CN113665207A - Method for efficiently reducing thermal expansion coefficient of polytetrafluoroethylene copper-clad plate - Google Patents
Method for efficiently reducing thermal expansion coefficient of polytetrafluoroethylene copper-clad plate Download PDFInfo
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- CN113665207A CN113665207A CN202110957271.6A CN202110957271A CN113665207A CN 113665207 A CN113665207 A CN 113665207A CN 202110957271 A CN202110957271 A CN 202110957271A CN 113665207 A CN113665207 A CN 113665207A
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- polytetrafluoroethylene
- copper
- clad plate
- tungstate
- expansion coefficient
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- -1 polytetrafluoroethylene Polymers 0.000 title claims abstract description 99
- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 89
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 50
- 229920005989 resin Polymers 0.000 claims abstract description 42
- 239000011347 resin Substances 0.000 claims abstract description 42
- 239000000919 ceramic Substances 0.000 claims abstract description 40
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000465 moulding Methods 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 239000011889 copper foil Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 239000004744 fabric Substances 0.000 claims description 12
- 238000004026 adhesive bonding Methods 0.000 claims description 11
- 239000003365 glass fiber Substances 0.000 claims description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229910002113 barium titanate Inorganic materials 0.000 claims description 7
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 7
- 238000003490 calendering Methods 0.000 claims description 7
- 239000007822 coupling agent Substances 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000003921 oil Substances 0.000 claims description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- 150000002910 rare earth metals Chemical class 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 238000010345 tape casting Methods 0.000 claims description 7
- 239000002562 thickening agent Substances 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- OJLGWNFZMTVNCX-UHFFFAOYSA-N dioxido(dioxo)tungsten;zirconium(4+) Chemical compound [Zr+4].[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O OJLGWNFZMTVNCX-UHFFFAOYSA-N 0.000 description 25
- 229910052802 copper Inorganic materials 0.000 description 14
- 239000010949 copper Substances 0.000 description 14
- 239000011888 foil Substances 0.000 description 10
- 238000009702 powder compression Methods 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2258—Oxides; Hydroxides of metals of tungsten
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
Abstract
The invention discloses a method for efficiently reducing the thermal expansion coefficient of a polytetrafluoroethylene copper-clad plate, which relates to the technical field of copper-clad plates and adopts the technical scheme that: the method comprises the following specific steps: s1, primarily mixing electronic-grade tungstate with ceramic powder; s2, mixing the raw materials with polytetrafluoroethylene resin; s3, obtaining a double-sided copper foil of the bonding sheet by using a polytetrafluoroethylene copper-clad plate production process; s4, high-temperature vacuum hot-press molding, the method for efficiently reducing the thermal expansion coefficient of the polytetrafluoroethylene copper-clad plate has the beneficial effects that: by controlling the proportion of the tungstate to be 5 percent or more, the thermal expansion coefficient can be efficiently reduced, other basic electrical properties of the prepared copper-clad plate are not affected, the polytetrafluoroethylene copper-clad plate with low expansion coefficient and qualified performance can be obtained, the tungstate preparation process is further improved and optimized in the future, the tungstate cost is reduced, and the method is suitable for the industry of electronic copper-clad plates.
Description
Technical Field
The invention relates to the technical field of copper-clad plates, in particular to a method for efficiently reducing the thermal expansion coefficient of a polytetrafluoroethylene copper-clad plate.
Background
At present, the mainstream copper clad plates in the market comprise a polytetrafluoroethylene copper clad plate, a hydrocarbon copper clad plate, a polyphenyl ether copper clad plate, an epoxy resin copper clad plate and the like, the resin and ceramic powder are filled in a conventional preparation mode, the thermal expansion coefficient is reduced by using high-density resin and controlling the filler ratio of the ceramic powder or the form hardness of the ceramic powder, and other characteristics, for example, the polytetrafluoroethylene copper clad plate has large thermal expansion coefficient, soft texture, small bending strength, poor mechanical property and other defects, the thermal expansion coefficient is reduced by filling in methods of using the high-density resin and controlling the form hardness of the ceramic powder by using the high filler ratio, and the thermal expansion coefficient is difficult to further reduce, so that a method capable of effectively and efficiently reducing the thermal expansion coefficient is lacked.
