CN109735086B - High-frequency resin prepolymer and high-frequency resin composition, prepreg, laminated board and interlayer insulating film prepared from high-frequency resin prepolymer - Google Patents
High-frequency resin prepolymer and high-frequency resin composition, prepreg, laminated board and interlayer insulating film prepared from high-frequency resin prepolymer Download PDFInfo
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- 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
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- 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
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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
- 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
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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
- 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
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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
- 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
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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
- 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
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- 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
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- 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
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- 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
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Abstract
The invention discloses a high-frequency resin prepolymer, which is prepared by pre-polymerizing at least cage-type silsesquioxane and polyaryletherketone polymer, wherein the mass ratio of the cage-type silsesquioxane to the polyaryletherketone polymer is 100: 100-5000. Compared with the prior art, the POSS modified polyaryletherketone prepolymer prepared by the invention can reduce the dielectric constant of the material, and the resin composition and the laminated board prepared by using the prepolymer have excellent copper foil peeling strength and high glass transition temperature, and simultaneously keep the dielectric constant and low dielectric loss stable under the high-frequency condition, and can better meet the requirements of high frequency, high speed and high density interconnection.
Description
Technical Field
The invention relates to the technical field of electronic materials, in particular to a high-frequency resin prepolymer, and a high-frequency resin composition, a prepreg, a laminated board and an interlayer insulating film prepared from the high-frequency resin prepolymer.
Background
With the development of communication and electronic products towards high frequency and high speed, users have higher and higher performance requirements on the products, high frequency and high performance substrate materials have become important leading-edge technologies for the development of printed board industry, and more enterprises are added to the development of new copper-clad plate new materials. The traditional resin substrate material is replaced by a high-frequency, high-speed and high-reliability substrate material, and the market demand is increasing. The performance of high-frequency microwave circuit boards directly determines the high frequency, high speed, high reliability, and the like of high-end electronic information technology.
Currently, as a main resin in a high-frequency resin composition used for a high-frequency high-speed substrate, there are polyphenylene ether, polytetrafluoroethylene resin, and acid anhydride-based cured epoxy resin compositions. However, the material inevitably contains a large amount of hydrophilic groups after the epoxy resin is cured, thereby causing a large water absorption of the material. It is known that resin matrix absorbs moisture in a damp and hot environment, and the plasticizing and swelling action of the absorbed moisture on the matrix and microcracks caused by internal stress generated by mismatch of damp and hot expansion coefficients of resin and glass fiber cloth cause the properties of the substrate material to be rapidly reduced, such as thermal expansion coefficient, heat resistance, interlayer adhesion, dielectric constant, dielectric loss tangent value and the like, namely, the change of each property in two states of drying and moisture absorption is different. Therefore, the moist heat resistance of the cured resin is an important factor in determining the overall properties of the material.
Therefore, it is obvious that the development of a high-frequency resin composition having high moisture and heat resistance, high glass transition temperature, high toughness, low dielectric constant and low dielectric loss tangent to meet the requirements of high-performance printed wiring boards such as high-frequency, high-speed and high-density interconnection has positive practical significance.
Disclosure of Invention
An object of the present invention is to provide a high frequency resin prepolymer that solves the above technical problems, and a high frequency resin composition, a prepreg, a laminate, and an interlayer insulating film prepared using the same.
The high-frequency resin prepolymer is prepared by pre-polymerizing at least cage-type silsesquioxane and polyaryletherketone polymer, wherein the mass ratio of the cage-type silsesquioxane to the polyaryletherketone polymer is 100: 100-5000.
As a further improvement of the invention, the structure of the cage-type silsesquioxane contains one or more of amino, ester, epoxy, hydroxyl, carboxyl, carbonyl and free radical.
As a further improvement of the invention, the polyaryletherketone polymer has a structure with one or more of amino, ester, epoxy, hydroxyl, carboxyl, benzene carboxyl and free radical.
As a further improvement of the invention, the mass ratio of the cage-type silsesquioxane to the polyaryletherketone polymer is 100: 300-1000.
Accordingly, the present invention also provides a high frequency resin composition comprising, by solid weight:
the high-frequency resin prepolymer as described in any one of the above: 10-80 parts;
epoxy resin: 10-60 parts;
flame retardant: 5-40 parts;
accelerator (b): 0.001-2 parts;
filling: 0-70 parts.
