CN114574122B - Fluorine-containing resin-based high-frequency copper-clad plate high-heat-conductivity bonding sheet - Google Patents
Fluorine-containing resin-based high-frequency copper-clad plate high-heat-conductivity bonding sheet Download PDFInfo
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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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
- B32B15/04—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
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C09J127/00—Adhesives based on 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; Adhesives based on derivatives of such polymers
- C09J127/02—Adhesives based on 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; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J127/12—Adhesives based on 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; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09J127/18—Homopolymers or copolymers of tetrafluoroethene
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2427/00—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
- C08J2427/02—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
- C08J2427/12—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
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- C08J2427/12—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
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Abstract
The invention belongs to the technical field of communication materials, and particularly relates to a high-heat-conductivity bonding sheet for a fluorine-containing resin-based high-frequency copper-clad plate. The liquid nitrogen material is prepared by adding and stirring mixed raw material components in a liquid nitrogen medium; then carrying out liquid nitrogen volatilization operation on the liquid nitrogen material, then adding water and stirring, and then adding ammonia water and stirring to prepare an ammonia water material; then baking the ammonia water material, removing water and ammonia to obtain a fluorine-containing resin mixture; then adding and pressing the fluorine-containing resin mixture in a mould to prepare a rod-shaped material embryo; finally, under the protection of inert gas, performing hot pressing sintering-turning operation on the rod-shaped blank to obtain the final high-heat-conductivity bonding sheet.
Description
Technical Field
The invention belongs to the technical field of communication materials, and particularly relates to a high-heat-conductivity bonding sheet for a fluorine-containing resin-based high-frequency copper-clad plate.
Background
The copper-clad plate as a main carrier of the electronic component has higher and finer integration level and finer circuit, and has good heat dissipation function besides stable insulativity and thermal-mechanical performance to ensure the working stability of the electronic component.
The metal-based copper-clad plate has the best heat dissipation capability, but the manufacturing cost is high, the production difficulty is high, and the metal-based copper-clad plate is only used for high-current modules. Ceramic substrates such as alumina-based, aluminum nitride-based, and silicon nitride-based also possess good thermal conductivity, but ceramic substrates have poor mechanical properties.
The traditional epoxy resin-based copper-clad plate represented by FR-4 has excellent thermal-mechanical stability, but the thermal conductivity is only 0.25W/mK. Therefore, the copper-clad plate type is formed by filling a large amount of inorganic heat conducting material into the resin matrix, the heat conductivity of the composite material can be improved, but the processing performance is obviously reduced, the brittleness of the product is increased, and the adhesiveness between the resin matrix and the copper foil is poor. In addition, the transverse and longitudinal radiating effects are consistent, the requirement of a high-power device on transverse rapid radiating cannot be met, and the requirements of current high-speed, high-frequency, lossless and high-capacity information transmission are difficult to meet.
Furthermore, fluorine-containing resins represented by Polytetrafluoroethylene (PTFE) have various excellent properties such as low dielectric constant, low dielectric loss, high thermal stability and chemical stability, which are incomparable with other polymer resins, due to their unique chemical structures. Since the priority report of US patent 3136680, PTFE has been commonly used as a base material for copper-clad plates. However, the fluorine-containing resin itself has extremely low thermal conductivity (0.15W/mK), which limits its wider application, so the development of a fluorine-containing resin-based high-frequency copper-clad plate with high thermal conductivity is urgent.
Disclosure of Invention
The invention provides a fluorine-containing resin-based high-frequency copper-clad plate high-heat-conductivity bonding sheet, which can be used for preparing liquid nitrogen materials by adding and stirring mixed raw material components in a liquid nitrogen medium; then carrying out liquid nitrogen volatilization operation on the liquid nitrogen material, then adding water and stirring, and then adding ammonia water and stirring to prepare an ammonia water material; then baking the ammonia water material, removing water and ammonia to obtain a fluorine-containing resin mixture; then adding and pressing the fluorine-containing resin mixture in a mould to prepare a rod-shaped material embryo; finally, under the protection of inert gas, performing hot pressing sintering-turning operation on the rod-shaped blank to obtain the final high-heat-conductivity bonding sheet.
