CN111251676A - High-thermal-conductivity modified polytetrafluoroethylene copper-clad plate and preparation method thereof - Google Patents
High-thermal-conductivity modified polytetrafluoroethylene copper-clad plate and preparation method thereof Download PDFInfo
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- CN111251676A CN111251676A CN202010114174.6A CN202010114174A CN111251676A CN 111251676 A CN111251676 A CN 111251676A CN 202010114174 A CN202010114174 A CN 202010114174A CN 111251676 A CN111251676 A CN 111251676A
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- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 99
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 99
- -1 polytetrafluoroethylene Polymers 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000003292 glue Substances 0.000 claims abstract description 71
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-Tryptophan Natural products C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 claims abstract description 58
- 239000004744 fabric Substances 0.000 claims abstract description 55
- 239000003365 glass fiber Substances 0.000 claims abstract description 54
- 229960004799 tryptophan Drugs 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 238000007731 hot pressing Methods 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 14
- 239000011889 copper foil Substances 0.000 claims abstract description 13
- 238000010030 laminating Methods 0.000 claims abstract description 10
- 239000000839 emulsion Substances 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 33
- 238000007598 dipping method Methods 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 26
- 239000006185 dispersion Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- 239000012188 paraffin wax Substances 0.000 claims description 8
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 8
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 8
- 150000003333 secondary alcohols Chemical class 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 12
- 238000007605 air drying Methods 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 230000032798 delamination Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000002707 L-tryptophyl group Chemical group [H]C1=C([H])C([H])=C2C(C([C@](N([H])[H])(C(=O)[*])[H])([H])[H])=C([H])N([H])C2=C1[H] 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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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
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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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
-
- 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
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/08—Impregnating
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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
- B32B38/16—Drying; Softening; Cleaning
- B32B38/164—Drying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions 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; Compositions of derivatives of such polymers
- C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
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- 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
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/302—Conductive
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/12—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The invention discloses a high-thermal-conductivity modified polytetrafluoroethylene copper-clad plate and a preparation method thereof, and belongs to the technical field of copper-clad plates. The method comprises the steps of firstly pretreating glass fiber cloth by adopting a silane coupling agent, then preparing PTFE/PFEP/L-tryptophan modified graphene oxide dispersed glue solution, impregnating the glass fiber cloth pretreated by the silane coupling agent with the glue solution and drying to obtain an impregnated glue film, laminating the impregnated glue film into a raw substrate with a specified thickness, covering copper foils on two sides of the raw substrate, and carrying out hot-pressing sintering to obtain the modified PTFE copper-clad plate. The method is simple to operate, and the copper-clad plate prepared by the method has high thermal conductivity and excellent electrical performance.
Description
Technical Field
The invention relates to a copper-clad plate and a preparation method thereof, in particular to a high-thermal-conductivity modified polytetrafluoroethylene copper-clad plate and a preparation method thereof, and belongs to the technical field of copper-clad plates.
