CN117734286A - High-temperature-resistant low-dielectric hydrocarbon resin-based copper-clad plate and preparation method thereof - Google Patents
High-temperature-resistant low-dielectric hydrocarbon resin-based copper-clad plate and preparation method thereof Download PDFInfo
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- CN117734286A CN117734286A CN202410020859.2A CN202410020859A CN117734286A CN 117734286 A CN117734286 A CN 117734286A CN 202410020859 A CN202410020859 A CN 202410020859A CN 117734286 A CN117734286 A CN 117734286A
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- 239000013032 Hydrocarbon resin Substances 0.000 title claims abstract description 63
- 229920006270 hydrocarbon resin Polymers 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000178 monomer Substances 0.000 claims abstract description 40
- 239000002131 composite material Substances 0.000 claims abstract description 29
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 26
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003292 glue Substances 0.000 claims abstract description 24
- 239000003822 epoxy resin Substances 0.000 claims abstract description 18
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 17
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims abstract description 13
- GMGYYSMUGVAJHJ-UHFFFAOYSA-N C=C.CCO[SiH](OCC)OCC Chemical compound C=C.CCO[SiH](OCC)OCC GMGYYSMUGVAJHJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011889 copper foil Substances 0.000 claims abstract description 12
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims abstract description 12
- 239000004744 fabric Substances 0.000 claims abstract description 12
- 239000003365 glass fiber Substances 0.000 claims abstract description 12
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 239000011256 inorganic filler Substances 0.000 claims abstract description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 8
- 238000010030 laminating Methods 0.000 claims abstract description 5
- 238000007598 dipping method Methods 0.000 claims abstract description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 86
- 239000000243 solution Substances 0.000 claims description 83
- 238000006243 chemical reaction Methods 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 42
- 238000002156 mixing Methods 0.000 claims description 36
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 30
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 238000006116 polymerization reaction Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 238000004090 dissolution Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims description 12
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical group CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 9
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 9
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical group [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 9
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 9
- 239000000347 magnesium hydroxide Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 238000003475 lamination Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000002791 soaking Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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Abstract
The invention relates to the technical field of copper-clad plates, in particular to a high-temperature-resistant low-dielectric hydrocarbon resin-based copper-clad plate and a preparation method thereof. The invention obtains modified montmorillonite by adding sodium montmorillonite, ethanol water solution, ethylene triethoxysilane and gamma-aminopropyl trimethoxysilane; and then the modified montmorillonite, the dodecylbenzene sulfonic acid, the ferric trichloride hexahydrate and the pyrrole monomer are taken as raw materials to obtain the composite material. And then taking the benzoxazine monomer, the composite material, the epoxy resin and the hydrocarbon resin as raw materials to obtain the modified blend resin. Finally, adding modified blend resin, inorganic filler, initiator, accelerator and solvent to obtain hydrocarbon resin glue solution; and (3) dipping the glass fiber cloth in hydrocarbon resin glue solution to obtain a prepreg, overlapping copper foils on two sides of the prepreg, and laminating and forming to obtain a finished product. The finished product obtained by the invention has good dielectric property, waterproof property and high temperature resistance, and therefore has wide application prospect in the technical field of copper-clad plates.
Description
Technical Field
The invention relates to the technical field of copper-clad plates, in particular to a high-temperature-resistant low-dielectric hydrocarbon resin-based copper-clad plate and a preparation method thereof.
Background
The hydrocarbon resin-based copper-clad plate is a substrate material widely applied in the electronic field, and has a series of special background technologies. On one hand, the hydrocarbon resin-based copper-clad plate has good conductive performance and low dielectric constant, and can provide excellent signal transmission and circuit performance. On the other hand, the hydrocarbon resin-based copper-clad plate is popular in the high-frequency field, has lower transmission loss and excellent signal stability, and is suitable for high-speed data transmission, radio frequency circuits and other applications. However, in the practical application process, the hydrocarbon resin-based copper-clad plate has poor thermal stability, and the long-term exposure to high temperature easily causes material performance degradation and failure; and the hydrocarbon resin-based copper-clad plate is sensitive to a humid environment, and is easy to wet, degrease or other humidity-sensitive problems, so that the circuit performance and reliability are affected.
