CN109705284B - Low-dielectric-constant polyphenyl ether resin composition and prepreg prepared from same - Google Patents
Low-dielectric-constant polyphenyl ether resin composition and prepreg prepared from same Download PDFInfo
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Abstract
The invention relates to a polyphenylene ether resin composition with a low dielectric constant and a prepreg prepared from the same. The polyphenylene ether resin composition with low dielectric constant comprises the following components: functionalized polyphenylene ether resin, styrene monomer, crosslinking curing agent, initiator, polymerization inhibitor, inorganic filler, silane coupling agent, flame retardant and the like. The polyphenylene ether resin composition provided by the invention has the advantages that the functionalized polyphenylene ether resin is dispersed in a styrene monomer as a disperse phase, the styrene exists in a system as a solvent and a modifier, and the prepreg is prepared by drying, so that the polyphenylene ether resin composition has good process processability, maintains the excellent dielectric property of the polyphenylene ether, and is suitable for the fields of high-frequency and high-speed printed circuit boards and the like.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a low-dielectric-constant polyphenyl ether resin composition and a prepreg prepared from the same.
Background
Printed Circuit Boards (PCBs) are the basis for electronic devices, with electronic signals being transmitted through electrical currents in the PCB circuitry. Materials conventionally used in low frequency communication circuits generally have difficulty meeting the electrical performance requirements necessary for high frequency communications. In order to accommodate the requirements of high frequency and high speed data transmission, high performance circuit substrates are of critical importance, in addition to requirements in circuit design and PCB manufacture. At present, an epoxy resin glass cloth material (FR-4) is mostly adopted for a Printed Circuit Board (PCB), the dielectric constant of the PCB is usually more than 4.6, and the dielectric loss of the PCB is usually more than 0.01. However, new communication equipment has required the dielectric constant of the circuit board to be less than 4.0 and the dielectric loss to be less than 0.003.
Polyphenylene oxide has good dielectric properties and heat resistance, and the dielectric constant and the dielectric loss of the polyphenylene oxide are the smallest materials in engineering plastics, are hardly influenced by frequency, temperature and humidity, and have been studied by the majority of scientific research technicians as high-frequency high-speed materials.
Chinese patent CN102807658B uses functionalized polyphenylene ether resin to dissolve in organic solvent toluene, then adds cross-linking agent, flame retardant and other auxiliary agents to prepare glue solution, and finally dries the solvent to prepare prepreg. However, the prepared prepreg can not completely remove the clean solvent, so that the residue of the micromolecular compound can be caused, and the defect of tiny bubbles can be generated in the hot press molding process, thereby greatly reducing the dielectric property and the processing property of the polyphenyl ether high-frequency substrate.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a polyphenylene ether resin composition with a low dielectric constant and a prepreg prepared from the same.
The polyphenyl ether resin composition with low dielectric constant has good processing characteristics, and simultaneously, the dielectric property and the dielectric loss rate are improved to a certain degree.
The invention has the technical characteristics that the styrene is added into the polyphenyl ether composition and can be used as a solvent to well adjust the colloid viscosity of the composition, the processing is convenient, on one hand, after the styrene is removed, the residual styrene is used as a modifier to exist in the polyphenyl ether composition, and after crosslinking and curing, the excellent dielectric property of the polystyrene is kept, and meanwhile, the pore defect formed by the thermal volatilization of the small molecular solvent is reduced.
The purpose of the invention can be realized by the following technical scheme:
the polyphenyl ether resin composition with the low dielectric constant is prepared from the following raw materials in percentage by mass:
preferably, the polyphenylene ether resin composition with low dielectric constant is prepared from the following components in percentage by mass:
further preferably, the low dielectric constant polyphenylene ether resin composition is prepared from the following components in parts by weight:
the functionalized polyphenylene ether resin is dispersed in styrene, and a polyphenylene ether and styrene copolymerization crosslinking system is formed by adding a crosslinking curing agent, an initiator, a polymerization inhibitor, an inorganic filler, a silane coupling agent, a flame retardant and the like.
The functionalized polyphenylene ether resin is polyphenylene ether resin with unsaturated double bonds at the molecular tail end, and the relative molecular mass of the polyphenylene ether resin is 600-4000.
The styrene is a styrene monomer, and is used as a mixture solvent and a polyphenyl ether resin modifier. The styrene monomer is a micromolecular compound and has better solubility with the functionalized polyphenylene ether resin, the functionalized polyphenylene ether resin is dissolved in the styrene monomer, a large amount of styrene monomer is removed through vacuum after mixing, the amount of styrene in the composition is controlled, and crosslinking and curing are carried out together with the polyphenylene ether, so that the curing activity of the polyphenylene ether is enhanced in the curing process.