Background
Polytetrafluoroethylene (PTFE) has excellent electrical properties (low dielectric constant, low dielectric dissipation factor, very stable at higher temperatures and frequency ranges), as well as good chemical and thermal stability, and is widely used in the manufacturing industries of communication equipment, computers, automotive electronics, household appliances, and the like. The traditional preparation method of the PTFE copper-clad plate is characterized in that PTFE emulsion is used for impregnating glass fiber cloth, after moisture is dried at the temperature of about 100 ℃, a plurality of pieces of PTFE impregnated cloth are stacked and coated with copper foil for sintering to obtain the PTFE copper-clad plate, the PTFE copper-clad plate prepared by the traditional method is low in heat conductivity, and the heat dispersion of a Printed Circuit Board (PCB) is seriously influenced, so that the development of the PTFE copper-clad plate with high heat conductivity is of great significance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a high-thermal-conductivity modified polytetrafluoroethylene copper-clad plate and a preparation method thereof, wherein the preparation method is simple to operate, firstly, a glass fiber cloth pretreated by a silane coupling agent is soaked in PTFE/PFEP/L-tryptophan modified graphene oxide dispersed glue solution, then, the dried soaked glue solution is laminated into a raw substrate copper-clad foil, and the raw substrate copper-clad foil is sintered to obtain the modified polytetrafluoroethylene copper-clad plate.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a preparation method of a high-thermal-conductivity modified polytetrafluoroethylene copper-clad plate comprises the following steps:
(1) pretreatment of glass fiber cloth
Heating the glass fiber cloth at 450 ℃ for 30min, removing paraffin on the surface, soaking the glass fiber cloth after heat treatment in a silane coupling agent modifying solution for 5-10 min, naturally drying in the air, and baking at 110-120 ℃ for 30min for later use;
(2) preparation of glue solution
Firstly, putting 45 parts by weight of Polytetrafluoroethylene (PTFE) emulsion and 50-58 parts by weight of polytetrafluoroethylene (PFEP) emulsion into a beaker, and uniformly stirring to obtain PTFE/PFEP mixed emulsion; then dropwise adding 10-15 parts by weight of L-tryptophan modified graphene oxide dispersion liquid and 1-3 parts by weight of secondary alcohol polyoxyethylene ether into the PTFE/PFEP mixed emulsion while stirring at the rotating speed of 600r/min, and then stirring at the rotating speed of 1000r/min for 30-60 min to obtain a glue solution;
(3) preparation of modified PTFE copper-clad plate
And (2) dipping the glass fiber cloth processed in the step (1) in the glue solution prepared in the step (2) for 30-50 s, taking out the glass fiber cloth, drying, continuously repeating dipping and drying for several times to enable the glue content on the glass fiber cloth to reach 60% to obtain a dipping glue sheet, laminating the dipping glue sheet into a raw substrate with a specified thickness, covering copper foils on two sides of the raw substrate, and performing hot-pressing sintering under the conditions of pressure of 5-20 MPa and vacuum degree of- (90-100) Kpa to obtain the target modified PTFE copper-clad plate.
Preferably, the preparation method of the L-tryptophan-modified graphene oxide dispersion liquid in the step (2) comprises the following steps: adding equimolar L-tryptophan and sodium hydroxide into deionized water, stirring and dispersing for 1h to obtain a light yellow transparent L-tryptophan solution, wherein the mass ratio of the deionized water to the L-tryptophan is 30:1, dissolving graphene oxide slurry into the L-tryptophan solution according to the mass ratio of 0.8:1, stirring for 1h, carrying out ultrasonic water bath for 1.5h, and continuously stirring for 24h to obtain an L-tryptophan modified graphene oxide dispersion solution.
Preferably, the drying temperature in the step (3) is 220-250 ℃, and the drying time is 10-20 min.
Preferably, the hot-pressing sintering process in the step (3) is as follows: firstly heating to 300 ℃ at the speed of 15 ℃/min, then heating to 350-360 ℃ at the speed of 2.5 ℃/min, keeping the temperature for 90-120 min, then cooling to 300 ℃ at the speed of 2.5 ℃/min, and then naturally cooling to room temperature.
Preferably, the silane coupling agent described in step (1) is z-6032.
The modified PTFE copper-clad plate prepared by the preparation method is adopted.
From the above description, it can be seen that the present invention has the following advantages:
(1) the method comprises the steps of impregnating glass fiber cloth pretreated by a silane coupling agent with PTFE/PFEP/L-tryptophan modified graphene oxide dispersed glue solution, laminating the dried impregnated glue solution into a raw substrate copper clad laminate, and sintering to obtain the modified polytetrafluoroethylene copper clad laminate.