In order to overcome the defects of the prior art, the invention provides a high-temperature-resistant low-dielectric hydrocarbon resin-based copper-clad plate and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a high-temperature-resistant low-dielectric hydrocarbon resin-based copper-clad plate and a preparation method thereof, so as to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of a high-temperature-resistant low-dielectric hydrocarbon resin-based copper-clad plate comprises the following steps:
step one: adding modified montmorillonite and dodecylbenzene sulfonic acid into deionized water, and magnetically stirring for 100-150min to obtain a solution 1; mixing ferric trichloride hexahydrate with deionized water, and magnetically stirring for 20-30min to obtain a solution 2; mixing pyrrole monomer and deionized water, and stirring for 10-20min to obtain solution 3; uniformly mixing the solution 1 and the solution 2, dropwise adding the solution 3, performing polymerization reaction, and washing, filtering and drying after the reaction is finished to prepare a composite material;
step two: adding formaldehyde into ethanol for dissolution, adding aniline after full dissolution, carrying out water bath reaction, adding mixed solution of 2, 2-bis- (4-hydroxyphenyl) hexafluoropropane and ethanol after reaction, and carrying out polymerization reaction to prepare a benzoxazine monomer; blending benzoxazine monomer, composite material, epoxy resin and hydrocarbon resin in an ethanol solvent to prepare modified blend resin;
step three: mixing the modified blend resin, the inorganic filler, the initiator, the accelerator and the solvent to prepare hydrocarbon resin glue solution, dipping the glass fiber cloth in the hydrocarbon resin glue solution for 10-20min, taking out and curing to prepare a prepreg; and (3) laminating copper foils on two sides of the prepreg, and preparing a finished product after lamination molding.
More optimally, in the first step, the reaction mass ratio of the modified montmorillonite, the dodecylbenzene sulfonic acid, the ferric trichloride hexahydrate and the pyrrole monomer is 1-2:15:0.1:3.
more preferably, in the first step, the reaction temperature is 20-25 ℃ and the reaction time is 25-30h during the polymerization reaction.
More optimally, the preparation method of the modified montmorillonite comprises the following steps: adding sodium montmorillonite into ethanol water solution, stirring thoroughly, adding ethylene triethoxysilane and gamma-aminopropyl trimethoxysilane, stirring for reaction, washing after reaction, and drying to obtain modified montmorillonite.
More preferably, the mass ratio of sodium montmorillonite, ethylene triethoxysilane and gamma-aminopropyl trimethoxysilane is 1-2:2:2; the volume ratio of ethanol to water in the ethanol aqueous solution is 17:3-4; the reaction temperature is 50-70 ℃ and the reaction time is 6-8h when stirring and reacting.
More preferably, in the second step, the molar ratio of formaldehyde, aniline and 2, 2-bis- (4-hydroxyphenyl) hexafluoropropane is 4:2:1-2.
More preferably, in the second step, the reaction temperature is 80-90 ℃ and the reaction time is 6-8h during the polymerization reaction.
More optimally, in the second step, the mass ratio of the benzoxazine monomer to the composite material to the epoxy resin to the hydrocarbon resin is 6:1:1-1.5:2.
more optimally, in the third step, the hydrocarbon resin glue solution comprises the following components in percentage by weight: 120-130 parts of modified blend resin, 15-30 parts of inorganic filler, 50-70 parts of initiator, 0.03-0.05 part of accelerator and 80-100 parts of solvent by mass; wherein the inorganic filler is magnesium hydroxide, the initiator is di-tert-butyl peroxide, the accelerator is 2-ethyl-4-methylimidazole, and the solvent is acetone.
More preferably, in the third step, laminating and forming process parameters: the temperature is 150-200deg.C, the pressure is 2-4MPa, and the time is 100-180min.