As a further improvement of the present invention, the epoxy resin is selected from one or a mixture of several of 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, dicyclopentadiene epoxy resin, aralkyl novolac epoxy resin, glycidylamine epoxy resin, and glycidylester epoxy resin; the flame retardant is selected from one or a mixture of several of phosphorus-containing flame retardants and bromine-containing flame retardants.
As a further improvement of the invention, the filler is an inorganic filler and/or an organic filler, wherein the inorganic filler is one or a mixture of more than one of silica, boron nitride, aluminum hydroxide, boehmite, talc, clay, mica, kaolin, barium sulfate, calcium carbonate, magnesium hydroxide and zinc borate, and the organic filler is any one or a mixture of at least two of polytetrafluoroethylene powder, polyphenylene sulfide or polyether sulfone powder; the accelerator is imidazole and/or an organic metal salt.
Correspondingly, the invention also provides a prepreg, which is prepared by adding the solvent into the high-frequency resin composition to dissolve the high-frequency resin composition to prepare a glue solution, dipping the reinforcing material into the glue solution, and heating and drying the dipped reinforcing material.
Correspondingly, the invention also provides a laminated board, wherein the double surfaces of at least one prepreg are covered with release films, and the laminated board can be obtained by hot press forming.
Correspondingly, the invention also provides an interlayer insulating film, which is prepared by adding a solvent into the high-frequency resin composition to dissolve the high-frequency resin composition to prepare a glue solution, coating the glue solution on a carrier film, and heating and drying the carrier film coated with the glue solution.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
(1) according to the invention, the POSS modified polyaryletherketone prepolymer is selected, and the POSS has a hollow structure, so that the introduction of the POSS represents the introduction of air to a certain extent, the effect of reducing the dielectric property of the material can be achieved, and the POSS has larger free volume, so that the introduction of the POSS can correspondingly reduce the stacking density of the composite material, increase the free volume of the composite material and further reduce the dielectric constant of the material; POSS exists in the cured material in nano-dimensions, and it interacts with the polymeric material. When POSS exists in the composite material in a nano form below a critical dimension, a strong self-polarization induction effect is generated at the position of the POSS and a matrix polymer, so that the electron cloud of the composite material is radially localized, and when the composite material is under the condition of an external electric field, the polarization of the electron cloud of the composite material is restrained due to the POSS nano particles, so that the polarizability of the composite material is greatly reduced, namely the dielectric constant of the composite material is greatly reduced;
(2) the POSS modified polyaryletherketone prepolymer can be uniformly dispersed in the composite material, shows good compatibility and solves the problem that the thermoplastic material is difficult to dissolve;
(3) the POSS modified polyaryletherketone prepolymer contains a polyaryletherketone structure, so that the molecular chain rigidity is higher, and the product has good dimensional stability and small thermal expansion coefficient;
(4) the polyaryletherketone structure has strong self-extinguishing property, so that the dosage of the flame retardant is greatly reduced, and the negative effects of the flame retardant on dielectric property, humidity and heat resistance and the like are greatly reduced;
(5) the printed circuit laminated board prepared by the resin composition not only solves the problems of poor cohesiveness, poor mechanical property and the like caused by the defects of the resin, but also has excellent copper foil peeling strength and high glass transition temperature, and simultaneously has the advantages of stable dielectric constant and low dielectric loss under the condition of high frequency, and can meet the requirements of high frequency, high speed and high density interconnection.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments. These embodiments are not intended to limit the present invention, and structural, methodological, or functional changes made by those skilled in the art according to these embodiments are included in the scope of the present invention. Variations in reaction conditions, amounts of reactants or starting materials, which may be made by one of ordinary skill in the art in light of these examples, are within the scope of the invention.
In a specific embodiment of the present invention, a high-frequency resin prepolymer, specifically a POSS modified polyaryletherketone prepolymer, is prepared by at least pre-polymerizing polyhedral oligomeric silsesquioxane (polyhedral oligomeric silsesquioxane) and polyaryletherketone polymer, wherein the number average molecular weight of the POSS modified polyaryletherketone prepolymer is 500-20000. Preferably, the POSS modified polyaryletherketone prepolymer has a number average molecular weight of 800-.
