/DF polyimide layer
(Core) double-sided wiring board laminate, the LOW DK/DF polyimide layer (high frequency PI) and thermoplasticity high frequency glue are simultaneously taken
Copper foil with low roughness, the characteristic with high-transmission.
The polymeric composition (high frequency PI composition) that low DK and DF is used in method provided by the invention, has excellent resistance to
It is hot, using dicarboxylic anhydride/diamine monomer containing ester groups, wherein the collocation of the polymeric composition of low DK and DF and copper is made
With can effectively be fabricated to high frequency.The composition solid 30%, 30000~60000CPs of viscosity can be coated with via coating process
In on copper foil, sub- amidation is carried out to form LOW DK&DF polyimide polymer, the LOW DK& via heat treatment
DF polyimide polymer can be in the LOW DK&DF polyimide layer of copper foil surface generation heat resistance, and as high frequency is soft without glue system
The products such as property board substrate (2L-FCCL).
General double face copper can only be used in 4G or less transmission (df=0.008), and being such as used in 5G or more transmission can produce
Raw serious signal interference, raw material is using general diamines and dicarboxylic anhydride (aromatic series).The high frequency double face copper of the application because
Df0.002 is suitable for 5G or more product, in the following Internet of Things with greatly promoting, raw material using diamines and dicarboxylic anhydride (stationery with
Zhi Huan race), it can effectively reduce DF.
Detailed description of the invention
Fig. 1 is schematic diagram when conductor copper foil surface current flows through.
Fig. 2 is the schematic diagram that the material of the prior art and the application are attached on copper foil.
Fig. 3 is the flow diagram of the preparation method of high frequency double face copper of the invention.
Fig. 4 is the flow diagram of the preparation method high temperature cyclisation of high frequency double face copper of the invention.
Fig. 5 is the flow diagram of comparative example 2 and 3.
Specific embodiment
In order to illustrate more clearly of the present invention, below with reference to preferred embodiment, the present invention is described further.Ability
Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this
The protection scope of invention.
Agents useful for same of the embodiment of the present invention is as follows:
Diamines: the diamine monomer in the present invention can be aromatic diamine, can be following monomer, but not limited to this；In
Text: 3,5- diaminostilbenes, 2,4- triazoles, English: 1,2,4-Triazole-3,5-diamine, abbreviation: DTZ, CAS:1455-
77-2.Chinese: Isosorbide-5-Nitrae-phenylene is bis- (4-aminobenzoic acid ester), English: Isosorbide-5-Nitrae-phenylene bis (4-
Aminobenzoate) or Isosorbide-5-Nitrae-Bis (4-aminobenzo-yloxy) benzene, abbreviation: ABHQ, CAS:22095-98-3.
Chinese: two p-aminophenyl ester of terephthalic acid (TPA), English: Bis (4-aminophenyl) terephthalate, abbreviation: BPTP,
CAS:16926-73-1.Chinese: p-aminobenzoic acid p-aminophenyl ester, English: 4-Aminophenyl-4-
Aminobenzoate, abbreviation: APAB, CAS:20610-77-9.Chinese: bis- [4- (the 4- aminophenoxy phenyls)] third of 2,2'-
Alkane, English: 2,2-Bis [4- (4-aminophenoxy) phenyl] propane, abbreviation: BAPP, CAS:13080-86-9.In
Text: 4,4'- bis- (4- amino-benzene oxygen) biphenyl, English: 4,4-Bis (4-Aminophenoxy) Biphenyl, abbreviation: BAPB,
CAS:13080-85-8.Chinese: 4,4'- bis- (3- amino-benzene oxygen) biphenyl, English: 4,4-BIS (3-AMINOPHENOXY)
BIPHENYL, abbreviation: 43BAPOB, CAS:105112-76-3.Chinese: bis- [4- (4- amino-benzene oxygen) phenyl] -1,1 of 2,2-,
1,3,3,3- hexafluoropropane, English: 2,2-BIS [4- (4-AMINOPHENOXY) PHENYL] HEXAFLUOROPROPANE, contracting
It writes: HFBAPP, CAS:69563-88-8.Chinese: 1,3- bis- (4'- amino-benzene oxygen) benzene, English: 4,4'- (1,3-
Phenylenedioxy) dianiline, abbreviation: TPE-R, CAS:2479-46-1.Chinese: 4,4 '-diaminodiphenyl ethers, English
Text: 4,4'-oxybisbenzenamine, abbreviation: ODA.Chinese: bis- (4- aminophenyl) terephthalates, English: bis
(4-aminophenyl) terephthalate, abbreviation: BPBT.
