CN111775527A - Preparation method of composite medium copper-clad plate and printed circuit board - Google Patents

Preparation method of composite medium copper-clad plate and printed circuit board Download PDF

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Publication number
CN111775527A
CN111775527A CN202010666264.6A CN202010666264A CN111775527A CN 111775527 A CN111775527 A CN 111775527A CN 202010666264 A CN202010666264 A CN 202010666264A CN 111775527 A CN111775527 A CN 111775527A
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China
Prior art keywords
composite
copper
preset
substrate
clad plate
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黄国创
王和志
恽振阳
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AAC Technologies Holdings Nanjing Co Ltd
Ruisheng Technology Nanjing Co Ltd
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Ruisheng Technology Nanjing Co Ltd
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Priority to CN202010666264.6A priority Critical patent/CN111775527A/en
Priority to PCT/CN2020/106661 priority patent/WO2022007069A1/en
Publication of CN111775527A publication Critical patent/CN111775527A/en
Pending legal-status Critical Current

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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
    • 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
    • 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
    • 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
    • B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
    • 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
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
    • 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
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • 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
    • B32B38/18—Handling of layers or the laminate
    • B32B38/1808—Handling of layers or the laminate characterised by the laying up of the layers
    • B32B38/1816—Cross feeding of one or more of the layers
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/08—Interconnection of layers by mechanical means
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • 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
    • H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
    • 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
    • B32B2250/03—3 layers
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/107—Ceramic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • 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)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides a preparation method of a composite medium copper-clad plate and a printed circuit board, wherein the preparation method comprises the following steps: forming a substrate green compact by using an emulsion of a fluorine-containing material and a ceramic filler material; pre-sintering the substrate green body to form a composite substrate; carrying out vacuum sintering on the composite substrate at a preset sintering temperature and a preset hot-pressing pressure to form a composite medium copper-clad plate; wherein the preset sintering temperature range is 360-400 ℃, and the preset hot pressing pressure range is 0-8 Mpa. Through the embodiment, the peeling strength of the composite medium copper-clad plate can be improved, and the phenomenon that the copper foil falls off in the subsequent processing process of the composite medium copper-clad plate is ensured.

Description

Preparation method of composite medium copper-clad plate and printed circuit board
Technical Field
The invention relates to the technical field of composite medium copper-clad plate preparation, in particular to a preparation method of a composite medium copper-clad plate and a printed circuit board.
Background
With the coming of the 5G era, the development of electronic products tends to be multifunctional, parts are continuously developed in the directions of lightness, thinness, shortness, smallness and the like, and particularly, the wide application of high-density integrated circuit technology puts forward the requirements of high performance, high reliability and high safety on civil electronic products; the requirements of good technical performance, low cost and high energy consumption are provided for industrial electronic products.
Polytetrafluoroethylene (PTFE for short) has excellent microwave performance, the dielectric constant (r) is 2.0-2.2, the dielectric loss (tan) is 0.0002-0.0003, and the Polytetrafluoroethylene has good chemical stability and thermal stability and is suitable for high-frequency microwave circuits. The composite medium prepared by compounding the PTFE resin as a matrix with the fine electronic ceramic is very popular with microwave circuit design experts due to a series of advantages of excellent high-frequency dielectric property, low-cost metallization, convenient circuit processing and installation, difficult breakage when used in vibration occasions and the like.
At present, a composite medium substrate obtained by soaking PTFE emulsion in glass fiber cloth is the most common product with the widest dosage, has better dimensional stability and lower manufacturing cost, but because the dielectric constant of the glass fiber cloth is lower, the dielectric constant of the obtained glass fiber reinforced PTFE substrate is not high and is about between 2.3 and 2.8, and ceramic powder with high dielectric constant needs to be doped for obtaining a composite material with higher dielectric constant. Meanwhile, the glass fiber cloth contains more metal oxides and metal salt impurities, so that the dielectric loss of the composite substrate is also higher. In addition, the peel strength is an important index for inspecting the performance of the copper-clad plate, and is an index of quality problems frequently occurring in the production of the copper-clad plate. The problem of copper foil falling off occurs in the subsequent process such as printing plate processing or assembly welding due to low peel strength, so that the normal processing of the whole device is influenced finally, and the yield is reduced.
