CN117004172A - Preparation method of high-toughness phenolic resin glue solution for copper-clad plate - Google Patents
Preparation method of high-toughness phenolic resin glue solution for copper-clad plate Download PDFInfo
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- CN117004172A CN117004172A CN202311016227.0A CN202311016227A CN117004172A CN 117004172 A CN117004172 A CN 117004172A CN 202311016227 A CN202311016227 A CN 202311016227A CN 117004172 A CN117004172 A CN 117004172A
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- phenolic resin
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- copper
- butadiene rubber
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 92
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000003292 glue Substances 0.000 title claims description 36
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 55
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 51
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 36
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 24
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 16
- 150000003505 terpenes Chemical class 0.000 claims abstract description 16
- 235000007586 terpenes Nutrition 0.000 claims abstract description 16
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 14
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003822 epoxy resin Substances 0.000 claims abstract description 11
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 230000000977 initiatory effect Effects 0.000 claims abstract description 5
- 238000012650 click reaction Methods 0.000 claims abstract description 4
- 238000006266 etherification reaction Methods 0.000 claims abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 230000001678 irradiating effect Effects 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- 239000005543 nano-size silicon particle Substances 0.000 claims description 9
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229920003986 novolac Polymers 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000002861 polymer material Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 description 22
- 239000011347 resin Substances 0.000 description 21
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241000238367 Mya arenaria Species 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000005462 imide group Chemical group 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 241000218033 Hibiscus Species 0.000 description 1
- 235000005206 Hibiscus Nutrition 0.000 description 1
- 235000007185 Hibiscus lunariifolius Nutrition 0.000 description 1
- 241000209051 Saccharum Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- -1 meanwhile Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/14—Modified phenol-aldehyde condensates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The invention relates to the technical field of high polymer materials, in particular to a preparation method of high-toughness phenolic resin for a copper-clad plate. The specific proposal is as follows: step one: triggering dimercapto polyethylene glycol to perform click reaction with hydroxyethyl acrylate and maleimide through ultraviolet laser irradiation to prepare a flexible compound; then grafting the modified phenolic resin onto the phenolic resin through hydroxyl etherification reaction to obtain modified phenolic resin; step two: initiating polymerization by ultraviolet laser irradiation, grafting and wrapping a polyacrylamide layer on the surface of silicon nitride, and grafting polyacrylamide on styrene-butadiene rubber to obtain modified silicon nitride and modified styrene-butadiene rubber respectively; step three: 25-35 parts of terpene phenolic resin, 25-30 parts of bisphenol A type epoxy resin, 5-10 parts of modified linear phenolic resin, 10-25 parts of modified silicon nitride, 10-20 parts of modified styrene-butadiene rubber, 50-80 parts of butanone, 5-10 parts of curing agent and 0.05-0.2 part of curing accelerator are mixed to obtain the high-toughness phenolic resin for the copper-clad plate.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a preparation method of high-toughness phenolic resin for a copper-clad plate.
Background
With the rapid development of 5G technology, the electronic communication field is moving towards high frequency and high speed, such as satellite base station, automobile electronics, mobile phone and computer, etc., which have higher requirements for their printed circuit boards, and the copper-clad plate is used as a core element of the printed circuit board, playing an important role in information processing and transmission. Because the current electronic products are developed towards light, thin, small, high-density and multifunctional, the component assembly density and the integration level are higher and higher, the frequency of the transmitted signals is higher and higher, the interlayer distance of the circuit which plays a role in transmitting the signals is smaller and smaller, the line width is narrower and narrower, namely, the component works to generate larger temperature, and higher requirements are put forward on the heat conduction and toughness of the copper-clad plate.
The phenolic resin is a polymer material which achieves industrial production at the earliest, and the phenolic resin-based composite material has the characteristics of excellent low smoke, low toxicity, flame retardance, low price and the like, and is used as flame retardant resin with extremely high cost performance. The resin coating layer of the existing copper-clad plate mostly adopts phenolic resin, but due to poor flexibility of a phenolic resin molecular main chain, a high-rigidity network structure with high crosslinking density can be generated after curing, so that brittleness is high, impact resistance is poor, and self performance of the copper-clad plate is seriously affected.