Dicarboxylic anhydride: dianhydride monomer in the present invention can be aromatic tetracarboxylic dianhydride, be exemplified below, but not as
Limit；Chinese: the bis- tritrimellitate dianhydrides of p-phenylene-, English: p-phenylenebis (trimellitate
Anhydride), abridge: TAHQ, CAS:2770-49-2.Chinese: 3,3', 4,4'- biphenyltetracarboxylic dianhydrides, English: 3,3 ', 4,
4 '-Biphenyltetracarboxylic dianhydride, abbreviation: BPDA, CAS:2420-87-3.Chinese: bisphenol A-type two
Ether dianhydride, English: 4,4'- (4,4'-ISOPROPYLIDENEDIPHENOXY) BIS (PHTHALIC ANHYDRIDE), abbreviation:
BPADA, CAS:38103-06-9.
Filler characteristic is as shown in table 1:
Table 1
| Test item | Unit | FS06(ARA) | EA-2000 |
| CTE | PPM/℃ | 0.5 | 16 |
| Dielectric constant Dk (10GHZ) | - | 3.80 | 2.85 |
| Loss factor D f (10GHZ) | - | 0.003 | 0.001 |
High frequency PI:SR#SW (Kaneka) 25um；LCP:CT-Q(Kuraray)25um；Copper: Cu:BHFX-92F-HA-V2
(day mine) 12um；Filer:FS06 (silicon is than section)；Filer:EA-2000 (Asahi Chemical Industry).
The solid content of the polymeric composition of low DK and DF used in the embodiment of the present invention is 30wt% (low DK and DF polyamides
Amino acid solution), viscosity is 30000~60000CPs.
Embodiment 1-1~1-4
It is matched according to described in table 2, NMP, APAB, ODA, DTZ is separately added into 500mL reaction flask, to high-speed stirred
It to dissolution, adds BPDA and is stirred to react 12 hours, stirring and dissolving is to configure the polymeric composition for completing low DK and DF.
Table 2
Embodiment 1-5~1-8
It is matched according to described in table 3, NMP, APAB, ODA, DTZ is separately added into 500mL reaction flask, to high-speed stirred
It to dissolution, adds BPADA and is stirred to react 12 hours, stirring and dissolving is to configure the polymeric composition for completing low DK and DF.
Table 3
Embodiment 1-9~1-12
It is matched according to described in table 4, NMP, APAB, ODA, DTZ is separately added into 500mL reaction flask, to high-speed stirred
It to dissolution, adds TAHQ and is stirred to react 12 hours, stirring and dissolving is to configure the polymeric composition for completing low DK and DF.
Table 4
Embodiment 2-1~2-15
It is matched according to described in table 5~7, NMP, diamine monomer is separately added into 500mL reaction flask, extremely to high-speed stirred
After dissolution, BPDA is added and is stirred to react 4 hours, add filler (Filler) and stir 2 hours, dimethylbenzene (20ml) is added and adds
Heat flows back 4 hours to 180 DEG C, completes the low dielectric polymeric composite composition (thermoplastic high frequency glue) of configuration thermoplastic.
Table 5
Table 6
Table 7
Embodiment 2-16~2-20
It is matched according to described in table 8, NMP, diamine monomer is separately added into 500mL reaction flask, to high-speed stirred to molten
Xie Hou adds BPADA and is stirred to react 4 hours, adds filler (Filler) and stirs 2 hours, is added dimethylbenzene (20ml)
180 DEG C are heated to, is flowed back 4 hours, the low dielectric polymeric composite composition (thermoplastic high frequency glue) of configuration thermoplastic is completed.
Table 8
In above embodiments 2-1~2-20, each embodiment includes two products, such as embodiment 2-1, dicarboxylic anhydride,
Diamines, solvent are fixed, and when filler Filler is FS06, the product being prepared is thermoplastic high frequency glue (F), are defined as embodiment
2-1-1；When filler Filler is EA-2000, the product being prepared is thermoplastic high frequency glue (E), is defined as embodiment 2-1-
2；Such as embodiment 2-16, dicarboxylic anhydride, diamines, solvent are fixed again, and when filler Filler is FS06, the product being prepared is
Thermoplastic high frequency glue (F), is defined as embodiment 2-16-1；When filler Filler is EA-2000, the product being prepared is thermoplastic
High frequency glue (E), is defined as embodiment 2-16-2；Other embodiments are repeated no more with described herein as consistent.