Disclosure of Invention
The invention mainly provides a preparation method of a composite medium copper-clad plate and a printed circuit board, which can solve the problem that in the prior art, a composite medium copper-clad substrate obtained by soaking PTFE emulsion in glass fiber cloth causes copper foil falling off in the subsequent process due to low peel strength.
In order to solve the technical problems, the invention adopts a technical scheme that: the preparation method of the composite medium copper-clad plate comprises the following steps: forming a substrate green compact by using an emulsion of a fluorine-containing material and a ceramic filler material; pre-sintering the substrate green body to form a composite substrate; carrying out vacuum sintering on the composite substrate at a preset sintering temperature and a preset hot-pressing pressure to form the composite medium copper-clad plate; wherein the preset sintering temperature range is 360-400 ℃, and the preset hot pressing pressure range is 0-8 Mpa.
Wherein, sintering the composite substrate at a preset sintering temperature and a preset hot-pressing pressure to form the composite medium copper-clad plate comprises: covering copper foils with preset thicknesses on the opposite upper surface and the opposite lower surface of the composite substrate; placing the composite substrate covered with the copper foil into a die or a hot press; and sintering the composite substrate covered with the copper foil at a preset sintering temperature and a preset hot-pressing pressure to form the composite medium copper-clad plate.
Wherein the preset thickness of the copper foil is 10-40 μm.
Wherein the preset thickness of the copper foil is 18-35 μm.
Wherein the preset sintering temperature is in the range of 370-380 ℃. Wherein the forming of the substrate green compact with the emulsion of the fluorine-containing material and the ceramic filler material comprises: adding 20-60 parts by weight of the emulsion of the fluorine-containing material into a container for stirring; respectively adding 1-5 parts by weight of a first ceramic filling material and 40-70 parts by weight of a second ceramic filling material into the fluorine-containing material emulsion to form a mixed emulsion; performing emulsion breaking treatment on the mixed emulsion; baking the demulsified mixed emulsion to form a dough-like material; and carrying out forming treatment on the dough-shaped material to form the substrate green body, wherein the fluorine-containing material, the first ceramic filling material and the second ceramic filling material account for 100 parts by weight.
Wherein, the fluorine-containing material is one of polytetrafluoroethylene, hexafluoropropylene, tetrafluoroethylene and perfluoroalkyl vinyl ether.
Wherein the ceramic filling material is one of silicon dioxide, titanium dioxide, aluminum oxide, aluminum nitride, magnesium oxide, calcium oxide, zinc oxide and barium oxide.
The temperature range of pre-sintering the substrate green body is 240-320 ℃, and the time range of pre-sintering is 2-12 h.
In order to solve the technical problem, the invention adopts another technical scheme that: a printed circuit board is provided, and the printed circuit board comprises the composite medium copper-clad plate prepared by any one of the preparation methods.
The invention has the beneficial effects that: the invention provides a preparation method of a composite medium copper-clad plate and a printed circuit board, which are different from the prior art, and the peeling strength of the composite medium copper-clad plate is greatly improved by adjusting a thermal process, so that the copper foil can not fall off in the subsequent processing process of the copper-clad plate.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without inventive efforts, wherein:
FIG. 1 is a schematic flow diagram of one embodiment of a composite dielectric copper-clad plate preparation method of the invention;
FIG. 2 is a schematic flow chart illustrating an embodiment of step S100 in FIG. 1 according to the present invention;
FIG. 3 is a flowchart illustrating an embodiment of step S300 in FIG. 1 according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, fig. 1 is a schematic flow chart of an embodiment of a method for manufacturing a composite dielectric copper-clad plate according to the present invention, and as shown in fig. 1, the method for manufacturing a composite dielectric copper-clad plate according to the present invention specifically includes the following steps:
and S100, forming a substrate green body by using the emulsion of the fluorine-containing material and the ceramic filling material.