The invention has the beneficial effects that:
the invention prepares modified montmorillonite by adding sodium montmorillonite, ethanol water solution, ethylene triethoxysilane and gamma-aminopropyl trimethoxysilane; and then the modified montmorillonite, the dodecylbenzene sulfonic acid, the ferric trichloride hexahydrate and the pyrrole monomer are used as raw materials to prepare the composite material. Then aniline, formaldehyde alcohol solution and 2, 2-bis- (4-hydroxyphenyl) hexafluoropropane alcohol solution are added to prepare a benzoxazine monomer; and then the benzoxazine monomer, the composite material, the epoxy resin and the hydrocarbon resin are used as raw materials to prepare the modified blend resin. Finally, adding modified blend resin, inorganic filler, initiator, accelerator and solvent to obtain hydrocarbon resin glue solution; and (3) dipping the glass fiber cloth in hydrocarbon resin glue solution to obtain a prepreg, overlapping copper foils on two sides of the prepreg, and laminating and forming to obtain a finished product.
The invention is characterized in that in the first step, the montmorillonite is modified in a combined way by adding ethylene triethoxysilane and gamma-aminopropyl trimethoxysilane, so that the agglomeration phenomenon of the montmorillonite can be effectively improved; then, by adopting an intercalation polymerization method, the polypyrrole is intercalated into an interlayer structure of the modified montmorillonite, so that the interlayer spacing of the modified montmorillonite can be increased, and a composite material with good waterproof property and corrosion resistance can be obtained. In the second step, aniline, formaldehyde alcohol solution and 2, 2-bis- (4-hydroxyphenyl) hexafluoropropane alcohol solution are added to prepare a benzoxazine monomer with a lower dielectric constant, and then the benzoxazine monomer, the composite material, the epoxy resin and the hydrocarbon resin are used as raw materials to prepare the modified blend resin. Wherein the mass ratio of the benzoxazine monomer to the composite material to the epoxy resin to the hydrocarbon resin is 6:1:1-1.5:2, by adjusting the proportion of the epoxy resin within the range, the polymerization crosslinking between the three materials, namely the benzoxazine monomer, the composite material and the hydrocarbon resin, and the epoxy resin can be ensured to be optimal, and the modified blend resin with good water resistance, low dielectric property and high temperature resistance is prepared.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely in connection with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The raw material sources are as follows:
sodium montmorillonite, provided by Hebei Jiuyan engineering materials Co., ltd, with a product number of 220822-G; epoxy resin, provided by the manufacturing company, dry environmental protection technology Co., ltd., model E-44; hydrocarbon resin, available from Shanghai Mitian chemical Co., ltd., model number Plastolyn 290; the electronic glass fiber cloth is provided by Chijia thermal insulation material limited company in Hejia, and the model is 2116; copper foil, T2 Red copper, available from Wenzhou Hongfeng electrical alloy Co., ltd, has a thickness of 6. Mu.m.
Example 1: step one: 10 parts of sodium montmorillonite were added to 100 parts of an aqueous ethanol solution, in which the volume ratio of ethanol to water was 17:3, adding 20 parts of ethylene triethoxysilane and 20 parts of gamma-aminopropyl trimethoxysilane after fully stirring, stirring at 70 ℃ for reaction for 8 hours, and washing and drying after the reaction is finished to prepare the modified montmorillonite;
step two: adding 1 part of modified montmorillonite and 15 parts of dodecylbenzenesulfonic acid into 200 parts of deionized water, and magnetically stirring for 150min to obtain a solution 1; mixing 0.1 part of ferric trichloride hexahydrate and 10 parts of deionized water, and magnetically stirring for 30min to obtain a solution 2; mixing 3 parts of pyrrole monomer with 20 parts of deionized water, and fully stirring for 20min to obtain a solution 3; uniformly mixing the solution 1 and the solution 2, dropwise adding the solution 3, carrying out polymerization reaction for 30 hours at 25 ℃, and washing, filtering and drying after the reaction is finished to prepare a composite material;
step three: adding 4 parts of formaldehyde into 300 parts of ethanol for dissolution, adding 2 parts of aniline after full dissolution, carrying out water bath reaction, adding a mixed solution of 1 part of 2, 2-bis- (4-hydroxyphenyl) hexafluoropropane and 500 parts of ethanol after the reaction is finished, and carrying out polymerization reaction for 8 hours at 90 ℃ to obtain a benzoxazine monomer; 6 parts of benzoxazine monomer, 1 part of composite material, 1 part of epoxy resin and 2 parts of hydrocarbon resin are blended in an ethanol solvent to prepare modified blend resin;
step four: mixing 120 parts of modified blend resin, 15 parts of magnesium hydroxide, 50 parts of di-tert-butyl peroxide, 0.03 part of 2-ethyl-4-methylimidazole and 80 parts of acetone to prepare hydrocarbon resin glue solution, soaking glass fiber cloth in the hydrocarbon resin glue solution for 20min, taking out and curing to prepare a prepreg; copper foil is laminated on two sides of the prepreg, and the prepreg is laminated for 180min at the temperature of 200 ℃ and the pressure of 4MPa, so that a finished product is obtained.