Comparative example 1-1
It is matched according to described in table 8, is separately added into NMP, BAPP in 500mL reaction flask, after high-speed stirred to after dissolving,
BPDA is added to be stirred to react 4 hours, dimethylbenzene (20ml) is added and is heated to 180 DEG C, flows back 4 hours, it is multiple to complete configuration macromolecule
Condensation material composition.
Embodiment 3-1~3-4
A kind of preparation method of the high frequency double face copper, comprising the following steps:
In table 9, polymeric composition of the embodiment 3-1 using the embodiment 1-1 low DK and DF prepared, embodiment 2-
The low dielectric polymeric composite composition of thermoplastic (thermoplastic high frequency glue) of 16-1 preparation；Embodiment 3-2 is using embodiment
The polymeric composition of the low DK and DF of 1-2 preparation, the low dielectric polymer composite group of thermoplastic of embodiment 2-16-1 preparation
It closes object (thermoplastic high frequency glue)；Embodiment 3-3 using the embodiment 1-3 low DK and DF prepared polymeric composition,
The low dielectric polymeric composite composition of thermoplastic (thermoplastic high frequency glue) of embodiment 2-16-1 preparation；Embodiment 3-
4 using the low DK and DF of embodiment 1-4 preparation polymeric composition, the low dielectric of thermoplastic of embodiment 2-16-1 preparation is high
Molecular composite material composition (thermoplastic high frequency glue).
By the polymeric composition (high frequency PI composition) of 5g low DK and DF, via coating process, (temperature is 140 DEG C of holdings
10min.140 DEG C of 10min) it is coated on copper foil, the polyimide layer of low DK and DF, the high temperature ring are formed by high temperature cyclization
Change condition are as follows: at room temperature, be warming up to 150 DEG C through 15min, keep the temperature 5min, be warming up to 200 DEG C through 10min, keep the temperature 5min, warp
10min is warming up to 250 DEG C, keeps the temperature 5min, is cooled to 200 DEG C through 10min, keeps the temperature 20min, is warming up to 250 DEG C through 10min, protects
Warm 20min, is then down to room temperature through 60min；Then via coating process, (temperature is 140 DEG C of holdings on polyimide layer
10min.) the low dielectric polymeric composite composition (thermoplastic high frequency glue) of coating 5g thermoplastic, thermoplastic is formed by high temperature cyclization
High frequency glue-line obtains single-side coated copper plate, the high temperature cyclization condition are as follows: at room temperature, is warming up to 150 DEG C through 15min, heat preservation
5min, is warming up to 200 DEG C through 10min, keeps the temperature 5min, is warming up to 250 DEG C through 10min, keeps the temperature 5min, be cooled to 200 through 10min
DEG C, 20min is kept the temperature, 250 DEG C is warming up to through 10min, keeps the temperature 20min, being then down to room temperature through 60min, (Fig. 4 is height of the invention
The flow diagram of the preparation method high temperature cyclisation of frequency double face copper.)；Then two above-mentioned single-side coated copper plates are coated with
The one side of coating is placed with respect to lamination, obtains high frequency double face copper by pressing (temperature is 350-400 DEG C), specific such as Fig. 3
Shown, Fig. 3 is the flow diagram of the preparation method of high frequency double face copper of the invention.
The high frequency double face copper of preparation successively includes copper foil, polyimide layer, thermoplastic high frequency glue-line, gathers from top to bottom
Imide layer, copper foil, copper foil with a thickness of 12 or 18um, BHFX-92F-HA-V2-12 μm of copper foil model, RZ=0.45 (day
Mine)；The polyimide layer is that copper foil surface is coated on by the polymeric composition of the low DK and DF by heating high temperature ring
Change formed, polyimide layer with a thickness of 9-50um；The thermoplastic high frequency glue-line is compound by the low dielectric macromolecule of the thermoplastic
Material compositions be coated on polyimides layer surface by heating high temperature cyclization formed, thermoplastic high frequency glue-line with a thickness of 8-
21um。
DK and DF is tested to the high frequency double face copper of preparation, then tests peel strength, finally carries out drift tin test, drift
Tin test continues 10sec in 340 DEG C of conditions of temperature, indicates to pass through.
