CN114292427A - Hot-pressing high-temperature-resistant prepreg PI (polyimide) and preparation method thereof - Google Patents
Hot-pressing high-temperature-resistant prepreg PI (polyimide) and preparation method thereof Download PDFInfo
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- CN114292427A CN114292427A CN202111599568.6A CN202111599568A CN114292427A CN 114292427 A CN114292427 A CN 114292427A CN 202111599568 A CN202111599568 A CN 202111599568A CN 114292427 A CN114292427 A CN 114292427A
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 12
- 238000007731 hot pressing Methods 0.000 title claims description 23
- 239000004642 Polyimide Substances 0.000 title description 2
- 239000000203 mixture Substances 0.000 claims abstract description 28
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011324 bead Substances 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 20
- 239000000945 filler Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
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- 238000003756 stirring Methods 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 9
- 239000003822 epoxy resin Substances 0.000 claims description 8
- 229920000647 polyepoxide Polymers 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 229920001228 polyisocyanate Polymers 0.000 claims description 7
- 239000005056 polyisocyanate Substances 0.000 claims description 7
- 239000004814 polyurethane Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 229920005749 polyurethane resin Polymers 0.000 claims description 4
- 238000007790 scraping Methods 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- -1 amine ester Chemical class 0.000 claims description 3
- 239000002113 nanodiamond Substances 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 23
- 239000011889 copper foil Substances 0.000 abstract description 23
- 238000003825 pressing Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 17
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 12
- 238000010030 laminating Methods 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000007667 floating Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
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- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
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- 239000007787 solid Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 2
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- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
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- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a heat-pressing high-temperature-resistant prepreg PI sheet and a preparation method thereof, wherein the prepreg PI sheet comprises a high-heat-conductivity film and a prepreg composition which are mutually attached; the semi-cured composition comprises a heat-conducting filler, semi-curable resin, a curing agent, an accelerator and zirconium beads; the high-thermal-conductivity film comprises one or two of a polyimide film, a polyimide film and a PET film, and the high-thermal-conductivity film is obtained by fully mixing a semi-solidified composition, coating the mixture on the high-thermal-conductivity film and baking the mixture. The semi-cured PI sheet prepared by the invention has good bonding performance and heat conductivity, can be hot-pressed with copper foil for 30min within a certain pressure and temperature range, and has good peel strength.
Description
Technical Field
The invention relates to the technical field of prepregs, in particular to a hot-pressing high-temperature-resistant prepreg PI and a preparation method thereof.
Background
With the continuous transition of digital circuits to high speed, high frequency and intelligence, the conventional single-layer wiring circuit board cannot meet the application requirements. As an important component of the design of base materials and multilayer boards for manufacturing high-frequency copper-clad plates, the adhesive sheet materials are also increasingly valued by numerous enterprises, and the performance and the structure of the adhesive sheet materials determine the performance index and the processability of final products.
The prepreg is a thermosetting resin system bonding sheet material, also called thermosetting resin prepreg, and is placed in the middle of a copper-clad plate in the process of manufacturing a multilayer plate, the multilayer plate to be pressed is obtained by positioning and clamping, then the multilayer plate is pressed and formed in a laminating machine according to a certain operation program, so that the multilayer plate can be manufactured, the resin flowing under uniform and stable pressure can be well filled into the microscopic grooves of the substrate at a set temperature, and the multilayer plate is solidified into a multilayer plate whole after cooling.
The conventional prepreg mainly comprises resin and a reinforcing material, the reinforcing material is divided into several types such as glass fiber cloth, paper base, composite material and the like, and most prepregs (bonding sheets) used for manufacturing the multilayer printed board adopt the glass fiber cloth as the reinforcing material. However, the prepreg has almost no heat conduction capability, and the prepreg resin has too high fluidity, which causes severe gummosis and reduced electrical performance, and cannot meet the use requirements of the bonding plate. With the development of advanced electronic and high-frequency communication technologies, the power and wiring density of electronic components have increased greatly, and the amount of heat generated per unit volume during operation has increased dramatically. The resulting thermal pile-up phenomenon can cause signal delay, crosstalk and power consumption between lines, and seriously affect the performance reliability and service life of the device. The development of electronic products puts forward more strict requirements on the performance of the copper-clad plate, namely, the copper-clad plate has lower dielectric constant and lower dielectric loss, ensures the speed and quality of signal transmission, has higher thermal conductivity, reduces heat accumulation, has higher peel strength, higher breakdown voltage and better heat resistance, and thus the performance of the copper-clad plate needs to be improved.