Further, the mass ratio of the cage-type silsesquioxane to the polyaryletherketone polymer is 100: 100-.
Furthermore, the cage-type silsesquioxane has one or more of amino, ester, epoxy, hydroxyl, carboxyl, carbonyl and free radical in the structure, and the cage-type silsesquioxane preferably has amino and epoxy.
Furthermore, the polyaryletherketone polymer has one or more of amino, ester, epoxy, hydroxyl, carboxyl, benzene carboxyl and free radical in the structure, and the invention preferably has carboxyl and benzene carboxyl.
The present invention also provides a high-frequency resin composition comprising, based on solid weight:
the high-frequency resin prepolymer, namely the POSS modified polyaryletherketone prepolymer: 10-80 parts;
epoxy resin: 10-60 parts;
flame retardant: 5-40 parts;
accelerator (b): 0.001-2 parts;
filling: 0-70 parts.
Further, the epoxy resin is selected from one or a mixture of several of bisphenol A epoxy resin, bisphenol F epoxy resin, phosphorus-containing epoxy resin, bromine-containing epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol A phenol formaldehyde epoxy resin, phenol formaldehyde epoxy resin, trifunctional phenol type epoxy resin, tetraphenylethane epoxy resin, biphenyl type epoxy resin, naphthalene ring type epoxy resin, dicyclopentadiene type epoxy resin, aralkyl novolac epoxy resin, glycidylamine type epoxy resin and glycidylester type epoxy resin. The epoxy resin is preferably a halogen-free epoxy resin, and more preferably a bisphenol a epoxy resin, a bisphenol F epoxy resin, a phosphorus-containing epoxy resin, a biphenyl type epoxy resin, a naphthalene ring type epoxy resin, or a dicyclopentadiene type epoxy resin.
Further, the flame retardant is selected from one or a mixture of several of phosphorus-containing flame retardants and bromine-containing flame retardants, wherein the phosphorus-containing flame retardants are selected from one or a mixture of several of phosphorus-containing epoxy resins, phosphorus-containing phenolic resins, phosphazene compounds, phosphate ester compounds, phosphorus-containing cyanate esters and phosphorus-containing bismaleimides; the bromine-containing flame retardant is selected from one or a mixture of more of tribromophenyl maleimide, tetrabromobisphenol A allyl ether, decabromodiphenylethane, brominated polystyrene, brominated polycarbonate, tetrabromobisphenol A and brominated epoxy resin, and the flame retardant is preferably a phosphorus-containing flame retardant in the invention.
Further, the filler is an inorganic filler and/or an organic filler, wherein the inorganic filler is selected from one or a mixture of more than one of silica, boron nitride, aluminum hydroxide, boehmite, talc, clay, mica, kaolin, barium sulfate, calcium carbonate, magnesium hydroxide and zinc borate; the organic filler is any one or a mixture of at least two of polytetrafluoroethylene powder, polyphenylene sulfide powder or polyether sulfone powder. Furthermore, the filler has a median particle size of 0.3-20 μm, more preferably 0.5-5 μm, and the filler in this size range 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 to 60 parts. Further preferred are surface-treated inorganic fillers, most preferred is surface-treated silica. The surface treatment agent for performing surface treatment on the inorganic filler is any one or a mixture of at least two of a silane coupling agent, an organic silicon oligomer or a titanate coupling agent.
Further, the accelerator is an imidazole, an organometallic salt or a mixture of imidazole and organometallic. Wherein imidazole is selected from 2-methylimidazole, 2-phenylimidazole or 2-ethyl-4-methylimidazole; the organic metal salt is selected from zinc octoate, cobalt octoate, zinc isooctanoate, stannous octoate, dibutyltin dilaurate, zinc naphthenate, cobalt naphthenate, aluminum acetylacetonate, cobalt acetylacetonate or copper acetylacetonate, preferably zinc octoate and cobalt octoate, and the content of the accelerator in the resin composition is 0.01-1 part.
Furthermore, toughening agent can be added into the high-frequency resin composition, wherein the toughening agent is selected from at least one of high molecular weight epoxy resin, phenoxy resin, rubber and cyclic olefin polymer, and the content of the toughening agent in the resin composition is 0.1-10 parts.