Therefore, it is necessary to invent a method for efficiently reducing the thermal expansion coefficient of the polytetrafluoroethylene copper-clad plate.
Disclosure of Invention
Therefore, the invention provides a method for efficiently reducing the thermal expansion coefficient of a polytetrafluoroethylene copper-clad plate, which is characterized in that electronic-grade tungstate is selected to be primarily mixed with ceramic powder, wherein the electronic-grade tungstate is one or a mixture of more of zirconium tungstate, hafnium tungstate and scandium tungstate, the zirconium tungstate, the hafnium tungstate and the scandium tungstate are negative thermal expansion materials with excellent performance, the negative thermal expansion materials have negative thermal expansion performance within a temperature range of 0.3-1050.0K, and the electronic copper-clad plate can be suitable for the electronic copper-clad plate through refining and purification and has stable electrical performance so as to solve the problem that the thermal expansion coefficient is difficult to further reduce.
In order to achieve the above purpose, the invention provides the following technical scheme: a method for efficiently reducing the thermal expansion coefficient of a polytetrafluoroethylene copper-clad plate comprises the following specific steps:
s1, primarily mixing electronic-grade tungstate with ceramic powder;
s2, mixing the raw materials with polytetrafluoroethylene resin;
s3, obtaining a double-sided copper foil of the bonding sheet by using a polytetrafluoroethylene copper-clad plate production process;
and S4, high-temperature vacuum hot-press molding.
In S1, the electronic-grade tungstate is ZrW2O8Zirconium tungstate and HfW2O8(hafnium tungstate), Sc2W3O12(scandium tungstate) and the like. The purity is more than or equal to 99.0 percent, the grain diameter is 0.5-25 mu m, preferably, zirconium tungstate is used, and the proportion of zirconium tungstate is 3-35 percent;
the ceramic powder is electronic grade ceramic powder with particle size of 0.5-25 μm, sphericity degree higher than 90%, and comprises one or more of aluminum oxide, magnesium oxide, silicon dioxide, titanium dioxide, strontium titanate, barium titanate, and rare earth, wherein the ceramic powder accounts for 30-75%.
Preferably, in S2, the raw material of tetrafluoroethylene resin is a concentrated solution of polytetrafluoroethylene, a dispersion resin of polytetrafluoroethylene, and a fine suspension powder of polytetrafluoroethylene, the initial mixture in S1 is mixed with the raw material of tetrafluoroethylene resin and stirred at a slow speed of 300 rpm for 3 hours, and a coupling agent, a dispersant, and a thickener are added to control the viscosity and the solution consistency, so that the mixed solution is uniformly suspended.
Preferably, in S3, the process for producing the ptfe copper-clad plate includes dipping the electronic grade fiberglass cloth in the ptfe concentrated solution for sizing or tape casting, and molding the fluororesin powder by compression molding or extrusion calendering.
Preferably, in S4, the high-temperature vacuum hot press molding is performed by laminating the bonding sheet obtained in S3 with copper foil on both sides, and then hot press molding is performed by using an oil press under vacuum conditions at a material temperature of 380 ℃ to 410 ℃ and a pressure of 2 Mpa to 20 Mpa.