Table 9
Embodiment 3-5~3-8
A kind of preparation method of the high frequency double face copper, comprising the following steps:
In table 10, polymeric composition of the embodiment 3-5 using the embodiment 1-1 low DK and DF prepared, embodiment
The low dielectric polymeric composite composition of thermoplastic (thermoplastic high frequency glue) of 2-16-2 preparation；Embodiment 3-6 is using implementation
The polymeric composition of the low DK and DF of example 1-2 preparation, the low dielectric polymer composite of thermoplastic of embodiment 2-16-2 preparation
Composition (thermoplastic high frequency glue)；Polymeric composition of the embodiment 3-7 using the embodiment 1-3 low DK and DF prepared, reality
Apply the low dielectric polymeric composite composition of thermoplastic (thermoplastic high frequency glue) of 2-16-2 preparation；Embodiment 3-8 using
The low dielectric macromolecule of thermoplastic of the polymeric composition of the low DK and DF of embodiment 1-4 preparation, embodiment 2-16-2 preparation is compound
Material compositions (thermoplastic high frequency glue).
Other are the same as embodiment 3-1~3-4.
Table 10
Embodiment 3-9~3-12
A kind of preparation method of the high frequency double face copper, comprising the following steps:
In table 11, polymeric composition of the embodiment 3-9 using the embodiment 1-5 low DK and DF prepared, embodiment
The low dielectric polymeric composite composition of thermoplastic (thermoplastic high frequency glue) of 2-16-1 preparation；Embodiment 3-10 is using implementation
The polymeric composition of the low DK and DF of example 1-6 preparation, the low dielectric polymer composite of thermoplastic of embodiment 2-16-1 preparation
Composition (thermoplastic high frequency glue)；Polymeric composition of the embodiment 3-11 using the embodiment 1-7 low DK and DF prepared, reality
Apply the low dielectric polymeric composite composition of thermoplastic (thermoplastic high frequency glue) of 2-16-1 preparation；Embodiment 3-12 using
The low dielectric macromolecule of thermoplastic of the polymeric composition of the low DK and DF of embodiment 1-8 preparation, embodiment 2-16-1 preparation is compound
Material compositions (thermoplastic high frequency glue).
Other are the same as embodiment 3-1~3-4.
Table 11
Embodiment 3-13~3-16
A kind of preparation method of the high frequency double face copper, comprising the following steps:
In table 12, polymeric composition of the embodiment 3-13 using the embodiment 1-5 low DK and DF prepared, embodiment
The low dielectric polymeric composite composition of thermoplastic (thermoplastic high frequency glue) of 2-16-2 preparation；Embodiment 3-14 is using implementation
The polymeric composition of the low DK and DF of example 1-6 preparation, the low dielectric polymer composite of thermoplastic of embodiment 2-16-2 preparation
Composition (thermoplastic high frequency glue)；Polymeric composition of the embodiment 3-15 using the embodiment 1-7 low DK and DF prepared, reality
Apply the low dielectric polymeric composite composition of thermoplastic (thermoplastic high frequency glue) of 2-16-2 preparation；Embodiment 3-16 using
The low dielectric macromolecule of thermoplastic of the polymeric composition of the low DK and DF of embodiment 1-8 preparation, embodiment 2-16-2 preparation is compound
Material compositions (thermoplastic high frequency glue).
Other are the same as embodiment 3-1~3-4.
Table 12
Embodiment 3-17~3-20
A kind of preparation method of the high frequency double face copper, comprising the following steps:
In table 13, polymeric composition of the embodiment 3-17 using the embodiment 1-9 low DK and DF prepared, embodiment
The low dielectric polymeric composite composition of thermoplastic (thermoplastic high frequency glue) of 2-16-1 preparation；Embodiment 3-18 is using implementation
The polymeric composition of the low DK and DF of example 1-10 preparation, the low dielectric polymer composite of thermoplastic of embodiment 2-16-1 preparation
Composition (thermoplastic high frequency glue)；Embodiment 3-19 using the embodiment 1-11 low DK and DF prepared polymeric composition,
The low dielectric polymeric composite composition of thermoplastic (thermoplastic high frequency glue) of embodiment 2-16-1 preparation；What embodiment 3-20 was used
It is the polymeric composition of the low DK and DF of embodiment 1-12 preparation, the low dielectric macromolecule of thermoplastic of embodiment 2-16-1 preparation is multiple
Condensation material composition (thermoplastic high frequency glue).
