CN113150457A - Modified hydrocarbon-modified syndiotactic polystyrene composite material, copper-clad plate containing modified hydrocarbon-modified syndiotactic polystyrene composite material and preparation method of copper-clad plate - Google Patents
Modified hydrocarbon-modified syndiotactic polystyrene composite material, copper-clad plate containing modified hydrocarbon-modified syndiotactic polystyrene composite material and preparation method of copper-clad plate Download PDFInfo
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- CN113150457A CN113150457A CN202110008503.3A CN202110008503A CN113150457A CN 113150457 A CN113150457 A CN 113150457A CN 202110008503 A CN202110008503 A CN 202110008503A CN 113150457 A CN113150457 A CN 113150457A
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- China
- Prior art keywords
- modified
- resin
- hydrocarbon
- syndiotactic polystyrene
- composite material
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- 229920010524 Syndiotactic polystyrene Polymers 0.000 title claims abstract description 92
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims description 15
- 229920005989 resin Polymers 0.000 claims abstract description 58
- 239000011347 resin Substances 0.000 claims abstract description 58
- 239000013032 Hydrocarbon resin Substances 0.000 claims abstract description 51
- 229920006270 hydrocarbon resin Polymers 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000003960 organic solvent Substances 0.000 claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 21
- 239000003292 glue Substances 0.000 claims abstract description 16
- 239000011889 copper foil Substances 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- 238000010030 laminating Methods 0.000 claims abstract description 12
- 238000004132 cross linking Methods 0.000 claims abstract description 11
- 239000004744 fabric Substances 0.000 claims abstract description 11
- 239000002667 nucleating agent Substances 0.000 claims abstract description 10
- 239000003365 glass fiber Substances 0.000 claims abstract description 8
- 150000001721 carbon Chemical class 0.000 claims abstract description 6
- 239000003999 initiator Substances 0.000 claims description 21
- 239000004793 Polystyrene Substances 0.000 claims description 18
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 18
- 229920002223 polystyrene Polymers 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 13
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 claims description 12
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 12
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 12
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 12
- 229940087101 dibenzylidene sorbitol Drugs 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 238000007731 hot pressing Methods 0.000 claims description 9
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 238000005086 pumping Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 150000002978 peroxides Chemical class 0.000 claims description 7
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
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- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- 229920002367 Polyisobutene Polymers 0.000 claims description 3
- 239000002174 Styrene-butadiene Substances 0.000 claims description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- HNHVTXYLRVGMHD-UHFFFAOYSA-N n-butyl isocyanate Chemical compound CCCCN=C=O HNHVTXYLRVGMHD-UHFFFAOYSA-N 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 239000011115 styrene butadiene Substances 0.000 claims description 3
- HDUNAIVOFOKALD-RLCYQCIGSA-N (1s,2s)-1-[(4r)-2-(4-methylphenyl)-1,3-dioxolan-4-yl]-2-[(4s)-2-(4-methylphenyl)-1,3-dioxolan-4-yl]ethane-1,2-diol Chemical compound C1=CC(C)=CC=C1C1O[C@@H]([C@@H](O)[C@H](O)[C@H]2OC(OC2)C=2C=CC(C)=CC=2)CO1 HDUNAIVOFOKALD-RLCYQCIGSA-N 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims 1
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 9
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- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
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- -1 polytetrafluoroethylene Polymers 0.000 description 7
- 239000008096 xylene Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 230000008054 signal transmission Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
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- 229920001721 polyimide Polymers 0.000 description 3
- 239000009719 polyimide resin Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- CTPBWPYKMGMLGS-CIAFKFPVSA-N (3s,4s,5s,6r)-1,8-bis(4-methylphenyl)octa-1,7-diene-2,3,4,5,6,7-hexol Chemical compound C1=CC(C)=CC=C1C=C(O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=CC1=CC=C(C)C=C1 CTPBWPYKMGMLGS-CIAFKFPVSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
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- 239000004643 cyanate ester Substances 0.000 description 1
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Classifications
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Abstract
The invention discloses a modified hydrocarbon-modified syndiotactic polystyrene composite material and a copper-clad plate prepared by using the same. Adding organic solvent into a composite material formed by 40-50 mass percent of SPS resin, 40-50 mass percent of hydrocarbon resin, 10-15 mass percent of modified SPS resin mixed solution, 4-8 mass percent of modified hydrocarbon resin, 0.5-2 mass percent of cross-linking agent, 0.2-1 mass percent of cross-linking accelerator and 0.1-0.5 mass percent of nucleating agent for mixing to obtain modified hydrocarbon-modified syndiotactic polystyrene composite glue solution, soaking glass fiber cloth in the modified hydrocarbon-modified syndiotactic polystyrene composite glue solution uniformly dispersed solution, and baking to obtain the modified hydrocarbon-modified syndiotactic polystyrene prepreg; and then laminating the prepreg with electrolytic copper foil to prepare the modified carbon hydrogen-modified syndiotactic polystyrene composite material copper-clad plate through a high-temperature laminating process. The composite material has a dielectric constant and dielectric loss that meet the ultra-low dielectric requirements of high frequency, high speed, high density boards.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a modified carbon-hydrogen-modified syndiotactic polystyrene composite material copper-clad plate and a preparation method thereof.