The invention adopts the technical proposal that: the preparation method of the high-heat-conductivity bonding sheet for the fluorine-containing resin-based high-frequency copper-clad plate sequentially comprises the following steps of:
s1, adding and stirring mixed raw material components in a liquid nitrogen medium to prepare a liquid nitrogen material;
s2, performing liquid nitrogen volatilization operation on the liquid nitrogen material, then adding water and stirring, and then adding ammonia water and stirring to obtain an ammonia water material;
s3, baking the ammonia water material, removing water and ammonia to obtain a fluorine-containing resin mixture;
s4, adding and pressing the fluorine-containing resin mixture in a mold to prepare a rod-shaped blank;
s5, under the protection of inert gas, performing hot-pressing sintering-turning operation on the rod-shaped blank to obtain the final high-heat-conductivity bonding sheet.
In the S2 of the invention, the temperature of stirring by adding ammonia water is 15-50 ℃ and the time is 24-96h.
The further preferable technical scheme is as follows: in S1, the raw material components comprise tetrafluoroethylene, tetrafluoroethylene-perfluoro alkoxy vinyl ether copolymer, other fluorine-containing resin, polyvinylidene fluoride, boron nitride with the surface modified by a coupling agent and part of fluorine-containing polymer, auxiliary filler and release agent.
The further preferable technical scheme is as follows: in S1, the addition amount of the polyvinylidene fluoride accounts for 0.5-10wt% of the fluorine-containing resin mixture, the concentration of the ammonia water is 1-28wt%, and the volume of the ammonia water is 0.1-300 times of the mass of the polyvinylidene fluoride.
In the invention, the volume unit of the ammonia water is L, and the mass unit of the polyvinylidene fluoride is kg.
The further preferable technical scheme is as follows: in the S1, the other fluorine-containing resin is any one or a mixture of more than one of poly perfluoroethylene propylene, ethylene-tetrafluoroethylene copolymer, poly chlorotrifluoroethylene and ethylene-chlorotrifluoroethylene copolymer.
In the invention, the other fluorine-containing resin is used in an amount of 20wt% or less based on the fluorine-containing resin mixture.
The further preferable technical scheme is that the preparation method of the boron nitride with the surface modified by the coupling agent and part of the fluorine-containing polymer sequentially comprises the following steps:
t1, preparing an activated coupling agent solution and preparing a boron nitride uniform dispersion;
t2, stirring and mixing the activated coupling agent solution and the boron nitride uniform dispersion liquid, filtering and washing for a plurality of times, and leaching by using an organic solvent to obtain coupling agent modified boron nitride;
t3, preparing a coupling agent modified boron nitride uniform dispersion liquid;
and T4, adding part of fluorine-containing polymer emulsion into the coupling agent modified boron nitride uniform dispersion liquid, stirring and mixing, removing the solvent, and drying to finally prepare the boron nitride with the surface modified by the coupling agent and part of fluorine-containing polymer.
In the present invention, the surface is jointly modified with the coupling agent and a part of the fluorine-containing polymer to form boron nitride, the particle diameter D50 of which is controlled to be between 0.3 and 40um, and the amount of the boron nitride is 5 to 55 weight percent of the fluorine-containing resin mixture.
In the T1 of the invention, the coupling agent is a silane coupling agent, and the dosage of the coupling agent is 0.1-10wt% of boron nitride.
In the T4 of the invention, the part of fluorine-containing polymer is any one or a mixture of more than one of ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer and polyvinylidene fluoride, and the part of fluorine-containing polymer accounts for 1-10wt% of boron nitride.
The further preferable technical scheme is as follows: in T1, the activated coupling agent solution is a water/alcohol mixed solution of a coupling agent, and the boron nitride uniform dispersion liquid is prepared through ball milling operation.
In the T1 of the invention, the pH value of the water/alcohol mixed solution of the coupling agent is firstly adjusted to be between 2 and 5, and the water/alcohol mixed solution is stirred and activated for 5 to 30 minutes at the temperature of 20 to 60 ℃ to obtain the activated coupling agent solution, wherein the alcohol is any one or a mixture of methanol, ethanol and isopropanol.
