CN109867914B - Polydopamine modified hydrocarbon composition-based prepreg and copper-clad plate prepared from same - Google Patents
Polydopamine modified hydrocarbon composition-based prepreg and copper-clad plate prepared from same Download PDFInfo
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Abstract
The invention belongs to the field of communication materials, and particularly relates to a Polydopamine (PDA) modified hydrocarbon composition-based prepreg and a copper-clad plate prepared from the same. The invention selects the polyarylether or polyolefin resin modified by terminal hydroxyl, terminal amino or terminal sulfydryl as the matrix resin and the epoxy resin as the main curing agent to construct the hydrocarbon composition with excellent dielectric property. In the invention, the prepreg prepared by impregnating the dispersion liquid of the hydrocarbon composition with the reinforcing material and then baking and drying has uniform gel content, good gum dipping quality, strong resin adhesive force, smooth surface, and proper toughness and viscosity. Furthermore, the high-frequency copper clad laminate manufactured by the prepreg and the copper foil has good thermal-mechanical property, excellent dielectric property, good comprehensive property stability, good uniformity and high copper foil peeling strength, and can meet various comprehensive property requirements of the high-frequency and high-speed communication field on substrate materials.
Description
Technical Field
The invention belongs to the field of communication materials, and particularly relates to a polydopamine modified hydrocarbon composition-based prepreg and a copper-clad plate prepared from the same.
Background
At present, the information electronics industry is in a high-speed development stage, and is gradually becoming one of the post industries of various countries. Copper-clad plates are one of key materials in the information electronics industry, and have been widely applied to a plurality of fields such as communication base stations, satellites, unmanned vehicles, unmanned aerial vehicles and intelligent robots. The traditional thermosetting copper-clad plate represented by epoxy resin has the advantages of high thermo-mechanical property, low thermal expansion coefficient, high quality, low price, convenient processing, strong universality and most extensive application. Researchers can prepare various epoxy resin-based copper-clad plates with good comprehensive performance by continuously optimizing the formula and the process parameters, and the most basic requirements of each subdivision field of the electronic communication industry on the copper-clad plates are met. However, the epoxy resin-based copper clad laminate has high dielectric constant and high dielectric loss, so that they can only be used at low frequency, and cannot meet the higher performance requirements of the substrate material in the current high-frequency and high-speed communication fields.
Later, people developed polyphenyl ether-based and polydiene-based thermosetting copper-clad plates, and the dielectric properties of the plates in the high-frequency field are improved. Among them, thermosetting polyphenylene ether resins mainly have two major types of modification of side vinyl group and modification of terminal vinyl group. The preparation process of the side vinyl modified polyphenyl ether needs to use substances with strong reactivity, high risk and large toxicity, such as butyl lithium, and the production process is very complicated. Vinyl-terminated modified polyphenylene ethers have been commercialized, however, the curing process thereof requires the addition of an additional crosslinking agent. For example, CN1745142A and WO2006/023371a1 adopt TAIC, unsaturated olefin monomer and the like as small-molecule crosslinking curing agents of thermosetting polyphenylene ether, however, in the production processes of gumming, prepreg baking and the like, such small-molecule crosslinking curing agents are very volatile, which results in difficult control of the curing degree of polyphenylene ether and the quality of prepreg, and serious pollution. To solve this problem, CN102807658B and CN103467967A were modified with a polymeric crosslinking curing agent such as polydiene. However, polyphenylene ethers, except polystyrene, generally have poor compatibility with other resins, resulting in severe phase separation of the resins in the prepreg composite matrix.