Example 2: step one: 10 parts of sodium montmorillonite were added to 100 parts of an aqueous ethanol solution, in which the volume ratio of ethanol to water was 17:3, adding 20 parts of ethylene triethoxysilane and 20 parts of gamma-aminopropyl trimethoxysilane after fully stirring, stirring at 65 ℃ for 7.5 hours, washing and drying after the reaction is finished, and preparing the modified montmorillonite;
step two: adding 1 part of modified montmorillonite and 15 parts of dodecylbenzenesulfonic acid into 200 parts of deionized water, and magnetically stirring for 137min to obtain a solution 1; mixing 0.1 part of ferric trichloride hexahydrate and 10 parts of deionized water, and magnetically stirring for 27min to obtain a solution 2; mixing 3 parts of pyrrole monomer with 20 parts of deionized water, and fully stirring for 17min to obtain a solution 3; uniformly mixing the solution 1 and the solution 2, dropwise adding the solution 3, carrying out polymerization reaction at 24 ℃ for 26 hours, and washing, filtering and drying after the reaction is finished to prepare a composite material;
step three: adding 4 parts of formaldehyde into 300 parts of ethanol for dissolution, adding 2 parts of aniline after full dissolution, carrying out water bath reaction, adding a mixed solution of 1 part of 2, 2-bis- (4-hydroxyphenyl) hexafluoropropane and 500 parts of ethanol after the reaction is finished, and carrying out polymerization reaction for 7.5 hours at 87 ℃ to prepare a benzoxazine monomer; 6 parts of benzoxazine monomer, 1 part of composite material, 1 part of epoxy resin and 2 parts of hydrocarbon resin are blended in an ethanol solvent to prepare modified blend resin;
step four: mixing 120 parts of modified blend resin, 15 parts of magnesium hydroxide, 50 parts of di-tert-butyl peroxide, 0.03 part of 2-ethyl-4-methylimidazole and 80 parts of acetone to prepare hydrocarbon resin glue solution, soaking glass fiber cloth in the hydrocarbon resin glue solution for 17min, taking out and curing to prepare a prepreg; copper foil is laminated on two sides of the prepreg, and the prepreg is laminated for 160min at the temperature of 190 ℃ and the pressure of 3.5MPa, so that a finished product is obtained.
