CN114434901A - Copper-clad plate and preparation method thereof - Google Patents

Copper-clad plate and preparation method thereof Download PDF

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Publication number
CN114434901A
CN114434901A CN202111516805.8A CN202111516805A CN114434901A CN 114434901 A CN114434901 A CN 114434901A CN 202111516805 A CN202111516805 A CN 202111516805A CN 114434901 A CN114434901 A CN 114434901A
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China
Prior art keywords
film
fluororesin
copper
clad plate
emulsion
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Granted
Application number
CN202111516805.8A
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Chinese (zh)
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CN114434901B (en
Inventor
万里鹏
高峰
蔡黎
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Huawei Technologies Co Ltd
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Huawei Technologies Co Ltd
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Priority to CN202111516805.8A priority Critical patent/CN114434901B/en
Publication of CN114434901A publication Critical patent/CN114434901A/en
Priority to PCT/CN2022/133330 priority patent/WO2023109440A1/en
Priority to TW111147437A priority patent/TWI828470B/en
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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
    • 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
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
    • 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
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • 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
    • 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
    • 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
    • B32B37/1018—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 using only vacuum
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
    • H05K1/056—Insulated conductive substrates, e.g. insulated metal substrate the metal substrate being covered by an organic insulating layer
    • 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
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

The embodiment of the application provides a copper-clad plate and a preparation method thereof, wherein the copper-clad plate comprises a substrate, wherein first fluororesin emulsion films are arranged on two opposite surfaces of the substrate, one surface of the first fluororesin emulsion, which is back to the substrate, is provided with a puffed fluororesin film, and one surface of the puffed fluororesin film, which is back to the substrate, is superposed with a copper foil layer. The middle layer of the copper-clad plate is a substrate with first fluororesin emulsion films arranged on two sides, the Dk value and the Df value are higher, and the upper side and the lower side of the middle layer are expanded fluororesin film layers with lower Dk value and Df value and better dimensional stability, so that the copper-clad plate with high Dk value, low Df value and low expansion and contraction is obtained, and the dimensional stability of the copper-clad plate is improved while the performance of the copper-clad plate is improved.

Description

Copper-clad plate and preparation method thereof
Technical Field
The application relates to the technical field of circuit boards, in particular to a copper-clad plate and a preparation method thereof.
Background
With the rapid development of the electronic industry, wearable and portable devices become indispensable in people's daily life, such as foldable mobile phones, watches, tablet computers and other electronic devices. Among them, a Flexible Printed Circuit Board (FPC) plays a key role in connecting electronic devices, and a Copper Clad Laminate (CCL) is widely used as a base Board of the Flexible Printed Circuit Board in the electronic devices.
At present, the copper-clad plate mostly uses wood pulp paper or glass fiber cloth and the like as reinforcing materials, and fluorine resin layers are formed on the surfaces of two sides of the copper-clad plate, and the common copper-clad plate can be a polytetrafluoroethylene resin layer. For example, in the copper clad laminate, a glass fiber cloth is used as a substrate, a polytetrafluoroethylene resin film is laminated on two opposite side surfaces of the glass fiber cloth after the polytetrafluoroethylene resin film is formed, a copper foil is laminated on one surface of the polytetrafluoroethylene resin film, which is opposite to the glass fiber cloth, and then the copper clad laminate is formed in a hot pressing mode.
However, the fluororesin is a thermoplastic material, and the formed copper-clad plate has a high thermal expansion coefficient, a low dielectric constant value and a high dielectric loss value, so that the insertion loss of the copper-clad plate is large and the performance of the copper-clad plate is affected.
Disclosure of Invention
The application provides a copper-clad plate and a preparation method thereof, which solve the problem that the performance of the existing copper-clad plate is influenced by large insertion loss due to high thermal expansion coefficient, low dielectric constant value and high dielectric loss value.
The first aspect of the application provides a copper-clad plate, which comprises a substrate, a puffed fluororesin film, a first fluororesin emulsion film and a copper foil layer;
the two opposite surfaces of the substrate are provided with the first fluororesin emulsion film;
the surface, opposite to the substrate, of the first fluororesin emulsion film is provided with the expanded fluororesin film, and the expanded fluororesin film has a plurality of microporous structures;
the copper foil layer is arranged on one surface of the expanded fluororesin membrane, which faces away from the substrate. The middle layer of the copper-clad plate (taking the substrate as the center, the substrate and the film layer arranged on the substrate can be used as the middle layer) is the film layer with higher Dk value and Df value, and the upper side and the lower side of the middle layer adopt the film layers with lower Dk value and Df value and better dimensional stability (lower Ds value). The copper-clad plate has higher Dk value and lower Df value, and the performance of the copper-clad plate is effectively improved. Meanwhile, the upper and lower two layers of high-dimensional-stability film layers can effectively reduce thermal expansion and shrinkage of the copper-clad plate, reduce the dimensional deformation of the copper-clad plate and improve the overall dimensional stability of the copper-clad plate. The obtained copper-clad plate can achieve Dk more than or equal to 2.8, Df less than or equal to 0.0008 (under the frequency test condition of 10 GHz), Ds less than or equal to 1000ppm, and CTE of the copper-clad plate reaches 20-25ppm, so that the size stability of the copper-clad plate is improved while the performance of the copper-clad plate is improved.
In one possible embodiment, the bulked fluororesin membrane comprises a bulked base membrane and a filled membrane, the microporous structure being located in the bulked base membrane;
the filling films are respectively positioned on two opposite surfaces of the bulked base film, and the filling films fill the microporous structures. The filling film can effectively reduce the void ratio of the expanded base film, so that the overall void ratio of the copper-clad plate is reduced, the solvent resistance of the copper-clad plate is improved, and the performance of the copper-clad plate is further ensured.
In one possible embodiment, the filler film is a fluororesin film disposed on the bulked base film. With resin fluoride film stack setting on popped base film, the in-process of pressfitting when copper-clad plate shaping makes resin fluoride film and popped base film pressfitting, and resin fluoride film fills to the microporous construction of popped base film, and easy operation is convenient, and has better filling effect to popped base film, helps further reducing the size of covering copper board and warp.
Simultaneously be provided with the fluororesin membrane between copper foil layer and popped base film, help promoting the combination fastness between copper foil layer and the popped base film, reduce the surface deformation of copper-clad plate, further promote the size stability of copper-clad plate.
In one possible embodiment, the filled film is a second fluororesin emulsion film. The second fluorine resin emulsion can be filled into the microporous structure of the expanded base film in the process of forming a film on the expanded base film to form a second fluorine resin emulsion film, and the structure is simple and convenient to realize.
In one possible embodiment, the expanded base film further comprises a fluororesin film disposed on a side of the second fluororesin emulsion film facing away from the expanded base film. That is, be provided with the fluororesin membrane between copper foil layer and second fluororesin emulsion membrane to and between second fluororesin emulsion membrane and the first fluororesin emulsion membrane, help promoting the cohesion between copper foil layer and the popped fluororesin membrane, between first fluororesin emulsion membrane and the second fluororesin emulsion membrane, and then promote the bonding fastness between each rete in the copper-clad plate, further reduce the size deformation of copper-clad plate, promote the size stability of copper-clad plate.