In summary, in order to improve the defects of the current phenolic resin glue solution for copper-clad plates in performance, the phenolic resin glue solution needs to be effectively toughened and modified, which has important significance.
Disclosure of Invention
The invention aims to provide a preparation method of high-toughness phenolic resin glue solution for a copper-clad plate, which aims to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
the high-toughness phenolic resin glue solution for the copper-clad plate comprises the following components in parts by weight: 25-35 parts of terpene phenolic resin, 25-30 parts of bisphenol A type epoxy resin, 5-10 parts of modified linear phenolic resin, 10-25 parts of modified silicon nitride, 10-20 parts of modified styrene-butadiene rubber, 50-80 parts of solvent, 5-10 parts of curing agent and 0.05-0.2 part of curing accelerator.
Further, the preparation method of the high-toughness phenolic resin glue solution for the copper-clad plate comprises the following steps:
step one: triggering dimercapto polyethylene glycol to perform click reaction with hydroxyethyl acrylate and maleimide through ultraviolet laser irradiation to prepare a flexible compound; then grafting the modified phenolic resin onto the phenolic resin through hydroxyl etherification reaction to obtain modified phenolic resin;
step two: initiating polymerization reaction by ultraviolet laser irradiation, and grafting and wrapping a polyacrylamide layer on the surface of the silicon nitride to obtain modified silicon nitride;
step three: initiating polymerization reaction by ultraviolet laser irradiation, and grafting polyacrylamide on the styrene-butadiene rubber to obtain modified styrene-butadiene rubber;
step four: and mixing the terpene phenolic resin, the bisphenol A epoxy resin, the modified linear phenolic resin, the modified silicon nitride, the modified styrene-butadiene rubber, the butanone, the curing agent and the curing accelerator to obtain the high-toughness phenolic resin glue solution for the copper-clad plate.
Further, the preparation method of the flexible compound comprises the following steps: (1) Preparing dimercapto polyethylene glycol and ethanol into dimercapto polyethylene glycol solution, adding hydroxyethyl acrylate, a photoinitiator and hydroquinone into the dimercapto polyethylene glycol solution, performing ultrasonic dispersion for 5-15 min, and performing ultraviolet irradiation reaction for 30-60 min at 365nm in a nitrogen environment to obtain a reactant A; (2) And adding maleimide into the reactant A, performing ultrasonic dispersion for 5-15 min, performing irradiation reaction for 30-60 min by using 365nm ultraviolet light in a nitrogen environment, and performing filtration, washing and drying to obtain the flexible compound.
Further, the mass ratio of the dimercapto polyethylene glycol to the hydroxyethyl acrylate to the maleimide is 1:0.12:0.1; the addition amount of hydroquinone is 0.5-2% of that of hydroxyethyl acrylate; the addition amount of the photoinitiator is 1-5% of the mass of the dimercapto polyethylene glycol.
Further, the preparation method of the modified linear phenolic resin comprises the following steps: adding the phenolic resin, the flexible compound and 15wt% sulfuric acid into a reaction container, uniformly stirring, heating to 100-200 ℃, carrying out reflux reaction for 6-12 h, ending the reaction, naturally cooling the reaction system to room temperature, and filtering, washing and drying to obtain the modified phenolic resin.
Further, the addition amount of the phenolic novolac resin and the flexible compound is (1-1.2): the addition amount of the 1, 15wt% sulfuric acid is 3-8% of that of the phenolic novolac resin.
Further, the preparation method of the modified silicon nitride comprises the following steps: mixing nano silicon nitride, an acrylamide aqueous solution and a photoinitiator, irradiating for 0.5-2 h under 254nm ultraviolet light in a nitrogen environment, and filtering, washing and drying to obtain the modified silicon nitride.
