CN117560841A - Copper-clad plate, preparation method thereof and electronic equipment - Google Patents
Copper-clad plate, preparation method thereof and electronic equipment Download PDFInfo
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- CN117560841A CN117560841A CN202311444220.9A CN202311444220A CN117560841A CN 117560841 A CN117560841 A CN 117560841A CN 202311444220 A CN202311444220 A CN 202311444220A CN 117560841 A CN117560841 A CN 117560841A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 77
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 73
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 73
- 239000000835 fiber Substances 0.000 claims abstract description 70
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000011889 copper foil Substances 0.000 claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 claims abstract description 37
- 239000010410 layer Substances 0.000 claims description 209
- 239000011347 resin Substances 0.000 claims description 61
- 229920005989 resin Polymers 0.000 claims description 61
- 239000000843 powder Substances 0.000 claims description 47
- 239000003292 glue Substances 0.000 claims description 46
- 239000000919 ceramic Substances 0.000 claims description 43
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 42
- 229910052731 fluorine Inorganic materials 0.000 claims description 42
- 239000011737 fluorine Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 32
- 238000003475 lamination Methods 0.000 claims description 30
- 239000012790 adhesive layer Substances 0.000 claims description 24
- 239000003365 glass fiber Substances 0.000 claims description 24
- 239000002131 composite material Substances 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000839 emulsion Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 16
- 239000012784 inorganic fiber Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 14
- 238000003825 pressing Methods 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 229920001780 ECTFE Polymers 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 229910002113 barium titanate Inorganic materials 0.000 claims description 6
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 6
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052599 brucite Inorganic materials 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 239000008262 pumice Substances 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000010456 wollastonite Substances 0.000 claims description 3
- 229910052882 wollastonite Inorganic materials 0.000 claims description 3
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract description 5
- 230000004907 flux Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 17
- 239000004812 Fluorinated ethylene propylene Substances 0.000 description 12
- 229920009441 perflouroethylene propylene Polymers 0.000 description 12
- 239000004744 fabric Substances 0.000 description 11
- 239000011521 glass Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000004513 sizing Methods 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000003989 dielectric material Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
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- 238000003756 stirring Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- 229920001774 Perfluoroether Polymers 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- XIUFWXXRTPHHDQ-UHFFFAOYSA-N prop-1-ene;1,1,2,2-tetrafluoroethene Chemical group CC=C.FC(F)=C(F)F XIUFWXXRTPHHDQ-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides a copper-clad plate, a preparation method thereof and electronic equipment, which aim to solve the problems that the thickness requirement and low dielectric loss are difficult to meet in the existing ultrathin copper-clad plate manufacture, and the copper-clad plate comprises a dielectric layer and copper foil layers arranged on two sides of the dielectric layer, wherein the dielectric layer comprises a fiber layer, a soluble polytetrafluoroethylene bonding layer and an insulating layer, the insulating layers are arranged on two sides of the fiber layer, and the soluble polytetrafluoroethylene bonding layer is arranged between the insulating layer and the copper foil layers; the dielectric layer adopted by the invention has thin thickness and low dielectric loss, so that the copper-clad plate manufactured by the invention has good bending resistance and lower dielectric loss. According to the copper-clad plate manufacturing method, the manufacturing yield of the copper-clad plate can be improved, and the excellent electrical performance of the copper-clad plate can be realized, so that the manufactured copper-clad plate has high peel strength and excellent dimensional stability; can meet the production requirements of high efficiency, low cost and large flux and improve the production efficiency.
Description
Technical Field
The invention relates to the technical field of copper-clad plate manufacturing, in particular to a copper-clad plate, a preparation method thereof and electronic equipment.
Background
The flexible circuit board has the advantages of ultra-thin, light weight, small volume, good flexibility and the like, is a special functional unit with excellent electronic interconnection, is not only beneficial to realizing smaller size and lighter weight, but also can be bent and folded at will, thereby being suitable for flexible assembly of a three-dimensional space and saving space. Flexible circuit boards are widely used in the modern electronics industry as high-function modules. Particularly, along with the increasing demands of modern society on miniaturization, light weight and integration of electronic products, a flexible circuit board has become one of indispensable components in the manufacture of various high-tech electronic products, and is widely applied to the fields of automobiles, mobile phones, notebooks, digital cameras, medical appliances, liquid crystal displays, aerospace, wearable equipment, high-speed data transmission, intelligent robots, satellite positioning terminals and the like.
With the high frequency and high speed of communication signal transmission and the high integration and ultra-thin miniaturization of terminal electronic devices, low dielectric loss and ultra-high density wiring have become the current trend of flexible circuit boards. In this trend, there is an increasing demand for substrate materials that carry signal transmissions. For example, end-user 5G type antenna products require the use of low dielectric constant, high speed flexible copper clad laminates having a thickness of 0.5mm or less, typically 0.2 mm. The traditional flexible copper-clad plate based on polyimide resin is difficult to meet the requirements of highly integrated and ultra-thin miniaturized circuit board products on the ultra-thin dielectric thickness and extremely low dielectric property of the flexible copper-clad plate. In order to solve the above problems, it is necessary to develop an ultrathin flexible copper-clad plate suitable for high-frequency and high-speed signal transmission.
In addition, in order to pursue better signal integrity at high frequencies and high speeds, it is necessary to use insulating dielectric materials with low dielectric loss in the manufacture of ultra-thin copper clad laminates and to use them with ultra-low profile copper foils. A typical dielectric material with very low dielectric loss is Polytetrafluoroethylene (PTFE), however polytetrafluoroethylene materials have poor adhesion to low roughness profile copper foil. Thus, soluble polytetrafluoroethylene, such as tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer (PFA) and fluorinated ethylene propylene copolymer (FEP), are typically mixed in the PTFE resin matrix to promote adhesion between the dielectric material and the ultra-low roughness profile copper foil. However, the blending method is adopted to achieve ideal bonding strength, and a higher proportion of soluble polytetrafluoroethylene is often required to be added, so that the substrate material with extremely low dielectric loss is not beneficial to obtaining. Therefore, how to overcome the above-mentioned technical problems and drawbacks becomes an important problem to be solved.