In one possible embodiment, further comprising a reinforcement disposed within the first fluororesin emulsion film. The reinforcing piece can be reinforcing fillers such as ceramics, titanium dioxide and the like, and is favorable for improving the strength of the first fluororesin emulsion film and further favorable for improving the dimensional stability of the copper-clad plate. Meanwhile, the Dk value and the Df value of the first fluororesin emulsion film can be adjusted through the proportion of the reinforcing part and the like so as to meet the requirements of a copper-clad plate on high Dk value and low Df value.
In one possible embodiment, the molding material of the bulked base film, the filled film, and the first fluororesin emulsion film includes at least: polytetrafluoroethylene, fusible polytetrafluoroethylene, or perfluoroethylene propylene copolymer.
In one possible embodiment, the substrate comprises at least a glass fiber cloth. The glass fiber cloth has lower cost, and is favorable for improving the dimensional stability of the whole and the surface layer of the copper-clad plate, and further is favorable for reducing the size expansion and contraction of the copper-clad plate.
The second aspect of the application provides a preparation method of a copper-clad plate, which comprises the following steps:
providing a substrate;
obtaining a first fluororesin emulsion, immersing the substrate in the first fluororesin emulsion to form a first fluororesin emulsion film on opposite sides of the substrate;
obtaining a bulked fluororesin membrane having a plurality of microporous structures;
disposing the bulked fluororesin membrane on a side of the first fluororesin emulsion membrane facing away from the substrate;
providing a copper foil layer, and arranging the copper foil layer on one side of the expanded fluororesin membrane, which faces away from the substrate;
and pressing to obtain the copper-clad plate.
The copper-clad plate can be obtained by the method, has high Dk value, low Df value and low swell and shrink, and has better dimensional stability while improving the performance of the copper-clad plate, thereby improving the electrical performance and stability of the flexible circuit board.
In one possible embodiment, the bulked fluororesin membrane comprises a bulked base membrane in which the microporous structure is located and a filling membrane for filling the microporous structure;
said obtaining said expanded resin film comprises:
obtaining a puffed base film;
and filling films are arranged on two opposite sides of the expanded base film.
According to the copper-clad plate obtained by the method, the filling film is filled into the microporous structure, so that the void ratio of the copper-clad plate can be reduced, and the copper-clad plate has better dimensional stability and solvent resistance while the performance of the copper-clad plate is improved.
In one possible embodiment, the filling film is a fluororesin film. The method is simple to operate, the performance of the copper-clad plate is improved, the copper-clad plate has good dimensional stability, the void ratio of the copper-clad plate is further reduced, and the solvent resistance of the copper-clad plate can be further ensured. The method is simple to operate and has good applicability.
In one possible embodiment, the filled film is a second fluororesin emulsion film;
the setting of fill film on the opposite sides of the bulked base film comprises:
obtaining a second fluororesin emulsion, immersing the bulked base film in the second fluororesin emulsion to form a second fluororesin emulsion film on opposite sides of the bulked base film. The method is simple and convenient to realize, and has better dimensional stability and solvent resistance while improving the performance of the copper-clad plate.
In one possible embodiment, after the copper-clad plate further comprises a fluororesin film, and the expanded fluororesin film is disposed on a side of the first fluororesin emulsion film facing away from the substrate, the method further comprises:
providing a fluororesin film, and arranging the fluororesin film on one side of the second fluororesin emulsion film, which faces away from the bulked base film.
Therefore, the fluororesin films are arranged between the second fluororesin emulsion film and the copper foil layer and between the second fluororesin emulsion film and the first fluororesin emulsion film through the steps, and the fluororesin films can improve the bonding fastness between the film layers and further reduce the size deformation of the copper clad plate.
In one possible embodiment, said obtaining of the first fluororesin emulsion further comprises:
a reinforcement is added to the first fluororesin emulsion.
In a possible embodiment, the providing the copper foil layer further includes:
roughening the surface of the copper foil layer;
and performing fluorination treatment on the surface of the roughened copper foil layer. At first carry out the coarsening to the copper foil layer, then fluoridize the processing, can promote the fluorine content on copper foil layer surface, and make the copper foil layer surface have certain fluorine, can promote the bonding strength between copper foil layer and the popped fluororesin membrane, help promoting the holistic dimensional stability of copper-clad plate.
The third aspect of the application also provides a flexible circuit board, which at least comprises a circuit structure and any one of the copper-clad plates, wherein the circuit structure is arranged on the copper-clad plate.
The copper-clad plate with high Dk value, low Df value and low expansion and contraction can effectively improve the electrical property and stability of the flexible circuit board.
The fourth aspect of the present application also provides an electronic device, which at least includes a housing and the above-mentioned flexible circuit board, wherein the flexible circuit board is disposed in the housing.
Drawings
Fig. 1 is a schematic structural diagram of a copper-clad plate provided in an embodiment of the present application;
FIG. 2 is a schematic cross-sectional view of a copper-clad plate in the prior art;
FIG. 3 is a schematic cross-sectional view of the copper-clad plate of FIG. 1 taken along line A-A;
FIG. 4 is a flow chart of a method for manufacturing a copper-clad plate according to an embodiment of the present application;
fig. 5 is a schematic cross-sectional structure diagram of a copper-clad plate provided in the second embodiment of the present application;
FIG. 6 is a flow chart of a method for manufacturing a copper-clad plate according to the second embodiment of the present application;
fig. 7 is a schematic cross-sectional structure view of a copper-clad plate provided in the third embodiment of the present application;
FIG. 8 is a flow chart of a method for manufacturing a copper-clad plate according to the third embodiment of the present application;
fig. 9 is a schematic cross-sectional structure view of a copper-clad plate according to a fourth embodiment of the present application;
FIG. 10 is a flow chart of a method for manufacturing a copper-clad plate according to the fourth embodiment of the present application;
fig. 11 is a schematic cross-sectional view of a copper-clad plate provided in the fifth embodiment of the present application;
fig. 12 is a flowchart of a method for manufacturing a copper-clad plate according to the fifth embodiment of the present application.
Description of reference numerals:
100-copper clad laminate; 10-a substrate; 20-expanded fluororesin membrane;
21-puffing a base film; 22-a filled film; 22 a-a second fluororesin emulsion film;
22 b-a fluororesin film; 30-a first fluororesin emulsion film; 40-copper foil layer.
Detailed Description
The terminology used in the description of the embodiments section of the present application is for the purpose of describing particular embodiments of the present application only and is not intended to be limiting of the present application.
Fig. 1 is a schematic structural diagram of a copper-clad plate provided in an embodiment of the present application.
In the embodiment of the application, a Copper Clad Laminate (CCL) can be a basic Board of a Printed Circuit Board (PCB), also called a substrate.
In the embodiment of the present application, taking the copper-clad plate 100 in fig. 1 as a substrate of a Flexible Printed Circuit Board (FPCB), a Circuit structure may be disposed on the copper-clad plate 100 to form a Flexible Circuit Board.
The flexible circuit board can be applied to flexible architecture products of electronic equipment, such as flexible connection scenes of in-board jumper wires, board-to-board connection, packaging of flexible boards and the like.