The invention has the beneficial effects that:
by controlling the proportion of 5 percent or more of zirconium tungstate, the thermal expansion coefficient can be efficiently reduced, other basic electrical properties of the prepared copper-clad plate are not affected, the polytetrafluoroethylene copper-clad plate with low expansion coefficient and qualified performance can be obtained, the process for preparing zirconium tungstate is further improved and optimized in the future, the cost of zirconium tungstate is reduced, and the method is suitable for the industry of electronic copper-clad plates.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
Example 1:
the invention provides a method for efficiently reducing the thermal expansion coefficient of a polytetrafluoroethylene copper-clad plate, which comprises the following specific steps:
s1, 5% of electronic-grade tungstate is selected to be primarily mixed with 55% of ceramic powder, the electronic-grade tungstate is zirconium tungstate, the purity is larger than or equal to 99.0%, the particle size is 0.5 mu m, the ceramic powder is electronic-grade ceramic powder, the particle size is 0.5 mu m, the sphericity is higher than 90% when the powder is spherical, and the electronic-grade tungstate is mixed with one or more of alumina, magnesia, silica, titanium dioxide, strontium titanate, barium titanate, rare earth and the like, wherein the thermal expansion coefficient is reduced by mainly controlling the proportion of the zirconium tungstate and the ceramic powder, and the zirconium tungstate plays a main role;
s2, mixing the materials with a polytetrafluoroethylene resin raw material, wherein the polytetrafluoroethylene resin raw material refers to polytetrafluoroethylene concentrated solution, polytetrafluoroethylene dispersion resin and polytetrafluoroethylene suspension fine powder, the initial mixture in the S1 is mixed with the polytetrafluoroethylene resin raw material and stirred at a low speed of 300 revolutions per minute for 3 hours, a coupling agent, a dispersing agent and a thickening agent are added to control viscosity and solution consistency so that the mixed solution is uniformly suspended, the polytetrafluoroethylene resin raw material is preferably polytetrafluoroethylene concentrated solution, and the solid content of the resin is 59%;
s3, obtaining a bonding sheet double-sided copper clad foil by using a polytetrafluoroethylene copper clad plate production process, wherein the polytetrafluoroethylene copper clad plate production process is to use an electronic grade glass fiber cloth to dip polytetrafluoroethylene concentrated solution for gluing or tape casting forming, fluororesin powder compression molding or extrusion calendaring forming, most preferably to dip polytetrafluoroethylene concentrated solution by using an electronic glass fiber cloth 1080 for gluing once or for multiple times, obtaining the bonding sheet by low temperature 180 ℃/5min, medium temperature 240 ℃/5min and high temperature 355 ℃ sintering for 5min, and the double-sided copper clad foil is most preferably 35um reverse electrolytic copper foil;
and S4, carrying out high-temperature vacuum hot press molding, wherein the high-temperature vacuum hot press molding is carried out by overlapping the bonding sheet obtained in the S3 with copper foil on both sides, and then carrying out hot press molding by using an oil press under the vacuum condition at the material temperature of 385 ℃ and the pressure of 6.5 Mpa.
Example 2:
the invention provides a method for efficiently reducing the thermal expansion coefficient of a polytetrafluoroethylene copper-clad plate, which comprises the following specific steps:
s1, primarily mixing 8% of electronic-grade tungstate with 52% of ceramic powder, wherein the electronic-grade tungstate is zirconium tungstate, the purity is greater than or equal to 99.0%, the particle size is 3 mu m, the ceramic powder is electronic-grade ceramic powder, the particle size is 3 mu m, the sphericity is higher than 90% when the ceramic powder is spherical, and the electronic-grade tungstate is mixed with one or more of alumina, magnesia, silica, titanium dioxide, strontium titanate, barium titanate, rare earth and the like, wherein the proportion of the zirconium tungstate and the ceramic powder is mainly controlled to reduce the thermal expansion coefficient, and the zirconium tungstate plays a main role;
s2, mixing the materials with a polytetrafluoroethylene resin raw material, wherein the polytetrafluoroethylene resin raw material refers to polytetrafluoroethylene concentrated solution, polytetrafluoroethylene dispersion resin and polytetrafluoroethylene suspension fine powder, the initial mixture in the S1 is mixed with the polytetrafluoroethylene resin raw material and stirred at a low speed of 300 revolutions per minute for 3 hours, a coupling agent, a dispersing agent and a thickening agent are added to control viscosity and solution consistency so that the mixed solution is uniformly suspended, the polytetrafluoroethylene resin raw material is preferably polytetrafluoroethylene concentrated solution, and the solid content of the resin is 59%;
s3, obtaining a bonding sheet double-sided copper clad foil by using a polytetrafluoroethylene copper clad plate production process, wherein the polytetrafluoroethylene copper clad plate production process is to use an electronic grade glass fiber cloth to dip polytetrafluoroethylene concentrated solution for gluing or tape casting forming, fluororesin powder compression molding or extrusion calendaring forming, most preferably to dip polytetrafluoroethylene concentrated solution by using an electronic glass fiber cloth 1080 for gluing once or for multiple times, obtaining the bonding sheet by low temperature 180 ℃/5min, medium temperature 240 ℃/5min and high temperature 355 ℃ sintering for 5min, and the double-sided copper clad foil is most preferably 35um reverse electrolytic copper foil;
and S4, carrying out high-temperature vacuum hot press molding, wherein the high-temperature vacuum hot press molding is carried out by overlapping the bonding sheet obtained in the S3 with copper foil on both sides, and then carrying out hot press molding by using an oil press under the vacuum condition at the material temperature of 385 ℃ and the pressure of 6.5 Mpa.