The further preferable technical scheme is as follows: and in T2, firstly adding alkali liquor into the boron nitride uniform dispersion liquid, then carrying out ultrasonic reaction, then adding acid liquor, then pouring the activated coupling agent solution, and finally stirring for reaction, thus the filtering-water washing operation can be carried out.
In the invention, the boron nitride uniform dispersion liquid comprises a solvent A, wherein the solvent A, the solvent of alkali liquor and the solvent of acid liquor are any one or a mixture of a plurality of water, acetone, methanol, ethanol and isopropanol.
In the T2, the temperature of the ultrasonic reaction is 30-110 ℃, the time is 4-96h, the pH is regulated to 4-7 after acid liquor is added, and finally the temperature of the stirring reaction is 30-80 ℃ and the time is 4-24h.
In the T2, the alkali is any one or a mixture of a plurality of lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide and potassium tert-butoxide.
The further preferable technical scheme is as follows: in T3, the solid content of the coupling agent modified boron nitride uniform dispersion liquid is 1-40wt/v%.
In the T4 of the invention, the temperature of the stirring and mixing operation is 20-60 ℃ and the time is 0.5-72h.
The further preferable technical scheme is as follows: in S1, the release agent is any one or a mixture of more than one of amide, silicone powder, silicone oil, talcum powder, mica powder, clay and clay.
In the present invention, the release agent is used in an amount of 0.05 to 0.5% by weight of the fluorine-containing resin mixture.
In the invention, the auxiliary filler is SiO 2 、Al 2 O 3 、TiO 2 、ZnO、MgO、Bi 2 O 3 、Al(OH) 3 、Mg(OH) 2 、BaTiO 3 、SrTiO 3 、Mg 2 TiO 4 、Bi 2 (TiO 3 ) 3 、PbTiO 3 、NiTiO 3 、CaTiO 3 、ZnTiO 3 、Zn 2 TiO 4 、BaSnO 3 、Bi 2 (SnO 3 ) 3 、CaSnO 3 、PbSnO 3 、MgSnO 3 、SrSnO 3 、ZnSnO 3 、BaZrO 3 、CaZrO 3 、PbZrO 3 、MgZrO 3 、SrZrO 3 、ZnZrO 3 One or a mixture of more of silicon carbide, silicon nitride, graphite oxide, graphite fluoride, talcum powder, mica powder, kaolin, clay, solid glass beads, hollow glass beads, diamond, glass fiber, basalt fiber and carbon fiber, and one or a mixture of more of polytetrafluoroethylene pre-sintered material, ultra-high molecular weight polyethylene fiber, kevlar fiber, polyimide, polyetherimide and polyether ether ketone; the auxiliary filler accounts for 5-50wt% of the fluorine-containing resin mixture.
The further preferable technical scheme is as follows: s5, the turning speed of the hot pressing sintering-turning operation is 10-250m/min, the feeding amount is 0.005-5mm/r, and the cutting depth is 0.005-5mm; the turning film with the thickness of at least 5mm on the surface layer of the rod-shaped blank is abandoned and is not used as a bonding sheet; the length of the rod-shaped embryo is 0.5-3m, and the diameter is 0.3-2m.
In the present invention, the temperature of the hot press sintering operation is 340-370 ℃ and pressure of 40-200kg/cm 2 The time is 2-72h; the temperature rising rate is 0.5-30 ℃/min; after the temperature reaches the sintering temperature, releasing the pressure to remove the bubbles, and repeating the steps for a plurality of times to fully remove the bubbles; and then cooling to room temperature at a cooling rate of 0.5-20 ℃/min.
The present invention has the following advantages.
First, commercial products of Polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer (PFA), and partially fluoropolymers often leave "defect" functionalities such as-CH 2-and-CHF-that can undergo a de-HF crosslinking reaction with each other or with polyvinylidene fluoride (PVDF) in the presence of aqueous ammonia, thereby introducing a crosslinked network structure into the adhesive sheet that, due to the establishment of the crosslinked network structure, significantly reduces the coefficient of thermal expansion of the sheet, and increases the flexural strength, mechanical stiffness, and dimensional stability of the sheet.
Second, PVDF is an inexpensive partially fluoropolymer, and its incorporation reduces the cost of producing the adhesive sheet.