The current research on improving the heat conductivity of the semi-cured insulating layer is different in method, the main mode is that various epoxy resins are used as base materials, the heat conductivity of the insulating layer is improved by improving the filling amount of inorganic heat conducting particles, and as a result, the requirement of large-scale electronic equipment on the heat dissipation performance of an aluminum-based copper-clad plate is still difficult to meet, and when hot-pressing treatment is carried out, the glue overflow condition is easy to occur.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the prepreg PI sheet capable of being hot-pressed and resisting high temperature and the preparation method thereof, so that the overall peel strength of the prepreg PI sheet is improved.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a hot-pressing high-temperature-resistant prepreg PI comprises a high-thermal-conductivity film and a prepreg composition which are mutually attached;
the semi-cured composition comprises a heat-conducting filler, semi-curable resin, a curing agent, an accelerator and zirconium beads;
the high-thermal-conductivity film comprises one or two of a polyimide film and a PET film;
further, the semi-curing composition comprises the following components in parts by weight:
8-10 parts of heat-conducting filler, 30-50 parts of semi-curable resin, 0.5-1 part of curing agent, 1-2 parts of accelerator, 0.5-1 part of zirconium beads and 5-10 parts of solvent.
Further, the semi-curable resin includes any one or more of epoxy resin, polyurethane resin, phenolic resin and acrylic resin. In the present invention, the semi-curable resin may be specifically 30, 31, 32, 35, 38, 40, 43, 45, 50 parts;
further, the heat conducting filler comprises any one or more of boron nitride, aluminum oxide, silicon carbide, aluminum nitride, magnesium oxide, zinc oxide, carbon nanotubes, graphene and nano diamond. In the present invention, the heat conductive filler may be 8, 8.5, 9, 9.5, 10 parts.
Further, the curing agent comprises any one or more of polyisocyanate, polyether amine ester, polyurethane, aliphatic polyisocyanate, anhydride curing agent, aliphatic polyamine curing agent, aromatic amine curing agent and polyamide curing agent. In the present invention, the curing agent may be specifically 0.5, 0.6, 0.7, 0.8, 0.9 or 1 part.
Further, the accelerator is a silane coupling agent, and specifically, any one of vinyltrimethoxysilane, vinyltriethoxysilane and vinyltris (beta-methoxyethoxy) silane can be selected. In the present invention, the accelerator may be specifically 1.0, 1.1, 1.2, 1.3, 1.4, 1.6, 1.7, 2.0 parts.
Further, the solvent comprises any one or more of butanone, ethyl acetate, EP and cyclohexanone. In the invention, the solvent can be 5, 6, 7, 8, 9 and 10 parts;
further, the zirconium beads are 65 zirconium beads. In the present invention, the 65 zirconium beads may be specifically 0.5, 0.6, 0.7, 0.8, 0.9, 1 part
A preparation method of a hot-pressing high-temperature-resistant prepreg PI sheet comprises the following steps:
s1 preparation of semi-solidified composition
1) Preparing raw materials according to the semi-solidified composition;
2) taking semi-curable resin, heat-conducting filler, solvent and zirconium beads, and mixing and stirring in a vacuum defoaming machine;
3) adding a curing agent and an accelerator, and fully mixing and stirring to obtain a bubble-free slurry of the semi-solidified composition;
s2, coating
Uniformly coating the slurry of the semi-solidified composition on the high-thermal-conductivity film in a scraping manner;
s3, baking
Baking at 100-120 deg.C for 1.5-2.0min to obtain semi-cured PI sheet.