Further, the concentration of the acrylamide aqueous solution is 2.5-10wt%; the mass ratio of the nano silicon nitride to the acrylamide to the photoinitiator is 1: (1-1.5): (0.15-0.2).
Further, the preparation method of the modified styrene-butadiene rubber comprises the following steps: adding styrene-butadiene rubber into toluene, stirring to dissolve, adding acrylamide and a photoinitiator, irradiating for 0.5-2 h under 254nm ultraviolet light in a nitrogen environment, filtering, washing, and drying to obtain the modified styrene-butadiene rubber.
Further, the addition amount of the acrylamide is 10-40% of the styrene-butadiene rubber, and the addition amount of the photoinitiator is 2-7% of the styrene-butadiene rubber.
Further, the solvent includes, but is not limited to, one or more combinations of butanone, acetone, propylene glycol methyl ether, and propylene glycol methyl ether acetate.
Further, the curing agent includes, but is not limited to, one or more combinations of triethanolamine curing agent, isocyanate curing agent, anhydride curing agent, and ammonium phosphate curing agent.
Further, the curing accelerator includes, but is not limited to, one of 2-methylimidazole, 2-phenylimidazole and 2-ethyl-4-methylimidazole.
Compared with the prior art, the invention has the following beneficial effects: because the phenolic aldehyde-epoxy resin system has the characteristic of large brittleness generally, and further the toughness performance of the obtained resin material is poor, the glue solution is prepared from terpene phenolic resin and bisphenol A epoxy resin, wherein the terpene phenolic resin can enable the glue solution to have better impact resistance performance after being coated compared with the linear phenolic resin, the brittleness is smaller, the toughness is better, and the heat resistance is improved; in order to further improve the defects of high brittleness and poor application performance of the phenolic-epoxy resin system in the copper-clad plate, the invention improves the linear phenolic resin, and the flexible compound is grafted on the surface of the linear phenolic resin, so that the toughness of the resin is improved, and the phenolic-epoxy resin system has better compatibility with an original system and stronger operability. According to the invention, silicon nitride is improved, a polyacrylamide layer is coated on the surface of the silicon nitride, a soft shell structure toughening agent taking a polyacrylamide elastomer as a soft shell is formed, toughening is realized from two aspects of a rigid body and an elastomer, meanwhile, polyacrylamide is grafted on the surface of styrene-butadiene rubber, the contact of modified silicon nitride and modified styrene-butadiene rubber is promoted, silver lines can be promoted to be generated by the combination of the modified silicon nitride and the modified styrene-butadiene rubber, energy can be absorbed by the combination of the modified silicon nitride and the modified styrene-butadiene rubber, and the silver lines can be better prevented from being further diffused by the modified styrene-butadiene rubber, so that the resin is toughened; on the other hand, after the modified silicon nitride and the modified styrene-butadiene rubber are contacted, the compatibility of the particles in the glue solution is poor, so that the resin system can be changed from a homogeneous system into a multiphase system, namely, a sea-island structure can be formed in the resin, and the toughness of the resin can be greatly improved; in addition, the imide group can also play a great role in improving the heat resistance of the material, and in conclusion, the phenolic resin for the copper-clad plate has the performances of high toughness, heat resistance and the like.
(1) Dimercapto polyethylene glycol, hydroxyethyl acrylate and maleimide are subjected to click reaction to synthesize a high polymer, and the high polymer has good flexibility, and in addition, the heat resistance of the resin can be improved by the imide group; and then the prepared flexible molecules are grafted into the linear phenolic resin to obtain the modified linear phenolic resin, so that the characteristic of high brittleness of a phenolic-epoxy resin system can be improved, the resin on the copper-clad plate is effectively toughened, and the modified linear phenolic resin also has a curing effect.