Background
With the rapid advance of information and electronic industries represented by intelligent electronic products, digital circuits gradually enter the stages of high speed information processing and high frequency signal transmission, and the entire electronic system is developed toward the direction of being light, thin, small, multifunctional, high-density, high-reliability, and low-cost. With the progress of high density of Printed Circuit Board (PCB) wiring and high speed of electrical signal transmission, it is necessary to realize a PCB substrate material having low dielectric constant (Dk) and low dielectric loss tangent (Df) properties.
The dielectric constant (Dk) and dielectric loss (Df) of the conventional CCL (copper clad laminate) are relatively high, and even though the PCB cannot fully satisfy the application requirements of signal transmission at high frequency and high speed and signal integrity by improving circuit design and lamination cost, the higher the dielectric constant is, the slower the signal transmission rate is, the higher the dielectric loss is, the more the signal is converted into heat energy, the loss in the substrate material is, the more incomplete the signal obtained by the terminal is, and thus the reduction of Dk/Df becomes a hot spot pursued by the copper clad laminate industry.
The most commonly used main resins for copper clad laminate are mainly epoxy resin (EP), phenol resin, polytetrafluoroethylene resin (PTFE), polyimide resin (PI), bismaleimide resin (BMI), polyester resin (PET), polyphenylene oxide resin (PPO or PPE), cyanate ester resin (CE), and the like.
The dielectric constant of epoxy resin, polyester resin and polyimide resin is between 3 and 4, the dielectric constant of the prepreg coated with the glass fiber cloth can be further increased to 4 to 5, and the dielectric loss is relatively high, so that the application of the prepreg to a high-frequency board, in particular to an HDI (high density interconnect) high-frequency PCB (printed circuit board) is limited. Therefore, the low-dielectric and low-loss base material of the PCB copper-clad plate is needed to meet the requirement of high-frequency and high-density iteration of the PCB.
At present, the process systems for realizing large-scale industrialization by applying the high-frequency plate mainly comprise two types: a class of thermoplastic process systems represented by PTFE matrices; in addition to excellent high frequency characteristics, PTFE resin has excellent moisture resistance, acid and alkali resistance, and chemical resistance. However, the polytetrafluoroethylene resin has some problems, which limits the large-scale application of the polytetrafluoroethylene resin in the field of electronic substrates. Such as:
1) the surface is inert, so that the activation is difficult, the combination with the copper foil is difficult, and the adhesion is poor;
2) the Tg is low, the thermal expansion is large, and the yield of fine circuit processing is very low;
3) insufficient mechanical properties, such as low tensile strength and modulus and low hardness of PTFE;
4) the PTFE source is less, the cost is higher, and the cost of the prepared copper-clad plate is extremely expensive;
the other is a process system represented by a thermosetting composite material matrix of hydrocarbon resin and other high-heat-resistance low-dielectric resins;
patent CN 111072980A-a modified hydrocarbon resin prepolymer, a modified hydrocarbon-DCPD epoxy composite material copper-clad plate and a preparation method thereof, and patent CN 111072979A-a modified hydrocarbon resin prepolymer, a modified hydrocarbon resin copper-clad plate and a preparation method thereof; the modified hydrocarbon-DCPD epoxy composite material disclosed by the patent uses a system combining modified hydrocarbon resin and epoxy resin/maleimide resin, reduces the dielectric constant DK and dielectric loss DF of a copper-clad plate to a certain extent, and has the characteristics of low water absorption, high glass transition temperature and high peel strength. Due to the gradual expansion of 5G commercial products, the dielectric performance requirements of mobile digital terminals with higher and higher integration density on circuit boards are higher and higher, and due to the introduction of a large amount of epoxy resin and other polar groups, the dielectric constant and the dielectric loss of the composite material can not meet the ultralow dielectric requirements of high-frequency and high-speed high-density boards.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a modified hydrocarbon resin-modified Syndiotactic Polystyrene (SPS) matrix copper-clad plate and a preparation method thereof, which have the characteristics of ultralow dielectric constant and ultralow dielectric loss, excellent heat resistance, good dimensional stability and high copper foil peeling strength and can be applied to high-frequency high-density interconnected PCB plates.