The invention also provides a prepreg prepared by adopting the high-frequency resin composition, which comprises the following preparation steps:
dissolving the high-frequency resin composition by using a solvent, uniformly stirring, and curing to prepare a resin composition glue solution;
and (3) soaking the reinforcing material in the high-frequency resin composition glue solution, and then baking the soaked reinforcing material at the temperature of 50-170 ℃ for 1-10min to dry to obtain the prepreg.
Among them, the reinforcing material is natural fiber, organic synthetic fiber, organic fabric or inorganic fabric, and the inorganic fabric is particularly preferably glass fiber cloth, and the glass fiber cloth is preferably open fiber cloth or flat cloth. In addition, in order to improve the interfacial bonding between the resin and the glass cloth, the glass cloth generally needs to be chemically treated, mainly by a coupling agent such as epoxy silane, amino silane, etc.
The solvent is selected from one or more of acetone, butanone, toluene, xylene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether and propylene glycol methyl ether.
The invention also provides a laminated board prepared by adopting the prepreg, which comprises the following preparation steps:
and covering a metal foil on one or two sides of one prepreg, or covering a metal foil on one or two sides of at least 2 prepregs after laminating, and performing hot press forming to obtain the metal foil laminated board.
The number of prepregs may be determined according to the thickness of the laminate desired, and one or more prepregs may be used. The metal foil may be a copper foil or an aluminum foil, and the thickness thereof is not particularly limited.
The above laminate is pressed under a pressure of 5-35kg/cm2Pressing for 70-200min under the pressure and the temperature of 180-210 ℃.
The invention also provides an interlayer insulating film prepared by adopting the prepreg, which comprises the following preparation steps:
adding a solvent into the high-frequency resin composition to dissolve the high-frequency resin composition to prepare a glue solution, coating the glue solution on a carrier film, and heating and drying the carrier film coated with the glue solution to obtain the interlayer insulating film. The heating and drying condition is baking at 50-170 deg.C for 1-10 min. The solvent is selected from one or more of acetone, butanone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether and propylene glycol methyl ether.
The carrier film is a polyethylene terephthalate (PET) film, a release film, a copper foil, an aluminum foil, or the like, and is preferably a PET film. In order to protect the interlayer insulating film, the other surface thereof may be covered with a protective film made of the same material as the carrier film.
In order to better illustrate the present invention, the following specific examples are provided and further description of the present invention is made, and specific synthetic examples are prepared for high frequency resin prepolymer, high frequency resin composition, prepreg and laminate:
hereinafter, unless otherwise specified, "part" means "part by weight" and "%" means "% by weight"
Synthesis example:
the preparation method comprises the following steps: according to the mass ratio, the cage type silsesquioxane: polyaryletherketone polymer 100: 100-1000, putting the polyhedral oligomeric silsesquioxane and the polyaryletherketone polymer into a reaction bottle, heating to room temperature to 200 ℃, reacting for 30-600min under the condition of keeping stirring to obtain a POSS modified polyaryletherketone prepolymer with the number average molecular weight of 500-20000, cooling to room temperature after the reaction is finished, and performing post-treatment for later use;
the first embodiment is as follows:
according to the method in the synthesis example, cage type silsesquioxane with amino is prepared by reacting at 60 ℃ for 120 min: carboxy polyaryletherketone ═ 10: 30g of 50 prepolymer is dissolved by adding a proper amount of N, N-dimethylacetamide; after the POSS modified polyaryletherketone prepolymer is completely dissolved, 30g of phosphorus-containing epoxy resin (XZ92530, Dow chemical), 30g of phenolic curing agent (PF-8011, Shandong Shengquan), 10g of phosphorus-containing phenolic aldehyde (XZ92741, Dow chemical), 0.01g of 2-ethyl-4 methylimidazole, 40g of spherical silica and a proper amount of butanone solvent are added, and the mixture is stirred and mixed uniformly to obtain a glue solution with the solid content of 60%.
The glue solution is soaked and coated on E glass fiber cloth (2116, the single weight is 104g/m2), and the semi-solidified sheet with 50 percent of resin content is prepared by drying in an oven at 135 ℃ for 5 min.