(2) The invention uses photoinitiated polymerization to modify silicon nitride, reduce reaction conditions, improve product purity, wrap a layer of polyacrylamide layer on the surface of silicon nitride, make a kind of core-shell structure modified silicon nitride which uses nano silicon nitride as core, polyacrylate as shell, it is applied to resin, toughen up and elastomer toughen up two mechanisms from the rigid body, in addition, in order to further improve toughen up the effect, have also modified the butadiene styrene rubber, have realized modified butadiene styrene rubber granule and core-shell modified silicon nitride and combined and coupled and toughen up, can promote the resin phase to produce the silver streak to absorb energy, can also correspondingly hinder the development of silver streak, finally achieve toughen up the effect. As the sea-island structure is an important factor for toughening the resin, namely, the formation of the sea-island structure can lead the cracking resistance of the resin to be suddenly changed, the fracture toughness of the material can be greatly improved, and other properties can not be greatly influenced.
(3) As the sea-island structure is an important factor for toughening the resin, namely, the formation of the sea-island structure can lead the cracking resistance of the resin to be suddenly changed, the fracture toughness of the material can be greatly improved, other properties can not be greatly influenced, and the compatibility of modified silicon nitride particles and modified styrene-butadiene rubber particles in the invention in glue solution can be poor, so that the resin system can be changed into a multiphase system from a homogeneous system, namely, the sea-island structure can be formed in the resin, and the toughness of the resin can be greatly improved.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious 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.
In the following examples, terpene phenolic resin model SNF-803L, cat: 203L (Shang Jiu Nan resin Co., ltd.), the purity of the phenolic novolac resin was 99%, CAS number: 65733-76-8 (Hubei Wan chemical Co., ltd.) bisphenol A type epoxy resin has a purity of 99% and a model: e-12 (604), part number: 0002 (Wuhan Prolover Biotechnology Co., ltd.) the purity of butanone was 99% (Nanjing reagent Co., ltd.), the purity of triethanolamine was 99% (Hebei ken Hibiscus Biotechnology Co., ltd.), the purity of 2-methylimidazole was 97%, CAS number: 693-98-1, cat No.: s25048 (Shanghai Yuan leaf Biotechnology Co., ltd.) dimercapto polyethylene glycol has a purity of 95%, a molecular weight of 2000, and a product number: 80020104 (Guangzhou, inc. of carbohydrate technologies Co., ltd.) the purity of ethanol was 99% (WU.S. Ji Xinyi, country biosciences Co., ltd.) the purity of hydroxyethyl acrylate was 99%, cat No.: r055 (Pande (Shanghai) International trade Co., ltd.) the purity of hydroquinone was 99.5% (Henan Jiuzhu Co., ltd.), the purity of maleimide was 98%, CAS number: 541-59-3, cat No.: s48137 (Shanghai Yuan Ye Biotech Co., ltd.) the concentration of sulfuric acid is 15wt% (Nanjing reagent Co., ltd.), the purity of nano silicon nitride is 99.99% (Shanghai Runfu nano technology Co., ltd.), the purity of acrylamide is 99% (Shanghai Fu Saccharum chemical Co., ltd.), the purity of photoinitiator is 98%, CAS number 606-28-0 (Wuhan Xin Wei Di chemical Co., ltd.), toluene (Nanjing reagent Co., ltd.), styrene-butadiene rubber type: model 1712 (Pandek (Shanghai) International trade company, inc.).