The crosslinking curing agent is a polyfunctional allyl compound, preferably a 3-5 functional allyl compound. The multifunctional allyl compound comprises triallyl isocyanurate, pentaerythritol triacrylate, trimethylolpropane triacrylate and trimethylolpropane trimethacrylate.
The initiator is a free radical initiator, the temperature of the 1h half-life period of the initiator is more than or equal to 90 ℃, and the initiator is selected from one or more of the following substances: dibenzoyl peroxide, tert-butyl peroxybenzoate, di-tert-butyl peroxyazelate, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane, 1-di-tert-butylperoxycyclohexane, tert-amyl peroxyacetate, dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, p-menthane hydroperoxide, tert-butyl hydroperoxide, dicumyl hydroperoxide, methyl ethyl ketone peroxide, acetylacetone peroxide, tert-amyl 2-ethylhexanoate peroxide, 1, 3-tetramethylbutyl hydroperoxide, tert-amyl hydroperoxide, and the like.
In the pre-reaction process for preparing the prepreg, styrene is easy to generate self-polymerization reaction, and in order to facilitate the long-term storage and use of the polyphenylene ether colloid, a polymerization inhibitor is required to be added into the composition, and is selected from one or more of the following substances: diethylhydroxylamine, nitrobenzene, nitrogen oxide, and the like.
The inorganic filler is selected from one or more of the following substances: silica, glass powder, boron nitride, aluminum nitride, silicon carbide, aluminum hydroxide, titanium dioxide, and the like, and the inorganic filler is a hollow sphere or a solid body.
The inorganic filler is chemically treated by using a silane coupling agent, wherein the silane coupling agent is one or a mixture of more of a vinyl silane coupling agent, an acrylic silane coupling agent, an aminosilane coupling agent and an epoxy silane coupling agent.
The flame retardant comprises a phosphorus-containing flame retardant or a bromine-containing flame retardant, and the phosphorus-containing flame retardant is selected from one or more of the following substances: alkylaryl phosphate, alkylaryl phosphatase, alkyl phosphine oxide, triphenyl phosphate, and the like; the bromine-containing flame retardant is selected from one or more of the following substances: decabromodiphenyl ether, decabromodiphenylethane, tetrabromobisphenol A, hexabromocyclododecane, etc.
The invention also relates to a prepreg prepared based on the low-dielectric-constant polyphenyl ether resin composition, which is prepared by immersing the substrate into the low-dielectric-constant polyphenyl ether resin composition and drying the substrate;
the substrate is a woven or non-woven fabric of glass fibers, carbon fibers or organic fibers.
Compared with the prior art, the polyphenylene ether resin composition provided by the invention has the advantages that the functionalized polyphenylene ether resin is dispersed in a styrene monomer as a disperse phase, the styrene exists in a system as a solvent and a modifier, and the prepreg is prepared by drying, so that the polyphenylene ether resin composition has good process processability, maintains the excellent dielectric property of the polyphenylene ether, and is suitable for the fields of high-frequency high-speed printed circuit boards and the like.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
Mixing 60 parts by mass of methacrylic acid-terminated polyphenyl ether resin and 70 parts by mass of styrene monomer, completely dissolving to obtain a styrene polyphenyl ether mixed solution, then adding 25 parts by mass of triallyl isocyanurate as a crosslinking curing agent, adding 2 parts by mass of dibenzoyl peroxide as an initiator, 6 parts by mass of decabromodiphenyl ether as a flame retardant, 5 parts by mass of nitrobenzene as a polymerization inhibitor, 20 parts by mass of silica powder as a filler, adding 4 parts by mass of vinyltrimethoxysilane coupling agent, stirring for 20min to obtain a resin composition, and simultaneously starting cooling water circulation.
And then impregnating the resin composition glue solution into E-glass fiber cloth, desolventizing at 90 ℃ and pre-reacting for 5min to obtain a prepreg.
Example 2
Mixing 60 parts by mass of methacrylic acid-terminated polyphenyl ether resin and 60 parts by mass of styrene monomer, completely dissolving to obtain a styrene polyphenyl ether mixed solution, then adding 30 parts by mass of triallyl isocyanurate as a crosslinking curing agent, adding 2 parts by mass of dibenzoyl peroxide as an initiator, 6 parts by mass of decabromodiphenylethane as a flame retardant, 5 parts by mass of nitrobenzene as a polymerization inhibitor, 20 parts by mass of silica powder as a filler, adding 5 parts by mass of vinyltrimethoxysilane coupling agent, mixing and stirring the mixture for 20min to obtain a resin composition, and simultaneously starting cooling water circulation.