In addition, the glass fiber cloth and inorganic fillers (such as silicon oxide, aluminum oxide and the like) which are commonly used in the manufacturing process of the copper-clad plate contain abundant hydrophilic functional groups, namely hydroxyl on the surface, and the vinyl-modified polyphenylene ether group and polydiene do not contain hydrophilic functional groups containing oxygen, nitrogen and the like, so that the compatibility with the glass fiber cloth and the inorganic fillers is poor, the dielectric properties and the uniformity of different parts of the prepared copper-clad plate are not perfect, and the copper-clad plate is not suitable for manufacturing a multilayer copper-clad plate, so that the requirements of the high frequency and high speed communication field on the function diversification and complication of the copper-clad plate material, high density of circuit arrangement and the like are difficult.
The coupling agent is used for surface modification of inorganic filler, glass fiber cloth or copper foil, and is a common method for enhancing the interaction force between the inorganic filler, the glass fiber cloth or the copper foil and matrix resin. Journal of scienceScience2007, 318, 426.) reports a substance that can rapidly and tightly adsorb on the surface of almost all materials by self-aggregation-Polydopamine (PDA). Meanwhile, PDA contains abundant hydroxyl and amino functional groups and can participate in the curing process of epoxy resin. Therefore, the PDA is a substance which can potentially and effectively improve the interaction force and the adhesive force among materials in the copper-clad plate matrix.
Disclosure of Invention
The invention aims to provide a polydopamine modified hydrocarbon composition-based prepreg.
The invention also aims to provide a high-frequency high-speed copper-clad plate which is prepared from the prepreg and has excellent thermo-mechanical property, good dielectric property and uniformity thereof and high copper foil peeling strength.
The technical scheme adopted by the invention for solving the problems is that the polydopamine modified hydrocarbon composition-based prepreg is prepared by the following steps in sequence:
s1, dipping the reinforcing material in 0.1-100 mg/mL dopamine-trihydroxymethyl aminomethane-hydrochloric acid buffer solution, airing in a non-inert atmosphere for 5-480 min, and drying to obtain a product, namely the reinforcing material with the surface modified with the PDA, which is marked as the PDA @ reinforcing material;
s2, adding 0.1-25 wt/v% of filler into 0.1-100 mg/mL dopamine trihydroxymethylaminomethane-hydrochloric acid buffer solution, stirring and dispersing uniformly in a non-inert atmosphere, soaking for 5-1440 min, filtering, washing and drying to obtain a product, namely the filler with the surface modified with PDA (personal digital assistant) @filler;
s3, preparing a uniform dispersion liquid of a hydrocarbon composition with a solid content of 35-75 wt/v%, impregnating the PDA @ reinforcing material with the uniform dispersion liquid, baking and drying to obtain a prepreg,
the hydrocarbon composition comprises six components of a terminal group modified hydrocarbon polymer, a main curing agent, a secondary curing agent, a curing accelerator, the PDA @ filler and a flame retardant.
The further preferred technical scheme is as follows: in the step S3, the hydrocarbon polymer modified by the end group is a mixture of one or more of polyarylether, polyolefin and derivatives thereof, the end group is one or more of amino, hydroxyl and sulfydryl, and the hydrocarbon polymer modified by the end group accounts for 4-25 wt% of the total hydrocarbon composition.
The further preferred technical scheme is as follows: in steps S1 and S2, the tris-hcl buffer solution is an alkaline aqueous solution having a pH > 7;
the non-inert atmosphere is an atmosphere containing oxygen, wherein the content of oxygen in the non-inert gas is more than or equal to 3 v/v%;
the reinforcing material is one of 106, 1080, 2116 and 7628 electronic grade alkali-free glass fiber cloth or fluororesin fiber woven cloth;
PDA in the PDA @ reinforcing material accounts for 0.03-2.0 wt% of the mass of the reinforcing material.