And placing a metal copper foil on each of the prepregs with the resin content of 50% and placing the prepregs in a vacuum hot press for pressing to obtain the copper-clad plate. The specific pressing process is pressing for 2 hours under the pressure of 1.5Mpa and the temperature of 195 ℃.
The properties of the copper-clad laminate obtained are shown in Table 1.
Example two:
according to the method in the synthesis example, cage type silsesquioxane with amino is prepared by reacting at 60 ℃ for 120 min: 10, benzene carboxyl polyaryletherketone: 30g of 80 prepolymer is dissolved by adding a proper amount of N, N-dimethylacetamide; after the POSS modified polyaryletherketone prepolymer is completely dissolved, 30g of naphthalene ring-containing epoxy resin (NC-7300, Japan chemical), 25g of phenolic curing agent (PF-8011, Shandong Shengquan), 15g of phosphorus-containing phenolic aldehyde (XZ92741, Dow chemical), 0.01g of 2-ethyl-4 methylimidazole, 40g of spherical silica and a proper amount of butanone solvent are added, and the mixture is stirred and mixed uniformly to obtain a glue solution with the solid content of 60%.
The preparation methods of the prepreg and the copper-clad laminate are the same as those of the first embodiment.
The properties of the copper-clad laminate obtained are shown in Table 1.
Example three:
according to the method in the synthesis example, cage type silsesquioxane with epoxy group is prepared by reacting at 60 ℃ for 120 min: carboxy polyaryletherketone ═ 10: 30g of prepolymer of 40, adding a proper amount of N, N-dimethylacetamide and dissolving; after the POSS modified polyaryletherketone prepolymer is completely dissolved, 30g of dicyclopentadiene type epoxy resin (XD-1000, Japan chemical), 22g of phenolic curing agent (PF-8011, Shandong Shengquan), 18g of phosphorus-containing phenolic (XZ92741, Dow chemical), 0.01g of 2-ethyl-4 methylimidazole, 40g of spherical silica and a proper amount of butanone solvent are added, and the mixture is stirred and mixed uniformly to obtain a glue solution with the solid content of 60%.
The preparation methods of the prepreg and the copper-clad laminate are the same as those of the first embodiment.
The properties of the copper-clad laminate obtained are shown in Table 1.
Comparative example 1
50g of phosphorus-containing epoxy resin (XZ92530, Dow chemical), 40g of phenolic curing agent (PF-8011, Shandong Shengquan), 10g of phosphorus-containing phenolic (XZ92741, Dow chemical), 0.05g of 2-ethyl-4-methylimidazole, 40g of spherical silica and a proper amount of butanone solvent are added, and the mixture is stirred and mixed uniformly to obtain a glue solution with the solid content of 60%.
The glue solution is soaked and coated on E glass fiber cloth (2116, the single weight is 104g/m2), and the semi-solidified sheet with 50 percent of resin content is prepared by drying in an oven at 135 ℃ for 5 min.
And placing a metal copper foil on each of the prepregs with the resin content of 50% and placing the prepregs in a vacuum hot press for pressing to obtain the copper-clad plate. The specific pressing process is pressing for 2 hours under the pressure of 1.5Mpa and the temperature of 220 ℃.
The properties of the copper-clad laminate obtained are shown in Table 1.
Comparative example No. two
50g of dicyclopentadiene type epoxy resin (XD-1000, Japan chemical), 25g of phenolic curing agent (PF-8011, Shandong Shengquan), 25g of phosphorus-containing phenolic (XZ92741, Dow chemical), 0.02g of 2-phenylimidazole, 40g of spherical silica and a proper amount of butanone solvent were added, and the mixture was stirred and mixed uniformly to obtain a glue solution with a solid content of 60%.
The preparation methods of the prepreg and the copper-clad laminate are the same as the comparative example I.
The properties of the copper-clad laminate obtained are shown in Table 1.
Table 1 shows the properties of copper-clad laminates obtained in different examples
The test methods for each property in the table above are as follows:
(1) glass transition temperature (Tg): according to differential scanning calorimetry, the measurement was carried out by the DSC method specified by IPC-TM-6502.4.25.