(2) According to the invention, polytetrafluoroethylene PTFE emulsion, polytetrafluoroethylene PFEP emulsion and L-tryptophan modified graphene oxide dispersion liquid in a proper proportion are blended to form a uniformly dispersed resin system (glue solution), so that the thermal conductivity, dielectric property and peel strength of the modified polytetrafluoroethylene copper-clad plate can be improved;
in addition, hetero atom N and conjugated pi electrons on an indole ring of an L-tryptophan side chain can be coordinated with a hollow d orbit on the surface of a copper foil to form a bond in the hot pressing process, so that the adhesive force of a resin melt to the metal copper foil is enhanced, and the peeling strength of the modified polytetrafluoroethylene copper-clad plate is improved;
the PFEP in the resin system can improve the compatibility of the L-tryptophan modified graphene oxide and the PTFE and prevent the L-tryptophan modified graphene oxide particles from agglomerating in the glue solution, thereby improving the dispersion uniformity and stability of the glue solution and improving the surface defects of the glass fiber cloth in the dipping process, and can also enhance the adhesive force of the resin melt to the metal copper foil and further improve the peeling strength of the modified polytetrafluoroethylene copper-clad plate.
(3) According to the method, the L-tryptophan is used as a modifier to modify the graphene oxide, because amino in an L-tryptophan structure reacts with oxygen-containing groups in a graphene oxide (Go) structure, and pi electrons of the L-tryptophan and pi electrons of adjacent graphene oxide are interacted, the Go is stripped from multiple layers to be a thinner sheet, the dispersion uniformity and stability of the modified L-tryptophan modified graphene oxide are remarkably improved, and the problems that the existing inorganic filler is easy to agglomerate and precipitate in glue solution are greatly improved.
(4) The temperature rise in the hot pressing process is beneficial to energy consumption and stress transmission in a step mode, so that the internal stress generated by the polymer in the hot pressing process is reduced, and the mechanical properties (such as bending strength) of the modified PTFE copper-clad plate are improved.
Detailed Description
The features of the invention will be further elucidated by the following examples, without limiting the claims of the invention in any way.
Example 1:
a preparation method of a high-thermal-conductivity modified polytetrafluoroethylene copper-clad plate comprises the following steps:
(1) pretreatment of glass fiber cloth
Heating glass fiber cloth at 450 deg.C for 30min, removing surface paraffin, soaking the glass fiber cloth in z-6032 silane coupling agent modified solution (cationic styryl amino, Dow Corning Co., Ltd., the same below) for 10min, naturally air drying, and baking at 115 deg.C for 30 min;
(2) preparation of glue solution
First, 45 parts by weight of a Polytetrafluoroethylene (PTFE) emulsion (60 wt.% solids, 5 × 10 viscosity)-3Pa.S, average particle size 0.25 μm, number average relative molecular weight 1.0 x 107Sanlofu Co., Ltd., the same below) and 50 parts by weight of a polytetrafluoroethylene PFEP emulsion (solid content 50 wt.%, viscosity 2X 10)-3Pa.S, average particle size 0.3 μm, number average relative molecular weight 5 x 105Sanai Fuji Co., Ltd., the same below) in a beaker and uniformly stirring to obtain PTFE/PFEP mixed emulsion; then 10 parts by weight of L-tryptophan modified graphene oxide dispersion liquid (self-made) and 1 part by weight of secondary alcohol polyoxyethylene ether (Dow, the same below) are dropwise added into the PTFE/PFEP mixed emulsion while stirring at the rotating speed of 600r/min, and then the mixture is stirred at the high speed of 1000r/min45min to obtain glue solution; placing the glue solution in an environment of 25 ℃ for 24h, wherein the glue solution is stable and has no delamination and no precipitation;
(3) preparation of modified PTFE copper-clad plate
Dipping the glass fiber cloth processed in the step (1) in the glue solution prepared in the step (2) for 30-50 s, taking out the glass fiber cloth, drying at 230 ℃ for 15min, continuously repeating dipping and drying for many times to enable the glue content on the glass fiber cloth to reach 60% to obtain a dipping glue sheet, laminating 16 dipping glue sheets to form a raw substrate, covering copper foils with the thickness of 0.035mm on two sides of the raw substrate respectively, performing hot-pressing sintering under the conditions of 10MPa pressure and-95 Kpa vacuum degree to obtain the modified PTFE copper-clad plate, wherein the hot-pressing sintering process comprises the steps of firstly heating to 300 ℃ at the speed of 15 ℃/min, then heating to 355 ℃ at the speed of 2.5 ℃/min, keeping the temperature for 100min, then cooling to 300 ℃ at the speed of 2.5 ℃/min, and naturally cooling to room temperature.