The further preferred technical scheme is as follows: in step S2, the filler is composed of an inorganic filler and an organic filler, wherein the inorganic filler is SiO2、Al2O3、TiO2、ZnO、MgO、Bi2O3、AlN、BN、SiC、Si3N4、Al(OH)3、Mg(OH)2、SrTiO3、BaTiO3、Mg2TiO4、Bi2(TiO3)3、PbTiO3、NiTiO3、CaTiO3、ZnTiO3、Zn2TiO4、BaSnO3、Bi2(SnO3)3、CaSnO3、PbSnO3、MgSnO3、SrSnO3、ZnSnO3、BaZrO3、CaZrO3、PbZrO3、MgZrO3、SrZrO3、ZnZrO3One or a mixture of more of graphite oxide, graphite fluoride, talcum powder, mica powder, kaolin, clay, solid glass beads, hollow glass beads, glass fibers, basalt fibers and carbon fibers, wherein the particle size of the inorganic filler is less than or equal to 100 mu m, and the inorganic filler accounts for 12-60 wt% of the hydrocarbon composition;
the organic filler is one or a mixture of more of ultra-high molecular weight polyethylene fiber, Kevlar fiber, fluororesin, polyimide and derivatives thereof, and the content of the organic filler is 0-20 wt% of the hydrocarbon composition;
PDA in the PDA @ filler accounts for 0.03-2.0 wt% of the filler.
The further preferred technical scheme is as follows: in step S3, the main curing agent is an epoxy resin, and includes one or a mixture of several of bisphenol a epoxy resin, hydrogenated bisphenol a epoxy resin, bisphenol S epoxy resin, bisphenol F epoxy resin, dicyclopentadiene epoxy resin, naphthalene ring structure epoxy resin, biphenyl epoxy resin, heterocyclic epoxy resin, novolac epoxy resin, silicone epoxy resin, polyfunctional epoxy resin, aliphatic epoxy resin, cyanate ester modified epoxy resin, and derivatives thereof, and the main curing agent accounts for 15 to 68wt% of the hydrocarbon composition;
the secondary curing agent is one or a mixture of more of active polyester, dihydric alcohol, polyalcohol, diamine, polyamine, dithiol, polythiol, dihydric phenol, polyhydric phenol, phenolic resin, cyanate ester resin, anhydride, dicyandiamide, benzoxazine and derivatives thereof, and accounts for 0-12 wt% of the hydrocarbon composition;
the curing accelerator is one or a mixture of more of tertiary amine compounds, imidazole compounds, phosphine compounds, substituted urea compounds, phenolic compounds and boron trifluoride amine complexes, and accounts for 0.02-5.0 wt% of the main curing agent;
the flame retardant is one or a mixture of more of aluminum-magnesium flame retardant, boron-zinc flame retardant, molybdenum-tin flame retardant, bromine flame retardant, antimony trioxide, phosphorus flame retardant, nitrogen flame retardant and derivatives thereof, and accounts for 0-50 wt% of the hydrocarbon composition.
The further preferred technical scheme is as follows: in step S3, the solvent of the uniform dispersion liquid is one or a mixture of several organic solvents capable of uniformly dispersing the hydrocarbon composition.
The further preferred technical scheme is as follows: in the step S3, the baking and drying are divided into two stages, wherein the baking and drying temperature in the first stage is 30-120 ℃, and the baking and drying temperature in the second stage is 120-200 ℃.
The copper-clad plate prepared from the polydopamine modified hydrocarbon composition based prepreg is prepared by the following steps in sequence: laminating the prepreg and the copper foil coated on the surface layer together to obtain the copper-clad plate, wherein the number of the prepreg is more than or equal to 1, the number of the copper foil is 1 or 2, the laminating temperature is 130-300 ℃, and the laminating pressure is 80-130 kg/cm2The laminating time is 5min to 480 min.