The invention provides a modified hydrocarbon-modified syndiotactic polystyrene composite material, which is characterized by comprising the following components in percentage by weight: 40-50% of SPS resin, 40-50% of hydrocarbon resin, 10-15% of modified SPS resin mixed solution, 4-8% of modified hydrocarbon resin, 0.5-2% of cross-linking agent, 0.2-1% of cross-linking accelerator and 0.1-0.5% of nucleating agent;
wherein the molecular weight of the SPS resin is Mw 200000-300000g/mol, and the syndiotactic degree is more than 95 percent; the modified SPS resin mixed solution is maleic anhydride grafted SPS resin, and the grafting rate is 1% -5%;
the hydrocarbon resin is selected from one or a mixture of more than two of styrene-butadiene resin, polybutadiene resin, polyisobutylene resin, polypentadiene resin, styrene-butadiene copolymer, styrene-isobutylene copolymer, styrene-divinylbenzene copolymer, polystyrene, 2-methyl polystyrene, 3-methyl polystyrene, 4-methyl polystyrene, 2, 4-diisopropyl polystyrene, 2, 4-dimethyl polystyrene, ethylene-propylene-diene copolymer (EPDM) and cycloolefin copolymer;
the modified hydrocarbon resin is maleic anhydride grafted hydrocarbon resin, and the grafting rate is 1-10%.
Preferably, the modified hydrocarbon resin is prepared by dissolving hydrocarbon resin in an organic solvent, adding maleic anhydride and an initiator, continuously stirring at the temperature of 80-120 ℃ and reacting.
More preferably, the modified hydrocarbon resin is prepared by dissolving 30-60 parts by mass of hydrocarbon resin in 200-350 parts by mass of organic solvent, adding 2-10 parts by mass of maleic anhydride and 0.2-2 parts by mass of initiator, continuously stirring and reacting at 80-120 ℃ for 3 hours, and then carrying out suction filtration, solvent washing, suction filtration and drying.
More preferably, the hydrocarbon resin is SEBS, and the mixture of SBS and EPDM is in the mass ratio of 2: 1: 2.
Preferably, the modified SPS resin is prepared by dissolving syndiotactic polystyrene in an organic solvent, adding maleic anhydride, an initiator and a styrene monomer, continuously stirring at the temperature of 80-120 ℃, and reacting to obtain a modified SPS resin mixed solution.
More preferably, the modified SPS resin is prepared by dissolving 50 parts by mass of syndiotactic polystyrene in 100 parts by mass of an organic solvent, adding 1-3 parts by mass of maleic anhydride, 0.2-2 parts by mass of an initiator and a styrene monomer, and continuously stirring at 80-120 ℃ for 3 hours to react to obtain a modified SPS resin mixed solution.
Preferably, the crosslinking agent is one or more of peroxide initiators such as DCP (dicumyl peroxide), BPO (benzoyl peroxide), BIBP (di-tert-butylperoxy-diisopropylbenzene) and the like.
Preferably, the co-crosslinking agent: one or more of triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), N' -m-phenylene bismaleimide (HVA-2).
Preferably, the nucleating agent is one or more of BIs (p-methylbenzylidene) sorbitol (MDBS), dibenzylidene sorbitol (DBS), n-butyl isocyanate ammonolyzed dibenzylidene sorbitol (DBS-BI), talcum powder and calcium carbonate.
Preferably, the organic solvent is one or more of toluene, xylene, cyclohexane and acetone.
The invention also provides a glue solution prepared from the modified hydrocarbon-modified syndiotactic polystyrene composite material, which is prepared by adding the composite material into an organic solvent and mixing to obtain the modified hydrocarbon-modified syndiotactic polystyrene composite glue solution.
The invention also provides a copper-clad plate made of the modified hydrocarbon-modified syndiotactic polystyrene composite material, which is prepared by adding the composite material into an organic solvent for mixing to obtain a modified hydrocarbon-modified syndiotactic polystyrene composite glue solution, uniformly dispersing the modified hydrocarbon-modified syndiotactic polystyrene composite glue solution to impregnate glass fiber cloth, and baking to obtain a modified hydrocarbon-modified syndiotactic polystyrene prepreg; and then laminating the prepreg with electrolytic copper foil to prepare the modified carbon hydrogen-modified syndiotactic polystyrene composite material copper-clad plate through a high-temperature laminating process.