Example 3:
the invention provides a method for efficiently reducing the thermal expansion coefficient of a polytetrafluoroethylene copper-clad plate, which comprises the following specific steps:
s1, primarily mixing 10% of electronic-grade tungstate with 50% of ceramic powder, wherein the electronic-grade tungstate is zirconium tungstate, the purity is greater than or equal to 99.0%, the particle size is 6 microns, the ceramic powder is electronic-grade ceramic powder, the particle size is 8 microns, the sphericity is higher than 90% when the ceramic powder is spherical, and the electronic-grade tungstate comprises one or more of aluminum oxide, magnesium oxide, silicon dioxide, titanium dioxide, strontium titanate, barium titanate, rare earth and the like, wherein the proportion of the zirconium tungstate and the ceramic powder is mainly controlled to reduce the thermal expansion coefficient, and the zirconium tungstate plays a main role;
s2, mixing the materials with a polytetrafluoroethylene resin raw material, wherein the polytetrafluoroethylene resin raw material refers to polytetrafluoroethylene concentrated solution, polytetrafluoroethylene dispersion resin and polytetrafluoroethylene suspension fine powder, the initial mixture in the S1 is mixed with the polytetrafluoroethylene resin raw material and stirred at a low speed of 300 revolutions per minute for 3 hours, a coupling agent, a dispersing agent and a thickening agent are added to control viscosity and solution consistency so that the mixed solution is uniformly suspended, the polytetrafluoroethylene resin raw material is preferably polytetrafluoroethylene concentrated solution, and the solid content of the resin is 59%;
s3, obtaining a bonding sheet double-sided copper clad foil by using a polytetrafluoroethylene copper clad plate production process, wherein the polytetrafluoroethylene copper clad plate production process is to use an electronic grade glass fiber cloth to dip polytetrafluoroethylene concentrated solution for gluing or tape casting forming, fluororesin powder compression molding or extrusion calendaring forming, most preferably to dip polytetrafluoroethylene concentrated solution by using an electronic glass fiber cloth 1080 for gluing once or for multiple times, obtaining the bonding sheet by low temperature 180 ℃/5min, medium temperature 240 ℃/5min and high temperature 355 ℃ sintering for 5min, and the double-sided copper clad foil is most preferably 35um reverse electrolytic copper foil;
and S4, carrying out high-temperature vacuum hot press molding, wherein the high-temperature vacuum hot press molding is carried out by overlapping the bonding sheet obtained in the S3 with copper foil on both sides, and then carrying out hot press molding by using an oil press under the vacuum condition at the material temperature of 385 ℃ and the pressure of 6.5 Mpa.
Example 4:
the invention provides a method for efficiently reducing the thermal expansion coefficient of a polytetrafluoroethylene copper-clad plate, which comprises the following specific steps:
s1, primarily mixing 15% of electronic-grade tungstate with 45% of ceramic powder, wherein the electronic-grade tungstate is zirconium tungstate, the purity is greater than or equal to 99.0%, the particle size is 15 microns, the ceramic powder is electronic-grade ceramic powder, the particle size is 15 microns, the sphericity is higher than 90% when the ceramic powder is spherical, and the ceramic powder comprises one or more of aluminum oxide, magnesium oxide, silicon dioxide, titanium dioxide, strontium titanate, barium titanate, rare earth and the like, and is mainly used for controlling the proportion of the zirconium tungstate and the ceramic powder to reduce the thermal expansion coefficient and playing a main role in zirconium tungstate;
s2, mixing the materials with a polytetrafluoroethylene resin raw material, wherein the polytetrafluoroethylene resin raw material refers to polytetrafluoroethylene concentrated solution, polytetrafluoroethylene dispersion resin and polytetrafluoroethylene suspension fine powder, the initial mixture in the S1 is mixed with the polytetrafluoroethylene resin raw material and stirred at a low speed of 300 revolutions per minute for 3 hours, a coupling agent, a dispersing agent and a thickening agent are added to control viscosity and solution consistency so that the mixed solution is uniformly suspended, the polytetrafluoroethylene resin raw material is preferably polytetrafluoroethylene concentrated solution, and the solid content of the resin is 59%;
s3, obtaining a bonding sheet double-sided copper clad foil by using a polytetrafluoroethylene copper clad plate production process, wherein the polytetrafluoroethylene copper clad plate production process is to use an electronic grade glass fiber cloth to dip polytetrafluoroethylene concentrated solution for gluing or tape casting forming, fluororesin powder compression molding or extrusion calendaring forming, most preferably to dip polytetrafluoroethylene concentrated solution by using an electronic glass fiber cloth 1080 for gluing once or for multiple times, obtaining the bonding sheet by low temperature 180 ℃/5min, medium temperature 240 ℃/5min and high temperature 355 ℃ sintering for 5min, and the double-sided copper clad foil is most preferably 35um reverse electrolytic copper foil;
and S4, carrying out high-temperature vacuum hot press molding, wherein the high-temperature vacuum hot press molding is carried out by overlapping the bonding sheet obtained in the S3 with copper foil on both sides, and then carrying out hot press molding by using an oil press under the vacuum condition at the material temperature of 385 ℃ and the pressure of 6.5 Mpa.