The invention selects the polyarylether or polyolefin resin modified by terminal hydroxyl, terminal amino or terminal sulfydryl as the matrix resin and the epoxy resin as the main curing agent to construct the hydrocarbon composition with excellent dielectric property. Meanwhile, PDA is modified on the surfaces of the reinforcing material and the filler, and the PDA contains abundant hydroxyl and amino functional groups and can participate in the crosslinking curing reaction of the end group modified polyarylether or polyolefin and the epoxy resin, so that the matrix resin is directly bonded to the surfaces of the reinforcing material and the filler, and the compatibility and the bonding force of the reinforcing material and the filler are obviously enhanced. In the invention, the prepreg prepared by impregnating the dispersion liquid of the hydrocarbon composition with the reinforcing material and then baking and drying has uniform gel content, good gum dipping quality, strong resin adhesive force, smooth surface, and proper toughness and viscosity. Furthermore, the high-frequency copper clad laminate manufactured by the prepreg and the copper foil has good thermal-mechanical property, excellent dielectric property, good comprehensive property stability, good uniformity and high copper foil peeling strength.
The applicant has also found that the modification amount of the PDA on the surface of the reinforcing material and filler must not be too small, otherwise the interaction force between the reinforcing material, filler and matrix resin is not significantly increased; but the modification amount of the PDA is not too much, otherwise, the dielectric loss of the copper-clad plate is increased.
The method has the advantages of mild preparation conditions, low production cost, easiness in batch and large-scale production, strong universality, good industrial production basis and wide application prospect.
Detailed Description
The invention provides a hydrocarbon composition-based prepreg modified by Polydopamine (PDA) and a high-frequency copper-clad plate prepared by using the prepreg, which are further described in detail by embodiments. However, this example is provided only as an illustration, and does not limit the present invention.
Examples 1 to 5
And (2) soaking 1080 glass fiber cloth in a Tris-HCl (pH = 8.6) buffer solution of 1.5wt% dopamine for 30min, and taking out to prepare 1080 glass fiber cloth with the surface modified with PDA, which is marked as 'PDA @1080 glass fiber cloth'. Stirring and soaking the filler in a Tris-HCl (pH = 8.6) buffer solution of dopamine for 30min, filtering, washing and drying to obtain the filler with the surface modified with PDA, which is marked as PDA @ filler. Uniformly dispersing a hydroxyl-terminated modified hydrocarbon polymer, a main curing agent, a secondary curing agent, a curing accelerator, PDA @ filler and a flame retardant in toluene, controlling the solid content of the dispersion liquid to be 60wt%, dipping the PDA @1080 glass fiber cloth in the uniform dispersion liquid, and baking to obtain a prepreg. The first stage baking and drying temperature is 60-100 ℃; the second stage baking and drying temperature is 120-190 ℃. And (3) superposing 8 prepregs, respectively attaching loz copper foils to two surfaces of the prepregs, and laminating the prepregs under vacuum, pressurization and high temperature for several hours to obtain the copper-clad plate. The specific formulation is detailed in the following table.
Comparative example 1
Comparative example 1 used 1080 fiberglass cloth and filler without PDA modification, and the other processes were the same as example 1.
Comparative example 2
Comparative example 2 used a PDA-modified filler, but not a PDA-modified 1080 glass cloth, and the other processes were the same as in example 1.
The prepreg and the copper-clad plate have various properties shown in the following table.
As shown in comparative example 1, if the surfaces of the glass fiber cloth and the filler are not modified by PDA, the matrix resin cannot be directly bonded to the surfaces of the glass fiber cloth and the filler, the bonding force between the three is not strong, and the dip-soldering resistance and the drilling resistance of the prepared copper-clad plate are not good. If PDA is only used for surface modification of the filler, as shown in comparative example 2, the bonding force of each component in the copper-clad plate substrate is improved, and the dip soldering resistance and the drilling resistance are improved, but the degree is not obvious. Only the surfaces of the glass fiber cloth and the filler are modified with PDA, as shown in examples 1-5, the PDA can participate in the cross-linking curing reaction of the end group modified polyarylether or polyolefin and the epoxy resin, the matrix resin is directly bonded to the surfaces of the glass fiber cloth and the filler, the bonding force among all components in the board-based copper matrix is improved to the maximum extent, and the water absorption rate and the dielectric loss of the copper-clad board are reduced to a certain extent due to the improvement of the uniformity of the board and the reduction of the free volume and defects in the matrix resin while the dip soldering resistance and the drilling performance of the board are further improved.