The preparation method of the L-tryptophan modified graphene oxide dispersion liquid in this embodiment is as follows: firstly, adding L-tryptophan (L-Trp, the content of which is 92 percent, Zhengzhou Yu and food additive Co., Ltd.) and sodium hydroxide into deionized water, stirring and dispersing for 1H to obtain a light yellow transparent L-tryptophan solution, wherein n (L-Trp): n (NaOH) ═ 1:1, m (L-Trp): m (H)2And (3) dissolving graphene oxide (Go) slurry (with the mass content of 60 percent, lake south Feng chemical materials development Co., Ltd.) in the prepared L-tryptophan solution according to the mass ratio m (Go) to m (L-Trp) of 0.8:1, stirring for 1h, performing ultrasonic water bath for 1.5h, and continuously stirring for 24h to obtain the L-tryptophan modified graphene oxide dispersion liquid.
Testing the thermal conductivity of the modified PTFE copper-clad plate prepared by the embodiment according to GB/T36476 and 2018; the modified PTFE copper clad laminate prepared in this example was tested for insulation resistance, peel strength, flexural strength, dielectric constant, and dielectric loss according to GB4722-2017, and the results are shown in tables 1 and 2.
Example 2:
a preparation method of a high-thermal-conductivity modified polytetrafluoroethylene copper-clad plate comprises the following steps:
(1) pretreatment of glass fiber cloth
Heating glass fiber cloth at 450 deg.C for 30min, removing surface paraffin, soaking the glass fiber cloth in z-6032 silane coupling agent modified solution (cationic styryl amino, Dow Corning Co., Ltd., the same below) for 10min, naturally air drying, and baking at 115 deg.C for 30 min;
(2) preparation of glue solution
First, 45 parts by weight of a Polytetrafluoroethylene (PTFE) emulsion (60 wt.% solids, 5 × 10 viscosity)-3Pa.S, average particle size 0.25 μm, number average relative molecular weight 1.0 x 107Sanlofu Co., Ltd., the same below) and 55 parts by weight of a polytetrafluoroethylene PFEP emulsion (solid content 50 wt.%, viscosity 2X 10)-3Pa.S, average particle size 0.3 μm, number average relative molecular weight 5 x 105Sanai Fuji Co., Ltd., the same below) in a beaker and uniformly stirring to obtain PTFE/PFEP mixed emulsion; then, 12 parts by weight of L-tryptophan modified graphene oxide dispersion liquid (self-made) and 2 parts by weight of secondary alcohol polyoxyethylene ether (Dow, the same below) are dropwise added into the PTFE/PFEP mixed emulsion while stirring at the rotating speed of 600r/min, and then the mixture is stirred at the high speed of 1000r/min for 45min to obtain glue solution; placing the glue solution in an environment of 25 ℃ for 24h, wherein the glue solution is stable and has no delamination and no precipitation;
(3) preparation of modified PTFE copper-clad plate
Dipping the glass fiber cloth processed in the step (1) in the glue solution prepared in the step (2) for 30-50 s, taking out the glass fiber cloth, drying at 230 ℃ for 15min, continuously repeating dipping and drying for many times to enable the glue content on the glass fiber cloth to reach 60% to obtain a dipping glue sheet, laminating 16 dipping glue sheets to form a raw substrate, covering copper foils with the thickness of 0.035mm on two sides of the raw substrate respectively, performing hot-pressing sintering under the conditions of 10MPa pressure and-95 Kpa vacuum degree to obtain the modified PTFE copper-clad plate, wherein the hot-pressing sintering process comprises the steps of firstly heating to 300 ℃ at the speed of 15 ℃/min, then heating to 355 ℃ at the speed of 2.5 ℃/min, keeping the temperature for 100min, then cooling to 300 ℃ at the speed of 2.5 ℃/min, and naturally cooling to room temperature.