Example 1: a preparation method of a high-toughness phenolic resin glue solution for a copper-clad plate comprises the following steps:
step one: the preparation method of the flexible compound comprises the following steps: (1) Preparing dimercapto polyethylene glycol 10 parts with enough ethanol into dimercapto polyethylene glycol solution, adding hydroxyethyl acrylate 1.2 parts, photoinitiator 0.3 parts and hydroquinone 0.012 parts into the dimercapto polyethylene glycol solution, performing ultrasonic dispersion for 10min, and performing irradiation reaction for 60min by using ultraviolet light of 365nm in a nitrogen environment to obtain a reactant A; (2) Then adding 1 part of maleimide into the reactant A, performing ultrasonic dispersion for 10min, performing irradiation reaction for 60min by using 365nm ultraviolet light in a nitrogen environment, and performing filtration, washing and drying to obtain a flexible compound;
the preparation method of the modified linear phenolic resin comprises the following steps: adding 10 parts of linear phenolic resin, 10 parts of flexible compound and 0.6 part of 15wt% sulfuric acid into a reaction container, uniformly stirring, heating to 150 ℃, carrying out reflux reaction for 8 hours, ending the reaction, and obtaining modified linear phenolic resin after the reaction system is naturally cooled to room temperature, filtering, washing and drying;
step two: the preparation method of the modified silicon nitride comprises the following steps: mixing 25 parts of nano silicon nitride, 320 parts of 8wt% acrylamide aqueous solution and 4 parts of photoinitiator, irradiating for 2 hours under 254nm ultraviolet light in a nitrogen environment, and filtering, washing and drying to obtain modified silicon nitride;
step three: the preparation method of the modified styrene-butadiene rubber comprises the following steps: adding 20 parts of styrene-butadiene rubber into enough toluene, stirring to dissolve the styrene-butadiene rubber, adding 6 parts of acrylamide and 0.8 part of photoinitiator, irradiating for 2 hours under 254nm ultraviolet light in a nitrogen environment, and filtering, washing and drying to obtain modified styrene-butadiene rubber;
step four: and uniformly mixing 30 parts of terpene phenolic resin, 25 parts of bisphenol A epoxy resin, 8 parts of modified linear phenolic resin, 18 parts of modified silicon nitride, 15 parts of modified styrene-butadiene rubber, 60 parts of butanone, 8 parts of triethanolamine and 0.1 part of 2-methylimidazole to obtain the high-toughness phenolic resin glue solution for the copper-clad plate.
Example 2: a preparation method of a high-toughness phenolic resin glue solution for a copper-clad plate comprises the following steps:
step one: the preparation method of the flexible compound comprises the following steps: (1) Preparing dimercapto polyethylene glycol solution by 10 parts of dimercapto polyethylene glycol and enough ethanol, adding 1.2 parts of hydroxyethyl acrylate, 0.1 part of photoinitiator and 0.006 part of hydroquinone into the dimercapto polyethylene glycol solution, performing ultrasonic dispersion for 10min, and performing irradiation reaction for 60min by using 365nm ultraviolet light in a nitrogen environment to obtain a reactant A; (2) Then adding 1 part of maleimide into the reactant A, performing ultrasonic dispersion for 10min, performing irradiation reaction for 60min by using 365nm ultraviolet light in a nitrogen environment, and performing filtration, washing and drying to obtain a flexible compound;
the preparation method of the modified linear phenolic resin comprises the following steps: adding 10 parts of linear phenolic resin, 10 parts of flexible compound and 0.3 part of 15wt% sulfuric acid into a reaction container, uniformly stirring, heating to 150 ℃, carrying out reflux reaction for 6 hours, ending the reaction, and obtaining modified linear phenolic resin after the reaction system is naturally cooled to room temperature, filtering, washing and drying;
step two: the preparation method of the modified silicon nitride comprises the following steps: mixing 25 parts of nano silicon nitride, 312.5 parts of 8wt% acrylamide aqueous solution and 3.75 parts of photoinitiator, irradiating for 0.5h under 254nm ultraviolet light in a nitrogen environment, and filtering, washing and drying to obtain modified silicon nitride;
step three: the preparation method of the modified styrene-butadiene rubber comprises the following steps: adding 20 parts of styrene-butadiene rubber into enough toluene, stirring to dissolve the styrene-butadiene rubber, adding 2 parts of acrylamide and 0.4 part of photoinitiator, irradiating for 0.5h under 254nm ultraviolet light in a nitrogen environment, filtering, washing and drying to obtain modified styrene-butadiene rubber;
step four: and uniformly mixing 30 parts of terpene phenolic resin, 25 parts of bisphenol A epoxy resin, 8 parts of modified linear phenolic resin, 18 parts of modified silicon nitride, 15 parts of modified styrene-butadiene rubber, 60 parts of butanone, 8 parts of triethanolamine and 0.1 part of 2-methylimidazole to obtain the high-toughness phenolic resin glue solution for the copper-clad plate.