Thirdly, introducing boron nitride with the surface modified by the coupling agent and part of fluorine-containing polymer through continuous modification, so that the interaction force and compatibility between the boron nitride and fluorine-containing resin are improved, the mechanical property and dielectric property of the bonding sheet are finally improved, and the Coefficient of Thermal Expansion (CTE) is reduced.
Fourth, boron nitride is used as a high heat conduction filler, and after modification, a good heat conduction and permeation network is established in the bonding sheet, so that the heat conductivity of the bonding sheet in the thickness direction is remarkably improved.
Fifth, the addition of tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer emulsion (PFA) reduces the processing temperature of PTFE.
Sixth, the turning process is widely applied and has strong universality, and the area and thickness of the bonding sheet can be quickly and simply adjusted by adjusting the turning process parameters.
Seventh, the bonding sheet prepared by the method has good uniformity and toughness, good compatibility with prepregs such as PTFE base and PPO base, strong bonding force, good self thermal-mechanical property, high stability and low hygroscopicity, and can meet the requirements of different communication fields on all comprehensive properties of the copper-clad plate containing the bonding sheet.
Eighth, the invention has simple operation process, mild preparation condition, low production cost, easy batch and large-scale production, strong universality, good industrial production foundation and wide application prospect.
Drawings
Fig. 1 is a main performance test result of the high thermal conductive adhesive sheet of the present invention.
Detailed Description
The following description is of the preferred embodiments of the invention and is not intended to limit the scope of the invention.
Synthesis example 1
120 parts of BN (D50=10um) is mixed into 3500 parts of pure water, after ball milling and dispersing for 30min, 70 parts of NaOH is added into the mixture, after ultrasonic auxiliary reaction for 8 hours at 80 ℃, acetic acid is added into the mixture to adjust the pH value between 6 and 7, and the reaction liquid of activated BN is obtained.
100 parts of a 2wt% H2O/ethanol mixed solution is prepared, 0.7 part of a coupling agent KH550 and 2.3 parts of a coupling agent KH570 are added, the mixture is stirred at 55 ℃ for 5min, the pH value of the system is adjusted to 3-5, and the mixture is continuously stirred for 15min, so that an activated composite coupling agent solution is obtained.
Pouring the activated composite coupling agent solution into the reaction solution of activated BN, continuously stirring for 4 hours at 60 ℃, filtering, and washing the product for multiple times until the pH value of the filtrate is between 7 and 8; finally, leaching the filter cake sequentially by ethanol and toluene to obtain modified BN co-modified by KH570/KH 550.
Preparing a modified BN uniform dispersion liquid with 30% of solid content and jointly modified KH570/KH550, adding 5 parts of ETFE emulsion (DuPont Teflon 532-6210), continuously stirring at 45 ℃ for 2 hours, filtering to remove the solvent, and drying to obtain modified BN with the surface jointly modified by KH570/KH550 and ETFE.
Synthesis example 2
120 parts of BN (D50=20um) is mixed into 3500 parts of pure water, after ball milling and dispersing for 30min, 80 parts of NaOH is added into the mixture, after ultrasonic auxiliary reaction for 12h at 80 ℃, acetic acid is added into the mixture to adjust the pH value between 6 and 7, and the reaction liquid of activated BN is obtained.
100 parts of a 2wt% H2O/ethanol mixed solution is prepared, 0.8 part of a coupling agent perfluoro decyl trimethoxy silane and 3.5 parts of a coupling agent KH570 are added, the mixture is stirred at 50 ℃ for 10min, the pH value of the system is regulated to 3-5, and the stirring is continued for 20min, so that an activated composite coupling agent solution is obtained.
Pouring the activated composite coupling agent solution into the reaction solution of activated BN, continuously stirring for 5 hours at 60 ℃, filtering, and washing the product for multiple times until the pH value of the filtrate is between 7 and 8; finally, the filter cake is sequentially leached by ethanol and toluene to obtain the modified BN co-modified by perfluoro decyl trimethoxy silane/KH 570.
A homogeneous dispersion of the modified BN co-modified with perfluorodecyl trimethoxysilane/KH 570 having a solids content of 30% was prepared, 6 parts of an ETFE emulsion (DuPont Teflon units 532-6210) was added and stirred at 30℃for 2h. Filtering to remove the solvent, and drying to obtain modified BN with the surface jointly modified by perfluoro decyl trimethoxy silane/KH 570 and ETFE.