The L-tryptophan-modified graphene oxide dispersion liquid in this example was prepared by the same method as in example 1.
The modified PTFE copper-clad plate prepared in this example was tested for thermal conductivity, insulation resistance, peel strength, flexural strength, dielectric constant, and dielectric loss according to the same test methods as in example 1, and the results are shown in tables 1 and 2.
Example 3:
a preparation method of a high-thermal-conductivity modified polytetrafluoroethylene copper-clad plate comprises the following steps:
(1) pretreatment of glass fiber cloth
Heating glass fiber cloth at 450 deg.C for 30min, removing surface paraffin, soaking the glass fiber cloth in z-6032 silane coupling agent modified solution (cationic styryl amino, Dow Corning Co., Ltd., the same below) for 10min, naturally air drying, and baking at 115 deg.C for 30 min;
(2) preparation of glue solution
First, 45 parts by weight of a Polytetrafluoroethylene (PTFE) emulsion (60 wt.% solids, 5 × 10 viscosity)-3Pa.S, average particle size 0.25 μm, number average relative molecular weight 1.0 x 107Sanlofu Co., Ltd., the same below) and 58 parts by weight of a polytetrafluoroethylene PFEP emulsion (solid content 50 wt.%, viscosity 2X 10)-3Pa.S, average particle size 0.3 μm, number average relative molecular weight 5 x 105Sanai Fuji Co., Ltd., the same below) in a beaker and uniformly stirring to obtain PTFE/PFEP mixed emulsion; then, 15 parts by weight of L-tryptophan modified graphene oxide dispersion liquid (self-made) and 3 parts by weight of secondary alcohol polyoxyethylene ether (Dow, the same below) are dropwise added into the PTFE/PFEP mixed emulsion while stirring at the rotating speed of 600r/min, and then the mixture is stirred at the rotating speed of 1000r/min for 45min to obtain glue solution; placing the glue solution in an environment of 25 ℃ for 24h, wherein the glue solution is stable and has no delamination and no precipitation;
(3) preparation of modified PTFE copper-clad plate
Dipping the glass fiber cloth processed in the step (1) in the glue solution prepared in the step (2) for 30-50 s, taking out the glass fiber cloth, drying at 230 ℃ for 15min, continuously repeating dipping and drying for many times to enable the glue content on the glass fiber cloth to reach 60% to obtain a dipping glue sheet, laminating 16 dipping glue sheets to form a raw substrate, covering copper foils with the thickness of 0.035mm on two sides of the raw substrate respectively, performing hot-pressing sintering under the conditions of 10MPa pressure and-95 Kpa vacuum degree to obtain the modified PTFE copper-clad plate, wherein the hot-pressing sintering process comprises the steps of firstly heating to 300 ℃ at the speed of 15 ℃/min, then heating to 355 ℃ at the speed of 2.5 ℃/min, keeping the temperature for 100min, then cooling to 300 ℃ at the speed of 2.5 ℃/min, and naturally cooling to room temperature.
The L-tryptophan-modified graphene oxide dispersion liquid in this example was prepared by the same method as in example 1.
The modified PTFE copper-clad plate prepared in this example was tested for thermal conductivity, insulation resistance, peel strength, flexural strength, dielectric constant, and dielectric loss according to the same test methods as in example 1, and the results are shown in tables 1 and 2.