The electronic device may include, but is not limited to, a fixed terminal or a mobile terminal such as a mobile phone, a tablet computer, a notebook computer, an ultra-mobile personal computer (UMPC), a handheld computer, a touch television, an intercom, a netbook, a POS machine, a Personal Digital Assistant (PDA), a wearable device, a virtual reality device, and the like.
In order to ensure the performance of electronic equipment, the electrical performance requirement of a flexible circuit board formed by a copper-clad plate is generally higher, and the flexible circuit board is required to have a lower insertion loss value, for example, to be kept within 0.4 dB/inch. The electrical performance of the flexible circuit board is greatly related to the performance of the copper-clad plate, so the performance of the flexible circuit board can be detected and measured after the copper-clad plate is obtained, wherein the judgment standard mainly comprises the dielectric Constant (Dk) of the copper-clad plate and the dielectric loss (Df) of the copper-clad plate.
Specifically, the dielectric constant Dk refers to that a medium generates induced charges when an electric field is applied to the medium to weaken the electric field, the ratio of the electric field reduction in the medium to the original applied electric field (in vacuum) is the relative dielectric constant, and the Dk value is a macroscopic physical quantity for measuring the polarization degree of the dielectric medium. The larger the Dk value is, the stronger the surface charge-binding capacity is, the less easily the charge is polarized, the weaker the polarization electric field is, and the better the insulating property of the material is.
The dielectric loss Df is the hysteresis effect of dielectric conductance and dielectric polarization in an alternating electric field of an insulating material or a dielectric medium, so that a certain phase difference is generated between a current phasor and a voltage phasor flowing in the dielectric medium, namely a certain phase angle is formed, the tangent value of the phase angle, namely the dielectric loss Df, is higher, the more obvious the hysteresis effect of the dielectric conductance and the dielectric polarization is, and the more the electric energy loss or the signal loss is.
In addition, in the examples of the present application, the Dimensional Stability (Ds) refers to the property of a material that does not change its external dimensions under the action of mechanical force, heat or other external conditions. The smaller the Ds value, the better the dimensional stability of the panel, and the smaller its dimensional expansion and contraction.
Fig. 2 is a schematic cross-sectional view of a copper-clad plate in the prior art.
Currently, most of copper-clad plates are formed by using wood pulp paper or fiberglass cloth and the like as a reinforced substrate, arranging resin layers on the surfaces of two sides of the substrate, then covering the resin layers with copper foils, and carrying out hot pressing. The resin layer material commonly used in the copper clad laminate is fluororesin such as polytetrafluoroethylene resin, for example, see fig. 2, a polytetrafluoroethylene copper clad laminate proposed in the related art is obtained by directly arranging a polytetrafluoroethylene resin film 2 on a glass fiber cloth 1, covering the glass fiber cloth with a copper foil layer 3, and performing thermocompression bonding.
Because the polytetrafluoroethylene material is a thermoplastic material, the Coefficient of Thermal Expansion (CTE) of the copper clad laminate is large, the copper clad laminate has the problem of Thermal Expansion and shrinkage and influences the dimensional stability of the copper clad laminate, and therefore, the Thermal Expansion and shrinkage, the dielectric constant and the dielectric loss become main indexes for judging the performance of the fluororesin type copper clad laminate. The copper-clad plate obtained by directly laminating the polytetrafluoroethylene resin on the glass fiber cloth through hot pressing has the advantages of poor dimensional stability (higher Ds value), severe dimensional expansion and shrinkage of the copper-clad plate, small electrical performance regulation range, low Dk value and high Df value, and is large in insertion loss and poor in overall performance.
Based on this, the embodiment of the application provides a copper-clad plate, the size expansion is reduced (the coefficient of thermal expansion CTE is between 20 and 25ppm, Ds is less than or equal to 1500ppm), the Dk value is high (Dk is more than or equal to 3), the Df value is low (Df is less than or equal to 0.0008), the performance of the copper-clad plate is effectively improved, and the electrical performance of a flexible circuit board is favorably improved.
The copper-clad plate and the preparation method thereof provided by the embodiment of the present application are described in detail below with reference to specific embodiments and drawings.
Example one
FIG. 3 is a schematic cross-sectional view of the copper-clad plate of FIG. 1 taken along line A-A.
Referring to fig. 3, in the embodiment of the application, a copper-clad plate100 comprises a substrate 10, the substrate 10 comprising at least glass fiber cloth, for example, the substrate 10 may be 1080 gauge glass fiber cloth, the nominal thickness may be 0.053mm, and the mass per unit area may be 46.8g/m2. The glass fiber cloth can effectively improve the dimensional stability of the whole and the surface layer of the copper-clad plate 100, and further contributes to reducing the size expansion and contraction of the copper-clad plate 100.
Of course, in some examples, the substrate 10 may also be a plate material formed of other reinforcing materials such as an organic fiber cloth, a fluorine resin film layer, and a polyimide film layer.
The copper-clad plate 100 further includes a first fluororesin emulsion film 30, the first fluororesin emulsion film 30 being disposed on opposite surfaces of the substrate 10, and specifically, the first fluororesin emulsion film 30 may be a film layer formed on opposite surfaces of the substrate 10 by immersing the substrate 10 in a first fluororesin emulsion. That is, the first fluororesin emulsion is formed on the surface of the substrate 10 by forming a film on the surface of the substrate 10 by dipping.
The fluororesin emulsion film formed by forming a film on the surface of the substrate 10 from the fluororesin emulsion has a high Dk value (for example, Dk ═ 3.7) and Df value (for example, Df ═ 0.0008), that is, the first fluororesin emulsion film 30 has a high Dk value and Df value.
The molding material of the first fluororesin emulsion film 30 may be Polytetrafluoroethylene (PTFE), or in some examples, the molding material of the first fluororesin emulsion film 30 may be other types of fluorine-containing resins, for example, may be meltable Polytetrafluoroethylene (PFA) or perfluoroethylene propylene copolymer (FEP), and the like.
The first fluororesin emulsion film may have reinforcing part of ceramic, titania, barium strontium acid and other reinforcing stuffing. Specifically, a reinforcing member can be added to the first fluororesin emulsion, and when the first fluororesin emulsion forms a film on the surfaces of the two sides of the substrate 10, the reinforcing member is distributed in the first fluororesin emulsion film 30, so that the strength of the first fluororesin emulsion film 30 is improved, and the dimensional stability of the copper-clad plate 100 is improved. Meanwhile, the Dk value and the Df value of the first fluororesin emulsion film 30 can be adjusted through the proportion of the reinforcing part and the like so as to meet the requirements of the copper-clad plate 100 on high Dk value and low Df value.
The copper-clad plate 100 further comprises an expanded fluororesin membrane 20 and a copper foil layer 40, wherein the expanded fluororesin membrane 20 is arranged on one surface of the first fluororesin emulsion membrane 30, which is opposite to the substrate 10. The expanded fluororesin membrane 20 is a fluororesin membrane having a film layer formed with a plurality of microporous structures and having a predetermined porosity. Most of them are obtained by dry powder fluororesin processing, for example, the dry powder fluororesin is treated with a solvent such as paraffin wax, ammonium perfluorooctanoate, etc., and then is single/biaxial rolled and stretched by a calender to have a certain porosity, thereby obtaining a bulked fluororesin membrane layer.
