WO2020143336A1 - High-frequency resin prepolymer, and high-frequency resin composition, prepreg, laminated board, and interlayer insulating film prepared by using same - Google Patents

High-frequency resin prepolymer, and high-frequency resin composition, prepreg, laminated board, and interlayer insulating film prepared by using same Download PDF

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Publication number
WO2020143336A1
WO2020143336A1 PCT/CN2019/119487 CN2019119487W WO2020143336A1 WO 2020143336 A1 WO2020143336 A1 WO 2020143336A1 CN 2019119487 W CN2019119487 W CN 2019119487W WO 2020143336 A1 WO2020143336 A1 WO 2020143336A1
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Prior art keywords
epoxy resin
frequency
resin
prepolymer
prepreg
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PCT/CN2019/119487
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French (fr)
Chinese (zh)
Inventor
杨宋
李兴敏
马建
崔春梅
陈诚
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苏州生益科技有限公司
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Publication of WO2020143336A1 publication Critical patent/WO2020143336A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols

Definitions

  • the invention relates to the technical field of electronic materials, in particular to a high-frequency resin prepolymer and a high-frequency resin composition prepared using the same, a prepreg, a laminate and an interlayer insulating film.
  • High-frequency high-performance substrate materials have become an important frontier technology for the development of the printed board industry. Many companies have joined the ranks of developing new materials and technologies for copper clad laminates. Traditional resin substrate materials are replaced by high-frequency, high-speed, and high-reliability substrate materials, and the market demand is increasing. The performance of high-frequency microwave circuit boards directly determines the high-frequency, high-speed, and high reliability of high-end electronic information technology.
  • the main resins include polyphenylene ether, polytetrafluoroethylene-based resin, and anhydride-based cured epoxy resin composition.
  • the cured epoxy material inevitably contains a large number of hydrophilic groups, resulting in a high water absorption rate. As we all know, the resin matrix will absorb moisture in a hot and humid environment.
  • An object of the present invention is to provide a high-frequency resin prepolymer that solves the above technical problems, a high-frequency resin composition prepared using the same, a prepreg, a laminate, and an interlayer insulating film.
  • the high-frequency resin prepolymer is at least pre-polymerized by cage silsesquioxane and polyaryl ether ketone polymer, and the mass ratio of the cage silsesquioxane and polyaryl ether ketone polymer It is 100:100-5000.
  • the structure of the cage silsesquioxane has one or more of an amino group, an ester group, an epoxy group, a hydroxyl group, a carboxyl group, a carbonyl group, and a radical.
  • the structure of the polyaryletherketone polymer carries one or more of amino groups, ester groups, epoxy groups, hydroxyl groups, carboxyl groups, phenyl carboxyl groups, and free radicals.
  • the mass ratio of the cage silsesquioxane to the polyaryl ether ketone polymer is 100:300-1000.
  • the present invention also provides a high-frequency resin composition, based on the weight of solids, which includes:
  • the high-frequency resin prepolymer according to any one of the above: 10-80 parts;
  • Epoxy resin 10-60 parts
  • the epoxy resin is selected from bisphenol A epoxy resin, bisphenol F epoxy resin, phosphorus-containing epoxy resin, bromine-containing epoxy resin, o-cresol novolac epoxy resin, bisphenol A Phenolic epoxy resin, phenol novolac epoxy resin, trifunctional phenol epoxy resin, tetraphenylethane epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, dicyclopentadiene epoxy resin , Aralkyl novolac epoxy resin, glycidyl amine epoxy resin, glycidyl ester epoxy resin one or more of the mixture; the flame retardant is selected from phosphorus-containing flame retardants and bromine-containing One or a mixture of several flame retardants.
  • the filler is an inorganic filler and/or an organic filler, wherein the inorganic filler is selected from silica, boron nitride, aluminum hydroxide, boehmite, talc, clay, mica, kaolin , Barium sulfate, calcium carbonate, magnesium hydroxide and zinc borate or one or more mixtures, the organic filler is any one selected from polytetrafluoroethylene powder, polyphenylene sulfide or polyethersulfone powder Or a mixture of at least two; the accelerator is imidazole and/or an organometallic salt.
  • the inorganic filler is selected from silica, boron nitride, aluminum hydroxide, boehmite, talc, clay, mica, kaolin , Barium sulfate, calcium carbonate, magnesium hydroxide and zinc borate or one or more mixtures
  • the organic filler is any one selected from polytetrafluoroethylene powder, polyphenylene
  • the present invention also provides a prepreg, in which a solvent is added to the high-frequency resin composition as described above to dissolve to make a glue solution, a reinforcement material is immersed in the glue solution, and the reinforced material after the immersion After heating and drying, the prepreg can be obtained.
  • the present invention also provides a laminate, which is coated with a release film on both sides of at least one prepreg as described above, and hot-pressed to obtain the laminate.
  • the present invention also provides an interlayer insulating film.
  • a solvent is added to the high-frequency resin composition as described above to dissolve to make a glue solution, the glue solution is coated on the carrier film, and the glue solution is applied After heating and drying the carrier film, the interlayer insulating film can be obtained.
  • the present invention has the following advantages compared with the prior art:
  • POSS modified polyaryl ether ketone prepolymer is selected.
  • POSS has a hollow structure, so the introduction of POSS represents the introduction of air to a certain extent, which can play a role in reducing the dielectric properties of the material.
  • POSS has Larger free volume, so the introduction of POSS will correspondingly reduce the packing density of the composite material and increase the free volume of the composite material, which will also reduce the dielectric constant of the material; POSS exists in the nanometer size in the cured material, then its Will interact with polymer materials.
  • POSS When POSS is present in the composite material in the form of nanometers below the critical size, it will produce a strong self-polarization-induced effect at the junction with the matrix polymer, making the electron cloud of the composite material radially localized, when the composite material is in Under the condition of an external electric field, the presence of POSS nanoparticles will constrain the polarization of the composite electron cloud, thereby greatly reducing the polarization rate of the composite material, that is, the dielectric constant of the composite material is greatly reduced;
  • the POSS modified polyaryl ether ketone prepolymer can be evenly dispersed in the composite material, showing good compatibility and solving the problem of the thermoplastic material being difficult to dissolve;
  • POSS modified polyaryletherketone prepolymer contains polyaryletherketone structure, which makes its molecular chain rigid, so its products have good dimensional stability and small thermal expansion coefficient;
  • polyaryl ether ketone has strong self-extinguishing, greatly reducing the amount of flame retardant and the negative impact of flame retardant on dielectric properties, humidity and heat resistance;
  • the printed circuit laminate prepared by using the resin composition of the present invention not only solves the problems of poor adhesion and poor mechanical properties caused by defects in the resin with polytetrafluoroethylene, but also has excellent copper Foil peel strength and high glass transition temperature, while having high-frequency dielectric constant and low dielectric loss to maintain stability, can better meet the requirements of high-frequency high-speed and high-density interconnection.
  • a high-frequency resin prepolymer specifically a POSS modified polyaryletherketone prepolymer, which is prepolymerized by at least a cage silsesquioxane and a polyaryletherketone polymer
  • the number average molecular weight of POSS modified polyaryletherketone prepolymer is 500-20000.
  • the POSS modified polyaryl ether ketone prepolymer has a number average molecular weight of 800-5000.
  • the mass ratio of cage silsesquioxane to polyaryl ether ketone polymer is 100:100-5000, preferably, the mass ratio of cage silsesquioxane to polyaryl ether ketone polymer is 100: 300-1000.
  • the cage silsesquioxane has one or more of amino group, ester group, epoxy group, hydroxyl group, carboxyl group, carbonyl group and free radical in the structure.
  • it preferably has amino group and epoxy group.
  • the structure of the polyaryl ether ketone polymer has one or more of amino group, ester group, epoxy group, hydroxyl group, carboxyl group, benzene carboxyl group and free radical, and the present invention preferably has carboxyl group and benzene carboxyl group.
  • the invention also provides a high-frequency resin composition, based on the weight of solids, including:
  • Epoxy resin 10-60 parts
  • the epoxy resin is selected from bisphenol A epoxy resin, bisphenol F epoxy resin, phosphorus-containing epoxy resin, bromine-containing epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, phenol Phenolic epoxy resin, trifunctional phenol epoxy resin, tetraphenylethane epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, dicyclopentadiene epoxy resin, aralkyl novolac One or a mixture of epoxy resin, glycidylamine epoxy resin, and glycidyl ester epoxy resin.