Disclosure of Invention
Aiming at the problem that the thickness requirement and dielectric loss are difficult to meet in the existing ultrathin copper-clad plate manufacturing, the invention provides a copper-clad plate, a preparation method thereof and electronic equipment.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a copper-clad plate which comprises a medium layer and copper foil layers arranged on two sides of the medium layer, wherein the medium layer comprises a fiber layer, a soluble polytetrafluoroethylene bonding layer and an insulating layer, the insulating layer is arranged on two sides of the fiber layer, and the soluble polytetrafluoroethylene bonding layer is arranged between the insulating layer and the copper foil layers.
Optionally, the fiber layer adopts a grid structure woven by inorganic fibers, the dielectric loss of the inorganic fibers is less than 0.005@10GHz, and the average diameter of the inorganic fibers is less than 10 mu m.
Optionally, the inorganic fiber comprises glass fiber, the fiber layer is woven by glass fiber, the thickness of the fiber layer is 5-30 μm, and the glass fiber comprises any one or a combination of more of E glass fiber, NE glass fiber, L glass fiber and quartz fiber.
Optionally, the thickness of the insulating layer ranges from 5 μm to 10 μm; the dielectric loss of the insulating layer is less than 0.001@10GHz, and the melting temperature of the insulating layer is more than 300 ℃.
Optionally, the insulating layers at two sides of the fiber layer partially penetrate into the fiber layer and are solidified into a whole, wherein the insulating layer is formed by solidifying fluorine-containing resin glue solution, and the fluorine-containing resin glue solution comprises polytetrafluoroethylene emulsion, ceramic powder, a silane coupling agent, a solvent and a soluble tetrafluoroethylene resin solution; 60-100 parts of polytetrafluoroethylene emulsion, 0-50 parts of ceramic powder, 1-10 parts of silane coupling agent, 40-70 parts of solvent and 0-20 parts of soluble tetrafluoroethylene resin solution.
Optionally, the soluble tetrafluoroethylene resin solution comprises a solution of any one or more of a poly perfluoroethylene propylene, a tetrafluoroethylene-perfluoro alkyl vinyl ether copolymer, an ethylene-tetrafluoroethylene copolymer, polyvinylidene fluoride, poly chlorotrifluoroethylene or an ethylene-chlorotrifluoroethylene copolymer.
Optionally, the solid content of the fluorine-containing resin glue solution is 30-70%, and the particle size of the resin particles in the fluorine-containing resin glue solution is 0.10-0.40 mu m.
Optionally, the ceramic powder includes one or more than two of silicon dioxide, titanium dioxide, aluminum oxide, barium titanate, talcum powder, mica, barium sulfate, calcium carbonate, kaolin, diatomite, pumice powder, bentonite, brucite, wollastonite powder and lithopone glass fiber, wherein the ceramic powder is preferably any one or a mixture of at least two of silicon dioxide, titanium dioxide and barium titanate.
Optionally, the particle size of the ceramic powder is 50nm-50 μm; the dielectric loss of the ceramic powder is less than 0.001@10GHz.
Optionally, the thickness of the soluble polytetrafluoroethylene adhesive layer ranges from 1 μm to 10 μm; the dielectric loss of the soluble polytetrafluoroethylene adhesive layer is less than 0.001@10GHz, and the melting temperature of the soluble polytetrafluoroethylene adhesive layer is more than 250 ℃.
Optionally, the soluble polytetrafluoroethylene adhesive layer is formed by drying soluble polytetrafluoroethylene glue solution; the soluble polytetrafluoroethylene glue solution comprises one or more of the compositions of polytetrafluoroethylene propylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, polyvinylidene fluoride, polytrifluoroethylene or ethylene-chlorotrifluoroethylene copolymer.
Optionally, the copper foil layer is selected from one of a rolled copper foil and an electrolytic copper foil.
Optionally, the thickness of the copper foil layer is 1-18 μm, and the roughness Rz value of one side of the copper foil layer close to the soluble polytetrafluoroethylene bonding layer is 0.2-2 μm.
The invention also provides a manufacturing method of the copper-clad plate, which comprises the following steps:
preparing an insulating layer:
soaking the fiber layer in fluorine-containing resin glue solution; solidifying the fluorine-containing resin glue solution to obtain insulating layers on two sides of the fiber layer;
preparing a dielectric layer:
applying a soluble polytetrafluoroethylene glue solution on the outer side of the insulating layer to obtain a dielectric layer;
and (3) preparation of a copper-clad plate:
and respectively paving the copper foil layers on the outer sides of the dielectric layers, and pressing to obtain the copper-clad plate.
Optionally, in the operation of "pressing", it includes: the temperature range of the pressing preheating section in the pressing process is 100-150 ℃; the temperature of the lamination composite section is set to be 250-380 ℃, and the temperature of the lamination cooling section is set to be 100-250 ℃; the lamination composite pressure is set to be 1-8 MPa, and the lamination linear speed is set to be 0.5-5 m/min.
The invention further provides electronic equipment, which comprises the copper-clad plate.
According to the copper-clad plate provided by the invention, the thickness of the dielectric layer prepared by adopting the fiber layer, the soluble polytetrafluoroethylene bonding layer and the insulating layer is thin, and the dielectric loss is low, so that the prepared copper-clad plate has good bending resistance and lower dielectric loss. According to the copper-clad plate manufacturing method, the manufacturing yield of the copper-clad plate can be improved, and the excellent electrical performance of the copper-clad plate can be realized, so that the manufactured copper-clad plate has high peel strength and excellent dimensional stability; can meet the production requirements of high efficiency, low cost and large flux and improve the production efficiency.
Drawings
Fig. 1 is a schematic structural view of a copper-clad plate according to an embodiment of the present invention;
reference numerals in the drawings of the specification are as follows:
1-a fibrous layer; 2-an insulating layer; 3-a soluble polytetrafluoroethylene adhesive layer; 4 copper foil layer.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be understood that the present invention may be embodied in various forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. In the drawings, the dimensions and relative dimensions of layers and regions may be exaggerated for the same elements throughout for clarity.
It will be understood that when an element or layer is referred to as being "on" …, "" adjacent to "…," "connected to" or "coupled to" another element or layer, it can be directly on, adjacent to, connected to or coupled to the other element or layer, or intervening elements or layers may be present. In contrast, when an element is referred to as being "directly on" …, "" directly adjacent to "…," "directly connected to" or "directly coupled to" another element or layer, there are no intervening elements or layers present. It will be understood that, although the terms first, second, third, etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another element, component, region, layer or section. Thus, a first element, component, region, layer or section discussed below could be termed a second element, component, region, layer or section without departing from the teachings of the present invention.
