CN112721393A - Preparation process of fluorine-containing resin high-frequency flexible copper-clad plate - Google Patents
Preparation process of fluorine-containing resin high-frequency flexible copper-clad plate Download PDFInfo
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- CN112721393A CN112721393A CN202011576200.3A CN202011576200A CN112721393A CN 112721393 A CN112721393 A CN 112721393A CN 202011576200 A CN202011576200 A CN 202011576200A CN 112721393 A CN112721393 A CN 112721393A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
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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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0036—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
- B32B2037/243—Coating
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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
- B32B2255/00—Coating on the layer surface
- B32B2255/06—Coating on the layer surface on metal layer
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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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/204—Di-electric
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
- B32B2307/734—Dimensional stability
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Abstract
The invention relates to the technical field of communication materials, in particular to a preparation process of a fluorine-containing resin high-frequency flexible copper-clad plate, which comprises the following steps: a) providing a copper foil having a matte side, the matte side of the copper foil having at least a high performance fluororesin thereon; b) pressing the foil with the fluorine-containing resin layer outside and the resin layer inside by an equal-pressure-equalizing double-steel belt press to obtain a high-frequency flexible copper-clad plate; wherein the water absorption rate of the high-performance fluorine-containing resin is less than or equal to 0.1 percent. The preparation process of the invention has simple steps, the thermoplastic high polymer and the fluorine-containing resin are added into the fluorine-containing resin emulsion, the peel strength and the dimensional stability of the copper-clad plate are effectively improved on the basis of keeping excellent dielectric property, meanwhile, the traditional wheel type press is replaced by the equal-pressure-equalizing double-steel belt press, the pressing is crossed from a line type layer to a surface type layer, and the pressed flexible copper-clad plate can be continuously produced, does not generate wrinkles and has excellent uniformity and stability.
Description
Technical Field
The invention relates to the technical field of communication materials, in particular to a preparation process of a fluorine-containing resin high-frequency flexible copper-clad plate.
Background
The copper-clad plate is widely applied to the fields of mobile phones, computers, vending machines, communication base stations, satellites, wearable equipment, unmanned vehicles, unmanned aerial vehicles, intelligent robots and the like, and is one of key basic materials in electronic communication and information industries. Under the 5G trend, the requirements on communication frequency and network bandwidth are increased, the performance bottleneck of the traditional copper-clad plate cannot meet the current development direction, the performance of the copper-clad plate is improved, the selection of resin is greatly depended on, and the 5G copper-clad plate provides higher requirements for the resin, such as high heat resistance, low water absorption, low dielectric, good weather resistance, environmental protection and the like.
Fluorine-containing resins represented by polytetrafluoroethylene have excellent dielectric properties due to their own specific chemical structure, chemical corrosion resistance, heat resistance, flame retardancy, small dielectric constant and dielectric loss and small change in high frequency range, and have been widely used as base materials for copper-clad plates since the report of U.S. Pat. No. US 3136680. However, there are some problems to be solved, such as poor rigidity, large thermal expansion coefficient and poor copper foil binding property due to the molecular inertness of the polytetrafluoroethylene resin itself. And the fluorine-containing resin flexible copper-clad plate pressed by the traditional five-axis pressing machine has poor appearance, easy wrinkle on the surface, non-uniform thickness and poor stability.
Disclosure of Invention
Unless otherwise indicated, implied from the context, or customary in the art, all parts and percentages herein are by weight and the testing and characterization methods used are synchronized with the filing date of the present application. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.
The words "preferred", "preferably", "more preferred", and the like, in the present invention, refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention. The sources of components not mentioned in the present invention are all commercially available.
After earnest study to solve the problems, the inventor of the invention finds that the fluorine-containing resin emulsion with a specific structure and a specific composition and other components meet the requirements of dielectric constant and dielectric loss, and the flexible copper-clad plate obtained by combining with a specific preparation process has very good appearance and beneficial dimensional stability.
The invention provides a preparation process of a fluorine-containing resin high-frequency flexible copper-clad plate, which comprises the following steps:
a) providing a copper foil having a matte side, the matte side of the copper foil having at least a high performance fluororesin thereon;
b) pressing the foil with the fluorine-containing resin layer outside and the resin layer inside by an equal-pressure-equalizing double-steel belt press to obtain a high-frequency flexible copper-clad plate; wherein the water absorption rate of the high-performance fluorine-containing resin is less than or equal to 0.1 percent.