  • halogen-free epoxy resin more preferably bisphenol A epoxy resin, bisphenol F epoxy resin, phosphorus-containing epoxy resin, biphenyl type epoxy resin, naphthalene ring type epoxy resin, dicyclopentadiene type Epoxy resin.
  • the flame retardant is selected from a mixture of one or more of phosphorus-containing flame retardants and bromine-containing flame retardants, wherein the phosphorus-containing flame retardants are selected from phosphorus-containing epoxy resins, phosphorus-containing phenolic resins, phosphorus Nitrile compounds, phosphate compounds, phosphorus-containing cyanate esters, phosphorus-containing bismaleimide one or a mixture of several; bromine-containing flame retardant selected from tribromophenyl maleimide, tetrabromo One or more of bisphenol A allyl ether, decabromodiphenylethane, brominated polystyrene, brominated polycarbonate, tetrabromobisphenol A, brominated epoxy resin, the invention
  • the medium flame retardant is preferably a phosphorus-containing flame retardant.
  • the filler is an inorganic filler and/or an organic filler, wherein the inorganic filler is selected from silica, boron nitride, aluminum hydroxide, boehmite, talc, clay, mica, kaolin, barium sulfate, calcium carbonate, hydrogen One or more mixtures of magnesium oxide and zinc borate; the organic filler is any one or a mixture of at least two selected from polytetrafluoroethylene powder, polyphenylene sulfide, or polyethersulfone powder. Furthermore, the median particle size of the filler is 0.3-20 ⁇ m, more preferably 0.5-5 ⁇ m, and the filler located in this particle size section has good dispersibility and good processability.
  • the filler is preferably an inorganic filler, and the content of the filler in the resin composition is 5-60 parts.
  • the surface-treated inorganic filler is further preferred, and the surface-treated silica is most preferred.
  • the surface treatment agent for surface-treating the inorganic filler is selected from any one or a mixture of at least two of a silane coupling agent, a silicone oligomer, or a titanate coupling agent.
  • the accelerator is imidazole, an organic metal salt, or a mixture of imidazole and an organic metal.
  • the imidazole is selected from 2-methylimidazole, 2-phenylimidazole or 2-ethyl-4methylimidazole;
  • the organic metal salt is selected from zinc octoate, cobalt octoate, zinc isooctanoate, stannous octoate, dilaurate dilaurate Butyl tin, zinc naphthenate, cobalt naphthenate, aluminum acetylacetonate, cobalt acetylacetonate or copper acetylacetonate, preferably zinc octoate and cobalt octoate, the content of the accelerator in the resin composition is 0.01-1 part.
  • a toughener may be added to the high-frequency resin composition, and the toughener is at least one selected from the group consisting of high molecular weight epoxy resin, phenol oxide resin, rubber, and cycloolefin polymer, and its content in the resin composition 0.1-10 servings.
  • the invention also provides a prepreg prepared by using the above-mentioned high-frequency resin composition, and the preparation steps are as follows:
  • the prepreg in the present invention can be obtained by immersing the reinforcing material in the glue of the above-mentioned high-frequency resin composition, and then baking the immersed reinforcing material in an environment of 50-170°C for 1-10 minutes and drying.
  • the reinforcing material is natural fiber, organic synthetic fiber, organic fabric or inorganic fabric.
  • Inorganic fabric is particularly preferably glass fiber cloth, and glass fiber cloth is preferably open fiber cloth or flat cloth.
  • the glass fiber cloth in order to improve the interface between the resin and the glass fiber cloth, the glass fiber cloth generally needs to be chemically treated.
  • the main method is the coupling agent treatment.
  • the coupling agent used is epoxy silane, amino silane, etc.
  • the solvent is selected from acetone, methyl ethyl ketone, toluene, xylene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether One or a combination of several.
  • the invention also provides a laminate prepared by using the prepreg, and the preparation steps are as follows:
  • One side or both sides of one prepreg is covered with metal foil, or after stacking at least two of the above prepregs, one side or both sides are covered with metal foil, and hot-pressed to obtain a metal foil laminate.
  • the number of prepregs can be determined according to the required thickness of the laminate, and one or more sheets can be used.
  • the metal foil may be copper foil or aluminum foil, and their thickness is not particularly limited.
  • the pressing conditions of the above-mentioned laminate are: pressing at a pressure of 5-35 kg/cm 2 and a temperature of 180-210° C. for 70-200 min.
  • the invention also provides an interlayer insulating film prepared by using the prepreg, and the preparation steps are as follows:
  • the above-mentioned high-frequency resin composition is dissolved in a solvent to make a glue solution, the glue solution is coated on the carrier film, and the carrier film coated with the glue solution is heated and dried to obtain an interlayer insulating film.
  • the heating and drying conditions are baking at 50-170°C for 1-10 minutes.
  • the solvent is selected from one of acetone, methyl ethyl ketone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether or A mix of several.
  • the carrier film is a polyethylene terephthalate (PET) film, a release film, copper foil, aluminum foil, etc., preferably a PET film.
  • PET polyethylene terephthalate
  • the protective film may be covered on the other side, and the protective film and the carrier film have the same material.
  • cage silsesquioxane: polyaryl ether ketone polymer 100: 100-1000, take cage silsesquioxane, polyaryl ether ketone polymer in the reaction bottle , Heated to room temperature -200 °C, and maintained under stirring, the reaction is 30-600min to obtain a uniform and transparent POSS modified polyaryl ether ketone prepolymer with a number average molecular weight of 500-20000, after the reaction is completed, it is cooled to room temperature. After processing, stand by;
  • carboxy polyaryl ether ketone 10:50 prepolymer 30g, adding an appropriate amount of N, N-dimethyl ethyl Dissolve the amide
  • the glue solution was impregnated and coated on E glass fiber cloth (2116, unit weight 104g/m2), and baked in an oven at 135°C for 5 minutes to prepare a prepreg with a resin content of 50%.
  • the prepared prepreg with a resin content of 50% is placed with a metal copper foil up and down and placed in a vacuum hot press to obtain a copper clad laminate.
  • the specific pressing process is pressing at 1.5Mpa and 195°C for 2 hours.
  • phenylcarboxy polyaryl ether ketone 10: 80 prepolymer 30g, adding an appropriate amount of N, N-
  • the preparation method of the prepreg and the copper-clad laminate are the same as in the first embodiment.
  • dicyclopentadiene epoxy resin XD-1000, Japanese chemical
  • 22g of phenolic curing agent PF-8011, Shandong Holy spring
  • the preparation method of the prepreg and the copper-clad laminate are the same as in the first embodiment.
  • the glue solution was impregnated and coated on E glass fiber cloth (2116, unit weight 104g/m2), and baked in an oven at 135°C for 5 minutes to prepare a prepreg with a resin content of 50%.
  • the prepared prepreg with a resin content of 50% is placed with a metal copper foil up and down and placed in a vacuum hot press to obtain a copper clad laminate.
  • the specific pressing process is pressing at 1.5Mpa and 220°C for 2 hours.
  • Table 1 is the performance of copper-clad laminates obtained by using different examples
  • Glass transition temperature (Tg) It is measured according to the DSC method specified in IPC-TM-650 2.4.25 according to differential scanning calorimetry.
  • Thermal decomposition temperature Td measured according to the method of IPC-TM-650 2.4.26.
  • Dielectric constant According to IPC-TM-650 2.5.5.9, use the flat plate method to measure the dielectric constant at 1 GHz.
  • Dielectric loss tangent According to IPC-TM-650 2.5.5.9, use the flat plate method to measure the dielectric loss factor at 1 GHz.
  • Falling weight impact toughness (brittleness of laminate): Use an impact meter. The drop height of the impact meter is 45cm, and the weight of the falling weight is 1kg. Judgment of good and poor toughness: the cross is clear, indicating the better the toughness of the product, which is indicated by the character ⁇ ; the cross is fuzzy, indicating that the product has poor toughness and brittleness, and is indicated by the character ⁇ ; The toughness of the product is average, indicated by the character ⁇ .
  • Example 1 and Comparative Example 1 are superior in glass transition temperature, moisture and heat resistance, dielectric properties and toughness, especially the dielectric constant can be reduced to 4.0 level; and then by Example 2 and Example 3 and Comparative Example 2, the laminate made by the present invention not only has better moisture and heat resistance, but also can obtain excellent dielectric properties, high glass transition temperature and higher Toughness, especially in terms of dielectric properties and heat and humidity resistance, is very excellent in reliability.