(2) Peel Strength (PS): the peel strength of the metal cap was tested according to the "post thermal stress" experimental conditions in the IPC-TM-6502.4.8 method.
(3) Tin immersion heat resistance: A50X 50mm sample with copper on both sides was immersed in solder at 288 ℃ and the time for delamination of the bubbles was recorded.
(4) Tin immersion heat resistance after moisture treatment: 25 pieces of 100X 100mm substrate samples were held in a pressure cooker at 121 ℃ and 105Kpa for 3hr, and then immersed in a solder bath at 288 ℃ for 2min to observe whether or not delamination and bubbling occurred in the samples.
(5) Thermal decomposition temperature Td: the measurement was carried out according to the IPC-TM-6502.4.26 method.
(6) Dielectric constant: the dielectric constant at 1GHz was measured by the plate method according to IPC-TM-6502.5.5.9.
(7) Dielectric loss tangent: the dielectric dissipation factor at 1GHz was measured by the plate method according to IPC-TM-6502.5.5.9.
(8) Drop hammer impact toughness (laminate brittleness): an impact meter was used, the height of the drop weight of the impact meter was 45cm, and the weight of the drop weight was 1 kg. Evaluation of good and poor toughness: the cross is clear, which indicates that the toughness of the product is better, and the character is four-day; the cross is fuzzy, which indicates that the product has poor toughness and large brittleness and is expressed as a character ^ x; the cross clarity is between clarity and fuzziness, which indicates that the toughness of the product is general, and is denoted by the character diamond.
(9) Thermal stratification time T-300: the measurement was carried out according to the IPC-TM-6502.4.24 method.
(10) Flame resistance (flame retardancy): measured according to the UL94 method.
(11) Solubility: after mixing the dope, the mixture was left to stand for 24 hours, and whether or not there was a phenomenon of precipitation or delamination was observed, and if there was any, it was represented by a symbol √ indicating a symbol, and if so, it was represented by a symbol X.
As can be seen from the above table, example 1, comparative example 1 is superior in glass transition temperature, moist heat resistance, dielectric properties and toughness, and the dielectric constant can be reduced to 4.0 level even under the ordinary curing agent system; further, in examples 2 and 3 and comparative example 2, the laminate obtained by the present invention is excellent in moist heat resistance, and also excellent in dielectric properties, high glass transition temperature and high toughness, and particularly excellent in reliability in dielectric properties and moist heat resistance.
The resin composition has high humidity resistance, high glass transition temperature, low dielectric constant and dielectric loss tangent value, and can meet the requirements of high-performance printed circuit boards such as high-frequency, high-speed and high-density interconnection.
It should be understood that although the present description refers to embodiments, not every embodiment contains only a single technical solution, and such description is for clarity only, and those skilled in the art should make the description as a whole, and the technical solutions in the embodiments can also be combined appropriately to form other embodiments understood by those skilled in the art.
The above-listed detailed description is only a specific description of a possible embodiment of the present invention, and they are not intended to limit the scope of the present invention, and equivalent embodiments or modifications made without departing from the technical spirit of the present invention should be included in the scope of the present invention.
Claims (10)
1. The high-frequency resin prepolymer is characterized by being prepared by pre-polymerizing at least cage-type silsesquioxane and polyaryletherketone polymer, wherein the mass ratio of the cage-type silsesquioxane to the polyaryletherketone polymer is 100: 100-5000; the number average molecular weight of the high-frequency resin prepolymer is 800-.
2. The high-frequency resin prepolymer according to claim 1, wherein the cage-type silsesquioxane has a structure with one or more of amino groups, ester groups, epoxy groups, hydroxyl groups, carboxyl groups and carbonyl groups.
3. The high frequency resin prepolymer according to claim 1, wherein the polyaryletherketone polymer has a structure with one or more of amino groups, ester groups, epoxy groups, hydroxyl groups, and carboxyl groups.
4. The high-frequency resin prepolymer as claimed in claim 1, wherein the weight ratio of the cage-type silsesquioxane to the polyaryletherketone polymer is 100: 300-1000.
5. A high-frequency resin composition characterized by comprising, by solid weight:
the high-frequency resin prepolymer as claimed in any one of claims 1 to 4: 10-80 parts;
epoxy resin: 10-60 parts;
flame retardant: 5-40 parts;
accelerator (b): 0.001-2 parts;
filling: 0-70 parts.