Spatially relative terms, such as "under …," "under …," "below," "under …," "above …," "above," and the like, may be used herein for ease of description to describe one element or feature's relationship to another element or feature as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use and operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements or features described as "under" or "beneath" other elements would then be oriented "on" the other elements or features. Thus, the exemplary terms "under …" and "under …" may include both an upper and a lower orientation. The device may be otherwise oriented (rotated 90 degrees or other orientations) and the spatially relative descriptors used herein interpreted accordingly.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. As used herein, the term "and/or" includes any and all combinations of the associated listed items.
The invention provides a copper-clad plate on one hand, which comprises a copper foil layer 4, wherein a medium layer is arranged on two sides of the medium layer, the medium layer comprises a fiber layer 1, a soluble polytetrafluoroethylene bonding layer 3 and an insulating layer 2, the insulating layer 2 is arranged on two sides of the fiber layer 1, and the soluble polytetrafluoroethylene bonding layer 3 is positioned between the insulating layer 2 and the copper foil layer 4.
Specifically, the thickness of the dielectric layer is 10-50 mu m, and the dielectric loss is less than 0.003@10GHz.
In a preferred embodiment, the dielectric layer has a thickness of 20-40 μm; for example, any one or any two of the point values 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm, 30 μm, 31 μm, 12 μm, 33 μm, 34 μm, 35 μm, 36 μm, 37 μm, 38 μm, 39 μm, 40 μm, 41 μm, 42 μm, 43 μm, 44 μm, 45 μm, 46 μm, 47 μm, 48 μm, 49 μm or 50 μm.
In a preferred embodiment, the dielectric layer has a dielectric loss of < 0.001@10GHz.
The dielectric layer prepared by the fiber layer 1, the soluble polytetrafluoroethylene adhesive layer 3 and the insulating layer 2 is thin in thickness and low in dielectric loss, so that the copper-clad plate prepared by the method has good bending resistance and low dielectric loss. According to the copper-clad plate manufacturing method, the manufacturing yield of the copper-clad plate can be improved, and the excellent electrical performance of the copper-clad plate can be realized, so that the manufactured copper-clad plate has high peel strength and excellent dimensional stability; can meet the production requirements of high efficiency, low cost and large flux and improve the production efficiency.
In one embodiment, the fiber layer 1 is a mesh-like structure woven by inorganic fibers, the dielectric loss of the inorganic fibers is less than 0.005@10GHz, and the average diameter of the inorganic fibers is less than 10 mu m.
The fiber layer 1 is a fabric woven from inorganic fibers by crisscross weaving of warp and weft. The composite material has the properties of insulation, heat insulation, corrosion resistance, incombustibility, high temperature resistance, high strength, small moisture absorption, softness, high tensile strength and the like; the fibrous layer 1 may be used as a reinforcing material in a copper-clad plate.
In a preferred embodiment, the dielectric loss of the inorganic fiber is < 0.003@10GHz.
In a preferred embodiment, the inorganic fibers have an average diameter of < 5 μm.
When the fiber layer 1 is applied to a copper-clad plate, the prior art is to glue the fiber layer 1, desize and smolder the fiber layer to form a bonding sheet, and the bonding sheet is coated with copper foil and the like to prepare the copper-clad plate.
In this application, through be in the both sides of fibrous layer 1 symmetry in proper order be equipped with insulating layer 2 soluble polytetrafluoroethylene adhesive layer 3 with copper foil layer 4 makes the copper-clad plate.
The fiber layer 1 adopted by the invention has a small thickness and low dielectric loss, so that the copper-clad plate manufactured by the fiber layer has good bending resistance and lower dielectric loss, and the excellent electrical performance of the copper-clad plate is realized.
In one embodiment, the inorganic fibers include glass fibers, the fiber layer 1 is woven from glass fibers, the thickness of the fiber layer 1 ranges from 5 μm to 30 μm, and the glass fibers include any one or a combination of more than one of E glass fibers, NE glass fibers, L glass fibers and quartz fibers.
The glass fiber is also called glass fiber, is an inorganic nonmetallic material with excellent performance, and comprises the components of silicon dioxide, aluminum oxide, calcium oxide, boron oxide, magnesium oxide, sodium oxide and the like. The fiber layer 1 is manufactured by taking glass as a raw material through the processes of high-temperature melting, wire drawing, winding, weaving and the like, and various products are finally formed. The diameter of the glass fiber filaments ranges from a few micrometers to twenty-few micrometers, which is equivalent to 1/20-1/5 of one hair filament, and each bundle of fiber filaments consists of hundreds or even thousands of filaments.
In a preferred embodiment, the thickness of the fibrous layer 1 is in the range of 10-20 μm; for example, any one or a range of values consisting of any two of 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm or 30 μm.
In one embodiment, the thickness of the insulating layer 2 is in the range of 5-10 μm; the dielectric loss of the insulating layer 2 is less than 0.001@10GHz, and the melting temperature of the insulating layer 2 is more than 300 ℃.
In a preferred embodiment, the thickness of the insulating layer 2 is in the range of 6-8 μm; for example any point value or range of values consisting of any two point values of 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm.
In a preferred embodiment, the dielectric loss of the insulating layer 2 is < 0.0005@10GHz.
In a preferred embodiment, the melting temperature of the insulating layer 2 is > 310 ℃.
In one embodiment, the insulating layers at two sides of the fiber layer are partially permeated into the fiber layer and are solidified into a whole, the insulating layer is formed by solidifying fluorine-containing resin glue solution, and the fluorine-containing resin glue solution comprises polytetrafluoroethylene emulsion, ceramic powder, a silane coupling agent, a solvent and a soluble tetrafluoroethylene resin solution; 60-100 parts of polytetrafluoroethylene emulsion, 0-50 parts of ceramic powder, 1-10 parts of silane coupling agent, 40-70 parts of solvent and 0-20 parts of soluble tetrafluoroethylene resin solution.
In preferred embodiments, 70 parts to 90 parts of the polytetrafluoroethylene emulsion, for example, 60 parts, 65 parts, 70 parts, 72 parts, 75 parts, 80 parts, 83 parts, 85 parts, 88 parts, 90 parts, 92 parts, 95 parts, 97 parts, or 100 parts, or a range of values consisting of any one or any two of the point values.