Comparative example 1:
a preparation method of a modified polytetrafluoroethylene copper-clad plate comprises the following steps:
(1) pretreatment of glass fiber cloth
Heating glass fiber cloth at 450 deg.C for 30min, removing surface paraffin, soaking the glass fiber cloth in z-6032 silane coupling agent modified solution (cationic styryl amino, Dow Corning Co., Ltd., the same below) for 10min, naturally air drying, and baking at 115 deg.C for 30 min;
(2) preparation of glue solution
First, 45 parts by weight of a Polytetrafluoroethylene (PTFE) emulsion (60 wt.% solids, 5 × 10 viscosity)-3Pa.S, average particle size 0.25 μm, number average relative molecular weight 1.0 x 107Sanlofu Co., Ltd., the same below) and 50 parts by weight of a polytetrafluoroethylene PFEP emulsion (solid content 50 wt.%, viscosity 2X 10)-3Pa.S, average particle size 0.3 μm, number average relative molecular weight 5 x 105Sanai Fuji Co., Ltd., the same below) in a beaker and uniformly stirring to obtain PTFE/PFEP mixed emulsion; then dripping 1 weight part of secondary alcohol polyoxyethylene ether (Dow, the same below) into the PTFE/PFEP mixed emulsion while stirring at the rotating speed of 600r/min, and then stirring at the rotating speed of 1000r/min for 45min to obtain glue solution; placing the glue solution in an environment of 25 ℃ for 24h, wherein the glue solution is stable and has no delamination and no precipitation;
(3) preparation of modified PTFE copper-clad plate
Dipping the glass fiber cloth processed in the step (1) in the glue solution prepared in the step (2) for 30-50 s, taking out the glass fiber cloth, drying at 230 ℃ for 15min, continuously repeating dipping and drying for many times to enable the glue content on the glass fiber cloth to reach 60% to obtain a dipping glue sheet, laminating 16 dipping glue sheets to form a raw substrate, covering copper foils with the thickness of 0.035mm on two sides of the raw substrate respectively, performing hot-pressing sintering under the conditions of 10MPa pressure and-95 Kpa vacuum degree to obtain the modified PTFE copper-clad plate, wherein the hot-pressing sintering process comprises the steps of firstly heating to 300 ℃ at the speed of 15 ℃/min, then heating to 355 ℃ at the speed of 2.5 ℃/min, keeping the temperature for 100min, then cooling to 300 ℃ at the speed of 2.5 ℃/min, and naturally cooling to room temperature.
The modified PTFE copper-clad plate prepared in this example was tested for thermal conductivity, insulation resistance, peel strength, flexural strength, dielectric constant, and dielectric loss according to the same test methods as in example 1, and the results are shown in tables 1 and 2.
Comparative example 2:
a preparation method of a modified polytetrafluoroethylene copper-clad plate comprises the following steps:
(1) pretreatment of glass fiber cloth
Heating glass fiber cloth at 450 deg.C for 30min, removing surface paraffin, soaking the glass fiber cloth in z-6032 silane coupling agent modified solution (cationic styryl amino, Dow Corning Co., Ltd., the same below) for 10min, naturally air drying, and baking at 115 deg.C for 30 min;
(2) preparation of glue solution
First, 45 parts by weight of a Polytetrafluoroethylene (PTFE) emulsion (60 wt.% solids, 5 × 10 viscosity)-3Pa.S, average particle size 0.25 μm, number average relative molecular weight 1.0 x 107Sanlofu Co., Ltd., the same below) and 50 parts by weight of a polytetrafluoroethylene PFEP emulsion (solid content 50 wt.%, viscosity 2X 10)-3Pa.S, average particle size 0.3 μm, number average relative molecular weight 5 x 105Sanai Fuji Co., Ltd., the same below) in a beaker and uniformly stirring to obtain PTFE/PFEP mixed emulsion; then dripping 10 parts by weight of graphene oxide slurry (with the mass content of 60 percent, Hunan Feng material development Co., Ltd.) and 1 part by weight of secondary alcohol polyoxyethylene ether (Dow, the same below) into the PTFE/PFEP mixed emulsion while stirring at the rotating speed of 600r/min, and then stirring at the rotating speed of 1000r/min for 45min to obtain glue solution; placing the glue solution in an environment at 25 ℃ for 24h, and precipitating in the glue solution;
(3) preparation of modified PTFE copper-clad plate
Dipping the glass fiber cloth processed in the step (1) in the glue solution prepared in the step (2) for 30-50 s, taking out the glass fiber cloth, drying at 230 ℃ for 15min, continuously repeating dipping and drying for many times to enable the glue content on the glass fiber cloth to reach 60% to obtain a dipping glue sheet, laminating 16 dipping glue sheets to form a raw substrate, covering copper foils with the thickness of 0.035mm on two sides of the raw substrate respectively, performing hot-pressing sintering under the conditions of 10MPa pressure and-95 Kpa vacuum degree to obtain the modified PTFE copper-clad plate, wherein the hot-pressing sintering process comprises the steps of firstly heating to 300 ℃ at the speed of 15 ℃/min, then heating to 355 ℃ at the speed of 2.5 ℃/min, keeping the temperature for 100min, then cooling to 300 ℃ at the speed of 2.5 ℃/min, and naturally cooling to room temperature.