The expanded fluororesin membrane layer has a relatively low Dk value (e.g., Dk of 2.6) and Df value (e.g., Df of 0.0003). And because the expanded fluororesin membrane 20 has a plurality of micropore structures, the dimension stability is better, and the Ds value is about equal to 1500 ppm.
The first fluororesin emulsion films 30 are disposed on two opposite surfaces of the substrate 10, as shown in fig. 3, that is, two layers of the first fluororesin emulsion films 30 are disposed on the substrate, and the two layers of the first fluororesin emulsion films 30 facing away from the substrate may be respectively disposed with the expanded fluororesin films 20, that is, the copper-clad plate 100 includes two layers of the expanded fluororesin films 20.
The Dk value and the Df value of the expanded fluororesin membrane 20 can be adjusted by a film forming process of dry powder fluororesin. Meanwhile, when the expanded fluororesin membrane 20 is formed into a membrane, a filler (such as inorganic oxide fillers of silicon dioxide, titanium dioxide and the like) is added, namely, the filler is added into the dry fluororesin, and the adjustment and control of the porosity of the expanded fluororesin membrane 20 can be realized by adjusting the proportion of the filler and the dry fluororesin and the membrane forming process, so that the overall porosity of the copper-clad plate 100 is adjusted, and the porosity of the copper-clad plate 100 can be ensured to be 0%, thereby improving the solvent resistance of the copper-clad plate 100 and ensuring the performance of the copper-clad plate 100.
In this embodiment, the expanded fluororesin membrane 20 is a membrane layer formed by forming a single fluororesin membrane, and the formed membrane layer is expanded by stretching or the like to form a microporous structure, for example, the expanded fluororesin membrane 20 is a membrane layer formed by directly processing dry fluororesin. Of course, in some examples, the expanded fluororesin membrane 20 may be a composite membrane of a single fluororesin membrane layer having a microporous structure and other membrane layers (e.g., a filled membrane, etc.).
The molding material of the expanded fluororesin membrane 20 may be polytetrafluoroethylene, or may be other types of fluorine-containing resins, such as meltable polytetrafluoroethylene or perfluoroethylene propylene copolymer. The material for forming the expanded fluororesin membrane 20 may be the same as the material for forming the first fluororesin emulsion membrane 30, for example, the expanded fluororesin membrane 20 and the first fluororesin emulsion membrane 30 may be formed of polytetrafluoroethylene films, or the materials for forming the expanded fluororesin membrane 20 and the first fluororesin emulsion membrane 30 may be different.
The copper foil layer 40 is arranged on one surface of the expanded fluororesin membrane 20, which is opposite to the substrate 10, and specifically, the copper foil layers 40 are respectively superposed on one surfaces of the two layers of expanded fluororesin membranes 20, which are opposite to the substrate 10, so as to form the copper-clad plate 100.
That is to say, in the copper-clad plate 100 provided in the embodiment of the present application, the intermediate layer (the substrate 10 is used as the center, and the substrate 10 and the film layer disposed thereon can be used as the intermediate layer) is a film layer with a higher Dk value and Df value, and the upper and lower sides of the intermediate layer are provided with film layers with lower Dk value and Df value and better dimensional stability (lower Ds value). The copper-clad plate 100 has a high Dk value and a low Df value, and the performance of the copper-clad plate 100 is effectively improved. Meanwhile, the upper and lower two layers of high-dimensional-stability film layers can effectively reduce thermal expansion and contraction of the copper-clad plate 100, reduce dimensional deformation of the copper-clad plate 100 and improve the overall dimensional stability of the copper-clad plate 100.
The following table 1 shows a combination mode of the expanded fluororesin film and the first fluororesin emulsion film included in the copper-clad plate in one example, and the following table 2 shows the performance of the copper-clad plate obtained in one example. The combination ratio of the expanded fluororesin membranes 20 is, for example, 50 μm when the film thickness of two expanded fluororesin membranes 20 located on the upper and lower sides of the substrate 10 and the thickness of a single expanded fluororesin membrane 20 are 25 μm. Accordingly, the combination ratio of the first fluororesin emulsion films 30 means the sum of the film thicknesses of the two first fluororesin emulsion films 30 located on the upper and lower sides of the substrate 10.
Table 1 shows a performance table of a film layer in a copper-clad plate provided in an embodiment of the application
Combination of Df Dk Combination ratio (μm) Volume ratio of
Expanded fluororesin film 0.0002 2.2 50 50.00％
First fluororesin emulsion film 0.0008 3.8 50 50.00％
Table 2 shows a performance table of a copper-clad plate provided in the first embodiment of the present application
Df Dk Thickness of
Copper-clad plate 0.0005 3 6mil
It can be known from table 1 and table 2 that the first fluororesin emulsion film 30 with high Dk value and Df value is formed on the surface of the substrate 10 by dipping as the middle layer of the copper-clad plate 100, and the expanded fluororesin film 20 with low Dk value and Df value and good dimensional stability is arranged on the upper and lower sides of the middle layer, so that the copper-clad plate 100 can reach Dk more than or equal to 2.8, Df less than or equal to 0.0008 (under the frequency test condition of 10 GHz), Ds less than or equal to 1000ppm, and CTE of the copper-clad plate 100 reaches 20-25ppm, thereby forming the copper-clad plate 100 with high Dk value, low Df value and low expansion and contraction, effectively improving the performance of the copper-clad plate 100, and improving the dimensional stability of the copper-clad plate 100.
Fig. 4 is a flowchart of a method for manufacturing a copper-clad plate according to an embodiment of the present application.
The embodiment of the application also provides a preparation method of the copper-clad plate, and specifically, the method comprises the following steps:
s101: a substrate is provided.
S102: a first fluororesin emulsion is obtained, and the substrate is dipped in the first fluororesin emulsion to form a first fluororesin emulsion film on the opposite sides of the substrate.
After the first fluororesin emulsion is obtained, additives, reinforcing fillers and the like can be added into the first fluororesin emulsion according to a certain proportion, and then the first fluororesin emulsion is stirred by a high-speed stirrer and is homogenized for later use. Wherein the additive can be organic solvent such as diethyl ether and formaldehyde.
The substrate is immersed in the first fluororesin emulsion, specifically, the standby first fluororesin emulsion is added into a dipping tank of the gluing machine, and the substrate passes through the dipping tank to realize the immersion of the substrate in the first fluororesin emulsion.
In the dipping process of the substrate, the dipping amount of the first fluororesin emulsion on the substrate can be controlled by a glue scraping roller, and the thickness of the first fluororesin emulsion film formed on the surface of the substrate is further controlled.
After the impregnation is completed, the substrate impregnated with the first fluororesin emulsion may be dried, for example, by placing the substrate in an oven to dry to remove the additive, thereby forming a film of the first fluororesin emulsion on the surface of the substrate.
S103: an expanded fluororesin film was obtained.