The copper foil can be an electrolytic copper foil or a rolled copper foil, and the bonding surface of the copper foil and the high-performance fluorine-containing resin is generally roughened before coating to obtain a roughened surface, wherein the roughening process is performed in order to improve the peeling strength of the high-performance fluorine-containing resin on the coated copper foil; the roughening method may be any method, but the present invention is not limited thereto, and examples thereof include roughening treatment by electrodeposition.
As the finish treatment after roughening, ordinary copper plating or the like is also performed to prevent the removal of the deposit. In the present invention, such post-treatment and finishing treatment are also included, and if necessary, known treatment related to roughening of copper foil is also included, and collectively referred to as roughening.
< high Performance fluorine-containing resin >
The roughened surface is further provided with high-performance fluorine-containing resin, the high-performance fluorine-containing resin can improve the performance of the copper-clad plate, and the electronic equipment applied to the communication field can enable the signal transmission speed to be high-speed and high-functional. The thickness of the roughened surface can be customized and adjusted according to the need, generally the thickness is 5-100 μm, preferably 8-60 μm, and the thicknesses of the copper clad plates with different specifications are different, and the invention is not limited at all.
The high-performance fluorine-containing resin in the invention has preferably water absorption of less than or equal to 0.1 percent, more preferably water absorption of less than or equal to 0.08 percent; in order to obtain a copper-clad plate with less influence on the environment under the condition of ensuring good insulation resistance, the high-performance fluorine-containing resin is preferably used, wherein the dielectric constant of the high-performance fluorine-containing resin at 10GHZ is 1.5-2.5, and the dielectric loss of the high-performance fluorine-containing resin at 10GHZ is 0.0005-0.0015; more preferably, the high-performance fluorine-containing resin has a dielectric constant of 1.5 to 2.5 at 10GHZ and a dielectric loss of 0.0005 to 0.0015 at 10 GHZ.
The high performance fluorine-containing resin on the roughened surface is usually processed by a conventional coating process, and may be applied by dipping, both of which are liquid forms of the special performance resin applied to the roughened surface.
To obtain the high-performance fluorine-containing resin of the invention, the rough surface of the copper foil is preferably coated with fluorine-containing resin emulsion, dried and sintered. The fluorine-containing resin emulsion is obtained by preparing a specific fluorine-containing resin composition into a solution, and a solvent which can be used for preparing the solution is usually N-methyl pyrrolidone; the fluorine-containing resin emulsion preferably comprises at least (a) a thermoplastic polymer having an ether group and an ester group in the main chain and (b) a fluorine-containing resin containing polytetrafluoroethylene.
(a) Thermoplastic polymer having ether group in main chain
The (a) thermoplastic polymer containing an ether group in the main chain can be an aliphatic ether group, wherein the aliphatic ether group is preferably a C2-15 aliphatic or alicyclic group; or an aromatic ether group, an aliphatic-aromatic ether group, or the like. In order to obtain better processing stability, bisphenol A is preferably contained in the main chain in addition to ether groups, and can provide high temperature resistance and mechanical properties to the thermoplastic polymer. In addition, in view of adhesion to the copper clad laminate, the thermoplastic polymer preferably contains an ether group and a bisphenol a type structure in the main chain, and the main chain or the side chain contains an ester group, and the ester group may be an aromatic ester group, an aliphatic or alicyclic ester group, and is preferably an aromatic ester group obtained by reacting an aromatic acid with an aromatic acid.
Through research, the ether group structure in the thermoplastic high polymer suitable for the invention is the molecular structure in formula 1;
formula 1:
preferably, the bisphenol a type structure in the thermoplastic polymer suitable for the present invention is a molecular structure in formula 2;
formula 2:
preferably, the ester group structure in the thermoplastic polymer suitable for the present invention is a molecular structure in formula 3;
formula 3:
wherein R1 to R6 represent the main chain of the prepolymer of the thermoplastic polymer, which are not particularly limited, and are the same or different, and are preferably independently an alkyl chain or an ether group chain.