Example 3: step one: 10 parts of sodium montmorillonite were added to 100 parts of an aqueous ethanol solution, in which the volume ratio of ethanol to water was 17:3, adding 20 parts of ethylene triethoxysilane and 20 parts of gamma-aminopropyl trimethoxysilane after fully stirring, stirring at 60 ℃ for reaction for 7 hours, and washing and drying after the reaction is finished to prepare the modified montmorillonite;
step two: adding 1 part of modified montmorillonite and 15 parts of dodecylbenzenesulfonic acid into 200 parts of deionized water, and magnetically stirring for 125min to obtain a solution 1; mixing 0.1 part of ferric trichloride hexahydrate and 10 parts of deionized water, and magnetically stirring for 25min to obtain a solution 2; mixing 3 parts of pyrrole monomer with 20 parts of deionized water, and fully stirring for 15min to obtain a solution 3; uniformly mixing the solution 1 and the solution 2, dropwise adding the solution 3, carrying out polymerization reaction at 23 ℃ for 27 hours, and washing, filtering and drying after the reaction is finished to prepare a composite material;
step three: adding 4 parts of formaldehyde into 300 parts of ethanol for dissolution, adding 2 parts of aniline after full dissolution, carrying out water bath reaction, adding a mixed solution of 1 part of 2, 2-bis- (4-hydroxyphenyl) hexafluoropropane and 500 parts of ethanol after the reaction is finished, and carrying out polymerization reaction for 7 hours at 85 ℃ to obtain a benzoxazine monomer; 6 parts of benzoxazine monomer, 1 part of composite material, 1 part of epoxy resin and 2 parts of hydrocarbon resin are blended in an ethanol solvent to prepare modified blend resin;
step four: mixing 120 parts of modified blend resin, 15 parts of magnesium hydroxide, 50 parts of di-tert-butyl peroxide, 0.03 part of 2-ethyl-4-methylimidazole and 80 parts of acetone to prepare hydrocarbon resin glue solution, soaking glass fiber cloth in the hydrocarbon resin glue solution for 15min, taking out and curing to prepare a prepreg; copper foil is laminated on two sides of the prepreg, and the prepreg is laminated for 140min at the temperature of 175 ℃ and the pressure of 3MPa, so that a finished product is obtained.
Example 4: step one: 10 parts of sodium montmorillonite were added to 100 parts of an aqueous ethanol solution, in which the volume ratio of ethanol to water was 17:3, adding 20 parts of ethylene triethoxysilane and 20 parts of gamma-aminopropyl trimethoxysilane after fully stirring, stirring at 55 ℃ for reaction for 6.5 hours, and washing and drying after the reaction is finished to prepare the modified montmorillonite;
step two: adding 1 part of modified montmorillonite and 15 parts of dodecylbenzenesulfonic acid into 200 parts of deionized water, and magnetically stirring for 112min to obtain a solution 1; mixing 0.1 part of ferric trichloride hexahydrate and 10 parts of deionized water, and magnetically stirring for 23min to obtain a solution 2; mixing 3 parts of pyrrole monomer with 20 parts of deionized water, and fully stirring for 13min to obtain a solution 3; uniformly mixing the solution 1 and the solution 2, dropwise adding the solution 3, carrying out polymerization reaction at 21 ℃ for 26 hours, and washing, filtering and drying after the reaction is finished to prepare a composite material;
step three: adding 4 parts of formaldehyde into 300 parts of ethanol for dissolution, adding 2 parts of aniline after full dissolution, carrying out water bath reaction, adding a mixed solution of 1 part of 2, 2-bis- (4-hydroxyphenyl) hexafluoropropane and 500 parts of ethanol after the reaction is finished, and carrying out polymerization reaction for 6.5 hours at 83 ℃ to prepare a benzoxazine monomer; 6 parts of benzoxazine monomer, 1 part of composite material, 1 part of epoxy resin and 2 parts of hydrocarbon resin are blended in an ethanol solvent to prepare modified blend resin;
step four: mixing 120 parts of modified blend resin, 15 parts of magnesium hydroxide, 50 parts of di-tert-butyl peroxide, 0.03 part of 2-ethyl-4-methylimidazole and 80 parts of acetone to prepare hydrocarbon resin glue solution, soaking glass fiber cloth in the hydrocarbon resin glue solution for 13min, taking out and curing to prepare a prepreg; copper foil is laminated on two sides of the prepreg, and the prepreg is laminated for 120min at 162 ℃ under the pressure of 2.5MPa, so that a finished product is obtained.