In a preferred embodiment, the ceramic powder is 10 parts to 40 parts, for example, 0 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, or 50 parts, or any point value or any two point value range.
In preferred embodiments, the silane coupling agent is 3 parts to 8 parts, for example 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts, or any two point value or range of values.
In preferred embodiments, the solvent is 40 parts to 60 parts, for example 40 parts, 42 parts, 44 parts, 46 parts, 48 parts, 50 parts, 52 parts, 54 parts, 56 parts, 58 parts, 60 parts, 62 parts, 64 parts, 66 parts, 68 parts, or 70 parts, or any two point value ranges.
Specifically, the solvent is selected from any one or more of deionized water or ethanol.
In a preferred embodiment, the soluble tetrafluoroethylene resin solution is 0 parts to 20 parts, for example, 0 parts, 3 parts, 5 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts or 20 parts, or any two of the point values.
The introduced ceramic powder can reduce the problems of wrinkling, warping and even cracking of the process medium material caused by uneven sizing to a certain extent.
In one embodiment, the soluble tetrafluoroethylene resin solution comprises a solution of any one or more of a polyperfluoroethylene propylene, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, an ethylene-tetrafluoroethylene copolymer, polyvinylidene fluoride, polytrifluoroethylene, or an ethylene-chlorotrifluoroethylene copolymer.
The soluble tetrafluoroethylene resin is a high molecular compound which can be dissolved under the action of a certain solvent and has fluorine atoms in molecules, and the resin has certain polarity, so that the resin has certain adhesiveness unlike insoluble Polytetrafluoroethylene (PTFE).
In one embodiment, the solid content of the fluorine-containing resin glue solution is 30-70%, and the particle size of the latex particles in the fluorine-containing resin glue solution is 0.10-0.40 μm.
In a preferred embodiment, the fluorine-containing resin glue solution has a solids content of 40-60%, for example 30 parts, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58%, 60%, 62%, 64%, 66%, 68% or 70% of any point value or any range of two point values.
In a preferred embodiment, the latex particles in the fluorine-containing resin dope have a particle diameter of 0.20 to 0.30 μm, for example, any one or a range of values of 0.10 μm, 0.11 μm, 0.12 μm, 0.13 μm, 0.14 μm, 0.15 μm, 0.16 μm, 0.17 μm, 0.18 μm, 0.19 μm, 0.20 μm, 0.21 μm, 0.22 μm, 0.23 μm, 0.24 μm, 0.25 μm, 0.26 μm, 0.27 μm, 0.28 μm, 0.29 μm, 0.30 μm, 0.31 μm, 0.32 μm, 0.33 μm, 0.34 μm, 0.35 μm, 0.36 μm, 0.37 μm, 0.38 μm, 0.39 μm or 0.40 μm.
In one embodiment, the ceramic powder includes one or more than two of silicon dioxide, titanium dioxide, aluminum oxide, barium titanate, talcum powder, mica, barium sulfate, calcium carbonate, kaolin, diatomite, pumice powder, bentonite, brucite, wollastonite powder and lithopone glass fiber, wherein any one or a mixture of at least two of silicon dioxide, titanium dioxide and barium titanate is preferred.
According to the invention, on one hand, ceramic powder is introduced and mixed in slurry, and the materials are piled up in a coating mode, so that not only is uniform and extremely thin insulating base materials easy to regulate and control, but also the dielectric properties of dielectric materials are easy to regulate and control by the variety proportion of the ceramic powder, and the problem that the extremely thin fiber layer 1 is subjected to non-uniformity of tension due to fine glass fibers can be avoided, and the problems of serious warping, uneven appearance, poor dimensional stability and the like of the prepared ultrathin copper-clad plate are caused in the processes of dipping, sizing and laminating.
Specifically, the weight ratio of the ceramic powder in the fluorine-containing resin glue solution is 30-70 wt%. On the premise of meeting the electric property of the dielectric layer, the proportion of the ceramic powder can be properly adjusted according to the specific application requirement.
In a preferred embodiment, the ceramic powder is preferably spherical or elliptical particles.
In one embodiment, the ceramic powder has a particle size of 50nm to 50 μm; the dielectric loss of the ceramic powder is less than 0.001@10GHz.
In a preferred embodiment, the particle size of the ceramic powder is in the range of 1 μm to 30 μm, for example any one or two of the values 50nm, 500nm, 5 μm or 50 μm.
In a preferred embodiment, the ceramic powder has a dielectric loss of < 0.0005@10GHz.
In one embodiment, the thickness of the soluble polytetrafluoroethylene adhesive layer 3 is in the range of 1-10 μm; the dielectric loss of the soluble polytetrafluoroethylene adhesive layer 3 is less than 0.001@10GHz, and the melting temperature of the soluble polytetrafluoroethylene adhesive layer 3 is more than 250 ℃.
In a preferred embodiment, the thickness of the soluble polytetrafluoroethylene adhesive layer 3 is in the range of 3-8 μm, for example, any one or any two point values of 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm.
In a preferred embodiment, the dielectric loss of the soluble polytetrafluoroethylene adhesive layer 3 is < 0.0005@10GHz.
In a preferred embodiment, the soluble polytetrafluoroethylene adhesive layer 3 has a melting temperature > 290 ℃.
In one embodiment, the soluble polytetrafluoroethylene adhesive layer 3 is formed by drying soluble polytetrafluoroethylene glue; the soluble polytetrafluoroethylene glue solution comprises one or more of the compositions of polytetrafluoroethylene propylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, polyvinylidene fluoride, polytrifluoroethylene or ethylene-chlorotrifluoroethylene copolymer.
In one embodiment, the copper foil layer 4 is selected from one of a rolled copper foil and an electrolytic copper foil.
In one embodiment, the thickness of the copper foil layer 4 is 1-18 μm, and the roughness Rz value of the side of the copper foil layer 4 near the soluble polytetrafluoroethylene adhesive layer 3 is 0.2-2 μm.
In a preferred embodiment, the copper foil layer 4 has a thickness of 5-15 μm, for example any one or a range of values of any two of 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm or 18 μm.
In a preferred embodiment, the roughness Rz value of the copper foil layer 4 on the side close to the soluble polytetrafluoroethylene adhesive layer 3 is 0.5 to 1.5 μm, for example, any one point value or any two point values of 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1.0 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.7 μm, 1.8 μm, 1.9 μm or 2.0 μm.