Example 3: a preparation method of a high-toughness phenolic resin glue solution for a copper-clad plate comprises the following steps:
step one: the preparation method of the flexible compound comprises the following steps: (1) Preparing dimercapto polyethylene glycol solution by 10 parts of dimercapto polyethylene glycol and enough ethanol, adding 1.2 parts of hydroxyethyl acrylate, 0.5 part of photoinitiator and 0.024 part of hydroquinone into the dimercapto polyethylene glycol solution, performing ultrasonic dispersion for 10min, and performing irradiation reaction for 60min by using 365nm ultraviolet light in a nitrogen environment to obtain a reactant A; (2) Then adding 1 part of maleimide into the reactant A, performing ultrasonic dispersion for 10min, performing irradiation reaction for 60min by using 365nm ultraviolet light in a nitrogen environment, and performing filtration, washing and drying to obtain a flexible compound;
the preparation method of the modified linear phenolic resin comprises the following steps: adding 12 parts of linear phenolic resin, 10 parts of flexible compound and 0.96 part of 15wt% sulfuric acid into a reaction container, uniformly stirring, heating to 150 ℃, carrying out reflux reaction for 12 hours, ending the reaction, and obtaining modified linear phenolic resin after the reaction system is naturally cooled to room temperature, filtering, washing and drying;
step two: the preparation method of the modified silicon nitride comprises the following steps: mixing 25 parts of nano silicon nitride, 468.8 parts of 8wt% acrylamide aqueous solution and 5 parts of photoinitiator, irradiating for 2 hours under 254nm ultraviolet light in a nitrogen environment, and filtering, washing and drying to obtain modified silicon nitride;
step three: the preparation method of the modified styrene-butadiene rubber comprises the following steps: adding 20 parts of styrene-butadiene rubber into enough toluene, stirring to dissolve the styrene-butadiene rubber, adding 8 parts of acrylamide and 1.4 parts of photoinitiator, irradiating for 2 hours under 254nm ultraviolet light in a nitrogen environment, and filtering, washing and drying to obtain modified styrene-butadiene rubber;
step four: and uniformly mixing 30 parts of terpene phenolic resin, 25 parts of bisphenol A epoxy resin, 8 parts of modified linear phenolic resin, 18 parts of modified silicon nitride, 15 parts of modified styrene-butadiene rubber, 60 parts of butanone, 8 parts of triethanolamine and 0.1 part of 2-methylimidazole to obtain the high-toughness phenolic resin glue solution for the copper-clad plate.
Comparative example 1: step four: uniformly mixing 30 parts of terpene phenolic resin, 25 parts of bisphenol A epoxy resin, 5 parts of modified linear phenolic resin, 10 parts of modified silicon nitride, 5 parts of modified styrene-butadiene rubber, 60 parts of butanone, 8 parts of triethanolamine and 0.1 part of 2-methylimidazole to obtain high-toughness phenolic resin glue solution for the copper-clad plate; otherwise, the same as in example 1;
comparative example 2: step four: uniformly mixing 30 parts of terpene phenolic resin, 25 parts of bisphenol A type epoxy resin, 10 parts of modified linear phenolic resin, 25 parts of modified silicon nitride, 20 parts of modified styrene-butadiene rubber, 60 parts of butanone, 8 parts of triethanolamine and 0.1 part of 2-methylimidazole to obtain high-toughness phenolic resin glue solution for the copper-clad plate; otherwise, the same as in example 1;
comparative example 3: the procedure of example 1 was repeated except that the modified phenolic novolac resin was not added; the method comprises the following steps: step four: uniformly mixing 30 parts of terpene phenolic resin, 25 parts of bisphenol A epoxy resin, 18 parts of modified silicon nitride, 15 parts of modified styrene-butadiene rubber, 60 parts of butanone, 8 parts of triethanolamine and 0.1 part of 2-methylimidazole to obtain high-toughness phenolic resin glue solution for the copper-clad plate;
comparative example 4: the modified silicon nitride and the modified styrene-butadiene rubber are not added, and are replaced by the styrene-butadiene rubber, and the other steps are the same as those in the example 1; the method comprises the following steps: step four: uniformly mixing 30 parts of terpene phenolic resin, 25 parts of bisphenol A type epoxy resin, 8 parts of modified linear phenolic resin, 33 parts of styrene-butadiene rubber, 60 parts of butanone, 8 parts of triethanolamine and 0.1 part of 2-methylimidazole to obtain high-toughness phenolic resin glue solution for the copper-clad plate;
comparative example 5: the terpene phenolic resin is not used, and is changed into linear phenolic resin; modified silicon nitride and modified styrene butadiene rubber are not added, and are replaced by styrene butadiene rubber only; no modified phenolic novolac resin is added; the method comprises the following steps: and uniformly mixing 30 parts of linear phenolic resin, 25 parts of bisphenol A type epoxy resin, 33 parts of styrene-butadiene rubber, 60 parts of butanone, 8 parts of triethanolamine and 0.1 part of 2-methylimidazole to obtain the high-toughness phenolic resin glue solution for the copper-clad plate.