  • the resin composition of the present invention has high moisture resistance and heat resistance, high glass transition temperature, low dielectric constant and dielectric loss tangent value, and can satisfy high-frequency high-speed and high-density interconnection and other high-performance printed circuit boards. Claim.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

Disclosed in the present invention are a high-frequency resin prepolymer, and a high-frequency resin composition, a prepreg, a laminated board, and an interlayer insulating film prepared by using same. The high-frequency resin prepolymer is prepared at least by prepolymerizing cage-type silsesquioxane and a polyaryletherketone polymer at a mass ratio of 100:100-5000.

Description

高频树脂预聚物及使用其制备的高频树脂组合物、半固化片、层压板和层间绝缘膜High-frequency resin prepolymer and high-frequency resin composition, prepreg, laminate and interlayer insulating film prepared using the same 技术领域Technical field
本发明涉及电子材料技术领域，特别涉及一种高频树脂预聚物及使用其制备的高频树脂组合物、半固化片、层压板和层间绝缘膜。The invention relates to the technical field of electronic materials, in particular to a high-frequency resin prepolymer and a high-frequency resin composition prepared using the same, a prepreg, a laminate and an interlayer insulating film.
背景技术Background technique
随着通信、电子产品向着高频、高速度化方向发展，用户对该类产品的性能要求越来越高，高频高性能基板材料已成为印制板行业发展的重要前沿技术，越来越多的企业加入到开发覆铜板新材料新技术的行列中。传统的树脂基板材料被高频化、高速化、高可靠性基板材料所替代，且市场需求越来越大。高频微波电路基板的性能直接决定了高端电子信息技术的高频、高速、及高可靠性等。With the development of communication and electronic products towards high frequency and high speed, users have higher and higher performance requirements for such products. High-frequency high-performance substrate materials have become an important frontier technology for the development of the printed board industry. Many companies have joined the ranks of developing new materials and technologies for copper clad laminates. Traditional resin substrate materials are replaced by high-frequency, high-speed, and high-reliability substrate materials, and the market demand is increasing. The performance of high-frequency microwave circuit boards directly determines the high-frequency, high-speed, and high reliability of high-end electronic information technology.
目前，用于高频高速基板的高频树脂组合物中，主体树脂有聚苯醚、聚四氟乙烯类树脂，以及酸酐类固化环氧树脂组合物。然而，环氧树脂固化后材料不可避免的含有大量的亲水基团，从而造成材料的吸水率大。众所周知，树脂基体在湿热的环境中会吸湿，吸入的水分对基体的塑化和溶胀作用以及因树脂与玻璃纤维布的湿热膨胀系数的不匹配所产生的内应力引起的微裂纹使基板材料的性能急剧下降，如热膨胀系数、耐热性、层间粘结力、介电常数、介质损耗正切值等，也就是说干燥和吸湿两个状态下各个性能的变化千差万别。因此，树脂固化物的耐湿热性是决定材料综合性能的重要因素。At present, in the high-frequency resin composition used for the high-frequency high-speed substrate, the main resins include polyphenylene ether, polytetrafluoroethylene-based resin, and anhydride-based cured epoxy resin composition. However, the cured epoxy material inevitably contains a large number of hydrophilic groups, resulting in a high water absorption rate. As we all know, the resin matrix will absorb moisture in a hot and humid environment. The plasticized and swollen effect of the absorbed moisture on the matrix and the internal cracks caused by the mismatch in the coefficient of hygrothermal expansion of the resin and glass fiber cloth cause the substrate material to The performance drops sharply, such as the coefficient of thermal expansion, heat resistance, interlayer adhesion, dielectric constant, dielectric loss tangent, etc., that is to say, the performance of each performance changes in the two states of dry and hygroscopic. Therefore, the moisture resistance of the cured resin is an important factor that determines the overall performance of the material.
因此，开发一种具有高的耐湿热性能、高玻璃化转变温度、高韧性、较低的介电常数和介电损耗正切值的高频树脂组合物，以满足高频高速及高密度互连等高性能印制线路板的要求，显然具有积极的现实意义。Therefore, develop a high-frequency resin composition with high humidity resistance, high glass transition temperature, high toughness, low dielectric constant and dielectric loss tangent to meet high-frequency high-speed and high-density interconnection The requirements for high-performance printed circuit boards are clearly of positive practical significance.
发明内容Summary of the invention
本发明的目的在于提供一种解决上述技术问题的高频树脂预聚物及使用其制备的高频树脂组合物、半固化片、层压板和层间绝缘膜。An object of the present invention is to provide a high-frequency resin prepolymer that solves the above technical problems, a high-frequency resin composition prepared using the same, a prepreg, a laminate, and an interlayer insulating film.
其中，所述高频树脂预聚物至少由笼型倍半硅氧烷和聚芳醚酮聚合物预聚而成，所述笼型倍半硅氧烷和聚芳醚酮聚合物的质量比例为100:100-5000。Wherein, the high-frequency resin prepolymer is at least pre-polymerized by cage silsesquioxane and polyaryl ether ketone polymer, and the mass ratio of the cage silsesquioxane and polyaryl ether ketone polymer It is 100:100-5000.
作为本发明的进一步改进，所述笼型倍半硅氧烷的结构中带有氨基、酯基、环氧基、羟基、羧基、羰基、自由基的一种或几种。As a further improvement of the present invention, the structure of the cage silsesquioxane has one or more of an amino group, an ester group, an epoxy group, a hydroxyl group, a carboxyl group, a carbonyl group, and a radical.
作为本发明的进一步改进，所述聚芳醚酮聚合物的结构中带有氨基、酯基、环氧基、羟基、羧基、苯羧基、自由基的一种或几种。As a further improvement of the present invention, the structure of the polyaryletherketone polymer carries one or more of amino groups, ester groups, epoxy groups, hydroxyl groups, carboxyl groups, phenyl carboxyl groups, and free radicals.
作为本发明的进一步改进，所述笼型倍半硅氧烷和聚芳醚酮聚合物的质量比例为100:300-1000。As a further improvement of the present invention, the mass ratio of the cage silsesquioxane to the polyaryl ether ketone polymer is 100:300-1000.
相应地，本发明还提供一种高频树脂组合物，以固体重量计，其包括：Correspondingly, the present invention also provides a high-frequency resin composition, based on the weight of solids, which includes:
上述任一项所述的高频树脂预聚物：10-80份；The high-frequency resin prepolymer according to any one of the above: 10-80 parts;
环氧树脂：10-60份；Epoxy resin: 10-60 parts;
阻燃剂：5-40份；Flame retardant: 5-40 parts;
促进剂：0.001-2份；Accelerator: 0.001-2 copies;
填料：0-70份。Filler: 0-70 parts.
作为本发明的进一步改进，所述环氧树脂选自双酚A环氧树脂、双酚F环氧树脂、含磷环氧树脂、含溴环氧树脂、邻甲酚醛环氧树脂、双酚A酚醛环氧树脂、苯酚酚醛环氧树脂、三官能酚型环氧树脂、四苯基乙烷环氧树脂、联苯型环氧树脂、萘环型环氧树脂、双环戊二烯型环氧树脂、芳烷基线型酚醛环氧树脂、缩水甘油胺型环氧树脂、缩水甘油酯型环氧树脂中的一种或几种的混合；所述阻燃剂选自含磷阻燃剂和含溴阻燃剂中的一种或几种的混合。As a further improvement of the present invention, the epoxy resin is selected from bisphenol A epoxy resin, bisphenol F epoxy resin, phosphorus-containing epoxy resin, bromine-containing epoxy resin, o-cresol novolac epoxy resin, bisphenol A Phenolic epoxy resin, phenol novolac epoxy resin, trifunctional phenol epoxy resin, tetraphenylethane epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, dicyclopentadiene epoxy resin , Aralkyl novolac epoxy resin, glycidyl amine epoxy resin, glycidyl ester epoxy resin one or more of the mixture; the flame retardant is selected from phosphorus-containing flame retardants and bromine-containing One or a mixture of several flame retardants.