In one embodiment, the surface roughness Rz value of the copper foil layer 4 on the side far away from the soluble polytetrafluoroethylene adhesive layer 3 is 0.5-1 μm.
In a preferred embodiment, the surface roughness Rz value of the copper foil layer 4 on the side away from the soluble polytetrafluoroethylene adhesive layer 3 is 0.8 μm, for example, a range value composed of any one point value or any two point values of 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm or 1.0 μm.
The invention also provides a manufacturing method of the copper-clad plate, which comprises the following steps:
preparing an insulating layer:
soaking the fiber layer in fluorine-containing resin glue solution; solidifying the fluorine-containing resin glue solution to obtain insulating layers on two sides of the fiber layer;
preparing a dielectric layer:
applying a soluble polytetrafluoroethylene glue solution on the outer side of the insulating layer to obtain a dielectric layer;
and (3) preparation of a copper-clad plate:
and respectively paving the copper foil layers on the outer sides of the dielectric layers, and pressing to obtain the copper-clad plate.
Specifically, the preparation method also comprises the steps of preparing the fluorine-containing resin glue solution:
mixing polytetrafluoroethylene emulsion, ceramic powder, a silane coupling agent, a solvent and a soluble tetrafluoroethylene resin solution to prepare fluorine-containing resin glue solution;
in the process of preparing the insulating layer 2, it includes:
Immersing the fiber layer 1 in fluorine-containing resin glue solution; sizing the two sides of the fiber layer 1 at a speed of 1-5m/min, drying the impregnated fiber layer 1 at a temperature of 150-200 ℃ for 5-30min, continuously baking and sintering for 5-30min at a temperature of 250-360 ℃ and repeating the process for 2-8 times to obtain an insulating layer 2 formed by curing fluorine-containing resin glue solution;
specifically, in step 2, the coating-drying-sintering process is adopted, different fiber layers 1, ceramic powder and slurry formulations can be selected for various combinations, and then different coating parameters are matched, so that the requirements of the dielectric layer on thickness specification, dielectric property, mechanical property, heat conducting property and the like are realized, flexible regulation and control are realized, and a dielectric layer with uniform thickness and compactness is formed.
In the preparation process of the dielectric layer, the preparation method comprises the following steps:
specifically, the fiber layer 1 with the insulating layer 2 adhered on two sides is soaked in soluble polytetrafluoroethylene glue solution; and (3) rubberizing the two sides of the fiber layer 1 at the speed of 1-6m/min, drying the impregnated fiber layer 1 at the temperature of 150-200 ℃ for 5-30min, continuously baking and sintering for 5-30min at the temperature of 300-320 ℃ and repeating the process for 2-8 times to obtain the medium layer.
Further comprises: the soluble polytetrafluoroethylene adhesive layer 3 is manufactured by adopting the coating-drying-sintering process, so that the shrinkage and cracking problems caused by direct stacking and compounding of membranous materials can be avoided, the thin soluble polytetrafluoroethylene adhesive layer 3 with controllable thickness is formed by deposition on two sides of a medium layer of a core layer, and the excellent dielectric property of the medium layer material can be maintained.
In the preparation process of the copper-clad plate, the method comprises the following steps:
specifically, the copper foil layers 4 are respectively laid on the outer sides of the dielectric layers, and are continuously pressed in a roll-to-roll manner by using metal rollers or metal belt equipment, so that the copper-clad plate is manufactured.
Further comprises: respectively paving copper foils with the same size as the composite dielectric layer obtained in the step 3 on the outer side of the dielectric layer material by using reel equipment to obtain a laminated body; after copper foils are laminated on the two sides of the composite dielectric material, a metal roller or metal belt device is used for carrying out roll-to-roll continuous lamination, so that the copper-clad plate is manufactured.
By adopting the roll-to-roll process, the traditional roll-to-roll lamination mode which is time-consuming and labor-consuming is avoided, the rolled dielectric layer and copper foil are directly processed and produced through the arrangement and the manufacturing and forming of the multilayer functionalized films, the production mode of the low-loss electronic base material is changed from the traditional semi-automatic production to the full-automatic production, the production efficiency and the yield of the high-end high-performance electronic base material are greatly improved, and the production cost is greatly reduced. Meanwhile, compared with copper-clad plate products manufactured under different batches of different press equipment, the products manufactured under the same equipment and same parameter conditions have better consistency and better dimensional stability.
The hot metal roll and hot metal belt equipment are typically five-axis roll presses, and the hot metal belt equipment is typically a crawler-type continuous high-temperature press, and the difference between the two is that one is line pressure and the other is surface pressure.
The sheet-to-sheet refers to materials which are sheet-shaped, all materials are stacked in a sequential stacking mode to form a laminated body, and hot-pressing composite molding is carried out by a high-temperature hot press
The roll-to-roll refers to that materials are in a roll shape, the materials are piled up in a mode of unreeling a plurality of rolls at the same time and reeling a roll, and a laminated body is subjected to hot-pressing composite molding through the same heating component
According to the invention, the requirement of continuous production can be met by adopting the lamination process, the manufacturing of the light and thin flexible copper-clad plate is easy to realize, and the method is more suitable for manufacturing the copper-clad plate with large flux, high efficiency, high yield and low cost; the ultrathin flexible copper-clad plate manufactured by the invention has the advantages of thin medium thickness, good bending resistance, high peeling strength and good dimensional stability, and is suitable for high-frequency and high-speed signal transmission application.
In one embodiment, in the "press fit" operation, it includes: the temperature range of the pressing preheating section in the pressing process is 100-150 ℃; the temperature of the lamination composite section is set to be 250-380 ℃, and the temperature of the lamination cooling section is set to be 100-250 ℃; the lamination composite pressure is set to be 1-8 MPa, and the lamination linear speed is set to be 0.5-5 m/min.
In a preferred embodiment, the temperature of the nip pre-heating stage during the nip is in the range of 110 to 140 ℃, more preferably 120 to 130 ℃.
In a preferred embodiment, the lamination stage temperature is set at 300 to 380 ℃, more preferably 340 to 370 ℃.
In a preferred embodiment, the temperature of the nip pre-heating stage during the nip is in the range of 110 to 220 ℃, more preferably 150 to 170 ℃.