Performance test: the copper-clad plates prepared in examples 1 to 3 and comparative examples 1 to 5 are respectively impregnated with high-toughness phenolic resin by an impregnating glue solution method for 10min, so that the copper-clad plates are uniformly glued on 5 pieces of glass fiber cloth, and are baked in an oven at 140 ℃ for 30min to be cured to obtain 5 pieces of prepregs; 5 prepregs are stacked together, cut, covered with 18 mu m copper foil on both sides, and hot pressed for 4 hours at 220 ℃ under 15MPa to obtain the copper-clad plate. And bending performance is tested according to GB/T9341-2008 copper clad laminate; the heat resistance test was carried out by the wicking method, wicking at 288 ℃ for 10s once until delamination occurred.
| Examples | Flexural Strength (MPa) | Heat resistance test (secondary) |
| Example 1 | 258.1 | 23 |
| Example 2 | 247.1 | 20 |
| Example 3 | 252.3 | 22 |
| Comparative example 1 | 220.2 | 19 |
| Comparative example 2 | 252.2 | 22 |
| Comparative example 3 | 210.8 | 19 |
| Comparative example 4 | 191.2 | 15 |
| Comparative example 5 | 150.8 | 10 |
Analysis of results: from the table above, the high-toughness phenolic glue solution for the copper-clad plate prepared by the invention greatly improves the toughness of the resin, wherein the modified silicon nitride and the modified styrene-butadiene rubber have larger influence on the toughness, which indicates that the modified silicon nitride and the modified styrene-butadiene rubber can promote the formation of a sea-island structure and greatly improve the toughness of the resin; through a tin immersion test, the prepared copper-clad plate also has better heat resistance.
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 high-toughness phenolic resin glue solution for a copper-clad plate is characterized in that: the composition comprises the following components: the weight portions are as follows: 25-35 parts of terpene phenolic resin, 25-30 parts of bisphenol A type epoxy resin, 5-10 parts of modified linear phenolic resin, 10-25 parts of modified silicon nitride, 10-20 parts of modified styrene-butadiene rubber, 50-80 parts of solvent, 5-10 parts of curing agent and 0.05-0.2 part of curing accelerator.
2. The method for preparing the high-toughness phenolic resin glue solution for the copper-clad plate, which is disclosed in claim 1, is characterized in that: the method comprises the following steps:
step one: triggering dimercapto polyethylene glycol to perform click reaction with hydroxyethyl acrylate and maleimide through ultraviolet laser irradiation to prepare a flexible compound; then grafting the modified phenolic resin onto the phenolic resin through hydroxyl etherification reaction to obtain modified phenolic resin;
step two: initiating polymerization reaction by ultraviolet laser irradiation, and grafting and wrapping a polyacrylamide layer on the surface of the silicon nitride to obtain modified silicon nitride;
step three: initiating polymerization reaction by ultraviolet laser irradiation, and grafting polyacrylamide on the styrene-butadiene rubber to obtain modified styrene-butadiene rubber;
step four: and mixing the terpene phenolic resin, the bisphenol A epoxy resin, the modified linear phenolic resin, the modified silicon nitride, the modified styrene-butadiene rubber, the butanone, the curing agent and the curing accelerator to obtain the high-toughness phenolic resin glue solution for the copper-clad plate.