And then impregnating the resin composition glue solution into E-glass fiber cloth, desolventizing at 90 ℃ and pre-reacting for 5min to obtain a prepreg.
Example 3
Mixing 60 parts by mass of methacrylic acid-terminated polyphenyl ether resin and 50 parts by mass of styrene monomer, completely dissolving to obtain a styrene polyphenyl ether mixed solution, then adding 30 parts by mass of triallyl isocyanurate as a crosslinking curing agent, adding 2 parts by mass of dibenzoyl peroxide as an initiator, 6 parts by mass of decabromodiphenyl ether as a flame retardant, 5 parts by mass of nitrobenzene as a polymerization inhibitor, 20 parts by mass of silica powder as a filler, adding 6 parts by mass of vinyltrimethoxysilane coupling agent, mixing and stirring the mixture for 20min to obtain a resin composition, and simultaneously starting cooling water circulation.
And then impregnating the resin composition glue solution into E-glass fiber cloth, desolventizing at 90 ℃ and pre-reacting for 15min to obtain a prepreg.
Comparative example 1
Mixing 60 parts by mass of methacrylic acid-terminated polyphenyl ether resin and 60 parts by mass of toluene, completely dissolving to obtain polyphenyl ether solution, then adding 30 parts by mass of triallyl isocyanurate as a crosslinking curing agent, adding 2 parts by mass of dibenzoyl peroxide as an initiator, 6 parts by mass of decabromodiphenyl ether as a flame retardant, 5 parts by mass of nitrobenzene as a polymerization inhibitor, 20 parts by mass of silica powder as a filler, and adding 4 parts by mass of vinyltrimethoxysilane coupling agent, mixing and stirring the mixture for 20min to obtain a resin composition, and simultaneously starting cooling water circulation.
And then impregnating the resin composition glue solution into E-glass fiber cloth, desolventizing at 90 ℃ and pre-reacting for 15min to obtain a prepreg.
Performance testing
The prepregs of the examples 1-3 and the prepreg of the comparative example 1 are subjected to conventional performance test analysis, and compared with the prepreg of the comparative example 1, the dielectric constant, the dielectric loss, the solvent resistance, the rigidity and the apparent mass of the products of the examples 1-3 are improved to a certain extent. The relevant performance results are detailed in table 1.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (8)
1. The polyphenylene ether resin composition with the low dielectric constant is characterized by being prepared from the following raw materials in parts by mass:
functionalized polyphenylene ether resin 50% -90%
1 to 80 percent of styrene
5-50% of crosslinking curing agent
0.1-10% of initiator
0.1-10% of polymerization inhibitor
0.1-50% of inorganic filler
2-8% of silane coupling agent
0.1% -15% of flame retardant;
the functionalized polyphenylene ether resin is polyphenylene ether resin with molecular weight of 600-4000 and unsaturated double bonds at the molecular tail end;
the styrene is a styrene monomer and serves as a mixture solvent and a polyphenyl ether resin modifier;
the crosslinking curing agent is a multifunctional allyl compound.
2. The low dielectric constant polyphenylene ether resin composition according to claim 1, wherein said polyfunctional allyl compound comprises triallyl isocyanurate, pentaerythritol triacrylate, trimethylolpropane trimethacrylate.
3. The polyphenylene ether resin composition with a low dielectric constant as claimed in claim 1, wherein the initiator is a radical initiator, the 1h half-life temperature of the initiator is not less than 90 ℃,
the initiator is selected from one or more of the following substances: dibenzoyl peroxide, tert-butyl peroxybenzoate, di-tert-butyl peroxyazelate, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane, 1-di-tert-butylperoxycyclohexane, tert-amyl peroxyacetate, dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, p-menthane hydroperoxide, tert-butyl hydroperoxide, dicumyl hydroperoxide, methyl ethyl ketone peroxide, acetylacetone peroxide, tert-amyl 2-ethylhexanoate peroxide, 1, 3-tetramethylbutyl hydroperoxide, tert-amyl hydroperoxide.
4. The polyphenylene ether resin composition with a low dielectric constant as claimed in claim 1, wherein the polymerization inhibitor is selected from one or more of the following substances: diethylhydroxylamine, nitrobenzene, nitrogen oxide.