Specifically, the preheating section, the composite section and the cooling section can all be provided with multi-section gradient temperatures. For example, a preheating section, the first section temperature being 100 ℃, the second section being 250 ℃; for example, the composite section, the second section is 340 ℃, the second section is 370 ℃, the third section is 360 ℃, and the fourth section is 310 ℃; for example, the cooling section, the first section is 250 ℃, and the second section is 150 ℃.
In a preferred embodiment, the lamination composite pressure is set to 3 to 7MPa, more preferably 4 to 6MPa; in a preferred embodiment, the pressing line speed is set to 0.8 to 3m/min, more preferably 1 to 2m/min.
The lamination temperature, lamination pressure, and lamination line speed may be appropriately adjusted within the above ranges according to actual needs, and any combination thereof may be appropriately performed within the above ranges.
While the above description has been given of one embodiment of the present invention, the present invention is not limited to the above embodiment, and various modifications may be made to the present invention without departing from the gist of the present invention.
The invention further provides electronic equipment, which comprises the copper-clad plate.
The circuit board with the copper-clad plate vegetation can meet the use requirements of related electronic equipment.
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The materials involved in the examples and comparative examples are as follows:
spherical SiO 2 Ceramic powder: su zhou brocade art, SE0050, D50 3.3 μm;
spherical TiO 2 Ceramic powder: shandong national porcelain, QST series, D50 of 10 μm;
silane coupling agent: shandong Sidaceae, F823;
PTFE emulsion: the dupont's composition,PTFE DISP30, solid content 60%;
PFA emulsion: the dupont's composition,PFA D335D, solid content 60%;
FEP emulsion: the dupont's composition,FEP D121, 54% solids;
copper foil: ruxembourg, BF-ANP, rz:1.5 μm,18 μm;
copper foil: triplex copper foil, TQ-M4-VSP, rz:0.6 μm,18 μm;
Fiber layer: south asia electrons, BC3000, 1017, 14 μm;
fiber layer: macro and science, GD-BC1700, 1017, 11 μm;
Detailed Description
The following description is of the preferred embodiments of the invention and is not intended to limit the scope of the invention.
Example 1
Preparing a mixed solvent of 18 parts of deionized water and 80:20 parts by volume of ethanol, and adding 40 parts of spherical SiO into the mixed solvent 2 Ceramic powder (Suzhou brocade art) and stirring at room temperature for 3 hours to ensure uniformity. Subsequently, 2 parts of a silane coupling agent (F823, shandong silica family) was further added, and the mixed system was heated to 60℃and stirred for 6 hours. Subsequently, 100 parts of PTFE emulsion (dupont,PTFE DISP 30), stirring for 3 hours at room temperature to prepare the fluorine-containing resin glue solution.
And (3) dipping electronic grade glass cloth (Nanya, BC3000, 1017, 14 mu m) in the fluorine-containing resin glue solution at normal temperature, sizing the two sides of the electronic grade glass cloth at the speed of 0.5m/min, baking the fiber layer blank in a high-temperature oven at 150 ℃ for 30min, and then continuously baking at 360 ℃ for 30min to completely solidify the resin glue solution dipped on the fiber layer blank to obtain the shaped impregnated fiber layer. This procedure was repeated 4 times to obtain an insulating layer of a fiber-impregnated layer having a total thickness of 20 μm, which was obtained by curing the fluorine-containing resin dope.
Further, the impregnated fiber layer with insulating layers adhered on both sides was subjected to a PFA emulsion having a solid content of 60 parts (dupont,PFA D335D) container tank. And (3) sizing the two sides of the fiber layer at a speed of 0.5m/min, baking the impregnated fiber layer at a temperature of 150 ℃ for 30min, and then continuously baking and sintering at a temperature of 320 ℃ for 5-30min. This procedure was repeated 4 times to obtain a dielectric layer core board with a total thickness of 30 μm with a double surface coated with 5 μm PFA.
2 copper foils (BF-ANP, rz:1.5 μm) were laid on the upper and lower outer sides of the above-prepared dielectric layers, and "roll-to-roll" continuous lamination was performed by a metal tape apparatus. In the pressing process, the temperature of the preheating section is set to 120 ℃; the temperature of the composite section is set to 370 ℃, and the temperature of the cooling section is set to 120 ℃; the composite pressure is set to 5MPa, and the lamination linear speed is set to 2m/min, so that the copper-clad plate is manufactured.
Example 2
The difference from example 1 is that the thickness of the PFA double coated on both sides of the insulating layer of the impregnated fiber layer was 8 μm.
Example 3
The difference from example 1 is that the thickness of the PFA double coated on both sides of the insulating layer of the impregnated fiber layer was 3 μm.
Example 4
The difference compared with example 1 is that the spherical SiO in the fluorine-containing resin glue solution 2 The ceramic powder (Suzhou brocade art) is added in an amount of 20 parts.
Example 5
The difference compared with example 1 is that the spherical SiO in the fluorine-containing resin glue solution 2 The ceramic powder (Suzhou brocade art) is added in an amount of 60 parts.
Example 6
In comparison with example 1, the difference is that 40 parts of spherical TiO was added to the fluorine-containing resin dope 2 Ceramic powder (Sushandong national porcelain, QST series).
Example 7
In comparison with example 1, the difference is that 30 parts of spherical SiO was added to the fluorine-containing resin glue solution 2 Ceramic powder (QST series of Sushandong national porcelain) and 10 parts of spherical SiO 2 Ceramic powder (su zhou jin art).
Example 8
The difference from example 1 is that the electronic grade glass cloth was a glass cloth of low Dk (macro and science and technology, GD-BC1700, 1017, 11 μm).
Example 9
In contrast to example 1, the electronic grade glass cloth was low Dk glass cloth (macro and science, GD-BC1700, 1017, 11 μm), the fiber layer was directly immersed in PTFE emulsion (dupont,PTFE DISP 30), an impregnated fibrous layer insulating layer containing no ceramic powder having a thickness of 25 μm was obtained by impregnation. In addition, the copper foil of the copper clad laminate was a three-well copper foil (TQ-M4-VSP, rz:0.6 μm).
Example 10
Compared with the embodiment 9, the difference is that the press line speed is 1.5m/min in the manufacture of the copper-clad plate.
Example 11
Compared with the embodiment 10, the difference is that the lamination composite temperature in the production of the copper-clad plate is 380 ℃.
Example 12
Compared with the embodiment 10, the difference is that the lamination composite temperature in the manufacture of the copper-clad plate is 360 ℃.