Further, the process of mixing and stirring in the vacuum defoaming machine in the step S1 is as follows: the rotating speed and the time are respectively 600r/min for forward rotation for 300 s; the reverse rotation was carried out at 800r/min for 300s and at 1200r/min for 300 s.
Further, in step S3, the baking process includes: baking at 100 deg.C for 0.5min, and baking at 120 deg.C for 1 min.
In the present invention, in the step S1, if only the heat conductive filler, the semi-curable resin, and the solvent are subjected to vacuum defoaming stirring, the heat conductive filler cannot be well dispersed, and macromolecules may exist in the system and agglomerate, which may cause lines during blade coating or roughness of the film surface after surface drying, so that a certain gap is formed during hot pressing, the hot pressing attachment is poor, and the thermal resistance and the high temperature resistance of the semi-curable composition are increased. Therefore, in order to solve the problem, when vacuum defoaming stirring is carried out, zirconium beads in a certain proportion are added, the zirconium beads are stirred together with semi-curable resin and heat-conducting filler, and in the high-speed stirring process, the zirconium beads and the zirconium beads, the semi-curable resin and the heat-conducting filler, and the heat-conducting filler and the resin are mutually rubbed, so that the mixing uniformity between the heat-conducting filler and the resin is enhanced, the agglomeration between the heat-conducting fillers is reduced, the generation of lines during blade coating is avoided, and the smoothness of the film is increased.
After the conventional semi-solidified composition is subjected to hot pressing with the high-thermal-conductivity film, the semi-solidified composition has poor thermal peel strength due to no good adhesive force on the high-thermal-conductivity film, and at the moment, the semi-solidified composition is easy to separate from the high-thermal-conductivity film, so that the peel strength is greatly reduced, and the requirement of a semi-solidified PI sheet on the peel strength is far out of reach. In the invention, in order to solve the problem, a silane coupling agent is added during preparation of slurry of the semi-solidified composition, so that the affinity of the semi-solidified composition to a high heat-conducting film is improved, the semi-solidified composition is well adhered to the high heat-conducting film, and the overall peel strength of the semi-solidified PI sheet is improved.
The invention has the beneficial effects that:
the prepreg PI sheet capable of being hot-pressed and resisting high temperature, which is prepared by the invention, has good bonding performance and good heat conduction performance, can be hot-pressed and bonded with copper foil for more than 30min within a certain pressure and temperature range, has good peel strength, is simple in preparation method, and is suitable for mass production.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
The utility model provides a high temperature resistant semi-solid PI piece of can hot pressing, includes high thermal conductivity film and semi-solid composition of laminating each other, can coat semi-solid composition on one side or the two-sided of high thermal conductivity film specifically. The following preparation of a prepreg PI sheet was carried out by taking single-side coating as an example.
Example 1
A preparation method of a hot-pressing high-temperature-resistant prepreg PI sheet comprises the following steps:
taking 30 parts of solvent type epoxy resin 3700 (with solid content of 45-66%), 8 parts of heat-conducting filler which is irregular aluminum nitride with the particle size of less than 10um, adding 5 parts of butanone and 0.5 part of 65 zirconium beads, mixing and stirring in a vacuum defoaming machine, wherein the rotating speed and the time are respectively 600r/min for 300s in positive rotation; reversing at 800r/min for 300s, and reversing at 1200r/min for 300 s; then 0.5 part of polyether amine ester and 1 part of vinyl trimethoxy silane are added for mixing and stirring again, the rotating speed and the time are the same, and the bubble-free heat-conducting slurry is obtained after full stirring. And uniformly blade-coating the heat-conducting slurry on the polyimide film, baking for 30s at 100 ℃ and baking for 1min at 120 ℃ to obtain the semi-cured PI sheet.
The prepreg PI sheet has good adhesion property after being subjected to hot pressing and laminating tests of 130 ℃ (100min), 150 ℃ (60min) and 170 ℃ (30min) with a copper foil under the pressure of more than 0.5 MPa.