The alkyl chain is preferably- (CH)2)n-, n is 1 to 10; the ether chain is preferably- (OCH)2)n-or- (OC)6H4)n-；n＝1～10。
Preferably, the thermoplastic polymer is obtained by self-production, and the content of the thermoplastic polymer in the fluorine-containing resin emulsion is preferably 1 to 6%, more preferably 2 to 5%.
In order to obtain the above-mentioned preferred thermoplastic polymer having an ether group in the main chain and a bisphenol A type structure, the main chain or side chain of which contains an ester group, the monomer for its preparation may be selected as desired, for example, the bisphenol A type structural monomer may be provided by a bisphenol A monomer such as diallyl bisphenol A, the ether group-containing monomer may be provided by condensation polymerization of diphenyl ether and formaldehyde, and the ester group-containing monomer may be provided by p-hydroxybenzoic acid and its esters.
The preparation method of the thermoplastic high polymer comprises the following steps:
the materials are added for two times according to the formula proportion: 98 wt% of powder monomer is added in the first stage, 80% of the total volume of the solvent, the stirring speed is 1000-1400 rpm, the material temperature is controlled at 32-70 ℃ on the basis of no liquid splashing, and the viscosity is tested by sampling after stirring for 24 hours; if the viscosity exceeds 10 ten thousand cPs, adding the solvent with the residual volume of 20% in the second stage, and continuously stirring for 24 hours at the stirring speed of 1000-1400 rpm, wherein the material temperature is controlled at 30-40 ℃; if the viscosity is lower than 3 ten thousand cPs, adding the rest 2 wt% of powder monomers in the second stage, and continuing stirring for 24 hours at a stirring speed of 1000-1400 rpm under the condition that the material temperature is controlled at 30-40 ℃. According to an actual formula, the required prepolymer solution of the thermoplastic high polymer can be prepared according to the steps, and according to specific requirements, the solid content of the prepolymer solution can be regulated and controlled between 10 and 30 weight percent; the viscosity was measured by a rotational viscometer.
(b) Fluorine-containing resin containing polytetrafluoroethylene
The component (b) preferably contains at least polytetrafluoroethylene, and may further contain the other fluorine-containing resin, and the preferred fluorine-containing resin includes at least one selected from the group consisting of polytetrafluoroethylene, perfluoropropylperfluorovinylether-polytetrafluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer, and fluorine-containing derivatives thereof.
Preferably, the content of the polytetrafluoroethylene is 20 to 70 wt%, more preferably 20 to 50 wt%, based on the total mass of the fluorine-containing resin; most preferably 50 wt%.
The polytetrafluoroethylene is preferably polytetrafluoroethylene with a pH greater than 8, more preferably a pH greater than 9; in order to obtain better appearance, the pH value of the polytetrafluoroethylene is preferably more than 9, and the density is preferably 1.2-1.6 g/cm3To (c) to (d); more preferably, the polytetrafluoroethylene has a pH of greater than 9 and a density of 1.3 to 1.6g/cm3In the meantime.
In addition, in the research, in order to obtain excellent dimensional stability, the fluorine-containing resin further comprises tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, namely PFA, the AGC production is most preferable in the material of the PFA, the PFA with the brand of EA2000 is adopted, and the main chain of EA2000 is a perfluorinated skeleton, so that the fluorine-containing resin has excellent water and oil repellency.
The polytetrafluoroethylene resin is inert in molecules, CF2 in the molecules is not completely trans-oriented, and a helical twisted chain is formed due to the zigzag shape, while a perfluoro skeleton of PFA interacts with fluorine atoms on the surface of the helical chain to easily form a double helix overlapping structure which is not easy to shrink violently during a thermal curing relaxation movement, so that wrinkles are not easy to generate during sintering.
In the present invention, the component (b) most suitable for the present invention is a mixture of polytetrafluoroethylene and PFA in a ratio of 1:1, and the amount of the component (b) added to the fluorine-containing resin emulsion is preferably 20 to 50 wt%, more preferably 20 to 40 wt%.
Further, additives generally used in general, such as, but not limited to, flame retardants, lubricants, fillers, binders, and the like, may be further compounded without affecting the effect of the present invention.