作为本发明的进一步改进，所述填料为无机填料和/或有机填料，其中，所述无机填料选自二氧化硅、氮化硼、氢氧化铝、勃姆石、滑石、粘土、云母、高岭土、硫酸钡、碳酸钙、氢氧化镁和硼酸锌的一种或一种以上的混合物，所述有机填料为选自聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的任意一种或者至少两种的混合物；所述促进剂为咪唑和/或有机金属盐。As a further improvement of the present invention, the filler is an inorganic filler and/or an organic filler, wherein the inorganic filler is selected from silica, boron nitride, aluminum hydroxide, boehmite, talc, clay, mica, kaolin , Barium sulfate, calcium carbonate, magnesium hydroxide and zinc borate or one or more mixtures, the organic filler is any one selected from polytetrafluoroethylene powder, polyphenylene sulfide or polyethersulfone powder Or a mixture of at least two; the accelerator is imidazole and/or an organometallic salt.
相应地，本发明还提供一种半固化片，在采用如上所述的高频树脂组合物中加入溶剂溶解制成胶液，将增强材料浸渍在所述胶液中，将浸渍后的所述增强材料加热干燥后，即可得到所述半固化片。Correspondingly, the present invention also provides a prepreg, in which a solvent is added to the high-frequency resin composition as described above to dissolve to make a glue solution, a reinforcement material is immersed in the glue solution, and the reinforced material after the immersion After heating and drying, the prepreg can be obtained.
相应地，本发明还提供一种层压板，在至少一张如上所述的半固化片的双面覆上离型膜，热压成形，即可得到所述层压板。Correspondingly, the present invention also provides a laminate, which is coated with a release film on both sides of at least one prepreg as described above, and hot-pressed to obtain the laminate.
相应地，本发明还提供一种层间绝缘膜，在采用如上所述的高频树脂组合物中加入溶剂溶解制成胶液，在载体膜上涂覆所述胶液，将涂覆胶液的载体膜加热干燥后，即可得到所述层间绝缘膜。Correspondingly, the present invention also provides an interlayer insulating film. A solvent is added to the high-frequency resin composition as described above to dissolve to make a glue solution, the glue solution is coated on the carrier film, and the glue solution is applied After heating and drying the carrier film, the interlayer insulating film can be obtained.
由于上述技术方案运用，本发明与现有技术相比具有下列优点：Due to the application of the above technical solutions, the present invention has the following advantages compared with the prior art:
(1)本发明选用了POSS改性聚芳醚酮预聚物，POSS具有空心结构，因此POSS的引入在一定程度上代表着空气的引入，能够起到降低材料介电性能的作用，POSS具有较大的自由体积，因此POSS的引入也会相应地降低复合材料的堆砌密度，增加复合材料的自由体积，从而也会降低材料的介电常数；POSS在固化物中以纳米尺寸存在，则其会与聚合物材料发生相互作用。当POSS以低于临界尺寸的纳米形式存在于复合材料中时会在与基体聚合物相结合处产生强烈的自极化诱导效应，使得复合材料的电子云径向局域化，当复合材料处于外界电场条件下时，由于POSS纳米粒子的存在会束缚复合材料电子云的极化，从而大幅度降低复合材料的极化率，即表现为复合材料的介电常数大幅度的降低；(1) In the present invention, POSS modified polyaryl ether ketone prepolymer is selected. POSS has a hollow structure, so the introduction of POSS represents the introduction of air to a certain extent, which can play a role in reducing the dielectric properties of the material. POSS has Larger free volume, so the introduction of POSS will correspondingly reduce the packing density of the composite material and increase the free volume of the composite material, which will also reduce the dielectric constant of the material; POSS exists in the nanometer size in the cured material, then its Will interact with polymer materials. When POSS is present in the composite material in the form of nanometers below the critical size, it will produce a strong self-polarization-induced effect at the junction with the matrix polymer, making the electron cloud of the composite material radially localized, when the composite material is in Under the condition of an external electric field, the presence of POSS nanoparticles will constrain the polarization of the composite electron cloud, thereby greatly reducing the polarization rate of the composite material, that is, the dielectric constant of the composite material is greatly reduced;
(2)POSS改性聚芳醚酮预聚物能均匀地分散在复合材料中，表现出良好的相容性，解决热塑性材料较难溶解的问题；(2) The POSS modified polyaryl ether ketone prepolymer can be evenly dispersed in the composite material, showing good compatibility and solving the problem of the thermoplastic material being difficult to dissolve;
(3)POSS改性聚芳醚酮预聚物中含有聚芳醚酮结构，使其分子链刚性较大，所以其制品尺寸稳定性好，热膨胀系数小；(3) POSS modified polyaryletherketone prepolymer contains polyaryletherketone structure, which makes its molecular chain rigid, so its products have good dimensional stability and small thermal expansion coefficient;
(4)聚芳醚酮结构具有较强的自熄性，大大降低阻燃剂的用量以及阻燃剂对介电性能、耐湿热等负面影响；(4) The structure of polyaryl ether ketone has strong self-extinguishing, greatly reducing the amount of flame retardant and the negative impact of flame retardant on dielectric properties, humidity and heat resistance;
(5)采用本发明的树脂组合物制备的印刷电路层压板，不仅解决了带有聚四氟乙烯因树脂本身的缺陷所带来的粘结性差、力学性能差等问题，而且具有优异的铜箔剥离强度和高玻璃化转变温度，同时具有高频率条件下的介电常数和低介质损耗保持稳定，更能满足高频高速及高密度互连的要求。(5) The printed circuit laminate prepared by using the resin composition of the present invention not only solves the problems of poor adhesion and poor mechanical properties caused by defects in the resin with polytetrafluoroethylene, but also has excellent copper Foil peel strength and high glass transition temperature, while having high-frequency dielectric constant and low dielectric loss to maintain stability, can better meet the requirements of high-frequency high-speed and high-density interconnection.
具体实施方式detailed description
以下将结合具体实施方式对本发明进行详细描述。但这些实施方式并不限制本发明，本领域的普通技术人员根据这些实施方式所做出的结构、方法、或功能上的变换均包含在本发明的保护范围内。本领域的普通技术人员根据这些实施方式所做的反应条件、反应物或原料用量上的变换均包含在本发明的保护范围内。The present invention will be described in detail below in conjunction with specific embodiments. However, these embodiments do not limit the present invention, and structural, method, or functional changes made by those of ordinary skill in the art according to these embodiments are included in the protection scope of the present invention. Variations in reaction conditions, amounts of reactants or raw materials made by those of ordinary skill in the art according to these embodiments are all included in the protection scope of the present invention.
在本发明一具体实施方式中，一种高频树脂预聚物，具体为POSS改性聚芳醚酮预聚物，其至少由笼型倍半硅氧烷和聚芳醚酮聚合物预聚而成，POSS改性聚芳醚酮预聚物的数均分子量为500-20000。优选地，POSS改性聚芳醚酮预聚物的数均分子量为800-5000。In a specific embodiment of the present invention, a high-frequency resin prepolymer, specifically a POSS modified polyaryletherketone prepolymer, which is prepolymerized by at least a cage silsesquioxane and a polyaryletherketone polymer As a result, the number average molecular weight of POSS modified polyaryletherketone prepolymer is 500-20000. Preferably, the POSS modified polyaryl ether ketone prepolymer has a number average molecular weight of 800-5000.
进一步地，笼型倍半硅氧烷和聚芳醚酮聚合物的质量比例为100:100-5000，优选地，笼型倍半硅氧烷和聚芳醚酮聚合物的质量比例为100:300-1000。Further, the mass ratio of cage silsesquioxane to polyaryl ether ketone polymer is 100:100-5000, preferably, the mass ratio of cage silsesquioxane to polyaryl ether ketone polymer is 100: 300-1000.
进一步地，笼型倍半硅氧烷的结构中带有氨基、酯基、环氧基、羟基、羧基、羰基、自由基的一种或几种，本发明优选带有氨基、环氧基。Furthermore, the cage silsesquioxane has one or more of amino group, ester group, epoxy group, hydroxyl group, carboxyl group, carbonyl group and free radical in the structure. In the present invention, it preferably has amino group and epoxy group.
进一步地，聚芳醚酮聚合物的结构中带有氨基、酯基、环氧基、羟基、羧基、苯羧基、自由基的一种或几种，本发明优选带有羧基、苯羧基。Further, the structure of the polyaryl ether ketone polymer has one or more of amino group, ester group, epoxy group, hydroxyl group, carboxyl group, benzene carboxyl group and free radical, and the present invention preferably has carboxyl group and benzene carboxyl group.