Preferably, the glass fiber cloth is made of E glass, NE glass and D glass.
Preferably, the electrolytic copper foil is 1 to 3 OZ.
Preferably, the high temperature lamination process comprises the following 3 stages:
stage 1: and (3) hydrocarbon resin crosslinking and curing stage: this stage should be preceded by a pre-pressing stage, the process being characterized by a temperature range: 120 ℃ to 200 ℃, preferred temperature: 150 ℃ and 180 ℃, the pressure is 1.0-2.0MPa, and the duration is 1-3H;
and (2) stage: a crystallization temperature rise stage: the stage is a crystallization preparation stage, the temperature needs to be raised to 290-300 ℃ within 10-60 min, and in addition, the oxygen needs to be removed in a vacuum-pumping state hot-pressing process to prevent high-temperature thermal-oxygen aging;
and (3) stage: characteristic temperature of this stage: the temperature range is 290-310 ℃, the pressure is 0.2-1.0Mpa, the duration is 1-10min, and in addition, the hot pressing process needs to be carried out under the vacuum-pumping state to remove oxygen, so as to prevent high-temperature thermo-oxidative aging.
The invention also provides a preparation method of the modified hydrocarbon resin-modified Syndiotactic Polystyrene (SPS) matrix copper-clad plate, which comprises the following steps:
the first step is as follows: preparation of modified Hydrocarbon resins
Dissolving 30-60 parts by mass of hydrocarbon resin with 200-350 parts by mass of organic solvent, adding 2-10 parts by mass of maleic anhydride and 0.2-2 parts by mass of initiator, continuously stirring at 80-120 ℃, reacting for 3 hours to obtain mixed solution, performing suction filtration, solvent washing, suction filtration and drying to obtain modified hydrocarbon resin;
the hydrocarbon resin is selected from one or a mixture of more than two of styrene-butadiene resin, polybutadiene resin, polyisobutylene resin, polypentadiene resin, styrene-butadiene copolymer, styrene-isobutylene copolymer, styrene-divinylbenzene copolymer, polystyrene, 2-methyl polystyrene, 3-methyl polystyrene, 4-methyl polystyrene, 2, 4-diisopropyl polystyrene, 2, 4-dimethyl polystyrene, ethylene-propylene-diene copolymer and cycloolefin copolymer;
the initiator is one or more of peroxide initiators such as DCP (dicumyl peroxide), BPO (benzoyl peroxide), BIBP (di-tert-butylperoxy diisopropylbenzene) and the like;
the organic solvent A is one or more mixed solvents of toluene, xylene, cyclohexane and acetone, and the amount of the organic solvent is 60-200% of the total mass of the hydrocarbon resin;
the MAH is prepared by a n-butane oxidation method, and the purity requirement is more than 99.7%;
the grafting rate of the product modified hydrocarbon resin is 1-10%;
the second step is that: preparation of modified SPS resin
Dissolving syndiotactic polystyrene in an organic solvent A, adding maleic anhydride, an initiator and a styrene monomer, continuously stirring at the temperature of 80-120 ℃, and reacting for 3 hours to obtain a modified SPS resin mixed solution B; typical ratios are as follows:
the SPS manufacturer can select Dow company or Japan light-emitting company, the molecular weight range Mw 200000-300000 g/mol; the syndiotactic degree is more than 95 percent
The initiator is one or more of peroxide initiators such as DCP (dicumyl peroxide), BPO (benzoyl peroxide), BIBP (di-tert-butylperoxy diisopropylbenzene) and the like.
The purity of the styrene monomer is as follows: pure reagent, manufacturer: RiandBarcel industries Ltd.
The organic solvent A is one or more mixed solvents of toluene, xylene, cyclohexane and acetone.
The MAH is prepared by an n-butane oxidation method, the purity requirement is more than 99.7 percent, and the manufacturer: dalian Wanyuan chemical Co., Ltd.
The grafting rate of the product modified SPS resin is 1-5%.
The third step: dissolving the prepared modified hydrocarbon resin, modified SPS resin mixed solution B, SPS resin and unmodified hydrocarbon resin in a certain proportion by using an organic solvent A, and then adding a cross-linking agent, a cross-linking accelerator and a nucleating agent for mixing to obtain a modified hydrocarbon-modified syndiotactic polystyrene composite glue solution C.