In order to obtain better hardness and wear resistance, the coating of the high-frequency flexible copper-clad plate also comprises an inorganic filler, wherein the inorganic filler is preferably at least one of silica powder, silica dioxide, silicon carbide, titanium dioxide, calcium oxide and aluminum oxide, wherein the most preferable is silica, and the content of the silica is 5-25%, preferably 5-15% based on the total mass of the fluorine-containing resin emulsion.
< preparation technology of fluorine-containing resin high-frequency flexible copper-clad plate >
When the high-performance fluorine-containing resin is bonded to the rough surface of the copper foil, the rough surface of the copper foil is preferably coated with a fluorine-containing resin emulsion, dried and sintered.
In order to obtain smoothness of the periphery and the middle during coating, a coating machine is preferably adopted, the coating thickness can be adjusted by controlling the gap of a coating head scraper and the pump speed of the coating machine, and the thickness is selected according to the requirement; the coating line speed is preferably 0.5 to 4m/min, more preferably 2 m/min.
The linear velocity of coating should not be too large, and too large linear velocity makes the double helix structure of fluorine-containing resin easily scatter, and orientation reduces in sintering, leads to obvious thermal expansion change, and the phenomenon of inhomogeneous appears in too small linear velocity.
After coating, drying operation is carried out, wherein the drying process can be in an oven or at normal temperature, and is preferably in a constant-temperature oven. The drying temperature is 80-195 ℃, and preferably 100-155 ℃. And (3) sintering after drying, wherein the sintering temperature is 300-360 ℃, and inert gas protection is needed at the moment, and the preferable inert gas comprises but is not limited to nitrogen.
And (3) after sintering, pressing the foil with the fluorine-containing resin layer outside and the resin inside by an equal-pressure-equalizing double-steel belt press to obtain the high-frequency flexible copper-clad plate. The thickness of the fluororesin layer at this time is the sum of the two resin layers.
Has the advantages that: the flexible copper clad laminate obtained by the preparation process has perfect appearance, low dielectric constant and loss, good peel strength and dimensional stability, and can completely meet the requirements of high speed information processing and high frequency signal transmission. In addition, the preparation process steps are simple, the thermoplastic high polymer and the inorganic filler are added into the fluorine-containing resin emulsion, the peel strength and the dimensional stability of the copper-clad plate are effectively improved on the basis of keeping excellent dielectric property, meanwhile, the traditional wheel type press is replaced by the equal-pressure double-steel-belt press, the pressing is crossed from a line type layer to a surface type, and the pressed flexible copper-clad plate can be continuously produced, does not generate wrinkles and has excellent uniformity and stability.
Detailed Description
The present invention is described in detail below with reference to examples, which are provided for the purpose of further illustration only and are not to be construed as limiting the scope of the present invention, and the insubstantial modifications and adaptations thereof by those skilled in the art based on the teachings of the present invention will still fall within the scope of the present invention.
Example 1
The preparation process of the fluorine-containing resin high-frequency flexible copper-clad plate in the embodiment 1 comprises the following steps:
s1, preparing raw materials: 40 parts of PFA (produced by AGC and having a trademark of EA2000), 40 parts of PTFE (produced by Mitsubishi and having a trademark of TN56), 8 parts of thermoplastic polymer (self-made), 20 parts of silicon dioxide and 108 parts of N-methylpyrrolidone;
s2, preparing a fluorine-containing resin emulsion, namely preparing the fluorine-containing resin, a thermoplastic high polymer, an inorganic filler and an organic solvent according to a proportion, and uniformly stirring to obtain the fluorine-containing resin emulsion;
s3, emulsion coating, namely coating a layer of fluorine-containing resin emulsion on the rough surface of the copper foil through a coating machine, controlling the coating thickness by controlling the gap of a coating head scraper and the pump speed, and then drying in a coating machine oven (the setting interval of the oven temperature is 80-195 ℃, and the coating linear speed is 2m/min) to obtain a pretreated single-sided plate;
s4, sintering the resin layer, sintering the pretreated single-sided fluorine-containing resin layer obtained in the step S3 by an IR curing furnace, setting the temperature of a high-temperature section of the IR furnace to be 360 ℃, setting the linear speed to be 0.8m/min, and filling nitrogen in the cabin to protect copper foil to obtain a single-sided flexible copper-clad plate with the thickness of the fluorine-containing resin layer being 25 mu m;
and S5, pressing and forming, namely pressing the copper foil surface of the single-sided flexible copper-clad plate prepared in the step S4 inside the outer resin surface by two pairs of equal-pressure-equalizing double-steel-belt pressing machines to prepare the high-frequency flexible copper-clad plate with the fluorine-containing resin layer of 50 mu m, wherein the parameters of the equal-pressure-equalizing double-steel-belt pressing machines are set as shown in the table 1.