The preparation method has the advantages of mild preparation conditions, low production cost, easiness in batch and large-scale production, good industrial production basis and wide application prospect.
Claims (5)
1. The copper-clad plate prepared from the polydopamine modified hydrocarbon composition based prepreg is characterized by being prepared through the following steps in sequence:
s1, dipping the reinforcing material in 0.1-100 mg/mL dopamine-trihydroxymethyl aminomethane-hydrochloric acid buffer solution, airing in a non-inert atmosphere for 5-480 min, and drying to obtain a product, namely the reinforcing material with the surface modified with the PDA, which is marked as the PDA @ reinforcing material;
s2, adding 0.1-25 wt/v% of filler into 0.1-100 mg/mL dopamine trihydroxymethylaminomethane-hydrochloric acid buffer solution, stirring and dispersing uniformly in a non-inert atmosphere, soaking for 5-1440 min, filtering, washing and drying to obtain a product, namely the filler with the surface modified with PDA (personal digital assistant) @filler;
s3, preparing a uniform dispersion liquid of a hydrocarbon composition with a solid content of 35-75 wt/v%, impregnating the PDA @ reinforcing material with the uniform dispersion liquid, baking and drying to obtain a prepreg,
the hydrocarbon composition comprises six components of a terminal group modified hydrocarbon polymer, a main curing agent, a secondary curing agent, a curing accelerator, the PDA @ filler and a flame retardant,
in step S3, the hydrocarbon polymer modified by the end group is a mixture of one or more of polyarylether, polyolefin and derivatives thereof, the end group is one or more of amido, hydroxyl and sulfydryl, the hydrocarbon polymer modified by the end group accounts for 4-25 wt% of the total hydrocarbon composition,
in step S3, the main curing agent is an epoxy resin, and includes one or a mixture of several of bisphenol a epoxy resin, hydrogenated bisphenol a epoxy resin, bisphenol S epoxy resin, bisphenol F epoxy resin, dicyclopentadiene epoxy resin, naphthalene ring structure epoxy resin, biphenyl epoxy resin, heterocyclic epoxy resin, novolac epoxy resin, silicone epoxy resin, aliphatic epoxy resin, cyanate ester modified epoxy resin, and derivatives thereof, and the main curing agent accounts for 15 to 68wt% of the hydrocarbon composition;
the secondary curing agent is one or a mixture of more of active polyester, dihydric alcohol, diamine, dithiol, dihydric phenol, phenolic resin, cyanate ester resin, anhydride, dicyandiamide, benzoxazine and derivatives thereof, and accounts for 0-12 wt% of the hydrocarbon composition;
the curing accelerator is one or a mixture of more of tertiary amine compounds, imidazole compounds, phosphine compounds, substituted urea compounds, phenolic compounds and boron trifluoride amine complexes, and accounts for 0.02-5.0 wt% of the main curing agent;
the flame retardant is one or a mixture of more of aluminum-magnesium flame retardant, boron-zinc flame retardant, molybdenum-tin flame retardant, bromine flame retardant, antimony trioxide, phosphorus flame retardant, nitrogen flame retardant and derivatives thereof, the flame retardant accounts for 0-50 wt% of the hydrocarbon composition,
laminating the prepreg and the copper foil coated on the surface layer together to obtain the copper-clad plate, wherein the number of the prepreg is more than or equal to 1, the number of the copper foil is 1 or 2, the laminating temperature is 130-300 ℃, and the laminating pressure is 80-130 kg/cm2The laminating time is 5min to 480 min.