Example 13
Compared with the embodiment 10, the difference is that the press line speed is 1.0m/min in the manufacture of the copper-clad plate.
Example 14
Compared with the embodiment 13, the difference is that the lamination pressure is 3MPa in the manufacture of the copper-clad plate.
Example 15
In comparison with example 14, the difference is that, during the production of the dielectric layer, the impregnated fiber layer with the insulating layer adhered on both sides is subjected to an FEP emulsion with a solid content of 54 parts (dupont,FEP D121 A dielectric layer core plate with a total thickness of 30 μm coated with 5 μm FEP on both surfaces was obtained.
Example 16
Compared with the embodiment 14, the difference is that in the process of manufacturing the dielectric layer, the impregnated fiber layer with the insulating layers adhered on both sides is subjected to PFA with a solid content of 60 parts (DuPont,PFA D335D) and 54 parts of FEP emulsion (DuPont,/-DuPont)>FEP D121) was mixed in a 1:1 mix emulsion tank to give a dielectric layer core board with a double surface coated with 5 μm PFA/FEP with a total thickness of 30 μm.
Comparative example 1
In comparison with example 1, 100 parts of PTFE emulsion with a solids content of 60 parts was added to the vessel during the preparation of the fluorine-containing resin dope (dupont,PTFE DISP 30) and 20 parts of PFA (DuPont,/-A) with a solids content of 60 parts>PFA D335D), stirring for 3 hours at room temperature to prepare the fluorine-containing resin glue solution.
And (3) dipping electronic grade glass cloth (Nanya, BC3000, 1017, 14 mu m) in the fluorine-containing resin glue solution at normal temperature, sizing the two sides of the electronic grade glass cloth at the speed of 0.5m/min, baking the fiber layer blank in a high-temperature oven at 150 ℃ for 30min, and then continuously baking at 360 ℃ for 30min to completely solidify the resin glue solution dipped on the fiber layer blank to obtain the shaped impregnated fiber layer. This procedure was repeated 6 times to obtain an impregnated fiber layer having a total thickness of 30 μm which was obtained by curing the fluorine-containing resin dope.
2 copper foils (BF-ANP, rz:1.5 μm) were laid on the upper and lower outer sides of the above-prepared dielectric layers, and "roll-to-roll" continuous lamination was performed by a metal tape apparatus. In the pressing process, the temperature of the preheating section is set to 120 ℃; the temperature of the composite section is set to 370 ℃, and the temperature of the cooling section is set to 120 ℃; the composite pressure is set to 5MPa, and the lamination linear speed is set to 2m/min, so that the copper-clad plate is manufactured.
Comparative example 2
In comparison with example 9, 100 parts of PTFE emulsion with a solids content of 60 parts was added to the vessel during the preparation of the fluorine-containing resin dope (dupont,PTFE DISP 30) and 20 parts of PFA (DuPont,/-A) with a solids content of 60 parts>PFA D335D), stirring for 3 hours at room temperature to prepare the fluorine-containing resin glue solution.
And (3) dipping electronic grade glass cloth (macro and science and technology, GD-BC1700, 1017, 11 mu m) in the fluorine-containing resin glue solution at normal temperature, sizing the two sides of the electronic grade glass cloth at the speed of 0.5m/min, baking the fiber layer blank in a high-temperature oven at 150 ℃ for 30min, and then continuously baking at 360 ℃ for 30min to completely solidify the resin glue solution dipped on the fiber layer blank to obtain the shaped impregnated fiber layer. This procedure was repeated 6 times to obtain a ceramic powder-free impregnated fiber layer having a total thickness of 30 μm, which was obtained by curing a fluorine-containing resin dope.
2 copper foils (TQ-M4-VSP, 0.6 μm) were laid on the upper and lower outer sides of the above-prepared dielectric layers, and "roll-to-roll" continuous lamination was performed using a metal tape apparatus. In the pressing process, the temperature of the preheating section is set to 120 ℃; the temperature of the composite section is set to 370 ℃, and the temperature of the cooling section is set to 120 ℃; the composite pressure is set to 5MPa, and the lamination linear speed is set to 2m/min, so that the copper-clad plate is manufactured.
Comparative example 3
In comparison with comparative example 2, except that 40 parts of PFA having a solid content of 60 parts was added in the preparation of the fluorine-containing resin dope (dupont,PFA D335D)。
comparative example 4
In comparison with comparative example 2, the difference is that 40 parts of FEP emulsion with 54 parts of solid content (dupont,FEP D121)。
the copper clad laminates provided in examples 1 to 16 and comparative examples 1 to 4 were tested for dielectric properties and peel strength as follows:
(1) Dielectric properties: adopting SPDR (Split Post Dielectric Resonator) method to test dielectric constant Dk and dielectric loss Df of ceramic reinforced fluorine film and copper-clad plate, wherein the test condition is A state, and the frequency is 10GHz;
(2) Peel strength: the IPC-TM-650.2.5.6.2A method is adopted to test the copper-clad plate;
(3) CTE: the IPC-TM-650.2.4.24c method is adopted to test the copper-clad plate;
the performance test data for the corresponding copper clad laminate is summarized in table 1.
Table 1 test data for examples 1-16 and comparative examples 1-4
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As can be seen from comparative examples 1-3, properly increasing the PFA content of the coating helps to increase the peel strength, however, it leads to an increase in the dielectric loss of the material. Comparative examples 1, 4, 5 show that properly increasing the content of ceramic powder helps to reduce dielectric loss and CTE of the material while hardly affecting the peel strength of the material. As can be seen from comparative examples 1, 6 and 7, the different ceramic powders can have similar effects on the properties of the materials, and the addition of ceramic powders with multiple particle sizes can obtain better material properties. Comparative examples 8 and 9 show that the use of copper foil with lower roughness affects the peel strength of the material to some extent, but the PFA coating thickness of 5 μm can still ensure sufficient peel strength of the material. Comparative examples 10-12 demonstrate that appropriate increases in the lamination temperature can increase the peel strength of the material with a slight improvement in the CTE of the material. As can be seen from comparative examples 10-14, the appropriate increase in bonding compounding temperature, decrease in bonding wire speed, and increase in bonding strength all increase the peel strength of the material to some extent, while the CTE of the material is slightly improved. As can be seen from comparative examples 9, 15 and 16, the use of soluble polytetrafluoroethylene of different types and combinations allows good adhesion strength to be achieved.