The modified PTFE copper-clad plate prepared in this example was tested for thermal conductivity, insulation resistance, peel strength, flexural strength, dielectric constant, and dielectric loss according to the same test methods as in example 1, and the results are shown in tables 1 and 2.
Comparative example 3: changing the formulation
A preparation method of a modified polytetrafluoroethylene copper-clad plate comprises the following steps:
(1) pretreatment of glass fiber cloth
Heating glass fiber cloth at 450 deg.C for 30min, removing surface paraffin, soaking the glass fiber cloth in z-6032 silane coupling agent modified solution (cationic styryl amino, Dow Corning Co., Ltd., the same below) for 10min, naturally air drying, and baking at 115 deg.C for 30 min;
(2) preparation of glue solution
First 55 parts by weight of a polytetrafluoroethylene PTFE emulsion (60 wt.% solids, viscosity 5 x 10)-3Pa.S, average particle size 0.25 μm, number average relative molecular weight 1.0 x 107Sanlofu Co., Ltd., the same below) and 40 parts by weight of a polytetrafluoroethylene PFEP emulsion (solid content 50 wt.%, viscosity 2X 10)-3Pa.S, average particle size 0.3 μm, number average relative molecular weight 5 x 105Sanai Fuji Co., Ltd., the same below) in a beaker and uniformly stirring to obtain PTFE/PFEP mixed emulsion; then dropwise adding the mixture into the PTFE/PFEP mixed emulsion while stirring at the rotating speed of 600r/min10 parts by weight of L-tryptophan modified graphene oxide dispersion liquid (self-made) and 1 part by weight of secondary alcohol polyoxyethylene ether (Dow, the same below), and then stirring at a high speed of 1000r/min for 45min to obtain a glue solution; placing the glue solution in an environment of 25 ℃ for 24h, wherein the glue solution is stable and has no delamination and no precipitation;
(3) preparation of modified PTFE copper-clad plate
Dipping the glass fiber cloth processed in the step (1) in the glue solution prepared in the step (2) for 30-50 s, taking out the glass fiber cloth, drying at 230 ℃ for 15min, continuously repeating dipping and drying for many times to enable the glue content on the glass fiber cloth to reach 60% to obtain a dipping glue sheet, laminating 16 dipping glue sheets to form a raw substrate, covering copper foils with the thickness of 0.035mm on two sides of the raw substrate respectively, performing hot-pressing sintering under the conditions of 10MPa pressure and-95 Kpa vacuum degree to obtain the modified PTFE copper-clad plate, wherein the hot-pressing sintering process comprises the steps of firstly heating to 300 ℃ at the speed of 15 ℃/min, then heating to 355 ℃ at the speed of 2.5 ℃/min, keeping the temperature for 100min, then cooling to 300 ℃ at the speed of 2.5 ℃/min, and naturally cooling to room temperature.
The preparation method of the L-tryptophan modified graphene oxide dispersion liquid in this embodiment is as follows: firstly, adding L-tryptophan (L-Trp, the content of which is 92 percent, Zhengzhou Yu and food additive Co., Ltd.) and sodium hydroxide into deionized water, stirring and dispersing for 1H to obtain a light yellow transparent L-tryptophan solution, wherein n (L-Trp): n (NaOH) ═ 1:1, m (L-Trp): m (H)2And (3) dissolving graphene oxide (Go) slurry (with the mass content of 60 percent, lake south Feng chemical materials development Co., Ltd.) in the prepared L-tryptophan solution according to the mass ratio m (Go) to m (L-Trp) of 0.8:1, stirring for 1h, performing ultrasonic water bath for 1.5h, and continuously stirring for 24h to obtain the L-tryptophan modified graphene oxide dispersion liquid.