The fluorine-containing material provided by the invention can be one of Polytetrafluoroethylene (PTFE), Hexafluoropropylene (HFP), Tetrafluoroethylene (TFE) and perfluoroalkyl vinyl ether (PAVE). In the specific embodiment of the invention, the preparation method of the composite-media copper-clad plate of the invention is described in detail by taking the fluorine-containing material as Polytetrafluoroethylene (PTFE) as an example, and the method for manufacturing the composite-media copper-clad plate by taking the residual fluorine-containing material as a raw material is similar to the preparation method of the embodiment, and is not described herein again.
Optionally, the ceramic filling material in the embodiment of the present invention may be one of silicon dioxide, titanium dioxide, aluminum oxide, aluminum nitride, magnesium oxide, calcium oxide, zinc oxide, and barium oxide.
Referring to fig. 2, fig. 2 is a schematic flow chart of an embodiment of step S100 of the present invention, and as shown in fig. 2, step S100 further includes the following sub-steps:
s110, adding 20-60 parts by weight of the fluorine-containing material emulsion into a container and stirring.
20-60 parts by weight of the emulsion of the fluorine-containing material (the fluorine-containing material in the embodiment of the present invention is tetrafluoroethylene) is added into a container equipped with a mechanical stirrer for sufficient stirring, wherein the stirring time is in the range of 10-60min, specifically 20min, 40min, 60min and the like, and is not specifically limited herein, and preferably, the amount of the fluorine-containing material in the present invention is 30-50 parts by weight, specifically 30 parts by weight, 40 parts by weight, 50 parts by weight and the like, and is not specifically limited herein.
And S120, respectively adding 1-5 parts by weight of first ceramic filling material and 40-70 parts by weight of second ceramic filling material into the emulsion containing the fluorine material to form mixed emulsion.
Optionally, the first ceramic filler material is slowly added to the emulsion of the fluorine-containing material and stirred well to homogeneity. The first ceramic filler may be hydrophobic titanium dioxide, and the predetermined amount thereof may be 1 to 5 parts, specifically 1 part, 3 parts, 5 parts, and the like, which is not limited herein. Preferably, the first ceramic filler material may be 2 to 4 parts by weight, specifically 2 parts by weight, 3 parts by weight, 4 parts by weight, etc., and is not particularly limited herein.
Further, slowly adding a second ceramic filling material into the uniformly stirred emulsion, and fully stirring for 2-5h to uniformly mix the emulsion and the ceramic filling material to form a mixed emulsion. Optionally, the second ceramic filler material is silica, especially fused amorphous silica, and the predetermined amount thereof may be 40 to 70 parts, specifically 40 parts, 55 parts, 70 parts, and the like, and is not limited herein. Preferably, the second ceramic filler may be 50 to 65 parts by weight, specifically 50 parts by weight, 57.5 parts by weight, 65 parts by weight, and the like, and is not particularly limited herein.
However, the fluorine-containing material, the first ceramic filler material and the second ceramic filler material total 100 parts by weight.
S130, demulsifying the mixed emulsion.
Further, the mixed emulsion is subjected to emulsion breaking treatment, wherein emulsion breaking means that the emulsion is completely broken into two immiscible phases, and the emulsion breaking means a process of substantially eliminating emulsion stabilizing conditions, and aggregating and layering dispersed droplets. In the embodiment of the invention, the emulsion breaking treatment of the mixed emulsion can be realized by slowly adding the ethanol in the preset weight part while stirring the mixed emulsion, and the preset weight part of the ethanol can be 10-20 parts, specifically 10 parts, 15 parts, 20 parts and the like, which is not specifically limited herein.
S140, baking the demulsified mixed emulsion to form a dough-shaped material.
And putting the demulsified material into an oven, and baking within a preset temperature range to enable the mixed emulsion to form a dough-shaped material. The preset temperature range of the oven is 90-130 ℃, and specifically, the preset temperature range may be 90 ℃, 110 ℃, 130 ℃, and the like, and is not specifically limited herein. In a preferred embodiment of the present invention, the predetermined temperature range of the oven may be 100 ℃ to 120 ℃, specifically 100 ℃, 110 ℃, 120 ℃, etc.
S150, forming the bulk material to form a substrate green body.
Further, the dough-like material is put into a double-roller open mill or a calender, the base plate is molded according to certain temperature and roller speed, and meanwhile, the roller distance is adjusted to enable the thickness of the generated base plate green body to be uniform.