The test shows that the thermal conductivity of the prepreg PI is 0.75 w/m.k; after being hot-pressed with the copper foil, the peel strength is 0.9N/mm by a 90-degree test, and the phenomenon of arching shrinkage can not occur when the copper foil is subjected to tin floating for 10min at 280 ℃ in a high-temperature tin furnace.
Example 2:
a preparation method of a hot-pressing high-temperature-resistant prepreg PI sheet comprises the following steps:
firstly, 50 parts of polyurethane resin U87 are added with 10 parts of boron nitride with the particle size of 100 nm; adding 10 parts of ethyl acetate and 1 part of 65 zirconium beads, and mixing and stirring in a vacuum defoaming machine at the rotating speed and the time of respectively rotating for 300s at 600 r/min; reversing at 800r/min for 300s, and reversing at 1200r/min for 300 s; then 1 part of aliphatic polyisocyanate with solid content of 90 percent and 2 parts of vinyltriethoxysilane are added for vacuum defoaming, mixed and stirred again, the rotating speed and the time are the same, and the bubble-free heat-conducting slurry is obtained after full stirring. And uniformly coating the heat-conducting slurry on a PET film in a scraping way, baking for 30s at 100 ℃, and baking for 2min at 120 ℃ to obtain a semi-solidified PI sheet.
The prepreg PI sheet has good adhesion property after being subjected to hot pressing and laminating tests of 130 ℃ (100min), 150 ℃ (60min) and 170 ℃ (30min) with a copper foil under the pressure of more than 0.5 MPa.
The test shows that the thermal conductivity of the prepreg PI is 1.0 w/m.k; after being hot-pressed with the copper foil, the peel strength is 1.0N/mm by a 90-degree test, and the phenomenon of arching shrinkage can not occur when the copper foil is subjected to tin floating for 10min at 280 ℃ in a high-temperature tin furnace.
Example 3
A preparation method of a hot-pressing high-temperature-resistant prepreg PI sheet comprises the following steps:
firstly, 40 parts of phenolic resin and 9 parts of heat-conducting filler are irregular aluminum nitride with the particle size smaller than 10um, 8 parts of EP and 0.8 part of 65 zirconium beads are added, and the mixture is mixed and stirred in a vacuum defoaming machine at the rotating speed and the time of respectively rotating forward for 300s at 600 r/min; reversing at 800r/min for 300s, and reversing at 1200r/min for 300 s; then 0.8 part of aliphatic polyisocyanate and 1.5 parts of vinyl tri (beta-methoxy ethoxy) silane are added for mixing and stirring again, the rotating speed and the time are the same, and the bubble-free heat-conducting slurry is obtained after full stirring. And uniformly coating the heat-conducting slurry on the polyimide film in a scraping way, baking for 30s at 100 ℃, and baking for 1.5min at 120 ℃ to obtain the semi-cured PI sheet.
The prepreg PI sheet has good adhesion property after being subjected to hot pressing and laminating tests of 130 ℃ (100min), 150 ℃ (60min) and 170 ℃ (30min) with a copper foil under the pressure of more than 0.5 MPa;
the test shows that the thermal conductivity of the prepreg PI is 0.95 w/m.k; after being hot-pressed with the copper foil, the peel strength is 0.97N/mm by a 90-degree test, and the phenomenon of arching shrinkage can not occur when the copper foil is subjected to tin floating for 10min at 280 ℃ in a high-temperature tin furnace.