As is clear from comparative examples 1 to 4, it is necessary to increase the content of soluble polytetrafluoroethylene in the mixed fluororesin paste to obtain a higher peel strength, however, the dielectric loss of the material is increased. In addition, the addition of ceramic powders helps to reduce the CTE of the material.
The invention has the advantages of simple operation process, mild preparation condition, low production cost, easy batch and large-scale production, good industrial production foundation and wide application prospect. The prepared ultrathin flexible high-frequency copper-clad plate has low thermal expansion coefficient, excellent dielectric property and high copper foil peeling strength, and can meet the requirements of the high-frequency communication field on various comprehensive properties of substrate materials.
The embodiments of the present invention have been described in detail with reference to the drawings, but the present invention is not limited to the above embodiments, and various modifications may be made within the knowledge of those skilled in the art without departing from the spirit of the present invention. These are all non-inventive modifications which are intended to be protected by the patent laws within the scope of the appended claims.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (16)
1. The utility model provides a copper-clad plate which characterized in that: the novel copper foil comprises a medium layer and copper foil layers arranged on two sides of the medium layer, wherein the medium layer comprises a fiber layer, a soluble polytetrafluoroethylene bonding layer and an insulating layer, the insulating layer is arranged on two sides of the fiber layer, and the soluble polytetrafluoroethylene bonding layer is arranged between the insulating layer and the copper foil layers.
2. The copper-clad plate according to claim 1, wherein: the fiber layer adopts a grid-shaped structure woven by inorganic fibers, the dielectric loss of the inorganic fibers is less than 0.005@10GHz, and the average diameter of the inorganic fibers is less than 10 mu m.
3. The copper-clad plate according to claim 2, wherein: the inorganic fibers comprise glass fibers, the thickness of the fiber layer is in the range of 5-30 mu m, and the glass fibers comprise any one or more of E glass fibers, NE glass fibers, L glass fibers and quartz fibers.
4. The copper-clad plate according to claim 1, wherein: the thickness of the insulating layer ranges from 5 mu m to 10 mu m; the dielectric loss of the insulating layer is less than 0.001@10GHz, and the melting temperature of the insulating layer is more than 300 ℃.
5. The copper-clad plate according to claim 1, wherein: the insulation layers at two sides of the fiber layer are partially penetrated into the fiber layer and are solidified into a whole, the insulation layer is formed by solidifying fluorine-containing resin glue solution, and the fluorine-containing resin glue solution comprises polytetrafluoroethylene emulsion, ceramic powder, silane coupling agent, solvent and soluble tetrafluoroethylene resin solution; 60-100 parts of polytetrafluoroethylene emulsion, 0-50 parts of ceramic powder, 1-10 parts of silane coupling agent, 10-50 parts of solvent and 0-20 parts of soluble tetrafluoroethylene resin solution.
6. The copper-clad plate according to claim 5, wherein: the soluble tetrafluoroethylene resin solution comprises one or more of a solution of poly (perfluoroethylene propylene), a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, an ethylene-tetrafluoroethylene copolymer, polyvinylidene fluoride, poly (chlorotrifluoroethylene) or an ethylene-chlorotrifluoroethylene copolymer.
7. The copper-clad plate according to claim 5, wherein: the solid content of the fluorine-containing resin glue solution is 30-70%, and the particle size of the resin particles in the fluorine-containing resin glue solution is 0.10-0.40 mu m.
8. The copper-clad plate according to claim 5, wherein: the ceramic powder comprises one or more than two of silicon dioxide, titanium dioxide, aluminum oxide, barium titanate, talcum powder, mica, barium sulfate, calcium carbonate, kaolin, diatomite, pumice powder, bentonite, brucite, wollastonite powder and lithopone glass fiber, wherein the ceramic powder is preferably any one or a mixture of at least two of silicon dioxide, titanium dioxide and barium titanate.
9. The copper-clad plate according to claim 8, wherein: the particle size of the ceramic powder is 50nm-50 mu m; the dielectric loss of the ceramic powder is less than 0.001@10GHz.
10. The copper-clad plate according to claim 1, wherein: the thickness of the soluble polytetrafluoroethylene adhesive layer ranges from 1 μm to 10 μm; the dielectric loss of the soluble polytetrafluoroethylene adhesive layer is less than 0.001@10GHz, and the melting temperature of the soluble polytetrafluoroethylene adhesive layer is more than 250 ℃.
11. The copper-clad plate according to claim 10, wherein: the soluble polytetrafluoroethylene adhesive layer is formed by drying soluble polytetrafluoroethylene adhesive solution; the soluble polytetrafluoroethylene glue solution comprises one or more of the compositions of polytetrafluoroethylene propylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, polyvinylidene fluoride, polytrifluoroethylene or ethylene-chlorotrifluoroethylene copolymer.
12. The copper-clad plate according to claim 1, wherein: the copper foil layer is selected from one of rolled copper foil and electrolytic copper foil.
13. The copper-clad plate according to claim 12, wherein: the thickness of the copper foil layer is 1-18 mu m, and the roughness Rz value of one side of the copper foil layer close to the soluble polytetrafluoroethylene bonding layer is 0.2-2 mu m.
14. The method for manufacturing a copper-clad plate according to any one of claims 1 to 13, wherein: the method comprises the following steps:
Preparing an insulating layer:
soaking the fiber layer in fluorine-containing resin glue solution; solidifying the fluorine-containing resin glue solution to obtain insulating layers on two sides of the fiber layer;
preparing a dielectric layer:
applying a soluble polytetrafluoroethylene glue solution on the outer side of the insulating layer to obtain a dielectric layer;
and (3) preparation of a copper-clad plate:
and respectively paving the copper foil layers on the outer sides of the dielectric layers, and pressing to obtain the copper-clad plate.
15. The method for manufacturing a copper-clad plate according to claim 14, wherein: in the operation of "press fit", it includes: the temperature range of the pressing preheating section in the pressing process is 100-150 ℃; the temperature of the lamination composite section is set to be 250-380 ℃, and the temperature of the lamination cooling section is set to be 100-250 ℃; the lamination composite pressure is set to be 1-8 MPa, and the lamination linear speed is set to be 0.5-5 m/min.
16. An electronic device, characterized in that: a copper-clad plate comprising any one of claims 1 to 13.
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