Wherein, the expanded fluororesin membrane has a plurality of micropore structures, and concretely, the expanded fluororesin membrane can be formed by the following film forming method: the dry powdered fluororesin is treated by a solvent, and then is rolled and stretched into a film by a single/double shaft of a calender, and the porosity of the expanded fluororesin film can be controlled by adjusting the film forming process, namely the Dk value and the Df value of the expanded fluororesin film are adjusted.
Wherein the solvent may be paraffin, ammonium perfluorooctanoate, etc.
S104: the expanded fluororesin membrane is disposed on a side of the first fluororesin emulsion membrane facing away from the substrate.
That is, the expanded fluororesin membrane is superimposed on the first fluororesin emulsion membrane. Wherein, the surface of each layer of the first fluororesin emulsion film, which is back to the substrate, is provided with a puffed fluororesin film.
S105: providing a copper foil layer, and arranging the copper foil layer on one surface of the expanded fluororesin membrane, which faces away from the substrate.
Namely, a copper foil layer is laminated on the expanded fluororesin membrane. Wherein, a copper foil layer is superposed on one surface of each layer of expanded fluororesin membrane, which is back to the substrate.
Wherein after providing the copper foil layer, the method may further comprise:
roughening the surface of the copper foil layer;
and performing fluorination treatment on the surface of the roughened copper foil layer.
At first carry out the coarsening to the copper foil layer, then fluoridize the processing, can promote the fluorine content on copper foil layer surface, and make the copper foil layer surface have certain fluorine, can promote the bonding strength between copper foil layer and the popped fluororesin membrane, help promoting the holistic dimensional stability of copper-clad plate.
S106: and pressing to obtain the copper-clad plate.
The lamination can be realized through a vacuum press, namely, after the copper foil layer, the expanded fluororesin membrane, the first fluororesin emulsion membrane and the substrate are superposed according to the steps, the copper clad laminate can be obtained through the vacuum press under the regulation of vacuum, high pressure and high temperature and then the temperature is reduced and the plate is disassembled.
The copper-clad plate with the Dk value, the low Df value and the low swell and shrink can be obtained through the steps, the performance of the copper-clad plate is improved, meanwhile, the copper-clad plate has high dimensional stability, and further the electrical performance and the stability of the flexible circuit board are improved.
Example two
Fig. 5 is a schematic cross-sectional structure diagram of a copper-clad plate provided in the second embodiment of the present application.
Referring to fig. 5, unlike the first embodiment, in the present embodiment, the expanded fluororesin membrane 20 includes an expanded base membrane 21 and a filling membrane 22, that is, the expanded fluororesin membrane 20 is a composite membrane layer of the expanded base membrane 21 and the filling membrane 22. The bulked base film 21 may be a single fluororesin film layer having a microporous structure and a predetermined porosity, similar to the bulked fluororesin film 20 of example one. The expanded basement membrane 21 can be obtained by processing dry powder fluororesin into a membrane, and the expanded fluororesin basement membrane has relatively low Dk value and Df value and good dimensional stability.
Filling film 22 can be for arbitrary fluorine-containing rete, and the microporous structure is arranged in popped base film 21, and filling film 22 is arranged in popped base film 21 relative two sides respectively, and filling film 22 fills the microporous structure, and filling film 22 just can effectual reduction popped base film 21's void fraction like this to reduce the holistic void fraction of copper-clad plate 100, thereby promote copper-clad plate 100's anti-solvent performance, further improve copper-clad plate 100's performance.
That is to say, in the copper-clad plate 100 provided in the embodiment of the present application, the intermediate layer is still the substrate 10 with the first fluororesin emulsion film 30 disposed on both sides thereof, and has a higher Dk value and Df value, and the expanded base films 21 with the filling films 22 are disposed on both sides of the intermediate layer, so as to maintain a lower Dk value and Df value, and a better dimensional stability, and also have a lower porosity. The copper-clad plate has high Dk value, low Df value and low expansion and contraction performance, the performance of the copper-clad plate 100 is improved, the size deformation of the copper-clad plate 100 is reduced, and the solvent resistance of the copper-clad plate 100 is improved.
The molding material of the filling film 22 may be polytetrafluoroethylene, or in some examples, the molding material of the filling film 22 may be other types of fluorine-containing resin, for example, the filling film 22 may be meltable polytetrafluoroethylene or perfluoroethylene propylene copolymer. The molding material of the filling film 22 may be the same as that of the first fluororesin emulsion film 30 and the bulked base film 21, or may be different from each other.
The combination mode of the expanded fluororesin membrane 20 and the first fluororesin emulsion membrane 30 is shown in table 1 of the first embodiment, and in the embodiment of the application, the performance of the obtained copper-clad plate 100 can reach the same performance as the copper-clad plate 100 in the first embodiment, namely, the Df value of the copper-clad plate 100 is 0.0005, the Dk value of the copper-clad plate 100 is 3, the thickness of the copper-clad plate 100 is 6mil, and the void ratio of the copper-clad plate 100 is 0%.
That is, the expanded fluororesin membrane 20 comprises an expanded base membrane 21 and a filling membrane 22, a first fluororesin emulsion membrane 30 with high Dk value and Df value is formed on the surface of the substrate 10 by dipping to serve as a middle layer of the copper-clad plate 100, the expanded base membrane 21 of the filling membrane 22 is superposed on the upper side and the lower side of the middle layer, the upper side and the lower side of the middle layer still have low Dk value and Df value and have good dimensional stability, the copper-clad plate 100 can reach Dk more than or equal to 2.8, Df less than or equal to 0.0008 and Ds less than or equal to 1000ppm, the CTE of the copper-clad plate 100 reaches 20-25ppm, and the void ratio of the copper-clad plate 100 is 0%. Namely, the copper-clad plate 100 has high Dk value, low Df value, low expansion and shrinkage and high solvent resistance.
Fig. 6 is a flowchart of a method for manufacturing a copper-clad plate according to the second embodiment of the present application.
The embodiment of the application further provides a preparation method of the copper-clad plate, and specifically, in the embodiment of the application, the step S103: obtaining a puffed resin film, specifically comprising:
obtaining a puffed base film;
and filling films are arranged on two opposite sides of the expanded base film.
Like this when the pressfitting forms the copper-clad plate, the filling film can with popped base film pressfitting, the microporous structure of popped base film is filled to the filling film to form popped fluororesin membrane.
Referring to fig. 6, specifically, the preparation method of the copper-clad plate comprises the following steps:
s201: a substrate is provided.
S202: a first fluororesin emulsion is obtained, and the substrate is dipped in the first fluororesin emulsion to form a first fluororesin emulsion film on the opposite sides of the substrate.
S203: obtaining the expanded basement membrane.
The forming method of the expanded base film may be the same as the forming method of the expanded fluororesin film in the first embodiment, which is specifically referred to in the first embodiment and is not described again in this embodiment.
S204: and filling films are arranged on two opposite sides of the expanded base film.
The filling membrane can be formed by firstly forming a membrane and then arranging the membrane on two opposite surfaces of the expanded base membrane, or the filling membrane can be formed by immersing the expanded base membrane into the emulsion and forming the filling membrane on the surface of the filling membrane in a dipping mode.