The SPS manufacturer can select Dow company or Japan light-emitting company, the molecular weight range Mw 200000-300000 g/mol; the syndiotactic degree is more than 95 percent
The initiator is one or more of peroxide initiators such as DCP (dicumyl peroxide), BPO (benzoyl peroxide), BIBP (di-tert-butylperoxy diisopropylbenzene) and the like.
The organic solvent A is one or more mixed solvents of toluene, xylene, cyclohexane and acetone. The dosage of the organic solvent A is 80-300% of the mixed components.
The cross-linking agent is one or more of peroxide initiators such as DCP (dicumyl peroxide), BPO (benzoyl peroxide), BIBP (di-tert-butylperoxy diisopropylbenzene) and the like.
The auxiliary crosslinking agent is: one or more of triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), N' -m-phenylene bismaleimide (HVA-2).
The nucleating agent is one or more of di (p-methylbenzylidene) sorbitol (MDBS), dibenzylidene sorbitol (DBS), n-butyl isocyanate ammonolyzed dibenzylidene sorbitol (DBS-BI), talcum powder and calcium carbonate.
The fourth step: soaking the fiber cloth in the modified hydrocarbon-modified syndiotactic polystyrene composite glue solution C uniform dispersion solution, and baking for 1-10min at the temperature of 100-; and then laminating the prepreg with copper foil to prepare the modified carbon hydrogen-modified syndiotactic polystyrene composite material copper-clad plate through a high-temperature laminating process.
The glass fiber cloth is made of E glass, NE glass and D glass. The manufacturers can be selected from Taijia of Taiwan and Nidong of Japan
The electrolytic copper foil is 1-3OZ in specification, and manufacturers can select Taiwan south Asia, Taiwan Changchun, Anhui copper crown, Japan Tri-well and the like.
The high temperature lamination process comprises the following 3 critical stages.
Stage 1: and (3) hydrocarbon resin crosslinking and curing stage: this stage should be preceded by a pre-pressing stage, the process being characterized by a temperature range: 120 ℃ to 200 ℃, preferred temperature: 150 ℃ and 180 ℃, the pressure is 1.0-2.0MPa, and the duration is 1-3H.
And (2) stage: a crystallization temperature rise stage: the stage is a crystallization preparation stage, the temperature needs to be raised to 290-300 ℃ within 10-60 min, and in addition, the oxygen needs to be removed in a vacuum-pumping state hot-pressing process to prevent high-temperature thermal-oxygen aging.
And (3) stage: characteristic temperature of this stage: the temperature range is 290-310 ℃, the pressure is 0.2-1.0Mpa, and the duration is 1-10 min. In addition, the oxygen is removed in a vacuum-pumping state hot-pressing process, so that high-temperature thermal-oxygen aging is prevented.
The invention has the following beneficial effects:
on one hand, the invention creatively utilizes the crosslinking skeleton of the peroxide of the hydrocarbon resin and the good compatibility of the molecular structure layer of the hydrocarbon resin and the SPS resin to ensure that the system forms a semi-IPN structure with stable structure and uniform phase state. The structure provides the composition with good strength, toughness and dimensional stability. In addition, the low-dielectric high-crystallinity SPS resin has good heat resistance and high dimensional stability, but a copper-clad plate prepared from the unmodified carbon hydrogen-SPS composite material has the characteristic of low peel strength, and the crystallization control in the re-curing process after the SPS is dissolved can obviously influence the final heat resistance of the product. According to the invention, SPS resin and hydrocarbon resin are modified, and maleic anhydride grafted SPS and maleic anhydride grafted hydrocarbon resin are introduced, so that the bonding strength of the matrix to glass fiber cloth and copper foil is improved. By adding the nucleating agent and controlling the laminating temperature and time, the crystallinity of SPS in the copper-clad plate substrate can be controlled, and the heat resistance of the system is further improved. Finally, the copper clad laminate with ultralow dielectric constant and ultralow dielectric loss, excellent heat resistance, good dimensional stability and high copper foil peel strength is prepared. The copper-clad plate can meet the requirements of a 5G high-frequency and high-density interconnection process.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present application without making any creative effort, shall fall within the protection scope of the present application.
In the description of the embodiments of the present application, it should be noted that the terms "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", and the like indicate orientations or positional relationships based on the orientations or positional relationships shown or orientations or positional relationships conventionally found in use of the products of the present invention, and are used for convenience of description and simplicity of description only, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as limiting the present application. Furthermore, the terms "first," "second," "third," and the like are used solely to distinguish one from another and are not to be construed as indicating or implying relative importance.