Example 1
75 parts of PTFE (Japanese Dajin PTFE M-18), 75 parts of PFA (DuPont Teflon PFA 340), 15 parts of FEP (Japanese Dajin Neoflon FEP NC-1539), 40 parts of silicon oxide, 2 parts of mica powder, 5 parts of PVDF and 120 parts of modified BN in synthetic example 1 are weighed, stirred in a high-speed stirrer for 2 hours in liquid nitrogen to be uniformly mixed, volatilized from the liquid nitrogen, added with excessive water to be uniformly stirred and dispersed, then added with 50 parts of commercial ammonia water solution (the mass percentage concentration is 26%), stirred and mixed for 24 hours at 25 ℃, and dried at 100 ℃ to obtain a fluorine-containing resin mixture.
Placing the fluorine-containing resin mixture in a mold, pressing to obtain a blank, and heating to 360 deg.C under nitrogen atmosphere at 70kg/cm 2 After sintering for 24 hours under hot pressing, turning to obtain a bonding sheet with the thickness of about 0.095-0.105mm; after the bonding sheet and the PTFE-based prepreg are pressed together at high temperature to obtain the substrate for the high-frequency copper-clad plate, the substrate is treated for 5 minutes at 300 ℃ and repeated for 5 times, no bubbling and delamination of the substrate can be observed, and the appearance, the strength and the toughness are unchanged.
Example 2
75 parts of PTFE (Japanese Dajin PTFE M-18), 75 parts of PFA (DuPont Teflon PFA 340), 15 parts of FEP (Japanese Dajin Neoflon FEP NC-1539), 40 parts of silicon oxide, 2 parts of mica powder, 5 parts of PVDF and 120 parts of modified BN in synthetic example 2 are weighed, stirred in a high-speed stirrer for 2 hours in liquid nitrogen to be uniformly mixed, volatilized from the liquid nitrogen, added with excessive water to be uniformly stirred and dispersed, then added with 50 parts of commercial ammonia water solution (the mass percentage concentration is 26%), stirred and mixed for 24 hours at 25 ℃, and dried at 100 ℃ to obtain a fluorine-containing resin mixture.
Placing the fluorine-containing resin mixture in a mold, pressing to obtain a blank, and heating to 360 deg.C under nitrogen atmosphere at 70kg/cm 2 After sintering for 24 hours under hot pressing, turning to obtain a bonding sheet with the thickness of about 0.095-0.105mm; after the bonding sheet and the PTFE-based prepreg are pressed together at high temperature to obtain the substrate for the high-frequency copper-clad plate, the substrate is treated for 5 minutes at 300 ℃ and repeated for 5 times, no bubbling and delamination of the substrate can be observed, and the appearance, the strength and the toughness are unchanged.
Example 3
90 parts of PTFE (Japanese David PTFE M-18), 75 parts of PFA (DuPont Teflon PFA 340), 15 parts of FEP (Japanese David Neoflon FEP NC-1539), 5 parts of silicon oxide, 45 parts of titanium oxide, 2 parts of mica powder, 3 parts of PVDF and 100 parts of modified BN in synthetic example 1 are weighed, stirred in a high-speed stirrer for 2 hours in liquid nitrogen to uniformly mix, volatilize the liquid nitrogen, add excessive water to uniformly stir and disperse, then add 50 parts of commercial ammonia water solution (the mass percentage concentration is 26%), stir and mix for 24 hours at 25 ℃, and then dry at 100 ℃ to obtain a fluorine-containing resin mixture.
Placing the fluorine-containing resin mixture in a mold, pressing to obtain a blank, and heating to 370deg.C under nitrogen atmosphere at 80kg/cm 2 After sintering for 24 hours under hot pressing, turning to obtain a bonding sheet with the thickness of about 0.105-0.115mm; after the bonding sheet and the PTFE/PPO-based prepreg are pressed together at high temperature to obtain the substrate for the high-frequency copper-clad plate, the substrate is treated for 5 minutes at 300 ℃ and repeated for 5 times, no bubbling and delamination of the substrate can be observed, and the appearance, the strength and the toughness are unchanged.