Example 5:
the invention provides a method for efficiently reducing the thermal expansion coefficient of a polytetrafluoroethylene copper-clad plate, which comprises the following specific steps:
s1, primarily mixing 0% of electronic-grade tungstate with 60% of ceramic powder, wherein the electronic-grade tungstate is zirconium tungstate, the purity is greater than or equal to 99.0%, the particle size is 25 micrometers, the ceramic powder is electronic-grade ceramic powder, the particle size is 25 micrometers, the sphericity is higher than 90% when the ceramic powder is spherical, and the ceramic powder comprises one or more of aluminum oxide, magnesium oxide, silicon dioxide, titanium dioxide, strontium titanate, barium titanate, rare earth and the like, and is mainly used for controlling the proportion of the zirconium tungstate and the ceramic powder to reduce the thermal expansion coefficient and the zirconium tungstate plays a main role;
s2, mixing the materials with a polytetrafluoroethylene resin raw material, wherein the polytetrafluoroethylene resin raw material refers to polytetrafluoroethylene concentrated solution, polytetrafluoroethylene dispersion resin and polytetrafluoroethylene suspension fine powder, the initial mixture in the S1 is mixed with the polytetrafluoroethylene resin raw material and stirred at a low speed of 300 revolutions per minute for 3 hours, a coupling agent, a dispersing agent and a thickening agent are added to control viscosity and solution consistency so that the mixed solution is uniformly suspended, the polytetrafluoroethylene resin raw material is preferably polytetrafluoroethylene concentrated solution, and the solid content of the resin is 59%;
s3, obtaining a bonding sheet double-sided copper clad foil by using a polytetrafluoroethylene copper clad plate production process, wherein the polytetrafluoroethylene copper clad plate production process is to use an electronic grade glass fiber cloth to dip polytetrafluoroethylene concentrated solution for gluing or tape casting forming, fluororesin powder compression molding or extrusion calendaring forming, most preferably to dip polytetrafluoroethylene concentrated solution by using an electronic glass fiber cloth 1080 for gluing once or for multiple times, obtaining the bonding sheet by low temperature 180 ℃/5min, medium temperature 240 ℃/5min and high temperature 355 ℃ sintering for 5min, and the double-sided copper clad foil is most preferably 35um reverse electrolytic copper foil;
and S4, carrying out high-temperature vacuum hot press molding, wherein the high-temperature vacuum hot press molding is carried out by overlapping the bonding sheet obtained in the S3 with copper foil on both sides, and then carrying out hot press molding by using an oil press under the vacuum condition at the material temperature of 385 ℃ and the pressure of 6.5 Mpa.
Comparing the polytetrafluoroethylene copper-clad plates prepared in the above examples 1-5 to obtain the following data:
each proportion combination meter (watch one)
Watch 1
Proportioning property (watch two)
Watch two
According to the first table and the second table, the thermal expansion coefficient can be efficiently reduced by controlling the proportion of 5 percent of zirconium tungstate and above, other basic electrical properties of the prepared copper-clad plate are not influenced, the polytetrafluoroethylene copper-clad plate with low expansion coefficient and qualified performance can be obtained, the method for efficiently reducing the thermal expansion coefficient of the polytetrafluoroethylene copper-clad plate is feasible, the process for preparing the zirconium tungstate is further improved and optimized in the future, the cost of the zirconium tungstate is reduced, and the method is suitable for the industry of electronic copper-clad plates.