S205: the expanded fluororesin membrane is disposed on a side of the first fluororesin emulsion membrane facing away from the substrate.
Namely, the bulked base film with the filling film on both sides is arranged on the first fluororesin emulsion film.
S206: providing a copper foil layer, and arranging the copper foil layer on one surface of the expanded fluororesin membrane, which faces away from the substrate.
S207: and pressing to obtain the copper-clad plate.
The copper-clad plate with Dk value, low Df value and low swell and shrink can be obtained through the steps, and the copper-clad plate has better solvent resistance and dimensional stability while the performance of the copper-clad plate is improved.
EXAMPLE III
Fig. 7 is a schematic cross-sectional structure view of a copper-clad plate provided in the third embodiment of the present application.
Referring to fig. 7, based on the second embodiment, in the second embodiment of the present application, the filling film 22 is a second fluororesin emulsion film 22a, and the second fluororesin emulsion film 22a may be a film layer formed on the surface of the bulked base film 21 by immersing the bulked base film 21 in the second fluororesin emulsion. That is, the second fluorine resin emulsion may be formed on the surface of the bulked base film 21 by film-forming the second fluorine resin emulsion on the surface of the bulked base film 21 by dipping.
In the process of impregnation, film forming and pressing of the copper-clad plate 100, the second fluororesin emulsion film 22a is filled into the microporous structure of the bulked base film 21, so that the porosity of the bulked base film 21 is reduced, the overall porosity of the copper-clad plate 100 is also reduced, and the solvent resistance of the copper-clad plate 100 is improved.
The molding material and molding manner of the second fluororesin emulsion film 22a may be the same as those of the first fluororesin emulsion film 30, for example, a reinforcement may be added to the second fluororesin emulsion to distribute the reinforcement in the second fluororesin emulsion film 22a when the second fluororesin emulsion is formed into a film, so as to further improve the dimensional stability of the expanded fluororesin film 20. Accordingly, additives may be added to the second fluorine resin emulsion.
Of course, in some examples, no reinforcement may be added to the second fluororesin emulsion, and the amount of additive added to the second fluororesin emulsion may also be reduced.
The combination of the expanded fluororesin membrane 20 and the first fluororesin emulsion membrane 30 is shown in table 1 of example 1. In the embodiment of the application, the performance of the obtained copper-clad plate 100 can also reach the same performance as the copper-clad plate 100 in the first embodiment, that is, the Df value of the copper-clad plate 100 is 0.0005, the Dk value of the copper-clad plate 100 is 3, the thickness of the copper-clad plate 100 is 6mil, and the void ratio of the copper-clad plate 100 is 0%.
That is, the filling film 22 is a second fluororesin emulsion film 22a, the second fluororesin emulsion film 22a is formed on the surface of the expanded base film 21 by dipping to form an expanded fluororesin film 20, the middle layer is a first fluororesin emulsion film 30, the expanded fluororesin film 20 is superposed on the upper side and the lower side of the middle layer, and the obtained copper-clad plate 100 has a Dk of more than or equal to 2.8, a Df of less than or equal to 0.0008, a Ds of less than or equal to 1000ppm, a CTE of 20-25ppm and a void ratio of 0% in the copper-clad plate 100. Namely, the copper-clad plate 100 has high Dk value, low Df value, low expansion and shrinkage and high solvent resistance.
Fig. 8 is a flowchart of a method for manufacturing a copper-clad plate according to the third embodiment of the present application.
The embodiment of the application further provides a preparation method of the copper-clad plate, and specifically, in the embodiment of the application, the step S204: set up the filling film on the relative two sides of popped base film, specifically include:
a second fluororesin emulsion is obtained and the bulked base film is dipped into the second fluororesin emulsion to form a second fluororesin emulsion film on opposite sides of the bulked base film.
After the second fluororesin emulsion is obtained, additives, reinforcements and the like can be added into the first fluororesin emulsion, and specific embodiments refer to example one, which is not described in detail in this example.
During impregnation, the second fluorine resin emulsion can be added into an impregnation tank of a gluing machine, so that the expanded base film passes through the impregnation tank, the impregnation amount of the second fluorine resin emulsion on the expanded base plate is controlled by scraping a glue stick, and the thickness of the second fluorine resin emulsion film formed on the surface of the expanded base film is further controlled. After the impregnation is completed, the swelling impregnated with the second fluororesin emulsion may be dried, thereby forming a film of the second fluororesin emulsion on the surface of the swelled base film.
Referring to fig. 8, specifically, the preparation method of the copper-clad plate comprises the following steps:
s301: a substrate is provided.
S302: a first fluororesin emulsion is obtained, and the substrate is dipped in the first fluororesin emulsion to form a first fluororesin emulsion film on the opposite sides of the substrate.
S303: obtaining the expanded basement membrane.
S304: a second fluororesin emulsion is obtained and the bulked base film is dipped into the second fluororesin emulsion to form a second fluororesin emulsion film on opposite sides of the bulked base film.
Thus, the expanded base film and the second fluororesin emulsion films disposed on opposite sides of the expanded base film together form an expanded fluororesin film.
S305: the expanded fluororesin membrane is disposed on a side of the first fluororesin emulsion membrane facing away from the substrate.
Namely, the bulked base film with the second fluororesin emulsion film formed on both sides is arranged on the first fluororesin emulsion film.
S306: providing a copper foil layer, and arranging the copper foil layer on one surface of the expanded fluororesin membrane, which faces away from the substrate.
S307: and pressing to obtain the copper-clad plate.
The copper-clad plate with Dk value, low Df value and low swell and shrink can be obtained through the steps, the performance of the copper-clad plate is improved, meanwhile, the copper-clad plate has high dimensional stability and solvent resistance, the electrical performance and stability of the flexible circuit board are further improved, and the method is simple and convenient to achieve.
Example four
Fig. 9 is a schematic cross-sectional structure view of a copper-clad plate according to a fourth embodiment of the present application.
Referring to fig. 9, in the present embodiment, the filling film 22 is a fluororesin film 22b, and the filling film 22 is disposed on the bulked base film 21 to form the bulked fluororesin film 20, the fluororesin film 22b having no microporous structure and having a void ratio of 0%, based on the second embodiment. That is, the filling film 22 is a film formed by a single fluororesin, the fluororesin film 22b is stacked on the expanded base film 21, and the expanded fluororesin film 20 is formed after the fluororesin film 22b and the expanded base film 21 are laminated in the laminating process during the formation of the copper clad laminate 100.
During the process that fluororesin membrane 22b and popped base film 21 pressfitting set up, fluororesin membrane 22b fills in to the microporous structure of popped base film 21 to reduce the void fraction of popped base film 21, also reduce the holistic void fraction of copper-clad plate 100, promote copper-clad plate 100's anti-solvent performance.
Moreover, the filling film 22 is a fluororesin film 22b, and in the process of pressing during the molding of the copper-clad plate 100, the fluororesin film 22b is pressed on the expanded base film 21, so that the filling effect on the expanded base film 21 can be effectively improved, and the solvent resistance of the copper-clad plate 100 is further ensured. Meanwhile, the fluororesin film 22b is arranged between the copper foil layer 40 and the expanded base film 21, so that the bonding fastness between the copper foil layer 40 and the expanded base film 21 is improved, the surface deformation of the copper-clad plate 100 is reduced, the size deformation of the copper-clad plate 100 is further reduced, and the size stability of the copper-clad plate 100 is improved.