And S200, pre-sintering the substrate green body to form the composite substrate.
Further, the green substrate is subjected to a pre-firing treatment to sufficiently exclude a stabilizer, a surfactant, and the like contained in the tetrafluoroethylene emulsion itself, thereby forming a composite substrate. The pre-sintering temperature range is 240-320 ℃, specifically 240 ℃, 270 ℃, 300 ℃ and the like, and is not specifically limited herein, and the pre-sintering time range is 2-12h, specifically 2h, 7h, 12h and the like, and is not specifically limited herein. Preferably, the pre-sintering temperature is 260-290 ℃, specifically 260 ℃, 275 ℃, 290 ℃ and the like, and the pre-sintering time is preferably 3-8h, specifically 3h, 5.5h, 8h and the like, which are not limited herein.
And S300, carrying out vacuum sintering on the composite substrate at a preset sintering temperature and a preset hot-pressing pressure to form the composite medium copper-clad plate.
With further reference to fig. 3, fig. 3 is a schematic flowchart of an embodiment of step S300 of the present invention, and as shown in fig. 3, step S300 further includes the following sub-steps:
and S310, covering copper foils with preset thicknesses on the opposite upper surface and lower surface of the composite substrate.
Optionally, copper foils of a predetermined thickness are coated on the opposite upper and lower surfaces of the composite substrate. In the embodiment of the present invention, the predetermined thickness of the copper foil may be 10 μm to 40 μm, and specifically may be 12 μm, 18 μm, 35 μm, and the like. In an embodiment of the present invention, the predetermined thickness of the copper foil is preferably 18 μm to 35 μm, and may be 18 μm or 35 μm, which is not limited herein.
And S310, placing the composite substrate covered with the copper foil into a mould or a hot press.
The composite substrate covered with the copper foil is placed in a specific mold or a hot press.
And S310, carrying out vacuum sintering on the composite substrate covered with the copper foil at a preset sintering temperature and a preset hot-pressing pressure to form the composite medium copper-clad plate.
Optionally, the composite substrate covered with the copper foil is subjected to vacuum sintering at a preset sintering temperature and a preset hot-pressing pressure for a certain time and temperature to obtain the composite medium copper-clad plate. The preset sintering temperature in the invention is higher than the melting point of the fluorine-containing material and lower than the decomposition temperature of the fluorine-containing material. Specifically, the preset sintering temperature range is 360 ℃ to 400 ℃, specifically 360 ℃, 380 ℃, 400 ℃ and the like, and is not specifically limited herein. Preferably, the sintering temperature range is adjusted comparatively between 370 ℃ and 380 ℃, and may be 370 ℃, 375 ℃, 380 ℃ or the like, which is not limited herein. The sintering time ranges from 1h to 8h, specifically 1h, 4.5h, 8h, etc., and in a preferred embodiment of the present invention, the sintering time may range from 2h to 6h, specifically 2h, 4h, 6h, etc., which is not limited herein.
In particular, in the embodiment of the invention, the tetrafluoroethylene has a melting point of between 320 ℃ and 345 ℃ and therefore a sintering temperature of greater than 345 ℃ and a decomposition temperature of about 400 ℃ and therefore a predetermined sintering temperature of not more than 400 ℃ is not allowed.
Further, the preset hot pressing pressure range is 0Mpa to 8Mpa, and specifically, 0Mpa, 4Mpa, 8Mpa, and the like, which is not specifically limited herein. In a preferred embodiment of the present invention, the predetermined hot pressing pressure range may be 2Mpa to 4Mpa, and specifically, may be 2Mpa, 3Mpa, 4Mpa, or the like.
In the embodiment, the use thickness of the copper foil is changed by adjusting the thermal sintering temperature and the thermal pressing pressure, so that the peel strength of the composite medium copper-clad plate is greatly improved, and the copper foil can be prevented from falling off in the subsequent processing process of the copper-clad plate.
The following details describe the test of the peeling performance of the composite medium copper clad laminate prepared by the preparation method of the invention:
preparation of composite medium copper-clad plate sample
1. And cutting the prepared composite medium copper-clad plate sample into sample strips with the width of 5mm and the length range of 60-76mm, and trimming the sample strips and the like.