The modified PTFE copper-clad plate prepared in this example was tested for thermal conductivity, insulation resistance, peel strength, flexural strength, dielectric constant, and dielectric loss according to the same test methods as in example 1, and the results are shown in tables 1 and 2.
TABLE 1
TABLE 2
It should be understood that the detailed description of the invention is merely illustrative of the invention and is not intended to limit the invention to the specific embodiments described. It will be appreciated by those skilled in the art that the present invention may be modified or substituted equally as well to achieve the same technical result; as long as the use requirements are met, the method is within the protection scope of the invention.
Claims (6)
1. A preparation method of a high-thermal-conductivity modified polytetrafluoroethylene copper-clad plate is characterized by comprising the following steps:
(1) pretreatment of glass fiber cloth
Heating the glass fiber cloth at 450 ℃ for 30min, removing paraffin on the surface, soaking the glass fiber cloth after heat treatment in a silane coupling agent modifying solution for 5-10 min, naturally drying in the air, and baking at 110-120 ℃ for 30min for later use;
(2) preparation of glue solution
Firstly, putting 45 parts by weight of Polytetrafluoroethylene (PTFE) emulsion and 50-58 parts by weight of polytetrafluoroethylene (PFEP) emulsion into a beaker, and uniformly stirring to obtain PTFE/PFEP mixed emulsion; then dropwise adding 10-15 parts by weight of L-tryptophan modified graphene oxide dispersion liquid and 1-3 parts by weight of secondary alcohol polyoxyethylene ether into the PTFE/PFEP mixed emulsion while stirring at the rotating speed of 600r/min, and then stirring at the rotating speed of 1000r/min for 30-60 min to obtain a glue solution;
(3) preparation of modified PTFE copper-clad plate
And (2) dipping the glass fiber cloth processed in the step (1) in the glue solution prepared in the step (2) for 30-50 s, taking out the glass fiber cloth, drying, continuously repeating dipping and drying for several times to enable the glue content on the glass fiber cloth to reach 60%, laminating the dipped glue sheets into a raw substrate with a specified thickness, covering copper foils on two sides of the raw substrate, and performing hot-pressing sintering under the conditions of pressure of 5-20 MPa and vacuum degree of- (90-100) Kpa to obtain the target modified PTFE copper-clad plate.
2. The method according to claim 1, wherein the method for preparing the L-tryptophan-modified graphene oxide dispersion liquid in the step (2) comprises: adding equimolar L-tryptophan and sodium hydroxide into deionized water, stirring and dispersing for 1h to obtain a light yellow transparent L-tryptophan solution, wherein the mass ratio of the deionized water to the L-tryptophan is 30:1, dissolving graphene oxide slurry into the L-tryptophan solution according to the mass ratio of 0.8:1, stirring for 1h, carrying out ultrasonic water bath for 1.5h, and continuously stirring for 24h to obtain an L-tryptophan modified graphene oxide dispersion solution.
3. The method according to claim 1, wherein the drying temperature in the step (3) is 220 to 250 ℃ and the drying time is 10 to 20 min.
4. The method according to claim 1, wherein the hot press sintering process in the step (3) is: firstly heating to 300 ℃ at the speed of 15 ℃/min, then heating to 350-360 ℃ at the speed of 2.5 ℃/min, keeping the temperature for 90-120 min, then cooling to 300 ℃ at the speed of 2.5 ℃/min, and then naturally cooling to room temperature.
5. The method according to claim 1, wherein the silane coupling agent in the step (1) is z-6032.
6. The modified PTFE copper-clad plate prepared by the preparation method of any one of claims 1 to 6.
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Application publication date: 20200609 |
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