The preparation method of the thermoplastic high polymer comprises the following steps:
the materials are added for two times according to the formula proportion, and the formula is as follows: the mol ratio of 2,2' -diallyl bisphenol A, (4-vinyl) phenyl (4-vinyl) benzoate and diallyl phenyl ether is 1: 1: 2, AIBN (0.1 wt% of monomer) as initiator and NMP as solvent; 98 wt% of powder monomer is added in the first stage, 80% of the total volume of the solvent, the stirring speed is 1000-1400 rpm, the material temperature is controlled at 32-70 ℃ on the basis of no liquid splashing, and the viscosity is tested by sampling after stirring for 24 hours; if the viscosity exceeds 10 ten thousand cPs, adding the solvent with the residual volume of 20% in the second stage, and continuously stirring for 24 hours at the stirring speed of 1000-1400 rpm, wherein the material temperature is controlled at 30-40 ℃; if the viscosity is lower than 3 ten thousand cPs, adding the rest 2 wt% of powder monomers in the second stage, and continuing stirring for 24 hours at a stirring speed of 1000-1400 rpm under the condition that the material temperature is controlled at 30-40 ℃. According to an actual formula, the required prepolymer solution of the thermoplastic high polymer can be prepared according to the steps, and according to specific requirements, the solid content of the prepolymer solution can be regulated and controlled between 10 and 30 weight percent; the viscosity was measured by a rotational viscometer.
TABLE 1
Example 2
The preparation process of the fluorine-containing resin high-frequency flexible copper-clad plate in the embodiment 2 comprises the following steps:
s1, preparing raw materials: 40 parts of PFA (produced by AGC and having the brand number of EA2000), 40 parts of PTFE, 8 parts of thermoplastic polymer (self-made), 10 parts of silicon dioxide and 108 parts of N-methylpyrrolidone;
steps S2, S3, S4, S5 are the same as in example 1.
Comparative example 1
The preparation process of the fluorine-containing resin high-frequency flexible copper-clad plate in the comparative example 1 comprises the following steps:
steps S1, S2, S3, S4 are the same as in example 1;
and S5, pressing and forming, namely pressing the copper foil surface of the single-sided flexible copper clad laminate prepared in the step S4 inside the outer resin surface by two pairs of five-shaft pressing machine, wherein the linear speed of the five-shaft pressing machine is 1.5m/min, the pressure is 15kg, the temperature of a pressing wheel is 340 ℃, and the high-frequency flexible copper clad laminate with the thickness of the fluorine-containing resin layer being 50 microns is prepared.
Evaluation of Performance
And (3) carrying out performance tests on the examples 1 and 2 and the comparative example 1, wherein the test contents comprise the appearance, the dielectric constant, the dielectric loss factor, the peel strength and the dimensional stability of the flexible copper clad laminate.
1. Appearance of the flexible copper clad laminate: visually observed and recorded, and the results are shown in table 2.
2. Dielectric constant and dielectric dissipation factor: the dielectric constant and dielectric dissipation factor at 10GHz of the test specimen were measured according to IPC TM-650, and the results are shown in Table 2.
3. Peel strength: according to the peeling strength of the IPC TM-650 test sample, the copper foil is peeled off a small section and clamped by a clamp, so that the copper foil and the surface of the copper-clad plate material form an angle of 90 degrees, the copper foil is peeled off at a speed of 50mm/min, and the average value of the tensile test is recorded, and the result is shown in Table 2.
4. Coefficient of thermal expansion: dimensional stability was measured according to IPC-TM-6502.2.4 method B and the results are shown in Table 2.
TABLE 2
From the performance test result tables of the flexible copper clad laminates in the embodiments 1 and 2 and the comparative example, it can be seen that the flexible copper clad laminates in the embodiments 1 and 2 have perfect appearance, low dielectric constant and loss, good peel strength and dimensional stability, and various performance indexes superior to those of the flexible copper clad laminate in the comparative example.
Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention. It should therefore be understood that the scope of the present invention is not limited to the specific embodiments described above. It is therefore to be understood that changes and modifications in the detailed description, which may be made by those skilled in the art without departing from the scope and spirit of the present invention, are within the scope of the present invention. Also, the disclosure of the publications cited in this application are also incorporated herein by reference in their entirety.
Claims (10)
1. A preparation process of a fluorine-containing resin high-frequency flexible copper-clad plate is characterized by comprising the following steps:
a) providing a copper foil having a matte side, the matte side of the copper foil having at least a high performance fluororesin thereon;
b) pressing the foil with the fluorine-containing resin layer outside and the resin layer inside by an equal-pressure-equalizing double-steel belt press to obtain a high-frequency flexible copper-clad plate; wherein the water absorption rate of the high-performance fluorine-containing resin is less than or equal to 0.1 percent.
2. The process according to claim 1, wherein the high-performance fluorine-containing resin has a dielectric constant of 1.5 to 2.5 at 10 GHZ.
3. The process according to claim 2, wherein the dielectric loss of the high-performance fluorine-containing resin at 10GHZ is 0.0005-0.0015.
4. The process according to claim 3, wherein the thickness of the high-performance fluorine-containing resin on the rough surface is 5 to 100 μm.
5. The preparation process according to any one of claims 1 to 4, wherein the high-performance fluorine-containing resin on the rough surface is obtained by coating a fluorine-containing resin emulsion on the rough surface of the copper foil, drying and sintering.
6. The process according to claim 5, wherein the fluorine-containing resin emulsion comprises at least (a) a thermoplastic polymer having an ether group in its main chain and (b) a fluorine-containing resin comprising polytetrafluoroethylene.
7. The process of claim 6 wherein the polytetrafluoroethylene has a pH greater than 8.
8. The process according to claim 6, wherein the polytetrafluoroethylene has a density of 1.2 to 1.6g/cm3In the meantime.
9. The preparation process according to claim 6, wherein the coating linear speed is 0.5 to 4m/min, and the drying temperature is 80 to 195 ℃.
10. The preparation process according to claim 6, wherein the sintering temperature is 300-360 ℃, and the inert gas is used for protection during the sintering process.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114670512A (en) * | 2022-04-27 | 2022-06-28 | 中山新高电子材料股份有限公司 | Polytetrafluoroethylene flexible copper-clad plate containing glass fiber cloth and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01221244A (en) * | 1988-03-01 | 1989-09-04 | Mitsubishi Gas Chem Co Inc | Manufacture of copper-clad laminated sheet |
| CN106183337A (en) * | 2016-07-06 | 2016-12-07 | 武汉联恒电子材料有限公司 | Method for improving peel strength of PTFE (polytetrafluoroethylene) copper-clad plate with high dielectric constant |
| CN110181904A (en) * | 2018-12-31 | 2019-08-30 | 曾瑾 | A kind of high frequency is without glue double side flexible copper coated board and preparation method thereof |
| CN111154433A (en) * | 2020-01-14 | 2020-05-15 | 中山新高电子材料股份有限公司 | Fluorine-containing resin mixture and copper-clad plate prepared from same |
-
2020
- 2020-12-28 CN CN202011576200.3A patent/CN112721393A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01221244A (en) * | 1988-03-01 | 1989-09-04 | Mitsubishi Gas Chem Co Inc | Manufacture of copper-clad laminated sheet |
| CN106183337A (en) * | 2016-07-06 | 2016-12-07 | 武汉联恒电子材料有限公司 | Method for improving peel strength of PTFE (polytetrafluoroethylene) copper-clad plate with high dielectric constant |
| CN110181904A (en) * | 2018-12-31 | 2019-08-30 | 曾瑾 | A kind of high frequency is without glue double side flexible copper coated board and preparation method thereof |
| CN111154433A (en) * | 2020-01-14 | 2020-05-15 | 中山新高电子材料股份有限公司 | Fluorine-containing resin mixture and copper-clad plate prepared from same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114670512A (en) * | 2022-04-27 | 2022-06-28 | 中山新高电子材料股份有限公司 | Polytetrafluoroethylene flexible copper-clad plate containing glass fiber cloth and preparation method thereof |
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