Example 4
90 parts of PTFE (Japanese David PTFE M-18), 75 parts of PFA (DuPont Teflon PFA 340), 15 parts of FEP (Japanese David Neoflon FEP NC-1539), 5 parts of silicon oxide, 45 parts of titanium oxide, 2 parts of mica powder, 3 parts of PVDF and 100 parts of modified BN in synthetic example 2 are weighed, stirred in a high-speed stirrer for 2 hours in liquid nitrogen to uniformly mix, volatilize the liquid nitrogen, add excessive water to uniformly stir and disperse, then add 50 parts of commercial ammonia water solution (the mass percentage concentration is 26%), stir and mix for 24 hours at 25 ℃, and then dry at 100 ℃ to obtain a fluorine-containing resin mixture.
Placing the fluorine-containing resin mixture in a mold, pressing to obtain a blank, and heating to 370deg.C under nitrogen atmosphere at 80kg/cm 2 After sintering for 24 hours under hot pressing, turning to obtain a bonding sheet with the thickness of about 0.105-0.115mm; after the bonding sheet and the PTFE/PPO-based prepreg are pressed together at high temperature to obtain the substrate for the high-frequency copper-clad plate, the substrate is treated for 5 minutes at 300 ℃ and repeated for 5 times, no bubbling and delamination of the substrate can be observed, and the appearance, the strength and the toughness are unchanged.
Example 5
60 parts of PTFE (Japanese Dajin PTFE M-18), 90 parts of PFA (DuPont Teflon PFA 340), 30 parts of FEP (Japanese Dajin Neoflon FEP NC-1539), 5 parts of silicon oxide, 5 parts of aluminum oxide, 35 parts of titanium oxide, 2 parts of mica powder, 5 parts of PVDF and 120 parts of modified BN in synthetic example 1 are weighed, stirred in a high-speed stirrer for 2 hours in liquid nitrogen to be uniformly mixed, volatilized off the liquid nitrogen, added with excessive water to be uniformly stirred and dispersed, then added with 50 parts of commercial ammonia water solution (the mass percentage concentration is 26%), stirred and mixed at 25 ℃ for 24 hours, and dried at 100 ℃ to obtain a fluorine-containing resin mixture.
Placing the fluorine-containing resin mixture in a mold, pressing to obtain a blank, and heating to 360 deg.C under nitrogen atmosphere at 70kg/cm 2 After sintering for 24 hours under hot pressing, turning to obtain a bonding sheet with the thickness of about 0.105-0.115mm; after the bonding sheet and the PTFE-based prepreg are pressed together at high temperature to obtain the substrate for the high-frequency copper-clad plate, the substrate is treated for 5 minutes at 300 ℃ and repeated for 5 times, no bubbling and delamination of the substrate can be observed, and the appearance, the strength and the toughness are unchanged.
Example 6
75 parts of PTFE (Japanese Dajin PTFE M-18), 75 parts of PFA (DuPont Teflon PFA 340), 15 parts of FEP (Japanese Dajin Neoflon FEP NC-1539), 40 parts of silicon oxide, 2 parts of mica powder, 10 parts of PVDF and 120 parts of modified BN in synthetic example 1 are weighed, stirred in a high-speed stirrer for 2 hours in liquid nitrogen to be uniformly mixed, volatilized from the liquid nitrogen, added with excessive water to be uniformly stirred and dispersed, then added with 50 parts of commercial ammonia water solution (the mass percentage concentration is 26%), stirred and mixed for 24 hours at 25 ℃, and dried at 100 ℃ to obtain a fluorine-containing resin mixture.
Placing the fluorine-containing resin mixture in a mold, pressing to obtain a blank, and heating to 360 deg.C under nitrogen atmosphere at 70kg/cm 2 After sintering for 24 hours under hot pressing, turning to obtain a bonding sheet with the thickness of about 0.095-0.105mm; after the bonding sheet and the PTFE-based prepreg are pressed together at high temperature to obtain the substrate for the high-frequency copper-clad plate, the substrate is treated for 5 minutes at 300 ℃ and repeated for 5 times, no bubbling and delamination of the substrate can be observed, and the appearance, the strength and the toughness are unchanged.