2. The copper foil is separated from the substrate by cutting a strip across the strip with a blade and then pulling the foil up without damaging the foil, wherein the initial peel length should be greater than half the length of the strip.
Second, peeling test
1. The width of the test sample strip was measured, and the initial peeled sample strip was fixed with the initial peeling section below, and the peeled portion (composite substrate + non-peeled copper foil on the other side) was held by a jig.
2. And clamping the copper foil part of which the length is more than half of the length of the sample strip by using a clamp at the upper part of the copper foil part, and ensuring that the sample strip is vertically placed, namely the sample strip is vertical to the section of the clamp.
3. The strip speed was set at 25mm/min and 180 ° strip testing was started on the specimens.
4. The initial state is restored and the next test is continued, with the number of spline tests per sample ranging from 5 to 10.
5. And obtaining stripping test data, averaging the data of the middle 50% of the stripping section to be tested, and dividing the average value by the width of the stripped sample bar to obtain the stripping strength of the sample bar.
Through the peeling test, the peeling strength of the composite medium copper-clad plate prepared by the invention is greatly improved and reaches more than 2.0N/mm to the maximum. Meanwhile, the composite medium copper-clad plate prepared by the invention has excellent dielectric properties (the dielectric constant is adjustable from more than 2.1, the dielectric loss is low, tan is 0.002 and 1GHz), the water absorption is low (< 0.03%), and the thermal conductivity is high (> 0.5W/mk).
Further details are provided in connection with the embodiments of the invention:
preparation of composite medium copper-clad plate
Example 1
Weighing 48 parts by weight of fluorine-containing material (PTFE) emulsion, adding the emulsion into a container, stirring for 20-60min, weighing 4 parts by weight of first ceramic filling material TiO2 and 48 parts by weight of first ceramic filling material SiO2 powder, adding the powder into the PTFE emulsion, and stirring for 2-5h until the mixture is uniform. Then adding 10-20 parts by weight of ethanol dropwise to demulsify, baking the demulsifying dough-like material in an oven at the temperature of 100 ℃ and 120 ℃, and removing part of water and ethanol. And rolling the material baked to a certain degree into a substrate green sheet with a thinner thickness, and pre-sintering the substrate green sheet at 260-290 ℃ for 3-8h to obtain the composite substrate. And covering copper foils on the upper and lower surfaces of the pre-sintered composite substrate, and putting the composite substrate into a hot press, wherein the thickness of the copper foil is 18 mu m. And adjusting the sintering temperature to 370 ℃, the hot-pressing pressure of sintering to 8Mpa, and the sintering time to 2-4h, and performing vacuum sintering on the composite substrate to obtain the composite-medium copper-clad plate.
Example 2
Weighing 48 parts by weight of fluorine-containing material (PTFE) emulsion, adding the emulsion into a container, stirring for 20-60min, weighing 4 parts by weight of first ceramic filling material TiO2 and 48 parts by weight of first ceramic filling material SiO2 powder, adding the powder into the PTFE emulsion, and stirring for 2-5h until the mixture is uniform. Then adding 10-20 parts by weight of ethanol dropwise to demulsify, baking the demulsifying dough-like material in an oven at the temperature of 100 ℃ and 120 ℃, and removing part of water and ethanol. And rolling the material baked to a certain degree into a substrate green sheet with a thinner thickness, and pre-sintering the substrate green sheet at 260-290 ℃ for 3-8h to obtain the composite substrate. And covering copper foils on the upper and lower surfaces of the pre-sintered composite substrate, and putting the composite substrate into a hot press, wherein the thickness of the copper foil is 18 mu m. And further, adjusting the sintering temperature to 380 ℃, the sintering hot-pressing pressure to 8Mpa and the sintering time to 2-4h, and performing vacuum sintering on the composite substrate to obtain the composite medium copper-clad plate.