It should be understood that the fluororesin film 22b may be formed by various film-forming methods, and the fluororesin film 22b is formed by film-forming a fluororesin film and then disposed on the bulked base film 21, for example, the fluororesin film 22b may be formed by film-forming a fluororesin emulsion, the fluororesin film 22b may be formed by film-forming a dry fluororesin film, or a film layer formed by another film-forming method of a fluororesin.
The combination of the expanded fluororesin membrane 20 and the first fluororesin emulsion membrane 30 is shown in table 1 of example 1, wherein the thickness of the fluororesin membrane 22b may be 2 to 3 μm. In the embodiment of the application, the performance of the obtained copper-clad plate 100 can be the same as that of the copper-clad plate 100 in the first embodiment, that is, the Df value of the copper-clad plate 100 is 0.0005, the Dk value of the copper-clad plate 100 is 3, the thickness of the copper-clad plate 100 is 6mil, and the void ratio of the copper-clad plate 100 is 0%.
That is, the filling film 22 is a fluororesin film 22b, the fluororesin film 22b is directly pressed on the expanded base film 21 to form an expanded fluororesin film 20, the middle layer is a first fluororesin emulsion film 30, the expanded fluororesin film 20 is superposed on the upper side and the lower side of the middle layer, and the obtained copper-clad plate 100 can reach Dk more than or equal to 2.8, Df less than or equal to 0.0008, Ds less than or equal to 1000ppm, the CTE of the copper-clad plate 100 reaches 20-25ppm, and the void ratio of the copper-clad plate 100 is 0%. Namely, the copper-clad plate 100 has high Dk value, low Df value, low expansion and shrinkage and high solvent resistance.
Fig. 10 is a flowchart of a method for manufacturing a copper-clad plate according to the fourth embodiment of the present application.
The embodiment of the application further provides a preparation method of the copper-clad plate, and specifically, in the embodiment of the application, the step S204: set up the filling film on the relative two sides of popped base film, specifically include:
providing a fluororesin film, and disposing the fluororesin film on opposite sides of the bulked base film.
Referring to fig. 10, specifically, the preparation method of the copper-clad plate comprises the following steps:
s401: a substrate is provided.
S402: a first fluororesin emulsion is obtained, and the substrate is dipped in the first fluororesin emulsion to form a first fluororesin emulsion film on the opposite sides of the substrate.
S403: obtaining the expanded basement membrane.
S404: providing a fluororesin film, and disposing the fluororesin film on opposite sides of the bulked base film.
S405: the expanded fluororesin membrane is disposed on a side of the first fluororesin emulsion membrane facing away from the substrate.
Namely, the bulked base film having the fluororesin films respectively provided on both sides thereof is disposed on the first fluororesin emulsion film.
S406: providing a copper foil layer, and arranging the copper foil layer on one surface of the expanded fluororesin membrane, which faces away from the substrate.
S407: and pressing to obtain the copper-clad plate.
The copper-clad plate with Dk value, low Df value and low swell and shrink can be obtained through the steps, the performance of the copper-clad plate is improved, meanwhile, the copper-clad plate has good dimensional stability, the void ratio of the copper-clad plate is further reduced, and the solvent resistance of the copper-clad plate can be further ensured. The method is simple to operate and has good applicability.
EXAMPLE five
Fig. 11 is a schematic cross-sectional view of a copper-clad plate provided in the fifth embodiment of the present application.
Referring to fig. 11, in addition to the second embodiment, in the embodiment of the present application, the copper-clad plate 100 further includes a fluororesin film 22b, and the fluororesin film 22b is disposed on a side of the second fluororesin emulsion film 22a opposite to the bulked base film 21, that is, the fluororesin films 22b are disposed between the copper foil layer 40 and the second fluororesin emulsion film 22a, and between the second fluororesin emulsion film 22a and the first fluororesin emulsion film 30. The fluororesin film 22b is beneficial to improving the bonding force between the copper foil layer 40 and the expanded fluororesin film 20 and between the first fluororesin emulsion film 30 and the second fluororesin emulsion film 22a, so that the bonding fastness between the film layers in the copper-clad plate 100 is improved, the size deformation of the copper-clad plate 100 is further reduced, the surface deformation of the copper-clad plate 100 is especially beneficial to reducing, and the size stability of the copper-clad plate 100 is improved.
Here, the second fluororesin emulsion film 22a may be first formed on both opposite sides of the bulked base film 21 by means of impregnation, and then the fluororesin film 22b may be provided on a side of the second fluororesin emulsion film 22a facing away from the bulked base film 21.
Similarly, in the process of impregnation, film formation and lamination of the copper-clad plate 100, the second fluororesin emulsion film 22a is filled into the microporous structure of the expanded base film 21, so that the porosity of the expanded base film 21 is reduced, the overall porosity of the copper-clad plate 100 is reduced, and the solvent resistance of the copper-clad plate 100 is improved.
The forming method of the fluororesin film 22b may be the same as that in the fourth embodiment, and correspondingly, the forming method of the second fluororesin emulsion film 22a may be the same as that in the third embodiment, and details are not repeated in this embodiment. The fluororesin film 22b may be formed of the same material as the second fluororesin emulsion film 22a, the first fluororesin emulsion film 30 and the expanded fluororesin film 20, or may be formed of different materials, or any of them may be the same.
The combination of the expanded fluororesin membrane 20 and the first fluororesin emulsion membrane 30 is shown in example 1. The thickness of the fluororesin film 22b may be 2-3 μm, in the embodiment of the present application, the performance of the obtained copper-clad plate 100 may be the same as that of the copper-clad plate 100 in the first embodiment, that is, the Df value of the copper-clad plate 100 is 0.0005, the Dk value of the copper-clad plate 100 is 3, the thickness of the copper-clad plate 100 is 6mil, and the void ratio of the copper-clad plate 100 is 0%.
That is, the filling film 22 is a second fluororesin emulsion film 22a, the second fluororesin emulsion film 22a and the expanded base film 21 form an expanded fluororesin film 20, a fluororesin film 22b is arranged between the second fluororesin emulsion film 22a and the copper foil layer 40, the middle layer of the copper-clad plate 100 is the substrate 10 provided with the first fluororesin emulsion film 30, the fluororesin film 22b and the expanded fluororesin film 20 are respectively superposed on the upper side and the lower side of the middle layer, the obtained copper-clad plate 100 can reach a Dk of more than or equal to 2.8, a Df of less than or equal to 0.0008 and a Ds of less than or equal to 1000ppm, the CTE of the copper-clad plate 100 reaches 20-25ppm, and the void ratio of the copper-clad plate 100 is 0%. Namely, the copper-clad plate 100 has high Dk value, low Df value, low expansion and shrinkage and high solvent resistance.
Fig. 12 is a flowchart of a method for manufacturing a copper-clad plate according to the fifth embodiment of the present application.