Other are the same as embodiment 3-1~3-4.
Table 13
Embodiment 3-21~3-24
A kind of preparation method of the high frequency double face copper, comprising the following steps:
In table 14, polymeric composition of the embodiment 3-21 using the embodiment 1-9 low DK and DF prepared, embodiment
The low dielectric polymeric composite composition of thermoplastic (thermoplastic high frequency glue) of 2-16-2 preparation；Embodiment 3-22 is using implementation
The polymeric composition of the low DK and DF of example 1-10 preparation, the low dielectric polymer composite of thermoplastic of embodiment 2-16-2 preparation
Composition (thermoplastic high frequency glue)；Embodiment 3-23 using the embodiment 1-11 low DK and DF prepared polymeric composition,
The low dielectric polymeric composite composition of thermoplastic (thermoplastic high frequency glue) of embodiment 2-16-2 preparation；What embodiment 3-24 was used
It is the polymeric composition of the low DK and DF of embodiment 1-12 preparation, the low dielectric macromolecule of thermoplastic of embodiment 2-16-2 preparation is multiple
Condensation material composition (thermoplastic high frequency glue).
Other are the same as embodiment 3-1~3-4.
Table 14
Comparative example 1
As shown in table 14, using the polymeric composition of the low DK and DF of embodiment 1-1 preparation, comparative example 1-1 system
Standby polymeric composite composition；Preparation method is the same as embodiment 3-1.
Comparative example 2 and 3
Table 15
Comparative example 2 and comparative example 3 are specific as shown in Table 15.Model: SR#SW (Kaneka), model: CT-Q (Kuraray)
It is the film of commercially available purchase.The film of purchase is put on copper foil, single-side coated copper plate is obtained by pressing, then by two above-mentioned single sides
Copper-clad plate has the one side of film to place with respect to lamination, obtains double face copper by pressing (temperature is 350-400 DEG C).
It is illustrated in figure 5 the production procedure schematic diagram of comparative example 2 and comparative example 3, in the front end of equipment, is equipped with former film input
Roller 01 is mounted with coiled former film 21, model SR#SW (Kaneka) or CT-Q (Kuraray) thereon；It is inputted in the former film
Second protective film of upper and lower the first protective film input roller 02 for being respectively equipped with the first protective film 22 and the second protective film 23 of roller 01
The 125NPI of Kanaka product can be used in input roller 03, first protective film 22, the second protective film 23；It is additionally provided with the first copper foil
Layer input roller 04 and the second copper foil layer input roller 05 is mounted with the first coiled copper foil layer on the first copper foil layer input roller 04
24, it is located at the top of 21 input channel of former film；The second coiled copper foil layer is mounted on the second copper foil layer input roller 05
25, it is located at the lower section of 21 input channel of former film；Copper foil may each be in first copper foil layer 24, the second copper foil layer 25
BHFX-92F-HA-V2；First protective film 22, former film 21, is protected together with the second copper foil layer 25, second first copper foil layer 24
Film 23, with the releasing of identical linear velocity, is finally collected in sequence arrangement from top to bottom, and under the driving of respective input roller
Together, it is laminated by high temperature, last first copper foil layer 24, the second copper foil layer 25 fit to up and down the two of the former film 21 respectively
Melt and dissolved reaction occurs under high temperature action for side, forms double-sided copper-clad film 26, and last rolling roller 06 is wound, and forms double-sided copper-clad
Film roll 27, deliver to customer using；It is additionally provided with the first protective film wind-up roll 07 and the second protective film wind-up roll 08 in the rear end of equipment,
It is used to recycle the first protective film 22, the second protective film 23 after high temperature is laminated；In process of production some
Position can also be equipped with guide roller 09, be oriented on the traffic direction of film, it is ensured that production is gone on smoothly；The heat zone
Pressure is main to carry out high temperature lamination to the film layer after overlapping using 2 high temperature pinch rollers, is equipped with upper movable high-temperature along the vertical direction
Pinch roller 10, lower movable high-temperature pinch roller 11, the upper movable high-temperature pinch roller 10, lower movable high-temperature pinch roller 11 can according to production requirement into
Row height adjustment, and then to adjust the lamination pressure formed between upper and lower high temperature pinch roller, it is ensured that it is final it is laminated after product symbol
It closes and requires；It is equipped with heating device inside the movable upper movable high-temperature pinch roller 10, lower movable high-temperature pinch roller 11, so that high temperature pinch roller
Outer surface generates the high temperature for meeting production requirement, and in the present embodiment, the temperature that high temperature requires when being laminated is 300-380 DEG C, can
To meet production sets requirement by the set temperature for adjusting upper movable high-temperature pinch roller 10, lower movable high-temperature pinch roller 11.