Comparative example 1
75 parts of PTFE (Japanese Dajin PTFE M-18), 75 parts of PFA (DuPont Teflon PFA 340), 15 parts of FEP (Japanese Dajin Neoflon FEP NC-1539), 40 parts of silicon oxide, 2 parts of mica powder and 120 parts of modified BN in synthetic example 1 are weighed, stirred in liquid nitrogen by a high-speed stirrer for 2 hours to be uniformly mixed, the liquid nitrogen is volatilized, and the mixture is dried at 100 ℃ to obtain a fluorine-containing resin mixture.
Placing the fluorine-containing resin mixture in a mold, pressing to obtain a blank, and heating to 360 deg.C under nitrogen atmosphere at 70kg/cm 2 After sintering for 24 hours under hot pressing, turning to obtain a bonding sheet with the thickness of about 0.095-0.105mm; after the bonding sheet and the PTFE-based prepreg are pressed together at high temperature to obtain the substrate for the high-frequency copper-clad plate, the substrate is treated for 5 minutes at 300 ℃ and repeated for 5 times, no bubbling and delamination of the substrate can be observed, and the appearance, the strength and the toughness are unchanged.
Finally, the adhesive sheets of the above 6 examples and 1 comparative example were subjected to main performance tests, and the results are shown in fig. 1.
As shown in comparative example 1, the thermal conductivity of the bonding sheet for a high-frequency copper-clad laminate was only 0.9W/mK without adding PVDF and ammonia water, and the CTE in the Z-axis direction was as high as 80ppm/K.
However, after the combination of PVDF and ammonia water was introduced, the CTE in the Z-axis direction was significantly reduced to 50ppm/K as in example 3, the CTE was increased to 0.98W/mK, and the CTE in the Z-axis direction was further reduced and the CTE was significantly increased as in examples 1 and 6.
The perfluoro coupling agent can further improve the compatibility of the filler and the fluorine-containing resin, and can assist in improving the heat conductivity coefficient of the bonding sheet for the high-frequency copper-clad plate and reducing the heat expansion coefficient, as in examples 2 and 4. In actual production, the coupling agent may be selected in consideration of both performance and cost requirements.
The embodiments of the present invention have been described in detail with reference to the drawings, but the present invention is not limited to the above embodiments, and various modifications may be made within the knowledge of those skilled in the art without departing from the spirit of the present invention. These are all non-inventive modifications which are intended to be protected by the patent laws within the scope of the appended claims.
Claims (8)
1. The preparation method of the high-heat-conductivity bonding sheet for the fluorine-containing resin-based high-frequency copper-clad plate is characterized by comprising the following steps of:
s1, adding and stirring mixed raw material components in a liquid nitrogen medium to prepare a liquid nitrogen material;
s2, performing liquid nitrogen volatilization operation on the liquid nitrogen material, then adding water and stirring, and then adding ammonia water and stirring to obtain an ammonia water material;
s3, baking the ammonia water material, removing water and ammonia to obtain a fluorine-containing resin mixture;
s4, adding and pressing the fluorine-containing resin mixture in a mold to prepare a rod-shaped blank;
s5, under the protection of inert gas, performing hot-pressing sintering-turning operation on the rod-shaped blank to obtain a final high-heat-conductivity bonding sheet,
in S1, the raw material components comprise polytetrafluoroethylene, tetrafluoroethylene-perfluoro alkoxy vinyl ether copolymer, other fluorine-containing resin, polyvinylidene fluoride, boron nitride with the surface modified by a coupling agent and part of fluorine-containing polymer, auxiliary filler and release agent,
the addition amount of the polyvinylidene fluoride is 0.5-10wt% of the fluorine-containing resin mixture, the concentration of the ammonia water is 1-28wt%, the volume of the ammonia water is 0.1-300 times of the mass of the polyvinylidene fluoride, the volume unit of the ammonia water is L, and the mass unit of the polyvinylidene fluoride is kg.
2. The fluorine-containing resin-based high-frequency copper-clad plate-used high-heat conduction adhesive sheet according to claim 1, wherein: in the S1, the other fluorine-containing resin is any one or a mixture of more than one of poly perfluoroethylene propylene, ethylene-tetrafluoroethylene copolymer, poly chlorotrifluoroethylene and ethylene-chlorotrifluoroethylene copolymer.