The above description is only a preferred embodiment of the present invention, and any person skilled in the art may modify the present invention or modify it into an equivalent technical solution by using the technical solution described above. Therefore, any simple modifications or equivalent substitutions made in accordance with the technical solution of the present invention are within the scope of the claims of the present invention.
Claims (5)
1. A method for efficiently reducing the thermal expansion coefficient of a polytetrafluoroethylene copper-clad plate is characterized by comprising the following steps: the method comprises the following specific steps:
s1, primarily mixing electronic-grade tungstate with ceramic powder;
s2, mixing the raw materials with polytetrafluoroethylene resin;
s3, obtaining a double-sided copper foil of the bonding sheet by using a polytetrafluoroethylene copper-clad plate production process;
and S4, high-temperature vacuum hot-press molding.
2. The method for efficiently reducing the thermal expansion coefficient of the polytetrafluoroethylene copper-clad plate according to claim 1, wherein the method comprises the following steps: in S1, the electronic-grade tungstate is ZrW2O8Zirconium tungstate and HfW2O8(hafnium tungstate), Sc2W3O12(scandium tungstate) and the like, wherein the purity is more than or equal to 99.0%, the particle size is 0.5-25 mu m, and the proportion of tungstate is 3-35%;
the ceramic powder is electronic grade ceramic powder with particle size of 0.5-25 μm, sphericity degree higher than 90%, and comprises one or more of aluminum oxide, magnesium oxide, silicon dioxide, titanium dioxide, strontium titanate, barium titanate, and rare earth, wherein the ceramic powder accounts for 30-75%.
3. The method for efficiently reducing the thermal expansion coefficient of the polytetrafluoroethylene copper-clad plate according to claim 1, wherein the method comprises the following steps: in the S2, the tetrafluoroethylene resin raw material refers to polytetrafluoroethylene concentrated solution, polytetrafluoroethylene dispersion resin and polytetrafluoroethylene suspension fine powder, the initial mixture in the S1 is mixed with the tetrafluoroethylene resin raw material and stirred at a low speed of 300 revolutions per minute for 3 hours, and a coupling agent, a dispersing agent and a thickening agent are added to control the viscosity and the solution consistency so as to enable the mixed solution to be uniformly suspended.
4. The method for efficiently reducing the thermal expansion coefficient of the polytetrafluoroethylene copper-clad plate according to claim 1, wherein the method comprises the following steps: in S3, the production process of the polytetrafluoroethylene copper-clad plate is to dip electronic-grade glass fiber cloth into polytetrafluoroethylene concentrated solution for gluing or tape casting, and to perform compression molding or extrusion calendaring molding on fluororesin powder.
5. The method for efficiently reducing the thermal expansion coefficient of the polytetrafluoroethylene copper-clad plate according to claim 1, wherein the method comprises the following steps: and in the S4, the high-temperature vacuum hot press molding is carried out by overlapping the bonding sheet obtained in the S3, covering copper foil on two sides of the bonding sheet, and then using an oil press to carry out hot press molding under the vacuum condition, wherein the material temperature is 380-410 ℃ and the pressure is 2-20 Mpa.
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| CN109648935A (en) * | 2018-12-24 | 2019-04-19 | 嘉兴佳利电子有限公司 | A kind of preparation process of PTFE Ceramic Composite high-frequency copper-clad plate |
| CN112111144A (en) * | 2020-09-28 | 2020-12-22 | 常州中英科技股份有限公司 | Low-expansion crosslinkable hydrocarbon polymer composition, prepreg prepared from low-expansion crosslinkable hydrocarbon polymer composition and thermosetting copper-clad plate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109648935A (en) * | 2018-12-24 | 2019-04-19 | 嘉兴佳利电子有限公司 | A kind of preparation process of PTFE Ceramic Composite high-frequency copper-clad plate |
| CN112111144A (en) * | 2020-09-28 | 2020-12-22 | 常州中英科技股份有限公司 | Low-expansion crosslinkable hydrocarbon polymer composition, prepreg prepared from low-expansion crosslinkable hydrocarbon polymer composition and thermosetting copper-clad plate |
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