Examples 1 to 6:
a composite dope was prepared according to the formulation of each example in table 1 as follows.
The first step is as follows: preparation of modified Hydrocarbon resins
Dissolving 50 parts by mass of hydrocarbon resin by 120 parts by mass of an organic solvent A (the mass ratio of xylene to acetone is 3: 2), adding 5 parts by mass of maleic anhydride and 0.4 part by mass of an initiator BP0, continuously stirring at the temperature of 100 ℃, reacting for 3 hours to obtain a mixed solution, performing suction filtration, solvent washing, suction filtration and drying to obtain modified hydrocarbon resin; the grafting rate of the product modified hydrocarbon resin is 5 percent. The hydrocarbon resin is a mixture of SEBS, SBS and EPDM, the mass ratio is 2: 1: 2, the SEBS is Ketong G1651, the SBS is Yueming Ba Ling 561, and the EPDM is U.S. DOW company No. 3722P.
The second step is that: preparation of modified SPS resin
Dissolving 50 parts by mass of syndiotactic polystyrene in 100 parts by mass of an organic solvent A (the mass ratio of xylene to acetone is 3: 2), adding 3 parts by mass of maleic anhydride, 0.4 part by mass of a DCP initiator and 1.5 parts by mass of a styrene monomer, continuously stirring at the temperature of 120 ℃, and reacting for 3 hours to obtain a modified SPS resin mixed solution B;
the SPS resin is selected from the American DOW company, the molecular weight Mw is 230000g/mol, and the syndiotactic degree is more than 95 percent; the grafting rate of the product modified SPS resin is 2%.
The styrene monomer manufacturer is Liandersbal Industrial Corp, purity: the reagent is pure.
The third step: the prepared modified hydrocarbon resin, modified SPS resin mixed solution B, SPS resin and hydrocarbon resin are dissolved by using an organic solvent A (the mass ratio of xylene to acetone is 3: 2), and then a crosslinking agent BIBP (manufacturer Acksolberg, brand Perkadox14-40B-PD), a crosslinking accelerator TAIC (brand Rheofit TAIC/S) and a nucleating agent talcum powder (brand RB510) are added and mixed to obtain a modified hydrocarbon-modified syndiotactic polystyrene composite glue solution C (mass ratio is referred to examples 1-6).
The hydrocarbon resin is SEBS, and the mixture of SBS and EPDM is in the mass ratio of 2: 1: 2. SEBS is Ketong G1651, SBS is Yueyingba 561, EPDM is U.S. DOW company No. 3722P.
The fourth step: soaking fiber cloth in the modified hydrocarbon-modified syndiotactic polystyrene composite glue solution C uniform dispersion solution, and baking at 120 ℃ for 10min to obtain a modified hydrocarbon-modified syndiotactic polystyrene prepreg; and then laminating the prepreg with copper foil to prepare the modified carbon hydrogen-modified syndiotactic polystyrene composite material copper-clad plate through a high-temperature laminating process.
The glass fiber cloth is. The manufacturers can be selected from Taijia of Taiwan and Nidong of Japan
The electrolytic copper foil is 1-3OZ in specification,
the high-temperature laminating process comprises the following steps:
stage 1: and (3) hydrocarbon resin crosslinking and curing stage: this stage should be preceded by a pre-pressing stage, the process being characterized by a temperature range: 180 ℃, 1.5MPa pressure, duration 2H.
And (2) stage: a crystallization temperature rise stage: the stage is a crystallization preparation stage, the temperature needs to be raised to 300 ℃ within 20min, and in addition, the oxygen needs to be removed in a vacuum-pumping state hot-pressing process, so that the high-temperature thermal-oxygen aging is prevented.
And (3) stage: characteristic temperature of this stage: the temperature is 300 deg.C, the pressure is 0.3Mpa, and the duration is 2 min. In addition, the oxygen is removed in a vacuum-pumping state hot-pressing process, so that high-temperature thermal-oxygen aging is prevented.