本发明还提供一种高频树脂组合物，以固体重量计，包括：The invention also provides a high-frequency resin composition, based on the weight of solids, including:
上述高频树脂预聚物，即POSS改性聚芳醚酮预聚物：10-80份；The above high-frequency resin prepolymer, namely POSS modified polyaryl ether ketone prepolymer: 10-80 parts;
环氧树脂：10-60份；Epoxy resin: 10-60 parts;
阻燃剂：5-40份；Flame retardant: 5-40 parts;
促进剂：0.001-2份；Accelerator: 0.001-2 copies;
填料：0-70份。Filler: 0-70 parts.
进一步地，环氧树脂选自双酚A环氧树脂、双酚F环氧树脂、含磷环氧树脂、含溴环氧树脂、邻甲酚醛环氧树脂、双酚A酚醛环氧树脂、苯酚酚醛环氧树脂、三官能酚型环氧树脂、四苯基乙烷环氧树脂、联苯型环氧树脂、萘环型环氧树脂、双环戊二烯型环氧树脂、芳烷基线型酚醛环氧树脂、缩水甘油胺型环氧树脂、缩水甘油酯型环氧树脂中的一种或几种的混合。优选为无卤环氧树脂，更优选为双酚A环氧树脂、双酚F环氧树脂、含磷环氧树脂、 联苯型环氧树脂、萘环型环氧树脂、双环戊二烯型环氧树脂。Further, the epoxy resin is selected from bisphenol A epoxy resin, bisphenol F epoxy resin, phosphorus-containing epoxy resin, bromine-containing epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, phenol Phenolic epoxy resin, trifunctional phenol epoxy resin, tetraphenylethane epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, dicyclopentadiene epoxy resin, aralkyl novolac One or a mixture of epoxy resin, glycidylamine epoxy resin, and glycidyl ester epoxy resin. It is preferably halogen-free epoxy resin, more preferably bisphenol A epoxy resin, bisphenol F epoxy resin, phosphorus-containing epoxy resin, biphenyl type epoxy resin, naphthalene ring type epoxy resin, dicyclopentadiene type Epoxy resin.
进一步地，阻燃剂选自含磷阻燃剂和含溴阻燃剂中的一种或几种的混合，其中，含磷阻燃剂选自含磷环氧树脂、含磷酚醛树脂、磷腈化合物、磷酸酯化合物、含磷氰酸酯、含磷双马来酰亚胺中的一种或几种的混合；含溴阻燃剂选自三溴苯基马来酰亚胺、四溴双酚A烯丙基醚、十溴二苯乙烷、溴化聚苯乙烯、溴化聚碳酸酯、四溴双酚A、溴化环氧树脂中的一种或几种的混合，本发明中阻燃剂优选含磷阻燃剂。Further, the flame retardant is selected from a mixture of one or more of phosphorus-containing flame retardants and bromine-containing flame retardants, wherein the phosphorus-containing flame retardants are selected from phosphorus-containing epoxy resins, phosphorus-containing phenolic resins, phosphorus Nitrile compounds, phosphate compounds, phosphorus-containing cyanate esters, phosphorus-containing bismaleimide one or a mixture of several; bromine-containing flame retardant selected from tribromophenyl maleimide, tetrabromo One or more of bisphenol A allyl ether, decabromodiphenylethane, brominated polystyrene, brominated polycarbonate, tetrabromobisphenol A, brominated epoxy resin, the invention The medium flame retardant is preferably a phosphorus-containing flame retardant.
进一步地，填料为无机填料和/或有机填料，其中，无机填料选自二氧化硅、氮化硼、氢氧化铝、勃姆石、滑石、粘土、云母、高岭土、硫酸钡、碳酸钙、氢氧化镁和硼酸锌的一种或一种以上的混合物；有机填料为选自聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的任意一种或者至少两种的混合物。更进一步地，填料的粒径中度值为0.3-20μm，更优选为0.5-5μm，位于此粒径段的填料具有良好的分散性与较好的加工性。本发明中，填料优选无机填料，填料在树脂组合物中的含量为5-60份。进一步优选经过表面处理的无机填料，最优选经过表面处理的二氧化硅。对无机填料进行表面处理的表面处理剂选自硅烷偶联剂、有机硅低聚物或钛酸酯偶联剂中的任意一种或至少两种的混合物。Further, the filler is an inorganic filler and/or an organic filler, wherein the inorganic filler is selected from silica, boron nitride, aluminum hydroxide, boehmite, talc, clay, mica, kaolin, barium sulfate, calcium carbonate, hydrogen One or more mixtures of magnesium oxide and zinc borate; the organic filler is any one or a mixture of at least two selected from polytetrafluoroethylene powder, polyphenylene sulfide, or polyethersulfone powder. Furthermore, the median particle size of the filler is 0.3-20 μm, more preferably 0.5-5 μm, and the filler located in this particle size section has good dispersibility and good processability. In the present invention, the filler is preferably an inorganic filler, and the content of the filler in the resin composition is 5-60 parts. The surface-treated inorganic filler is further preferred, and the surface-treated silica is most preferred. The surface treatment agent for surface-treating the inorganic filler is selected from any one or a mixture of at least two of a silane coupling agent, a silicone oligomer, or a titanate coupling agent.
进一步地，促进剂为咪唑、有机金属盐或咪唑和有机金属的混合物。其中，咪唑选自2-甲基咪唑、2-苯基咪唑或2-乙基-4甲基咪唑；有机金属盐选自辛酸锌、辛酸钴、异辛酸锌、辛酸亚锡、二月桂酸二丁基锡、环烷酸锌、环烷酸钴、乙酰丙酮铝、乙酰丙酮钴或乙酰丙酮铜，优选辛酸锌、辛酸钴，促进剂在树脂组合物中的含量为0.01-1份。Further, the accelerator is imidazole, an organic metal salt, or a mixture of imidazole and an organic metal. Wherein, the imidazole is selected from 2-methylimidazole, 2-phenylimidazole or 2-ethyl-4methylimidazole; the organic metal salt is selected from zinc octoate, cobalt octoate, zinc isooctanoate, stannous octoate, dilaurate dilaurate Butyl tin, zinc naphthenate, cobalt naphthenate, aluminum acetylacetonate, cobalt acetylacetonate or copper acetylacetonate, preferably zinc octoate and cobalt octoate, the content of the accelerator in the resin composition is 0.01-1 part.
进一步地，高频树脂组合物中还可以添加增韧剂，增韧剂选自高分子量环氧树脂、酚氧树脂、橡胶、环烯烃聚合物中至少一种，其在树脂组合物中的含量为0.1-10份。Further, a toughener may be added to the high-frequency resin composition, and the toughener is at least one selected from the group consisting of high molecular weight epoxy resin, phenol oxide resin, rubber, and cycloolefin polymer, and its content in the resin composition 0.1-10 servings.
本发明还提供一种采用上述高频树脂组合物制备的半固化片，其制备步骤如下：The invention also provides a prepreg prepared by using the above-mentioned high-frequency resin composition, and the preparation steps are as follows:
将上述高频树脂组合物用溶剂溶解，搅拌均匀，并熟化，制成树脂组合物胶液；Dissolve the above high-frequency resin composition with a solvent, stir evenly, and ripen to make a resin composition glue;
将增强材料浸渍在上述高频树脂组合物胶液中，然后将浸渍后的增强材料在50-170℃环境下烘烤1-10min干燥后即可得本发明中的半固化片。The prepreg in the present invention can be obtained by immersing the reinforcing material in the glue of the above-mentioned high-frequency resin composition, and then baking the immersed reinforcing material in an environment of 50-170°C for 1-10 minutes and drying.
其中，增强材料为天然纤维、有机合成纤维、有机织物或者无机织物，无机织物，特别优选采用玻璃纤维布，玻璃纤维布优选使用开纤布或扁平布。此外，为了改善树脂与玻璃纤维布的界面结合，玻璃纤维布一般都需要进行化学处理，主要方法是偶联剂处理，所用偶联剂如环氧硅烷，氨基硅烷等。Among them, the reinforcing material is natural fiber, organic synthetic fiber, organic fabric or inorganic fabric. Inorganic fabric is particularly preferably glass fiber cloth, and glass fiber cloth is preferably open fiber cloth or flat cloth. In addition, in order to improve the interface between the resin and the glass fiber cloth, the glass fiber cloth generally needs to be chemically treated. The main method is the coupling agent treatment. The coupling agent used is epoxy silane, amino silane, etc.