In above-described embodiment, the first protective film 22, the second protective film 23 are mainly used to protect the outer surface of copper foil, prevent height
In warm lamination process, copper foil outer surface is scratched.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent defines.
Claims (10)
1. a kind of high frequency double face copper, it is characterised in that: from top to bottom successively include copper foil, polyimide layer, thermoplastic high frequency
Glue-line, polyimide layer, copper foil, the polyimide layer are to be coated on copper foil table by the polymeric composition of the low DK and DF
Face is formed by heating high temperature cyclization, and the thermoplastic high frequency glue-line is by the low dielectric polymeric composite composition of the thermoplastic
Polyimides layer surface is coated on to be formed by heating high temperature cyclization.
2. high frequency double face copper according to claim 1, it is characterised in that: the polyimide layer with a thickness of 9-
50um；
The copper foil with a thickness of 12-18um；
The thermoplastic high frequency glue-line with a thickness of 8-21um；
Described BHFX-92F-HA-V2-12 μm of copper foil model, RZ=0.45.
3. high frequency double face copper according to claim 2, it is characterised in that: the polymeric composition of the low DK and DF
It is made of the component of following parts by weight:
20~60 parts of dicarboxylic anhydride containing ester groups；
1~25 part of diamine monomer containing pyrimidine group；
100~180 parts of solvent.
4. high frequency double face copper according to claim 3, it is characterised in that: the dicarboxylic anhydride containing ester groups is
It is the bis- tritrimellitate dianhydrides of aromatic tetracarboxylic dianhydride, preferably p-phenylene-, 3,3', 4,4'- biphenyltetracarboxylic dianhydrides, double
Two ether dianhydride of phenol A type；
The diamine monomer containing pyrimidine group is aromatic diamine, preferably 3,5- diaminostilbene, 2,4- triazoles, Isosorbide-5-Nitrae-
Phenylene bis- (4-aminobenzoic acid esters), two p-aminophenyl ester of terephthalic acid (TPA), p-aminobenzoic acid p-aminophenyl ester, 4,4 '-
Diaminodiphenyl ether, bis- (4- aminophenyl) terephthalates；It is furthermore preferred that the diamine monomer containing pyrimidine group is
3,5- diaminostilbene, 2,4- triazole, p-aminobenzoic acid p-aminophenyl ester, 4,4 '-diaminodiphenyl ethers mixture；
The solvent is N-Methyl pyrrolidone, DMAC N,N' dimethyl acetamide, butyrolactone, N.N- dimethylformamide, dimethyl
Sulfoxide；
The solid content of the polymeric composition of the low DK and DF is 30wt%, and viscosity is 30000~60000CPs.
5. high frequency double face copper according to claim 3, it is characterised in that: the low dielectric macromolecule composite wood of the thermoplastic
Feed composition is made of the component of following parts by weight:
6. high frequency double face copper according to claim 5, it is characterised in that: the dicarboxylic anhydride is 3,3', 4,4'- biphenyl
Tetracarboxylic dianhydride, Bisphenol A Type Diether Dianhydride；
The diamine monomer is that the diamine monomer is 2,2'- bis- [4- (4- aminophenoxy phenyl)] propane, bis- (4- of 4,4'-
Amino-benzene oxygen) biphenyl, bis- (3- amino-benzene oxygen) biphenyl of 4,4'-, bis- [4- (4- amino-benzene oxygen) phenyl] -1,1,1 of 2,2-,
Bis- (4'- amino-benzene oxygen) benzene of 3,3,3- hexafluoropropane, 1,3-；
The solvent is N-Methyl pyrrolidone, DMAC N,N' dimethyl acetamide, butyrolactone, N.N- dimethylformamide, dimethyl
Sulfoxide, dimethylbenzene.