The components in the embodiments 1 to 6 are dissolved and mixed to form the corresponding composite glue solution C, and then the corresponding composite glue solution C is prepared into a prepreg through the same glass cloth coating process, and finally the corresponding prepreg is prepared into the copper-clad plate through the same hot pressing process. The performance of each example was tested according to the method and items in Table 2, and the performance was compared. (in the examples, the ratio of the organic solvent A to the composition in the formulation was 1: 1 by mass), and the example in which 920g of the organic solvent A was added has calculated the organic solvent A (80g) in the modified SPS resin mixture B) in Table 2, test items and standards
| Performance of | Test method and conditions | Unit of |
| Dielectric constant Dk | IPC-TM-650(2.5.5.9)(1GHZ) | - |
| Dielectric loss Df | IPC-TM-650(2.5.5.9)(1GHZ) | - |
| Coefficient of thermal expansion CTE | IPC-TM-650(2.4.24)(50-260℃) | ％ |
| Glass transition temperature Tg | IPC-TM-650(2.4.25)(DSC) | ℃ |
| Peel strength of copper foil | IPC-TM-650(2.4.8.1) | N/mm |
From examples 1-4, it can be seen that the graft modification of the modified SPS resin mixture and the modified hydrocarbon resin two-component both have an effect of improving the peel strength of the copper clad laminate. The performance data of examples 1 and 5 show that the addition of the crosslinking agent and the crosslinking accelerator can greatly increase the Tg of the material and significantly reduce the thermal expansion coefficient of the material. The performance data of examples 1 and 6 show that the addition of nucleating agents can also further raise the Tg of the material.
Table 3 performance of the copper clad laminates of examples 1-6 (the existing epoxy resin copper clad laminate is an outsourced low dielectric specification epoxy resin copper clad laminate.)
The above-mentioned embodiments only express the specific embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for those skilled in the art, without departing from the technical idea of the present application, several changes and modifications can be made, which are all within the protection scope of the present application.
Claims (10)
1. A modified hydrocarbon-modified syndiotactic polystyrene composite material is characterized by comprising the following components: 40-50% of SPS resin, 40-50% of hydrocarbon resin, 10-15% of modified SPS resin mixed solution, 4-8% of modified hydrocarbon resin, 0.5-2% of cross-linking agent, 0.2-1% of cross-linking accelerator and 0.1-0.5% of nucleating agent;
wherein the molecular weight of the SPS resin is Mw 200000-300000g/mol, and the syndiotactic degree is more than 95 percent; the modified SPS resin mixed solution is maleic anhydride grafted SPS resin, and the grafting rate is 1% -5%;
the hydrocarbon resin is selected from one or a mixture of more than two of styrene-butadiene resin, polybutadiene resin, polyisobutylene resin, polypentadiene resin, styrene-butadiene copolymer, styrene-isobutylene copolymer, styrene-divinylbenzene copolymer, polystyrene, 2-methyl polystyrene, 3-methyl polystyrene, 4-methyl polystyrene, 2, 4-diisopropyl polystyrene, 2, 4-dimethyl polystyrene, ethylene-propylene-diene copolymer and cycloolefin copolymer;
the modified hydrocarbon resin is maleic anhydride grafted hydrocarbon resin, and the grafting rate is 1-10%.
2. The modified hydrocarbon-modified syndiotactic polystyrene composite material of claim 1, wherein said modified hydrocarbon resin is prepared by dissolving hydrocarbon resin in organic solvent, adding maleic anhydride and initiator, continuously stirring at 80-120 deg.C, and reacting.
3. The modified hydrocarbon-modified syndiotactic polystyrene composite material of claim 1, wherein said modified SPS resin is prepared by dissolving syndiotactic polystyrene in organic solvent, adding maleic anhydride, initiator and styrene monomer, stirring continuously at 80-120 deg.C, and reacting to obtain modified SPS resin mixture.
4. The modified hydrocarbon-modified syndiotactic polystyrene composite material as defined in claim 2, wherein said modified hydrocarbon resin is prepared by dissolving 30-60 parts by mass of hydrocarbon resin in 350 parts by mass of organic solvent, adding 2-10 parts by mass of maleic anhydride and 0.2-2 parts by mass of initiator, continuously stirring at 80-120 ℃ for reaction for 3 hours, then carrying out suction filtration, solvent washing, suction filtration again and drying.
5. The modified hydrocarbon-modified syndiotactic polystyrene composite material of claim 3, wherein said modified SPS resin is prepared by dissolving 20-60 parts by mass of syndiotactic polystyrene in 50-100 parts by mass of organic solvent, adding 1-3 parts by mass of maleic anhydride, 0.2-2 parts by mass of initiator and styrene monomer, and continuously stirring at 80-120 deg.C for 3 hours to obtain a modified SPS resin mixture.
6. The modified hydrocarbon-modified syndiotactic polystyrene composite material in claim 1, wherein said crosslinking agent is one or more peroxide initiators selected from DCP (dicumyl peroxide), BPO (benzoyl peroxide), BIBP (di-t-butylperoxy-diisopropylbenzene); the auxiliary crosslinking agent is: one or more of triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), N' -m-phenylene bismaleimide (HVA-2).