溶剂选自选自丙酮、丁酮、甲苯、二甲苯、甲基异丁酮、N、N-二甲基甲酰胺、N、N-二甲基乙酰胺、乙二醇甲醚、丙二醇甲醚中的一种或几种的组合。The solvent is selected from acetone, methyl ethyl ketone, toluene, xylene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether One or a combination of several.
本发明还提供一种采用上述半固化片制备的层压板，其制备步骤如下：The invention also provides a laminate prepared by using the prepreg, and the preparation steps are as follows:
在一张上述半固化片的单面或双面覆上金属箔，或者将至少2张上述半固化片叠加后，在其单面或双面覆上金属箔，热压成形，即可得到金属箔层压板。One side or both sides of one prepreg is covered with metal foil, or after stacking at least two of the above prepregs, one side or both sides are covered with metal foil, and hot-pressed to obtain a metal foil laminate.
半固化片的数量可根据需要的层压板的厚度来确定，可用一张或多张。所述金属箔，可 以是铜箔，也可以是铝箔，它们的厚度没有特别限制。The number of prepregs can be determined according to the required thickness of the laminate, and one or more sheets can be used. The metal foil may be copper foil or aluminum foil, and their thickness is not particularly limited.
上述层压板的压制条件为，在5-35kg/cm 2压力和180～210℃温度下压制70-200min。 The pressing conditions of the above-mentioned laminate are: pressing at a pressure of 5-35 kg/cm 2 and a temperature of 180-210° C. for 70-200 min.
本发明还提供一种采用上述半固化片制备的层间绝缘膜，其制备步骤如下：The invention also provides an interlayer insulating film prepared by using the prepreg, and the preparation steps are as follows:
将上述高频树脂组合物加入溶剂溶解制成胶液，在载体膜上涂覆所述胶液，将涂覆胶液的载体膜加热干燥后，即可得到层间绝缘膜。加热干燥条件为在50-170℃下烘烤1-10分钟。溶剂选自丙酮、丁酮、甲苯、甲基异丁酮、N、N-二甲基甲酰胺、N、N-二甲基乙酰胺、乙二醇甲醚、丙二醇甲醚中的一种或几种的混合。The above-mentioned high-frequency resin composition is dissolved in a solvent to make a glue solution, the glue solution is coated on the carrier film, and the carrier film coated with the glue solution is heated and dried to obtain an interlayer insulating film. The heating and drying conditions are baking at 50-170°C for 1-10 minutes. The solvent is selected from one of acetone, methyl ethyl ketone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether or A mix of several.
其中，载体膜为聚乙烯对苯二甲酸酯(PET)膜、离型膜、铜箔、铝箔等，优选为PET膜。为了保护层间绝缘膜，可在其另一面覆盖保护膜，保护膜与载体膜的材质相同。Among them, the carrier film is a polyethylene terephthalate (PET) film, a release film, copper foil, aluminum foil, etc., preferably a PET film. In order to protect the interlayer insulating film, the protective film may be covered on the other side, and the protective film and the carrier film have the same material.
为了更好的阐述本发明，以下提供一些具体实施例，对本发明做进一步描述，以下为高频树脂预聚物、高频树脂组合物、半固化片和层压板制备具体合成例：In order to better illustrate the present invention, the following provides some specific examples to further describe the present invention. The following are specific synthesis examples for the preparation of high-frequency resin prepolymers, high-frequency resin compositions, prepregs and laminates:
下文中无特别说明，“份”代表“重量份”，“％”代表“重量％”There is no special explanation in the following, "parts" stands for "parts by weight", "%" stands for "wt%"
合成例：Synthesis example:
按照如下方法制得：按质量比，笼型倍半硅氧烷：聚芳醚酮聚合物＝100：100-1000，取笼型倍半硅氧烷、聚芳醚酮聚合物于反应瓶中，加热至室温-200℃，并保持搅拌的条件下，反应30-600min得到数均分子量为500-20000均匀透明的POSS改性聚芳醚酮预聚物，反应完成后冷却至室温，经过后处理后，待用；According to the mass ratio, cage silsesquioxane: polyaryl ether ketone polymer = 100: 100-1000, take cage silsesquioxane, polyaryl ether ketone polymer in the reaction bottle , Heated to room temperature -200 ℃, and maintained under stirring, the reaction is 30-600min to obtain a uniform and transparent POSS modified polyaryl ether ketone prepolymer with a number average molecular weight of 500-20000, after the reaction is completed, it is cooled to room temperature. After processing, stand by;
实施例一：Example one:
根据合成例中的方法，在60℃反应120min制得具有氨基的笼型倍半硅氧烷：羧基聚芳醚酮＝10：50的预聚体30g，加入适量N、N-二甲基乙酰胺溶解；待POSS改性聚芳醚酮预聚物完全溶解后，加入30g含磷环氧树脂(XZ92530，陶氏化学)、30g酚醛固化剂(PF-8011，山东圣泉)、10g含磷酚醛(XZ92741，陶氏化学)、0.01g 2-乙基-4甲基咪唑、40g球形二氧化硅、适量的丁酮溶剂，搅拌混合均匀得到60％固体含量的胶液。According to the method in the synthesis example, a cage-type silsesquioxane with an amino group was prepared by reacting at 60°C for 120 min: carboxy polyaryl ether ketone = 10:50 prepolymer 30g, adding an appropriate amount of N, N-dimethyl ethyl Dissolve the amide; after the POSS modified polyaryletherketone prepolymer is completely dissolved, add 30g phosphorus-containing epoxy resin (XZ92530, Dow Chemical), 30g phenolic curing agent (PF-8011, Shandong Shengquan), 10g phosphorus-containing Phenolic (XZ92741, Dow Chemical), 0.01g 2-ethyl-4 methylimidazole, 40g spherical silica, proper amount of methyl ethyl ketone solvent, stir and mix evenly to get 60% solid content glue.
将该胶液浸渍并涂布在E玻纤布(2116，单重为104g/m2)上，并在135℃烘箱中烘5min制得树脂含量50％的半固化片。The glue solution was impregnated and coated on E glass fiber cloth (2116, unit weight 104g/m2), and baked in an oven at 135°C for 5 minutes to prepare a prepreg with a resin content of 50%.
将该制得的树脂含量50％的半固化片，上下各放一张金属铜箔，置于真空热压机中压制得到覆铜板。具体的压合工艺为在1.5Mpa压力，195℃温度下压合2小时。The prepared prepreg with a resin content of 50% is placed with a metal copper foil up and down and placed in a vacuum hot press to obtain a copper clad laminate. The specific pressing process is pressing at 1.5Mpa and 195℃ for 2 hours.
获得的覆铜层压板性能如表1所示。The properties of the obtained copper-clad laminates are shown in Table 1.
实施例二：Example two:
根据合成例中的方法，在60℃反应120min制得具有氨基的笼型倍半硅氧烷：苯羧基聚芳醚酮＝10：80的预聚体30g，加入适量N、N-二甲基乙酰胺溶解；待POSS改性聚芳醚酮预聚物完全溶解后，加入30g含萘环型环氧树脂(NC-7300，日本化药)、25g酚醛固化剂(PF-8011，山东圣泉)、15g含磷酚醛(XZ92741，陶氏化学)、0.01g 2-乙基-4甲基咪唑、40g球形二氧化硅、适量的丁酮溶剂，搅拌混合均匀得到60％固体含量的胶液。According to the method in the synthesis example, a cage silsesquioxane having an amino group was prepared by reacting at 60°C for 120 min: phenylcarboxy polyaryl ether ketone = 10: 80 prepolymer 30g, adding an appropriate amount of N, N-dimethyl Acetamide dissolves; after the POSS modified polyaryletherketone prepolymer is completely dissolved, add 30g naphthalene ring-containing epoxy resin (NC-7300, Nippon Kayaku) and 25g phenolic curing agent (PF-8011, Shandong Shengquan ), 15g phosphorus-containing phenolic aldehyde (XZ92741, Dow Chemical), 0.01g 2-ethyl-4 methylimidazole, 40g spherical silica, appropriate amount of methyl ethyl ketone solvent, stirring and mixing to obtain 60% solids glue.
半固化片、覆铜层压板制备方法同实施例一。The preparation method of the prepreg and the copper-clad laminate are the same as in the first embodiment.
获得的覆铜层压板性能如表1所示。The properties of the obtained copper-clad laminates are shown in Table 1.