6. The high-frequency resin composition according to claim 5, wherein the epoxy resin is selected from one or a mixture of several of 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, tetraphenylethane epoxy resin, biphenyl type epoxy resin, naphthalene ring type epoxy resin, dicyclopentadiene type epoxy resin, aralkyl novolac epoxy resin, glycidylamine type epoxy resin, and glycidylester type epoxy resin; the flame retardant is selected from one or a mixture of several of phosphorus-containing flame retardants and bromine-containing flame retardants.
7. The high-frequency resin composition according to claim 5, wherein the filler is an inorganic filler selected from one or a mixture of more than one of silica, boron nitride, aluminum hydroxide, boehmite, talc, clay, mica, kaolin, barium sulfate, calcium carbonate, magnesium hydroxide, and zinc borate, and/or an organic filler selected from any one or a mixture of at least two of polytetrafluoroethylene powder, polyphenylene sulfide, and polyether sulfone powder; the accelerator is imidazole and/or an organic metal salt.
8. A prepreg, characterized in that a solvent is added into the high-frequency resin composition according to claim 5 to dissolve the composition to form a glue solution, a reinforcing material is immersed in the glue solution, and the immersed reinforcing material is heated and dried to obtain the prepreg.
9. A laminate which is obtained by coating at least one prepreg according to claim 8 on one or both sides with a metal foil and hot-press forming.
10. An interlayer insulating film, characterized in that a solvent is added to the high-frequency resin composition according to claim 5 to dissolve the composition to form a glue solution, the glue solution is coated on a carrier film, and the carrier film coated with the glue solution is heated and dried to obtain the interlayer insulating film.
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| CN201910016012.6A CN109735086B (en) | 2019-01-08 | 2019-01-08 | High-frequency resin prepolymer and high-frequency resin composition, prepreg, laminated board and interlayer insulating film prepared from high-frequency resin prepolymer |
| PCT/CN2019/119487 WO2020143336A1 (en) | 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 |
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| CN201910016012.6A CN109735086B (en) | 2019-01-08 | 2019-01-08 | High-frequency resin prepolymer and high-frequency resin composition, prepreg, laminated board and interlayer insulating film prepared from high-frequency resin prepolymer |
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| CN109735086B true CN109735086B (en) | 2020-08-21 |
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| CN102850726A (en) * | 2012-09-07 | 2013-01-02 | 广东生益科技股份有限公司 | Composite material, high frequency circuit substrate produced by using composite material, and production method of high frequency circuit substrate |
| CN103159948B (en) * | 2013-04-06 | 2014-12-10 | 吉林大学 | POSS (polyhedral oligomeric silsesquioxane) fluoric polyaryletherketone nano composite material with low dielectric coefficients and preparation method thereof |
| CN104109347B (en) * | 2014-05-28 | 2016-08-31 | 苏州生益科技有限公司 | A kind of halogen-free thermosetting resin composite, prepreg and laminate |
| CN105601935B (en) * | 2015-12-25 | 2018-06-05 | 吉林省聚科高新材料有限公司 | The poly aryl ether ketone polymer of structure containing polysilsesquioxane and preparation method |
| CN108440901B (en) * | 2018-03-26 | 2020-07-14 | 常熟生益科技有限公司 | High-frequency resin composition, and prepreg, interlayer insulating film and laminated board prepared from high-frequency resin composition |
| CN108623811A (en) * | 2018-05-23 | 2018-10-09 | 吉林大学 | One kind containing POSS structure ultralow dielectric poly aryl ether ketone polymers and preparation method thereof |
| CN109735088B (en) * | 2019-01-08 | 2021-04-27 | 苏州生益科技有限公司 | High-frequency resin composition, and prepreg, laminated board and interlayer insulating film prepared from high-frequency resin composition |
| CN109735086B (en) * | 2019-01-08 | 2020-08-21 | 苏州生益科技有限公司 | High-frequency resin prepolymer and high-frequency resin composition, prepreg, laminated board and interlayer insulating film prepared from high-frequency resin prepolymer |
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| WO2020143336A1 (en) | 2020-07-16 |
| CN109735086A (en) | 2019-05-10 |
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