Example 5: step one: 10 parts of sodium montmorillonite were added to 100 parts of an aqueous ethanol solution, in which the volume ratio of ethanol to water was 17:3, adding 20 parts of ethylene triethoxysilane and 20 parts of gamma-aminopropyl trimethoxysilane after fully stirring, stirring at 50 ℃ for reaction for 6 hours, and washing and drying after the reaction is finished to prepare the modified montmorillonite;
step two: adding 1 part of modified montmorillonite and 15 parts of dodecylbenzene sulfonic acid into 200 parts of deionized water, and magnetically stirring for 100min to obtain a solution 1; mixing 0.1 part of ferric trichloride hexahydrate and 10 parts of deionized water, and magnetically stirring for 20min to obtain a solution 2; mixing 3 parts of pyrrole monomer with 20 parts of deionized water, and fully stirring for 10min to obtain a solution 3; uniformly mixing the solution 1 and the solution 2, dropwise adding the solution 3, carrying out polymerization reaction at 20 ℃ for 25 hours, and washing, filtering and drying after the reaction is finished to prepare a composite material;
step three: adding 4 parts of formaldehyde into 300 parts of ethanol for dissolution, adding 2 parts of aniline after full dissolution, carrying out water bath reaction, adding a mixed solution of 1 part of 2, 2-bis- (4-hydroxyphenyl) hexafluoropropane and 500 parts of ethanol after the reaction is finished, and carrying out polymerization reaction for 6 hours at 80 ℃ to obtain a benzoxazine monomer; 6 parts of benzoxazine monomer, 1 part of composite material, 1 part of epoxy resin and 2 parts of hydrocarbon resin are blended in an ethanol solvent to prepare modified blend resin;
step four: mixing 120 parts of modified blend resin, 15 parts of magnesium hydroxide, 50 parts of di-tert-butyl peroxide, 0.03 part of 2-ethyl-4-methylimidazole and 80 parts of acetone to prepare hydrocarbon resin glue solution, soaking glass fiber cloth in the hydrocarbon resin glue solution for 10min, taking out and curing to prepare a prepreg; copper foil is laminated on two sides of the prepreg, and the prepreg is laminated for 100min at the temperature of 150 ℃ and the pressure of 2MPa, so that a finished product is obtained.
Comparative example 1: the preparation steps of the composite material were removed, and the rest was the same as in example 1, and the specific steps were as follows: step one: adding 4 parts of formaldehyde into 300 parts of ethanol for dissolution, adding 2 parts of aniline after full dissolution, carrying out water bath reaction, adding a mixed solution of 1 part of 2, 2-bis- (4-hydroxyphenyl) hexafluoropropane and 500 parts of ethanol after the reaction is finished, and carrying out polymerization reaction for 8 hours at 90 ℃ to obtain a benzoxazine monomer; 6 parts of benzoxazine monomer, 1 part of epoxy resin and 2 parts of hydrocarbon resin are blended in an ethanol solvent to prepare modified blend resin;
step two: mixing 120 parts of modified blend resin, 15 parts of magnesium hydroxide, 50 parts of di-tert-butyl peroxide, 0.03 part of 2-ethyl-4-methylimidazole and 80 parts of acetone to prepare hydrocarbon resin glue solution, soaking glass fiber cloth in the hydrocarbon resin glue solution for 20min, taking out and curing to prepare a prepreg; copper foil is laminated on two sides of the prepreg, and the prepreg is laminated for 180min at the temperature of 200 ℃ and the pressure of 4MPa, so that a finished product is obtained.