5. The polyphenylene ether resin composition with low dielectric constant as claimed in claim 1, wherein the inorganic filler is selected from one or more of the following substances: silicon dioxide, glass powder, boron nitride, aluminum nitride, silicon carbide, aluminum hydroxide and titanium dioxide, wherein the inorganic filler is a hollow sphere or a solid body.
6. The polyphenylene ether resin composition with a low dielectric constant as claimed in claim 1, wherein the silane coupling agent is a mixture of one or more of a vinyl silane coupling agent, an acrylic silane coupling agent, an aminosilane coupling agent and an epoxy silane coupling agent.
7. The low dielectric constant polyphenylene ether resin composition according to claim 1, wherein said flame retardant comprises a phosphorus-containing flame retardant or a bromine-containing flame retardant,
the phosphorus-containing flame retardant is selected from one or more of the following substances: alkyl aryl phosphate, alkyl phosphine oxide, triphenyl phosphate;
the bromine-containing flame retardant is selected from one or more of the following substances: decabromodiphenyl ether, decabromodiphenyl ethane, tetrabromobisphenol A and hexabromocyclododecane.
8. A prepreg manufactured based on the low dielectric constant polyphenylene ether resin composition according to any one of claims 1 to 7, wherein the prepreg is obtained by immersing a substrate in the low dielectric constant polyphenylene ether resin composition according to any one of claims 1 to 7 and drying;
the substrate is a woven or non-woven fabric of glass fibers, carbon fibers or organic fibers.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910032575.4A CN109705284B (en) | 2019-01-14 | 2019-01-14 | Low-dielectric-constant polyphenyl ether resin composition and prepreg prepared from same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111471144B (en) * | 2020-03-27 | 2022-05-31 | 顺德职业技术学院 | Acrylic acid modified low-dielectric fluorine-containing polyphenyl ether mixed glue and 5G copper-clad plate prepared from same |
| CN112430293A (en) * | 2020-11-23 | 2021-03-02 | 江苏诺德新材料股份有限公司 | Low-dielectric-constant organic fiber material and high-frequency copper-clad plate manufactured from same |
| CN113831720A (en) * | 2021-10-29 | 2021-12-24 | 无锡宏仁电子材料科技有限公司 | Trithiocyanuric acid or derivative composition or product thereof |
| CN114716604B (en) * | 2022-03-03 | 2023-03-21 | 重庆市化工研究院有限公司 | Production process of electronic resin material |
| CN116080211B (en) * | 2022-10-14 | 2023-12-29 | 江苏耀鸿电子有限公司 | Low-dielectric-loss PPO resin-based copper-clad plate and preparation method thereof |
| CN116041869B (en) * | 2022-12-21 | 2024-05-17 | 大连理工大学 | Low-dielectric polyphenyl ether modified polystyrene material and preparation method thereof |
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| JPH08231848A (en) * | 1995-02-27 | 1996-09-10 | Matsushita Electric Works Ltd | Production of prepreg |
| CN103467967A (en) * | 2013-09-16 | 2013-12-25 | 广东生益科技股份有限公司 | Thermosetting resin composition and use thereof |
| WO2015062057A1 (en) * | 2013-10-31 | 2015-05-07 | Dow Global Technologies Llc | Curable compositions which form interpenetrating polymer networks |
| CN106084654A (en) * | 2016-06-13 | 2016-11-09 | 电子科技大学中山学院 | Copper-clad plate resin glue solution and method for preparing copper-clad plate by applying resin glue solution |
| CN106398173A (en) * | 2015-07-30 | 2017-02-15 | 松下知识产权经营株式会社 | Thermosetting resin composition, and resin varnish, metal foil with resin, resin film, metal-clad laminate, and printed wiring board using the same |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08231848A (en) * | 1995-02-27 | 1996-09-10 | Matsushita Electric Works Ltd | Production of prepreg |
| CN103467967A (en) * | 2013-09-16 | 2013-12-25 | 广东生益科技股份有限公司 | Thermosetting resin composition and use thereof |
| WO2015062057A1 (en) * | 2013-10-31 | 2015-05-07 | Dow Global Technologies Llc | Curable compositions which form interpenetrating polymer networks |
| CN106398173A (en) * | 2015-07-30 | 2017-02-15 | 松下知识产权经营株式会社 | Thermosetting resin composition, and resin varnish, metal foil with resin, resin film, metal-clad laminate, and printed wiring board using the same |
| CN106084654A (en) * | 2016-06-13 | 2016-11-09 | 电子科技大学中山学院 | Copper-clad plate resin glue solution and method for preparing copper-clad plate by applying resin glue solution |
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