Example 4
A preparation method of a hot-pressing high-temperature-resistant prepreg PI sheet comprises the following steps:
firstly, 36 parts of acrylic resin and 9.5 parts of heat-conducting filler are irregular nano-diamonds (5 microns) with the particle size of less than 10 microns, 8 parts of cyclohexanone and 0.8 part of 65 zirconium beads are added, and the mixture is mixed and stirred in a vacuum defoaming machine, wherein the rotating speed and the time are respectively 600r/min for forward rotation and 300 s; reversing at 800r/min for 300s, and reversing at 1200r/min for 300 s; then 0.8 part of aliphatic polyisocyanate and 1.5 parts of vinyl tri (beta-methoxy ethoxy) silane are added for mixing and stirring again, the rotating speed and the time are the same, and the bubble-free heat-conducting slurry is obtained after full stirring. And uniformly coating the heat-conducting slurry on the polyimide film in a blade mode, baking the polyimide film for 40s at 100 ℃, and baking the polyimide film for 70s at 120 ℃ to obtain the semi-cured PI sheet.
The prepreg PI sheet has good adhesion property after being subjected to hot pressing and laminating tests of 130 ℃ (100min), 150 ℃ (60min) and 170 ℃ (30min) with a copper foil under the pressure of more than 0.5 MPa;
the test shows that the thermal conductivity of the prepreg PI is 0.98 w/m.k; after being hot-pressed with the copper foil, the peel strength is 0.97N/mm by a 90-degree test, and the phenomenon of arching shrinkage can not occur when the copper foil is subjected to tin floating for 10min at 280 ℃ in a high-temperature tin furnace.
Comparative example 1
No zirconium beads were added; the rest of the conditions were the same as the components and preparation method of example 1.
The prepared prepreg PI has good adhesion property at the pressure of more than 0.5MPa (0.7MPa) and after 130 ℃ (within 50 min), and poor bonding is realized after more than 50 min; the lamination was poor when tested by hot-press lamination with copper foil at 150 ℃ (after 30min) and 170 ℃ (after 5 min) under a pressure of 0.7 MPa.
The test shows that the thermal conductivity of the prepreg PI is 0.65 w/m.k; after hot pressing with the copper foil, the peel strength is 0.59/mm when tested at 90 degrees, and the arching shrinkage phenomenon can occur when the copper foil is subjected to tin bleaching for 5min at 280 ℃ in a high-temperature tin furnace.
Comparative example 2
No curing agent was added, and the remaining conditions were the same as those of the components and the preparation method of example 1.
When the prepared prepreg PI sheet is subjected to a hot-pressing laminating test with a copper foil at a temperature of 130 ℃ (after 5 min) under a pressure of more than 0.5MPa (0.7MPa), the laminating is poor; and the copper foil falls off after 1min when the copper foil is subjected to a hot-pressing lamination test at 150 ℃ or 170 ℃ under the pressure of 0.7 MPa.
The test shows that the thermal conductivity of the prepreg PI is 0.60 w/m.k; after being hot-pressed with copper foil, the peel strength is 0.06/mm by a 90-degree test, and the arching shrinkage phenomenon can occur when the copper foil is subjected to tin floating for 1min at 280 ℃ in a high-temperature tin furnace.
In example 1 and comparative example 2, the epoxy resin had a certain flexibility when it was surface-dried, but due to the presence of the curing agent, the epoxy resin was also slowly cured at normal temperature, with a consequent decrease in flexibility, and finally, had a certain brittleness. However, the polyurethane is cured only by heating and retains good flexibility. By the combination of polyurethane and epoxy resin, under the action of a curing agent, the polyurethane and the epoxy resin are crosslinked, so that the adhesive still has excellent flexibility after surface drying and curing, reduces brittleness after hot pressing, has a better bonding effect with a high-thermal-conductivity film and a copper foil, and further improves the peeling strength.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (10)
1. The utility model provides a can hot pressing high temperature resistance prepreg PI piece which characterized in that: the composite material comprises a high-thermal-conductivity film and a semi-solidified composition which are mutually attached;
the semi-cured composition comprises a heat-conducting filler, semi-curable resin, a curing agent, an accelerator and zirconium beads;
the high-thermal-conductivity film comprises one or two of a polyimide film, a polyimide film and a PET film.