2. The copper-clad plate prepared from the polydopamine modified hydrocarbon composition based prepreg according to claim 1, wherein the copper-clad plate is characterized in that: in steps S1 and S2, the tris-hcl buffer solution is an alkaline aqueous solution having a pH > 7;
the non-inert atmosphere is an atmosphere containing oxygen, wherein the content of oxygen in the non-inert gas is more than or equal to 3 v/v%;
the reinforcing material is one of 106, 1080, 2116 and 7628 electronic grade alkali-free glass fiber cloth or fluororesin fiber woven cloth;
PDA in the PDA @ reinforcing material accounts for 0.03-2.0 wt% of the mass of the reinforcing material.
3. The copper-clad plate prepared from the polydopamine modified hydrocarbon composition based prepreg according to claim 1, wherein the copper-clad plate is characterized in that: in step S2, the filler is composed of an inorganic filler and an organic filler, wherein the inorganic filler is SiO2、Al2O3、TiO2、ZnO、MgO、Bi2O3、AlN、BN、SiC、Si3N4、Al(OH)3、Mg(OH)2、SrTiO3、BaTiO3、Mg2TiO4、Bi2(TiO3)3、PbTiO3、NiTiO3、CaTiO3、ZnTiO3、Zn2TiO4、BaSnO3、Bi2(SnO3)3、CaSnO3、PbSnO3、MgSnO3、SrSnO3、ZnSnO3、BaZrO3、CaZrO3、PbZrO3、MgZrO3、SrZrO3、ZnZrO3One or a mixture of more of graphite oxide, graphite fluoride, talcum powder, mica powder, kaolin, clay, solid glass beads, hollow glass beads, glass fibers, basalt fibers and carbon fibers, wherein the particle size of the inorganic filler is less than or equal to 100 mu m, and the inorganic filler accounts for 12-60 wt% of the hydrocarbon composition;
the organic filler is one or a mixture of more of ultra-high molecular weight polyethylene fiber, Kevlar fiber, fluororesin, polyimide and derivatives thereof, and the content of the organic filler is 0-20 wt% of the hydrocarbon composition;
PDA in the PDA @ filler accounts for 0.03-2.0 wt% of the filler.
4. The copper-clad plate prepared from the polydopamine modified hydrocarbon composition based prepreg according to claim 1, wherein the copper-clad plate is characterized in that: in step S3, the solvent of the uniform dispersion liquid is one or a mixture of several organic solvents capable of uniformly dispersing the hydrocarbon composition.
5. The copper-clad plate prepared from the polydopamine modified hydrocarbon composition based prepreg according to claim 1, wherein the copper-clad plate is characterized in that: in the step S3, the baking and drying are divided into two stages, wherein the baking and drying temperature in the first stage is 30-120 ℃, and the baking and drying temperature in the second stage is 120-200 ℃.
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| CN111534076A (en) * | 2020-05-25 | 2020-08-14 | 常州中英科技股份有限公司 | Polyarylether base composition containing reversible thermal shrinkage and cold expansion structural unit and prepreg and thermosetting copper-clad plate prepared from polyarylether base composition |
| CN114044991A (en) * | 2021-11-29 | 2022-02-15 | 杨春生 | Flame-retardant PVC material and preparation method thereof |
| WO2024004528A1 (en) * | 2022-06-30 | 2024-01-04 | パナソニックＩｐマネジメント株式会社 | Composite material, application product thereof, and composite material manufacturing method |
| WO2024004527A1 (en) * | 2022-06-30 | 2024-01-04 | パナソニックＩｐマネジメント株式会社 | Composite material, product resulting from applying said composite material, and method for producing composite material |
| CN115449185B (en) * | 2022-09-21 | 2023-05-23 | 华南理工大学 | Glass fiber reinforced epoxy resin composite material and preparation method and application thereof |
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| CN104927302A (en) * | 2014-03-20 | 2015-09-23 | 江南大学 | Graphene-toughened epoxy resin composite material and preparation method thereof |
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