实施例三：Example three:
根据合成例中的方法，在60℃反应120min制得具有环氧基的笼型倍半硅氧烷：羧基聚芳醚酮＝10：40的预聚体30g，加入适量N、N-二甲基乙酰胺溶解；待POSS改性聚芳醚酮预聚物完全溶解后，加入30g双环戊二烯型环氧树脂(XD-1000，日本化药)、22g酚醛固化剂(PF-8011，山东圣泉)、18g含磷酚醛(XZ92741，陶氏化学)、0.01g 2-乙基-4甲基咪唑、40g球形二氧化硅、适量的丁酮溶剂，搅拌混合均匀得到60％固体含量的胶液。According to the method in the synthesis example, a cage-type silsesquioxane with an epoxy group was prepared by reacting at 60°C for 120 min: carboxy polyaryl ether ketone = 10: 40 prepolymer 30g, adding appropriate amount of N, N-dimethyl Dissolve the acetamide; after the POSS modified polyaryletherketone prepolymer is completely dissolved, add 30g of dicyclopentadiene epoxy resin (XD-1000, Japanese chemical), 22g of phenolic curing agent (PF-8011, Shandong Holy spring), 18g phosphorus-containing phenolic aldehyde (XZ92741, Dow Chemical), 0.01g 2-ethyl-4 methylimidazole, 40g spherical silica, appropriate amount of methyl ethyl ketone solvent, stirring and mixing to obtain 60% solid content glue liquid.
半固化片、覆铜层压板制备方法同实施例一。The preparation method of the prepreg and the copper-clad laminate are the same as in the first embodiment.
获得的覆铜层压板性能如表1所示。The properties of the obtained copper-clad laminates are shown in Table 1.
对比例一Comparative example one
取加入加入50g含磷环氧树脂(XZ92530，陶氏化学)、40g酚醛固化剂(PF-8011，山东圣泉)、10g含磷酚醛(XZ92741，陶氏化学)、0.05g 2-乙基-4甲基咪唑、40g球形二氧化硅、适量的丁酮溶剂，搅拌混合均匀得到60％固体含量的胶液。Add 50g phosphorus-containing epoxy resin (XZ92530, Dow Chemical), 40g phenolic curing agent (PF-8011, Shandong Shengquan), 10g phosphorus-containing phenolic resin (XZ92741, Dow Chemical), 0.05g 2-ethyl- 4 Methylimidazole, 40g spherical silica, proper amount of methyl ethyl ketone solvent, stir and mix to get 60% solid content glue.
将该胶液浸渍并涂布在E玻纤布(2116，单重为104g/m2)上，并在135℃烘箱中烘5min制得树脂含量50％的半固化片。The glue solution was impregnated and coated on E glass fiber cloth (2116, unit weight 104g/m2), and baked in an oven at 135°C for 5 minutes to prepare a prepreg with a resin content of 50%.
将该制得的树脂含量50％的半固化片，上下各放一张金属铜箔，置于真空热压机中压制得到覆铜板。具体的压合工艺为在1.5Mpa压力，220℃温度下压合2小时。The prepared prepreg with a resin content of 50% is placed with a metal copper foil up and down and placed in a vacuum hot press to obtain a copper clad laminate. The specific pressing process is pressing at 1.5Mpa and 220℃ for 2 hours.
获得的覆铜层压板性能如表1所示。The properties of the obtained copper-clad laminates are shown in Table 1.
对比例二Comparative Example 2
取加入50g双环戊二烯型环氧树脂(XD-1000，日本化药)、25g酚醛固化剂(PF-8011，山东圣泉)、25g含磷酚醛(XZ92741，陶氏化学)、0.02g 2-苯基咪唑、40g球形二氧化硅、适量的丁酮溶剂，搅拌混合均匀得到60％固体含量的胶液。Take 50g dicyclopentadiene type epoxy resin (XD-1000, Japanese chemical), 25g phenolic curing agent (PF-8011, Shandong Shengquan), 25g phosphorus-containing phenolic resin (XZ92741, Dow Chemical), 0.02g -Phenylimidazole, 40g spherical silica, appropriate amount of methyl ethyl ketone solvent, stirred and mixed to obtain a glue solution with a solid content of 60%.
半固化片、覆铜层压板制备方法同对比例一。The preparation methods of prepreg and copper-clad laminate are the same as Comparative Example 1.
获得的覆铜层压板性能如表1。The properties of the copper-clad laminates obtained are shown in Table 1.
表1为采用不同实施例所得的覆铜层压板性能Table 1 is the performance of copper-clad laminates obtained by using different examples
Figure PCTCN2019119487-appb-000001
Figure PCTCN2019119487-appb-000001
Figure PCTCN2019119487-appb-000002
Figure PCTCN2019119487-appb-000002
上表中各性能的测试方法如下：The test methods of each performance in the above table are as follows:
(1)玻璃化转变温度(Tg)：根据差示扫描量热法，按照IPC-TM-650 2.4.25所规定的DSC方法进行测定。(1) Glass transition temperature (Tg): It is measured according to the DSC method specified in IPC-TM-650 2.4.25 according to differential scanning calorimetry.
(2)剥离强度(PS)：按照IPC-TM-650 2.4.8方法中的“热应力后”实验条件，测试金属盖层的剥离强度。(2) Peel strength (PS): Test the peel strength of the metal capping layer in accordance with the "after thermal stress" test conditions in the IPC-TM-650 2.4.8 method.
(3)浸锡耐热性：使用50×50mm的两面带铜样品，浸入288℃的焊锡中，记录样品分层气泡的时间。(3) Heat resistance of immersion tin: use 50×50mm copper samples on both sides, immerse in solder at 288℃, and record the time of delamination bubbles of the sample.
(4)潮湿处理后浸锡耐热性：将25块100×100mm的基材试样在121℃、105Kpa的加压蒸煮处理装置内保持3hr后，浸入288℃的焊锡槽中2min，观察试样是否发生分层鼓泡等现象。(4) Heat resistance of tin immersion after humidity treatment: After holding 25 pieces of 100×100mm substrate samples in a pressure cooker at 121°C and 105Kpa for 3 hours, immerse them in a solder bath at 288°C for 2 minutes, observe and test Whether the phenomenon of stratified bubbling occurs.
(5)热分解温度Td：按照IPC-TM-650 2.4.26方法进行测定。(5) Thermal decomposition temperature Td: measured according to the method of IPC-TM-650 2.4.26.
(6)介电常数：按照IPC-TM-650 2.5.5.9使用平板法，测定1GHz下的介电常数。(6) Dielectric constant: According to IPC-TM-650 2.5.5.9, use the flat plate method to measure the dielectric constant at 1 GHz.
(7)介质损耗角正切：按照IPC-TM-650 2.5.5.9使用平板法，测定1GHz下的介电损耗因子。(7) Dielectric loss tangent: According to IPC-TM-650 2.5.5.9, use the flat plate method to measure the dielectric loss factor at 1 GHz.
(8)落锤冲击韧性(层压板脆性)：使用冲击仪，冲击仪落锤高度45cm，下落重锤重量1kg。韧性好与差的评判：十字架清晰，说明产品的韧性越好，以字符☆表示；十字架模糊，说明产品的韧性差、脆性大，以字符◎表示；十字架清晰程度介于清晰与模糊之间说明产品韧性一般，以字符◇表示。(8) Falling weight impact toughness (brittleness of laminate): Use an impact meter. The drop height of the impact meter is 45cm, and the weight of the falling weight is 1kg. Judgment of good and poor toughness: the cross is clear, indicating the better the toughness of the product, which is indicated by the character ☆; the cross is fuzzy, indicating that the product has poor toughness and brittleness, and is indicated by the character ◎; The toughness of the product is average, indicated by the character ◇.
(9)热分层时间T-300：按照IPC-TM-650 2.4.24方法进行测定。(9) Thermal stratification time T-300: measured according to the method of IPC-TM-650 2.4.24.
(10)耐燃烧性(难燃性)：依据UL94法测定。(10) Combustion resistance (flame retardance): measured according to UL94 method.
(11)溶解性：混制胶液后，静置24小时，观察是否有析出或分层现象，如没有，以字符√表示，若有，以字符×表示。(11) Solubility: After mixing the glue solution, let it stand for 24 hours to observe whether there is precipitation or delamination. If not, it is indicated by the character √, and if so, it is indicated by the character ×.