3. The method for preparing the high-toughness phenolic resin glue solution for the copper-clad plate according to claim 2, which is characterized by comprising the following steps: the preparation method of the flexible compound comprises the following steps:
(1) Preparing dimercapto polyethylene glycol and ethanol into dimercapto polyethylene glycol solution, adding hydroxyethyl acrylate, a photoinitiator and hydroquinone into the dimercapto polyethylene glycol solution, performing ultrasonic dispersion for 5-15 min, and performing ultraviolet irradiation reaction for 30-60 min at 365nm in a nitrogen environment to obtain a reactant A;
(2) And adding maleimide into the reactant A, performing ultrasonic dispersion for 5-15 min, performing irradiation reaction for 30-60 min by using 365nm ultraviolet light in a nitrogen environment, and performing filtration, washing and drying to obtain the flexible compound.
4. The method for preparing the high-toughness phenolic resin glue solution for the copper-clad plate according to claim 2, which is characterized by comprising the following steps: the preparation method of the modified linear phenolic resin comprises the following steps: and (3) uniformly mixing and stirring the linear phenolic resin, the flexible compound and 15wt% sulfuric acid, heating to 100-200 ℃, carrying out reflux reaction for 6-12 h, ending the reaction, naturally cooling the reaction system to room temperature, and filtering, washing and drying to obtain the modified linear phenolic resin.
5. The method for preparing the high-toughness phenolic resin glue solution for the copper-clad plate according to claim 3, wherein the method comprises the following steps: the mass ratio of the dimercapto polyethylene glycol to the hydroxyethyl acrylate to the maleimide is 1:0.12:0.1; the addition amount of hydroquinone is 0.5-2% of that of hydroxyethyl acrylate; the addition amount of the photoinitiator is 1-5% of the mass of the dimercapto polyethylene glycol.
6. The method for preparing the high-toughness phenolic resin glue solution for the copper-clad plate, which is disclosed in claim 4, is characterized in that: the mass ratio of the linear phenolic resin to the flexible compound is (1-1.2): the addition amount of the 1, 15wt% sulfuric acid is 3-8% of that of the phenolic novolac resin.
7. The method for preparing the high-toughness phenolic resin glue solution for the copper-clad plate according to claim 2, which is characterized by comprising the following steps: the preparation method of the modified silicon nitride comprises the following steps: mixing nano silicon nitride, an acrylamide aqueous solution and a photoinitiator, irradiating for 0.5-2 h under 254nm ultraviolet light in a nitrogen environment, and filtering, washing and drying to obtain the modified silicon nitride.
8. The method for preparing the high-toughness phenolic resin glue solution for the copper-clad plate, which is characterized in that: the concentration of the acrylamide aqueous solution is 2.5-10wt%; the mass ratio of the nano silicon nitride to the acrylamide to the photoinitiator is 1: (1-1.5): (0.15-0.2).
9. The method for preparing the high-toughness phenolic resin glue solution for the copper-clad plate according to claim 2, which is characterized by comprising the following steps: the preparation method of the modified styrene-butadiene rubber comprises the following steps: adding styrene-butadiene rubber, acrylamide and a photoinitiator into toluene, stirring and mixing uniformly, irradiating for 0.5-2 h under 254nm ultraviolet light in a nitrogen environment, and filtering, washing and drying to obtain the modified styrene-butadiene rubber.
10. The method for preparing the high-toughness phenolic resin glue solution for the copper-clad plate, which is characterized in that: the addition amount of the acrylamide is 10-40% of that of the styrene-butadiene rubber, and the addition amount of the photoinitiator is 2-7% of that of the styrene-butadiene rubber.
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