7. a kind of preparation method of high frequency double face copper as claimed in any one of claims 1 to 6, it is characterised in that: including with
Lower step:
The polymeric composition of low DK and DF is formed into low DK and DF by high temperature cyclization on copper foil via coating process coating
Polyimide layer, then combined on polyimide layer via the low dielectric polymer composite of coating process coating thermoplastic
Object forms thermoplastic high frequency glue-line by high temperature cyclization, obtains single-side coated copper plate, be then coated with two above-mentioned single-side coated copper plates
The one side of coating is placed with respect to lamination, obtains high frequency double face copper by pressing.
8. the preparation method of high frequency double face copper according to claim 7, it is characterised in that: the coating process condition
Are as follows: temperature is 140 DEG C of holding 10min；
The high temperature cyclization condition are as follows: at room temperature, 150 DEG C are warming up to through 15min, 5min is kept the temperature, is warming up to 200 DEG C through 10min,
5min is kept the temperature, 250 DEG C is warming up to through 10min, keeps the temperature 5min, 200 DEG C is cooled to through 10min, keeps the temperature 20min, heat up through 10min
To 250 DEG C, 20min is kept the temperature, is then down to room temperature through 60min；
The temperature of the pressing is 350-400 DEG C.
9. the preparation method of high frequency double face copper according to claim 7, it is characterised in that: the height of the low DK and DF
The preparation method of molecular composition, comprising the following steps:
The dicarboxylic anhydride containing ester groups, the diamine monomer containing pyrimidine group are dissolved in solvent by the proportion, stirred molten
Solution obtains the polymeric composition of the low DK and DF；
The preparation method of the low dielectric polymeric composite composition of the thermoplastic, comprising the following steps:
Dicarboxylic anhydride, diamine monomer are dissolved in solvent by the proportion, stirring and dissolving is added filler stirring, adds solvent
It is heated to reflux, obtains the low dielectric polymeric composite composition of the thermoplastic.
10. a kind of circuit board made of high frequency double face copper as claimed in any one of claims 1 to 6.
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| CN110027299A (en) * | 2019-04-25 | 2019-07-19 | 江阴骏驰复合材料有限公司 | A kind of liquid crystal polymer high frequency double face copper and preparation method thereof and pressing device |
| CN111867260A (en) * | 2019-08-23 | 2020-10-30 | 李龙凯 | Coating forming method of novel material layer structure of high-frequency circuit board and product thereof |
| CN112239539A (en) * | 2019-07-16 | 2021-01-19 | 臻鼎科技股份有限公司 | Polyamide acid composition, polyimide copper-clad plate and circuit board |
| CN113386416A (en) * | 2021-07-08 | 2021-09-14 | 江西柔顺科技有限公司 | Heat-conducting double-sided copper-clad plate and preparation method thereof |
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| CN109808259A (en) * | 2019-02-02 | 2019-05-28 | 江阴骏驰复合材料有限公司 | A kind of high frequency double face copper and the preparation method and application thereof |
| CN109808259B (en) * | 2019-02-02 | 2021-04-30 | 江阴骏驰新材料科技有限公司 | High-frequency double-sided copper-clad plate and preparation method and application thereof |
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| CN110027299B (en) * | 2019-04-25 | 2021-04-30 | 江阴骏驰新材料科技有限公司 | Liquid crystal polymer high-frequency double-sided copper-clad plate and preparation method and pressing device thereof |
| CN112239539A (en) * | 2019-07-16 | 2021-01-19 | 臻鼎科技股份有限公司 | Polyamide acid composition, polyimide copper-clad plate and circuit board |
| CN111867260A (en) * | 2019-08-23 | 2020-10-30 | 李龙凯 | Coating forming method of novel material layer structure of high-frequency circuit board and product thereof |
| WO2021035916A1 (en) * | 2019-08-23 | 2021-03-04 | 李龙凯 | Method for coating and molding novel material layer structure of high-frequency circuit board and product thereof |
| CN113386416A (en) * | 2021-07-08 | 2021-09-14 | 江西柔顺科技有限公司 | Heat-conducting double-sided copper-clad plate and preparation method thereof |
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