由上表可以看出，实施例1对比例1相比，玻璃化转变温度、耐湿热性、介电性能及韧性方面均优异，特别是普通固化剂体系下也可以将介电常数可降低至4.0水平；再由实施例2和实施例3与对比例2，本发明制得的层压板的不但耐湿热性较好，还可以获得优异的介电性能、高玻璃化转变温度以及较高的韧性，特别是在介电性能以及耐湿热性方面可靠性非 常优异。It can be seen from the table above that Example 1 and Comparative Example 1 are superior in glass transition temperature, moisture and heat resistance, dielectric properties and toughness, especially the dielectric constant can be reduced to 4.0 level; and then by Example 2 and Example 3 and Comparative Example 2, the laminate made by the present invention not only has better moisture and heat resistance, but also can obtain excellent dielectric properties, high glass transition temperature and higher Toughness, especially in terms of dielectric properties and heat and humidity resistance, is very excellent in reliability.
本发明的树脂组合物具有高的耐湿热性能、高玻璃化转变温度、较低的介电常数和介电损耗正切值，可以满足高频高速及高密度互连等高性能印制线路板的要求。The resin composition of the present invention has high moisture resistance and heat resistance, high glass transition temperature, low dielectric constant and dielectric loss tangent value, and can satisfy high-frequency high-speed and high-density interconnection and other high-performance printed circuit boards. Claim.
应当理解，虽然本说明书按照实施方式加以描述，但并非每个实施方式仅包含一个独立的技术方案，说明书的这种叙述方式仅仅是为清楚起见，本领域技术人员应当将说明书作为一个整体，各实施方式中的技术方案也可以经适当组合，形成本领域技术人员可以理解的其他实施方式。It should be understood that although this specification is described according to embodiments, not every embodiment only contains an independent technical solution. This description of the specification is for clarity only, and those skilled in the art should treat the specification as a whole, each The technical solutions in the embodiments can also be combined appropriately to form other embodiments that can be understood by those skilled in the art.
上文所列出的一系列的详细说明仅仅是针对本发明的可行性实施方式的具体说明，它们并非用以限制本发明的保护范围，凡未脱离本发明技艺精神所作的等效实施方式或变更均应包含在本发明的保护范围之内。The series of detailed descriptions listed above are only specific descriptions of feasible embodiments of the present invention, they are not intended to limit the scope of protection of the present invention, and equivalent embodiments or technical equivalents made without departing from the technical spirit of the present invention Changes should be included in the protection scope of the present invention.

Claims (10)

  1. 一种高频树脂预聚物，其特征在于，所述高频树脂预聚物至少由笼型倍半硅氧烷和聚芳醚酮聚合物预聚而成，所述笼型倍半硅氧烷和聚芳醚酮聚合物的质量比例为100:100-5000。A high-frequency resin prepolymer, characterized in that the high-frequency resin prepolymer is at least pre-polymerized by cage-type silsesquioxane and polyaryletherketone polymer, and the cage-type silsesquioxane The mass ratio of alkane and polyaryletherketone polymer is 100:100-5000.
  2. 根据权利要求1所述的高频树脂预聚物，其特征在于，所述笼型倍半硅氧烷的结构中带有氨基、酯基、环氧基、羟基、羧基、羰基、自由基的一种或几种。The high-frequency resin prepolymer according to claim 1, wherein the structure of the cage silsesquioxane has an amino group, an ester group, an epoxy group, a hydroxyl group, a carboxyl group, a carbonyl group, and a radical One or more.
  3. 根据权利要求1所述的高频树脂预聚物，其特征在于，所述聚芳醚酮聚合物的结构中带有氨基、酯基、环氧基、羟基、羧基、苯羧基、自由基的一种或几种。The high-frequency resin prepolymer according to claim 1, wherein the structure of the polyaryl ether ketone polymer has amino groups, ester groups, epoxy groups, hydroxyl groups, carboxyl groups, benzene carboxyl groups, and free radicals. One or more.
  4. 根据权利要求1所述的高频树脂预聚物，其特征在于，所述笼型倍半硅氧烷和聚芳醚酮聚合物的质量比例为100:300-1000。The high-frequency resin prepolymer according to claim 1, wherein the mass ratio of the cage silsesquioxane to the polyaryletherketone polymer is 100:300-1000.
  5. 一种高频树脂组合物，其特征在于，以固体重量计，包括：A high-frequency resin composition, characterized by solid weight, including:
    权利要求1所述的高频树脂预聚物：10-80份；The high-frequency resin prepolymer of claim 1: 10-80 parts;
    环氧树脂：10-60份；Epoxy resin: 10-60 parts;
    阻燃剂：5-40份；Flame retardant: 5-40 parts;
    促进剂：0.001-2份；Accelerator: 0.001-2 copies;
    填料：0-70份。Filler: 0-70 parts.
  6. 根据权利要求5所述的高频树脂组合物，其特征在于，所述环氧树脂选自双酚A环氧树脂、双酚F环氧树脂、含磷环氧树脂、含溴环氧树脂、邻甲酚醛环氧树脂、双酚A酚醛环氧树脂、苯酚酚醛环氧树脂、三官能酚型环氧树脂、四苯基乙烷环氧树脂、联苯型环氧树脂、萘环型环氧树脂、双环戊二烯型环氧树脂、芳烷基线型酚醛环氧树脂、缩水甘油胺型环氧树脂、缩水甘油酯型环氧树脂中的一种或几种的混合；所述阻燃剂选自含磷阻燃剂和含溴阻燃剂中的一种或几种的混合。The high-frequency resin composition according to claim 5, wherein the epoxy resin is selected from bisphenol A epoxy resin, bisphenol F epoxy resin, phosphorus-containing epoxy resin, bromine-containing epoxy resin, O-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, trifunctional phenol epoxy resin, tetraphenylethane epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin One or a mixture of resin, dicyclopentadiene epoxy resin, aralkyl novolac epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin; the flame retardant One or more types selected from phosphorus-containing flame retardants and bromine-containing flame retardants.
  7. 根据权利要求5所述的高频树脂组合物，其特征在于，所述填料为无机填料和/或有机填料，其中，所述无机填料选自二氧化硅、氮化硼、氢氧化铝、勃姆石、滑石、粘土、云母、高岭土、硫酸钡、碳酸钙、氢氧化镁和硼酸锌的一种或一种以上的混合物，所述有机填料为选自聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的任意一种或者至少两种的混合物；所述促进剂为咪唑和/或有机金属盐。The high-frequency resin composition according to claim 5, wherein the filler is an inorganic filler and/or an organic filler, wherein the inorganic filler is selected from silica, boron nitride, aluminum hydroxide, boron One or more mixtures of mica, talc, clay, mica, kaolin, barium sulfate, calcium carbonate, magnesium hydroxide and zinc borate, the organic filler is selected from polytetrafluoroethylene powder, polyphenylene sulfide Or any one of polyethersulfone powder or a mixture of at least two; the accelerator is imidazole and/or an organometallic salt.
  8. 一种半固化片，其特征在于，在采用如上权利要求5所述的高频树脂组合物中加入溶剂溶解制成胶液，将增强材料浸渍在所述胶液中，将浸渍后的所述增强材料加热干燥后，即可得到所述半固化片。A prepreg, characterized in that a solvent is added to the high-frequency resin composition according to claim 5 to dissolve to make a glue solution, a reinforcement material is immersed in the glue solution, and the reinforced material after the impregnation After heating and drying, the prepreg can be obtained.
  9. 一种层压板，其特征在于，在至少一张权利要求8所述的半固化片的单面或双面覆上金属箔，热压成形，即可得到所述层压板。A laminate, characterized in that at least one prepreg according to claim 8 is coated with metal foil on one or both sides, and then hot-pressed to obtain the laminate.
  10. 一种层间绝缘膜，其特征在于，在采用如上权利要求5所述的高频树脂组合物中加 入溶剂溶解制成胶液，在载体膜上涂覆所述胶液，将涂覆胶液的载体膜加热干燥后，即可得到所述层间绝缘膜。An interlayer insulating film, characterized in that a solvent is added to the high-frequency resin composition according to claim 5 to dissolve to make a glue, the glue is coated on the carrier film, and the glue is applied After heating and drying the carrier film, the interlayer insulating film can be obtained.
PCT/CN2019/119487 2019-01-08 2019-11-19 High-frequency resin prepolymer, and high-frequency resin composition, prepreg, laminated board, and interlayer insulating film prepared by using same WO2020143336A1 (en)

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