3. The high heat conductive adhesive sheet for fluorine-containing resin based high frequency copper clad laminate as claimed in claim 1, wherein the preparation method of boron nitride with the surface modified by coupling agent and part of fluorine-containing polymer comprises the following steps in order:
t1, preparing an activated coupling agent solution and preparing a boron nitride uniform dispersion;
t2, stirring and mixing the activated coupling agent solution and the boron nitride uniform dispersion liquid, filtering and washing for a plurality of times, and leaching by using an organic solvent to obtain coupling agent modified boron nitride;
t3, preparing a coupling agent modified boron nitride uniform dispersion liquid;
and T4, adding part of fluorine-containing polymer emulsion into the coupling agent modified boron nitride uniform dispersion liquid, stirring and mixing, removing the solvent, and drying to finally prepare the boron nitride with the surface modified by the coupling agent and part of fluorine-containing polymer.
4. The fluorine-containing resin-based high-frequency copper-clad plate-used high-heat conduction adhesive sheet according to claim 3, wherein: in T1, the activated coupling agent solution is a water/alcohol mixed solution of a coupling agent, and the boron nitride uniform dispersion liquid is prepared through ball milling operation.
5. The fluorine-containing resin-based high-frequency copper-clad plate-used high-heat conduction adhesive sheet according to claim 3, wherein: and in T2, firstly adding alkali liquor into the boron nitride uniform dispersion liquid, then carrying out ultrasonic reaction, then adding acid liquor, then pouring the activated coupling agent solution, and finally stirring for reaction, thus the filtering-water washing operation can be carried out.
6. The fluorine-containing resin-based high-frequency copper-clad plate-used high-heat conduction adhesive sheet according to claim 3, wherein: in T3, the solid content of the coupling agent modified boron nitride uniform dispersion liquid is 1-40wt%.
7. The fluorine-containing resin-based high-frequency copper-clad plate-used high-heat conduction adhesive sheet according to claim 1, wherein: in S1, the release agent is any one or a mixture of more than one of amide, silicone powder, silicone oil, talcum powder, mica powder, clay and clay.
8. The fluorine-containing resin-based high-frequency copper-clad plate-used high-heat conduction adhesive sheet according to claim 1, wherein: s5, the turning speed of the hot pressing sintering-turning operation is 10-250m/min, the feeding amount is 0.005-5mm/r, and the cutting depth is 0.005-5mm; the turning film with the thickness of at least 5mm on the surface layer of the rod-shaped blank is abandoned and is not used as a bonding sheet; the length of the rod-shaped embryo is 0.5-3m, and the diameter is 0.3-2m.
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| JP2000160118A (en) * | 1998-11-30 | 2000-06-13 | Asahi Glass Furoro Polymers Kk | Binder and method for binding powder |
| CN107639906A (en) * | 2017-07-17 | 2018-01-30 | 常州中英科技股份有限公司 | A kind of high heat conduction fluorine resin base prepreg and its copper-clad plate of preparation |
| CN112063025A (en) * | 2020-09-28 | 2020-12-11 | 常州中英科技股份有限公司 | Thermosetting hydrocarbon polymer-based prepreg and copper-clad plate prepared from same |
| CN114369428A (en) * | 2021-11-05 | 2022-04-19 | 常州中英科技股份有限公司 | Bonding sheet with low thermal expansion coefficient for high-frequency copper-clad plate |
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| JP2000160118A (en) * | 1998-11-30 | 2000-06-13 | Asahi Glass Furoro Polymers Kk | Binder and method for binding powder |
| CN107639906A (en) * | 2017-07-17 | 2018-01-30 | 常州中英科技股份有限公司 | A kind of high heat conduction fluorine resin base prepreg and its copper-clad plate of preparation |
| CN112063025A (en) * | 2020-09-28 | 2020-12-11 | 常州中英科技股份有限公司 | Thermosetting hydrocarbon polymer-based prepreg and copper-clad plate prepared from same |
| CN114369428A (en) * | 2021-11-05 | 2022-04-19 | 常州中英科技股份有限公司 | Bonding sheet with low thermal expansion coefficient for high-frequency copper-clad plate |
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