Example 3
Weighing 48 parts by weight of fluorine-containing material (PTFE) emulsion, adding the emulsion into a container, stirring for 20-60min, weighing 4 parts by weight of first ceramic filling material TiO2 and 48 parts by weight of first ceramic filling material SiO2 powder, adding the powder into the PTFE emulsion, and stirring for 2-5h until the mixture is uniform. Then adding 10-20 parts by weight of ethanol dropwise to demulsify, baking the demulsifying dough-like material in an oven at the temperature of 100 ℃ and 120 ℃, and removing part of water and ethanol. And rolling the material baked to a certain degree into a substrate green sheet with a thinner thickness, and pre-sintering the substrate green sheet at 260-290 ℃ for 3-8h to obtain the composite substrate. And covering copper foils on the upper and lower surfaces of the pre-sintered composite substrate, and putting the composite substrate into a hot press, wherein the thickness of the copper foil is 18 mu m. Further, the sintering temperature is adjusted to be 370 ℃, the sintering hot-pressing pressure is 2Mpa, and the sintering time is 2-4h, and the composite substrate is hot-pressed to obtain the composite medium copper-clad plate.
Example 4
Weighing 48 parts by weight of fluorine-containing material (PTFE) emulsion, adding the emulsion into a container, stirring for 20-60min, weighing 4 parts by weight of first ceramic filling material TiO2 and 48 parts by weight of first ceramic filling material SiO2 powder, adding the powder into the PTFE emulsion, and stirring for 2-5h until the mixture is uniform. Then adding 10-20 parts by weight of ethanol dropwise to demulsify, baking the demulsifying dough-like material in an oven at the temperature of 100 ℃ and 120 ℃, and removing part of water and ethanol. And rolling the material baked to a certain degree into a substrate green sheet with a thinner thickness, and pre-sintering the substrate green sheet at 260-290 ℃ for 3-8h to obtain the composite substrate. And covering copper foils on the upper and lower surfaces of the pre-sintered composite substrate, and putting the composite substrate into a hot press, wherein the thickness of the copper foil is 18 mu m. Further, the sintering temperature is adjusted to be 370 ℃, the sintering hot-pressing pressure is 4Mpa, and the sintering time is 2-4h, and the composite substrate is hot-pressed to obtain the composite medium copper-clad plate.
Example 5
Weighing 48 parts by weight of fluorine-containing material (PTFE) emulsion, adding the emulsion into a container, stirring for 20-60min, weighing 4 parts by weight of first ceramic filling material TiO2 and 48 parts by weight of first ceramic filling material SiO2 powder, adding the powder into the PTFE emulsion, and stirring for 2-5h until the mixture is uniform. Then adding 10-20 parts by weight of ethanol dropwise to demulsify, baking the demulsifying dough-like material in an oven at the temperature of 100 ℃ and 120 ℃, and removing part of water and ethanol. And rolling the material baked to a certain degree into a substrate green sheet with a thinner thickness, and pre-sintering the substrate green sheet at 260-290 ℃ for 3-8h to obtain the composite substrate. And covering copper foils on the upper and lower surfaces of the pre-sintered composite substrate, and putting the composite substrate into a hot press, wherein the thickness of the copper foil is 35 mu m. Further, the sintering temperature is adjusted to be 370 ℃, the sintering hot-pressing pressure is 8Mpa, and the sintering time is 2-4h, and the composite substrate is hot-pressed to obtain the composite medium copper-clad plate.
Comparison of Peel Strength
As shown in table 1, table 1 shows a comparison of peel strengths of the composite dielectric copper clad laminate prepared by the five embodiments of the present invention, and the present invention compares the peel strengths of the composite dielectric copper clad laminate obtained by the five experiments in a variable control manner, as shown in table 1:
group of Sintering temperature Hot pressing pressure Thickness of copper foil Peel strength
Example 1 370℃ 8Mpa 18μm 1.242N/mm
Example 2 380℃ 8Mpa 18μm 1.167N/mm
Example 3 370℃ 2Mpa 18μm 1.31N/mm
Example 4 370℃ 4Mpa 18μm 1.5N/mm
Example 5 370℃ 8Mpa 35μm 2.11N/mm
As can be seen from Table 1, the composite dielectric copper clad laminate prepared by the 5 embodiments of the invention has better peel strength. By adjusting the ranges of three parameters of the sintering temperature, the hot pressing pressure and the copper foil thickness, the peel strength of the composite medium copper-clad plate is improved, and the copper foil falling phenomenon can be avoided in the subsequent processing process of the copper-clad plate. Optionally, the peel strength of the composite dielectric copper clad laminate prepared when the sintering temperature is 370 ℃, the hot pressing pressure is 8Mpa, and the copper foil thickness is 35 μm can also be obtained at most 2.11N/mm from table 1.