2. The heat-pressable high-temperature resistant prepreg PI sheet as claimed in claim 1, wherein: the semi-solidified composition comprises the following components in parts by weight:
8-10 parts of heat-conducting filler, 30-50 parts of semi-curable resin, 0.5-1 part of curing agent, 1-2 parts of accelerator, 0.5-1 part of zirconium beads and 5-10 parts of solvent.
3. The heat-pressable high-temperature-resistant prepreg PI sheet as claimed in claim 2, wherein: the semi-curable resin comprises any one or more of epoxy resin, polyurethane resin, phenolic resin and acrylic resin.
4. The heat-pressable high-temperature-resistant prepreg PI sheet as claimed in claim 2, wherein: the heat conducting filler comprises any one or more of boron nitride, aluminum oxide, silicon carbide, aluminum nitride, magnesium oxide, zinc oxide, carbon nano tubes, graphene and nano diamonds.
5. The heat-pressable high-temperature-resistant prepreg PI sheet as claimed in claim 2, wherein: the curing agent comprises any one or more of polyisocyanate, polyether amine ester, polyurethane, aliphatic polyisocyanate, anhydride curing agent, aliphatic polyamine curing agent, aromatic amine curing agent and polyamide curing agent.
6. The heat-pressable high-temperature resistant prepreg PI sheet as claimed in claim 1, wherein: the accelerator is a silane coupling agent.
7. The heat-pressable high-temperature resistant prepreg PI sheet as claimed in claim 1, wherein: the zirconium beads are 65 zirconium beads.
8. A method for preparing the thermocompression temperature resistant prepreg PI according to any one of claims 1 to 7, comprising the steps of:
s1 preparation of semi-solidified composition
1) Preparing raw materials according to the semi-solidified composition;
2) taking semi-curable resin, heat-conducting filler, solvent and zirconium beads, and mixing and stirring in a vacuum defoaming machine;
3) adding a curing agent and an accelerator, and fully mixing and stirring to obtain a bubble-free slurry of the semi-solidified composition;
s2, coating
Uniformly coating the slurry of the semi-solidified composition on the high-thermal-conductivity film in a scraping manner;
s3, baking
Baking at 100-120 deg.C for 1.5-2.0min to obtain semi-cured PI sheet.
9. The method for preparing the prepreg PI sheet capable of being hot pressed and resisting high temperature according to claim 8, wherein the step S1 of mixing and stirring in a vacuum defoaming machine comprises the following steps: the rotating speed and the time are respectively 600r/min for forward rotation for 300 s; the reverse rotation was carried out at 800r/min for 300s and at 1200r/min for 300 s.
10. The method for preparing the prepreg PI sheet capable of being hot pressed and resisting high temperature according to claim 8, wherein the baking process in the step S3 is as follows: baking at 100 deg.C for 0.5min, and baking at 120 deg.C for 1 min.
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| JP2000290613A (en) * | 1999-04-13 | 2000-10-17 | Hitachi Chem Co Ltd | Thermosetting adhesive sheet |
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| CN102746798A (en) * | 2012-07-10 | 2012-10-24 | 广东汕头超声电子股份有限公司覆铜板厂 | High-heat-conductivity semi-cured glue film and preparation method of high-heat-conductivity semi-cured glue film |
| CN110982457A (en) * | 2019-10-16 | 2020-04-10 | 山东金鼎电子材料有限公司 | High-thermal-conductivity adhesive and preparation method thereof |
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2021
- 2021-12-24 CN CN202111599568.6A patent/CN114292427A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000290613A (en) * | 1999-04-13 | 2000-10-17 | Hitachi Chem Co Ltd | Thermosetting adhesive sheet |
| CN102127290A (en) * | 2010-12-23 | 2011-07-20 | 广东生益科技股份有限公司 | Epoxy resin composition and flexible copper-clad plate prepared from same |
| CN102746798A (en) * | 2012-07-10 | 2012-10-24 | 广东汕头超声电子股份有限公司覆铜板厂 | High-heat-conductivity semi-cured glue film and preparation method of high-heat-conductivity semi-cured glue film |
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Application publication date: 20220408 |