7. The modified hydrocarbon-modified syndiotactic polystyrene composite in claim 1, wherein said nucleating agent is one or more of BIs (p-methylbenzylidene) sorbitol (MDBS), dibenzylidene sorbitol (DBS), n-butyl isocyanate urethanized dibenzylidene sorbitol (DBS-BI), talc, and calcium carbonate.
8. A glue solution prepared from a modified hydrocarbon-modified syndiotactic polystyrene composite material, which is characterized in that the composite material of any one of claims 1 to 7 is added into an organic solvent to be mixed to obtain the modified hydrocarbon-modified syndiotactic polystyrene composite glue solution.
9. A copper-clad plate made of modified hydrocarbon-modified syndiotactic polystyrene composite material is characterized in that the composite material of any one of claims 1 to 7 is added with an organic solvent to be mixed to obtain modified hydrocarbon-modified syndiotactic polystyrene composite glue solution, the modified hydrocarbon-modified syndiotactic polystyrene composite glue solution is uniformly dispersed to impregnate glass fiber cloth, and then the mixture is baked to obtain the modified hydrocarbon-modified syndiotactic polystyrene prepreg; and then laminating the prepreg with electrolytic copper foil to prepare the modified carbon hydrogen-modified syndiotactic polystyrene composite material copper-clad plate through a high-temperature laminating process.
10. The copper-clad plate made of modified hydrocarbon-modified syndiotactic polystyrene composite material according to claim 9, wherein said high temperature lamination process comprises the following 3 stages:
stage 1: and (3) hydrocarbon resin crosslinking and curing stage: this stage should be preceded by a pre-pressing stage, the process being characterized by a temperature range: 120 ℃ to 200 ℃, preferred temperature: 150 ℃ and 180 ℃, the pressure is 1.0-2.0MPa, and the duration is 1-3H;
and (2) stage: a crystallization temperature rise stage: the stage is a crystallization preparation stage, the temperature needs to be raised to 290-300 ℃ within 10-60 min, and in addition, the oxygen needs to be removed in a vacuum-pumping state hot-pressing process to prevent high-temperature thermal-oxygen aging;
and (3) stage: characteristic temperature of this stage: the temperature range is 290-310 ℃, the pressure is 0.2-1.0Mpa, the duration is 1-10min, and in addition, the hot pressing process needs to be carried out under the vacuum-pumping state to remove oxygen, so as to prevent high-temperature thermo-oxidative aging.
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| CN202110008503.3A Pending CN113150457A (en) | 2021-01-05 | 2021-01-05 | Modified hydrocarbon-modified syndiotactic polystyrene composite material, copper-clad plate containing modified hydrocarbon-modified syndiotactic polystyrene composite material and preparation method of copper-clad plate |
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Cited By (3)
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| CN114410046A (en) * | 2022-01-28 | 2022-04-29 | 浙江大学 | Preparation method of hydrocarbon resin base plate material for high-frequency copper-clad plate |
| CN115322493A (en) * | 2022-08-31 | 2022-11-11 | 金发科技股份有限公司 | Glass fiber reinforced GPPS composite material and preparation method and application thereof |
| CN117734286A (en) * | 2024-01-08 | 2024-03-22 | 江苏耀鸿电子有限公司 | High-temperature-resistant low-dielectric hydrocarbon resin-based copper-clad plate and preparation method thereof |
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Cited By (5)
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| CN114410046A (en) * | 2022-01-28 | 2022-04-29 | 浙江大学 | Preparation method of hydrocarbon resin base plate material for high-frequency copper-clad plate |
| CN115322493A (en) * | 2022-08-31 | 2022-11-11 | 金发科技股份有限公司 | Glass fiber reinforced GPPS composite material and preparation method and application thereof |
| CN115322493B (en) * | 2022-08-31 | 2023-11-03 | 金发科技股份有限公司 | Glass fiber reinforced GPPS composite material and preparation method and application thereof |
| CN117734286A (en) * | 2024-01-08 | 2024-03-22 | 江苏耀鸿电子有限公司 | High-temperature-resistant low-dielectric hydrocarbon resin-based copper-clad plate and preparation method thereof |
| CN117734286B (en) * | 2024-01-08 | 2024-06-04 | 江苏耀鸿电子有限公司 | High-temperature-resistant low-dielectric hydrocarbon resin-based copper-clad plate and preparation method thereof |
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