Comparative example 2: the benzoxazine monomer preparation steps were removed and the remainder were the same as in example 1, the specific steps were as follows: step one: 10 parts of sodium montmorillonite were added to 100 parts of an aqueous ethanol solution, in which the volume ratio of ethanol to water was 17:3, adding 20 parts of ethylene triethoxysilane and 20 parts of gamma-aminopropyl trimethoxysilane after fully stirring, stirring at 70 ℃ for reaction for 8 hours, and washing and drying after the reaction is finished to prepare the modified montmorillonite;
step two: adding 1 part of modified montmorillonite and 15 parts of dodecylbenzenesulfonic acid into 200 parts of deionized water, and magnetically stirring for 150min to obtain a solution 1; mixing 0.1 part of ferric trichloride hexahydrate and 10 parts of deionized water, and magnetically stirring for 30min to obtain a solution 2; mixing 3 parts of pyrrole monomer with 20 parts of deionized water, and fully stirring for 20min to obtain a solution 3; uniformly mixing the solution 1 and the solution 2, dropwise adding the solution 3, carrying out polymerization reaction for 30 hours at 25 ℃, and washing, filtering and drying after the reaction is finished to prepare a composite material;
step three: blending 1 part of composite material, 1 part of epoxy resin and 2 parts of hydrocarbon resin in an ethanol solvent to prepare modified blend resin;
step four: mixing 120 parts of modified blend resin, 15 parts of magnesium hydroxide, 50 parts of di-tert-butyl peroxide, 0.03 part of 2-ethyl-4-methylimidazole and 80 parts of acetone to prepare hydrocarbon resin glue solution, soaking glass fiber cloth in the hydrocarbon resin glue solution for 20min, taking out and curing to prepare a prepreg; copper foil is laminated on two sides of the prepreg, and the prepreg is laminated for 180min at the temperature of 200 ℃ and the pressure of 4MPa, so that a finished product is obtained.
Detection test:
water contact angle test: the prepreg prepared by the invention is cut into a sample with the size of 25X 300mm, the sample is kept dry before the test, and then the water contact angle is measured by using a water contact angle measuring instrument of DataPhysics company of Germany.
Dielectric constant test: the prepreg prepared by the invention is cut into a sample with the size of 13X 8mm, and then the dielectric constant is measured by an E5071C ENA vector network analyzer (Agilent corporation of America).
Tensile strength test: the prepreg prepared by the method is cut into samples with the dimensions of 115 multiplied by 25 multiplied by 2mm, the experimental speed is 50mm/min +/-10%, three points are measured for each sample, the arithmetic average value is taken, and finally the tensile strength is calculated through a formula. The results are shown in the following table;
conclusion: the amounts of examples 1 to 5 were unchanged, and only part of the reaction parameters were modified. Experimental data show that the properties of the prepreg have no obvious fluctuation change. Comparative example 1: the procedure for preparing the composite material was removed, and the rest was the same as in example 1, and it was found from the experimental data that the contact angle was reduced to 85℃and the dielectric constant was increased to 2.93F/m and the tensile strength was reduced to 26.3MPa, compared with example 1, because of the analysis: after the preparation steps of the composite material are removed, the hydrophobic property of the prepreg is reduced, the polarizability is increased, and therefore, the water contact angle is reduced and the dielectric constant is increased.
Comparative example 2: the procedure for preparing the benzoxazine monomer was removed, and the rest was the same as in example 1, and as apparent from the experimental data, the contact angle was reduced to 97 °, the dielectric constant was increased to 3.51F/m, and the tensile strength was reduced to 26.7MPa, compared with example 1, because of the analysis: after the benzoxazine monomer preparation step is removed, the fluorine content of the prepreg is reduced, so that the water contact angle is reduced and the dielectric constant is increased.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a high-temperature-resistant low-dielectric hydrocarbon resin-based copper-clad plate is characterized by comprising the following steps of: the method comprises the following steps:
step one: adding modified montmorillonite and dodecylbenzene sulfonic acid into deionized water, and magnetically stirring for 100-150min to obtain a solution 1; mixing ferric trichloride hexahydrate with deionized water, and magnetically stirring for 20-30min to obtain a solution 2; mixing pyrrole monomer and deionized water, and stirring for 10-20min to obtain solution 3; uniformly mixing the solution 1 and the solution 2, dropwise adding the solution 3, performing polymerization reaction, and washing, filtering and drying after the reaction is finished to prepare a composite material;
step two: adding formaldehyde into ethanol for dissolution, adding aniline after full dissolution, carrying out water bath reaction, adding mixed solution of 2, 2-bis- (4-hydroxyphenyl) hexafluoropropane and ethanol after reaction, and carrying out polymerization reaction to prepare a benzoxazine monomer; blending benzoxazine monomer, composite material, epoxy resin and hydrocarbon resin in an ethanol solvent to prepare modified blend resin;
step three: mixing the modified blend resin, the inorganic filler, the initiator, the accelerator and the solvent to prepare hydrocarbon resin glue solution, dipping the glass fiber cloth in the hydrocarbon resin glue solution for 10-20min, taking out and curing to prepare a prepreg; and (3) laminating copper foils on two sides of the prepreg, and preparing a finished product after lamination molding.