The embodiment of the present application further provides a method for preparing a copper-clad plate, and specifically, in the embodiment of the present application, after step S305 is completed: after disposing the expanded fluororesin membrane on a side of the first fluororesin emulsion membrane facing away from the substrate, the method further comprises:
providing a fluororesin film, and arranging the fluororesin film on one side of the second fluororesin emulsion film, which faces away from the bulked base film.
That is, a first fluororesin emulsion film is formed on the opposite sides of the substrate, a second fluororesin emulsion film is formed on the opposite sides of the expanded base film, the second fluororesin emulsion film and the expanded base film together form an expanded fluororesin film, the expanded fluororesin film is disposed on the first fluororesin emulsion film, and the fluororesin film is stacked on the second fluororesin emulsion film of the expanded fluororesin film, respectively, by dipping.
Referring to fig. 12, specifically, the preparation method of the copper-clad plate comprises the following steps:
s501: a substrate is provided.
S502: a first fluororesin emulsion is obtained, and the substrate is dipped in the first fluororesin emulsion to form a first fluororesin emulsion film on the opposite sides of the substrate.
S503: obtaining the expanded basement membrane.
S504: a second fluororesin emulsion is obtained and the bulked base film is dipped into the second fluororesin emulsion to form a second fluororesin emulsion film on opposite sides of the bulked base film.
Wherein the second fluororesin emulsion film and the expanded base film together form an expanded fluororesin film.
S505: the expanded fluororesin membrane is disposed on a side of the first fluororesin emulsion membrane facing away from the substrate.
Namely, the bulked base film with the second fluororesin emulsion film formed on both sides is arranged on the first fluororesin emulsion film.
S506: providing a fluororesin film, and arranging the fluororesin film on one side of the second fluororesin emulsion film, which faces away from the bulked base film.
S507: providing a copper foil layer, and arranging the copper foil layer on one surface of the expanded fluororesin membrane, which faces away from the substrate.
S508: and pressing to obtain the copper-clad plate.
The copper-clad plate with the Dk value, the low Df value and the low swell and shrink can be obtained through the steps, the performance of the copper-clad plate is improved, the copper-clad plate has better solvent resistance, the size deformation of the copper-clad plate is further reduced, and the size stability of the copper-clad plate can be further improved.
In the description of the embodiments of the present application, it should be noted that unless otherwise explicitly stated or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be, for example, a fixed connection, an indirect connection via an intermediary, a connection between two elements, or an interaction between two elements. The specific meanings of the above terms in the embodiments of the present application can be understood by those of ordinary skill in the art according to specific situations. The terms "first," "second," "third," "fourth," and the like (if any) are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order.
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the embodiments of the present application, and are not limited thereto; although the embodiments of the present application have been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present application.

Claims (17)

1. The copper-clad plate is characterized by comprising a substrate, a puffed fluororesin film, a first fluororesin emulsion film and a copper foil layer;
the two opposite surfaces of the substrate are provided with the first fluororesin emulsion film;
the surface, opposite to the substrate, of the first fluororesin emulsion film is provided with the expanded fluororesin film, and the expanded fluororesin film has a plurality of microporous structures;
the copper foil layer is arranged on one surface of the expanded fluororesin membrane, which faces away from the substrate.
2. The copper-clad plate according to claim 1, wherein the bulked fluororesin film comprises a bulked base film and a filled film, and the microporous structure is located in the bulked base film;
the filling films are respectively positioned on two opposite surfaces of the bulked base film, and the filling films fill the microporous structures.
3. The copper-clad plate according to claim 2, wherein the filling film is a fluororesin film, and the fluororesin film is provided on the bulked base film.
4. The copper-clad plate according to claim 2, wherein the filling film is a second fluororesin emulsion film.
5. The copper-clad plate according to claim 4, further comprising a fluororesin film disposed on a side of the second fluororesin emulsion film facing away from the bulked base film.
6. The copper-clad plate according to any one of claims 1 to 5, further comprising a reinforcement member, wherein the reinforcement member is disposed within the first fluororesin emulsion film.
7. The copper-clad plate according to any one of claims 2 to 5, wherein the molding materials of the bulked base film, the filling film and the first fluororesin emulsion film at least comprise: polytetrafluoroethylene, fusible polytetrafluoroethylene, or perfluoroethylene propylene copolymer.
8. The copper-clad plate according to any one of claims 2 to 7, wherein the substrate comprises at least glass fiber cloth.
9. A preparation method of a copper-clad plate is characterized by comprising the following steps:
providing a substrate;
obtaining a first fluororesin emulsion, immersing the substrate in the first fluororesin emulsion to form a first fluororesin emulsion film on opposite sides of the substrate;
obtaining a bulked fluororesin membrane having a plurality of microporous structures;
disposing the bulked fluororesin membrane on a side of the first fluororesin emulsion membrane facing away from the substrate;
providing a copper foil layer, and arranging the copper foil layer on one side of the expanded fluororesin membrane, which faces away from the substrate;
and pressing to obtain the copper-clad plate.
10. The production method according to claim 9, wherein the bulked fluororesin film comprises a bulked base film in which the microporous structure is located and a filling film for filling the microporous structure;
said obtaining said expanded resin film comprises:
obtaining a puffed base film;
and filling films are arranged on two opposite surfaces of the expanded base film.
11. The production method according to claim 10, wherein the filling film is a fluororesin film;
the setting of fill film on the opposite sides of the bulked base film comprises:
providing a fluororesin film, and disposing the fluororesin film on opposite sides of the bulked base film.
12. The production method according to claim 10, wherein the filling film is a second fluorine resin emulsion film;
the setting of fill film on the opposite sides of the bulked base film comprises:
obtaining a second fluororesin emulsion, immersing the bulked base film in the second fluororesin emulsion to form a second fluororesin emulsion film on opposite sides of the bulked base film.
13. The method according to claim 12, wherein the copper-clad plate further comprises a fluororesin film, and after the expanded fluororesin film is disposed on a side of the first fluororesin emulsion film facing away from the substrate, the method further comprises:
providing a fluororesin film, and arranging the fluororesin film on one side of the second fluororesin emulsion film, which faces away from the bulked base film.
14. The method according to any one of claims 9 to 13, further comprising, after said obtaining the first fluororesin emulsion:
a reinforcement is added to the first fluororesin emulsion.
15. The method of any of claims 9-14, wherein after providing the copper foil layer, further comprising:
roughening the surface of the copper foil layer;
and performing fluorination treatment on the surface of the roughened copper foil layer.
16. A flexible circuit board, characterized in that, at least comprises a circuit structure and the copper-clad plate of any one of the above claims 1-8, wherein the circuit structure is arranged on the copper-clad plate.
17. An electronic device comprising at least a housing and the flexible circuit board of claim 16, said flexible circuit board being disposed within said housing.
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PCT/CN2022/133330 WO2023109440A1 (en) 2021-12-13 2022-11-21 Copper-clad laminate and preparation method therefor
TW111147437A TWI828470B (en) 2021-12-13 2022-12-09 Copper clad plate and manufacturing method thereof

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JP2016046433A (en) * 2014-08-25 2016-04-04 住友電工ファインポリマー株式会社 Printed wiring board and substrate for printed wiring board
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