In the embodiment, the peeling strength of the composite medium copper-clad plate is greatly improved by adjusting the thermal process, and the copper foil falling phenomenon can be avoided in the subsequent processing process of the copper-clad plate.
Optionally, the invention further provides a printed circuit board, the printed circuit board includes the composite dielectric copper-clad plate prepared by the preparation method in the embodiment of the invention, and the detailed preparation process and the strength peeling test of the composite dielectric copper-clad plate are described in detail in the above embodiment, and are not described herein again.
Different from the prior art, the embodiment of the invention provides a preparation method of a composite medium copper-clad plate and a printed circuit board, which can greatly improve the peeling strength of the composite medium copper-clad plate by adjusting a thermal process and ensure that the copper foil does not fall off in the subsequent processing process of the copper-clad plate.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification and drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (10)

1. The preparation method of the composite medium copper-clad plate is characterized by comprising the following steps:
forming a substrate green compact by using an emulsion of a fluorine-containing material and a ceramic filler material;
pre-sintering the substrate green body to form a composite substrate;
carrying out vacuum sintering on the composite substrate at a preset sintering temperature and a preset hot-pressing pressure to form the composite medium copper-clad plate;
wherein the preset sintering temperature range is 360-400 ℃, and the preset hot pressing pressure range is 0-8 Mpa.
2. The preparation method according to claim 1, wherein the sintering the composite substrate at a preset sintering temperature and a preset hot-pressing pressure to form the composite dielectric copper-clad plate comprises:
covering copper foils with preset thicknesses on the opposite upper surface and the opposite lower surface of the composite substrate;
placing the composite substrate covered with the copper foil into a die or a hot press;
and carrying out vacuum sintering on the composite substrate covered with the copper foil at a preset sintering temperature and a preset hot-pressing pressure to form the composite medium copper-clad plate.
3. The method of manufacturing according to claim 2, wherein the predetermined thickness of the copper foil is 10 μm to 40 μm.
4. The method of claim 3, wherein the predetermined thickness of the copper foil is 18 μm to 35 μm.
5. The method of claim 1, wherein the predetermined sintering temperature is in a range of 370 ℃ to 380 ℃.
6. The method of claim 1, wherein forming a green substrate from the emulsion of the fluorine-containing material and the ceramic filler material comprises:
adding 20-60 parts by weight of the emulsion of the fluorine-containing material into a container for stirring;
respectively adding 1-5 parts by weight of a first ceramic filling material and 40-70 parts by weight of a second ceramic filling material into the fluorine-containing material emulsion to form a mixed emulsion;
performing emulsion breaking treatment on the mixed emulsion;
baking the demulsified mixed emulsion to form a dough-like material;
forming the dough-like material to form the substrate green body;
wherein the fluorine-containing material, the first ceramic filling material and the second ceramic filling material account for 100 parts by weight.
7. The method according to claim 1, wherein the fluorine-containing material is one of polytetrafluoroethylene, hexafluoropropylene, tetrafluoroethylene, and perfluoroalkyl vinyl ether.
8. The method according to claim 1, wherein the ceramic filler is one of silicon dioxide, titanium dioxide, aluminum oxide, aluminum nitride, magnesium oxide, calcium oxide, zinc oxide, and barium oxide.
9. The preparation method of claim 1, wherein the pre-sintering temperature of the substrate green body is in a range of 240 ℃ to 320 ℃, and the pre-sintering time is in a range of 2h to 12 h.
10. A printed wiring board, characterized in that the printed wiring board comprises a composite dielectric copper clad laminate prepared by the preparation method of any one of claims 1 to 9.
CN202010666264.6A 2020-07-09 2020-07-09 Preparation method of composite medium copper-clad plate and printed circuit board Pending CN111775527A (en)

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