2. The method for preparing the high-temperature-resistant low-dielectric hydrocarbon resin-based copper-clad plate according to claim 1, which is characterized by comprising the following steps: in the first step, the mass ratio of the modified montmorillonite, the dodecylbenzene sulfonic acid, the ferric trichloride hexahydrate and the pyrrole monomer is 1-2:15:0.1:3.
3. the method for preparing the high-temperature-resistant low-dielectric hydrocarbon resin-based copper-clad plate according to claim 1, which is characterized by comprising the following steps: in the first step, the reaction temperature is 20-25 ℃ and the reaction time is 25-30h during the polymerization reaction.
4. The method for preparing the high-temperature-resistant low-dielectric hydrocarbon resin-based copper-clad plate according to claim 2, which is characterized by comprising the following steps: the preparation method of the modified montmorillonite comprises the following steps: adding sodium montmorillonite into ethanol water solution, stirring thoroughly, adding ethylene triethoxysilane and gamma-aminopropyl trimethoxysilane, stirring for reaction, washing after reaction, and drying to obtain modified montmorillonite.
5. The method for preparing the high-temperature-resistant low-dielectric hydrocarbon resin-based copper-clad plate according to claim 4, which is characterized by comprising the following steps: the mass ratio of the sodium montmorillonite to the ethylene triethoxysilane to the gamma-aminopropyl trimethoxysilane is 1-2:2:2; the volume ratio of ethanol to water in the ethanol aqueous solution is 17:3-4; the reaction temperature is 50-70 ℃ and the reaction time is 6-8h when stirring and reacting.
6. The method for preparing the high-temperature-resistant low-dielectric hydrocarbon resin-based copper-clad plate according to claim 1, which is characterized by comprising the following steps: in the second step, the molar ratio of formaldehyde, aniline and 2, 2-bis- (4-hydroxyphenyl) hexafluoropropane is 4:2:1-2.
7. The method for preparing the high-temperature-resistant low-dielectric hydrocarbon resin-based copper-clad plate according to claim 1, which is characterized by comprising the following steps: in the second step, the reaction temperature is 80-90 ℃ and the reaction time is 6-8h during the polymerization reaction.
8. The method for preparing the high-temperature-resistant low-dielectric hydrocarbon resin-based copper-clad plate according to claim 1, which is characterized by comprising the following steps: in the second step, the mass ratio of the benzoxazine monomer to the composite material to the epoxy resin to the hydrocarbon resin is 6:1:1-1.5:2.
9. the method for preparing the high-temperature-resistant low-dielectric hydrocarbon resin-based copper-clad plate according to claim 1, which is characterized by comprising the following steps: in the third step, the hydrocarbon resin glue solution comprises the following components in percentage by weight: 120-130 parts of modified blend resin, 15-30 parts of inorganic filler, 50-70 parts of initiator, 0.03-0.05 part of accelerator and 80-100 parts of solvent by mass; wherein the inorganic filler is magnesium hydroxide, the initiator is di-tert-butyl peroxide, the accelerator is 2-ethyl-4-methylimidazole, and the solvent is acetone.
10. The method for preparing the high-temperature-resistant low-dielectric hydrocarbon resin-based copper-clad plate according to claim 1, which is characterized by comprising the following steps: in the third step, lamination forming process parameters: the temperature is 150-200deg.C, the pressure is 2-4MPa, and the time is 100-180min.
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