CN111454539A - Thermosetting resin composition and application thereof in millimeter wave circuit substrate - Google Patents

Thermosetting resin composition and application thereof in millimeter wave circuit substrate Download PDF

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CN111454539A
CN111454539A CN202010307599.9A CN202010307599A CN111454539A CN 111454539 A CN111454539 A CN 111454539A CN 202010307599 A CN202010307599 A CN 202010307599A CN 111454539 A CN111454539 A CN 111454539A
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thermosetting resin
resin
stirring
parts
speed
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CN111454539B (en
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田琰
李智
林德宝
彭冲
刘欢
宋锡滨
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Shanghai Guoci New Material Technology Co ltd
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
    • B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
    • B29B15/10—Coating or impregnating independently of the moulding or shaping step
    • B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29K2705/00—Use of metals, their alloys or their compounds, for preformed parts, e.g. for inserts
    • B29K2705/08—Transition metals
    • B29K2705/10—Copper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2471/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
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    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
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Abstract

The invention relates to a thermosetting resin composition, in particular to an epoxy resin composition and application thereof in a millimeter wave circuit substrate. According to the thermosetting resin material, the cyanate ester resin is introduced into the polyphenyl ether modified epoxy system, so that the problem of compatibility between the polyphenyl ether and the epoxy resin can be solved, the dielectric constant of the resin system is reduced, and the thermosetting resin material is more favorable for application in the field of high-frequency and high-speed substrates. The millimeter wave circuit substrate prepared from the thermosetting resin material has low dielectric constant and dielectric loss in the range of 20-43.5GHz, has excellent heat resistance and mechanical properties, and is suitable for the application fields of high-frequency and high-speed PCB substrate materials and the like under 5G communication.

Description

Thermosetting resin composition and application thereof in millimeter wave circuit substrate
Technical Field
The invention relates to a thermosetting resin composition, in particular to an epoxy resin composition and application thereof in a millimeter wave circuit substrate.
Background
With the development of 5G communication technology, higher requirements are also put forward on the comprehensive performance of millimeter wave circuit substrate materials. In particular, the requirements of different specifications are also put forward on key properties of the resin matrix, such as dielectric constant and dielectric loss. Research shows that in the millimeter wave circuit, the lower the dielectric constant of the substrate material, the faster the rate of signal propagation, the smaller the loss tangent of the substrate, and the smaller the attenuation of signal propagation. In view of the fact that the dielectric property of the millimeter wave circuit substrate material mainly depends on the type of the used resin, the adoption of various novel resins is also one of important technical routes for the performance requirements and development of various copper-clad plates. Currently, various manufacturers of large copper clad laminates are still working on developing resin matrices with low dielectric constants and low dielectric losses.
Epoxy resin has the characteristics of low cost, good processability, excellent heat resistance and mechanical properties and the like, and is widely applied to Printed Circuit Boards (PCBs), wherein the largest amount of the epoxy resin is FR-4 type epoxy copper-clad plate, but the epoxy resin has the defects of poor heat resistance, lower glass transition temperature, poor moisture resistance, high dielectric loss, higher linear expansion coefficient, poor flame retardance and the like. Although the polyphenylene oxide resin has the advantages of excellent dielectric property, low water absorption, good adhesion with copper foil, heat resistance, flame retardance and the like, and can improve the dielectric property defect of an epoxy resin system matrix to a certain extent, the polyphenylene oxide resin is not suitable for practical application because the polyphenylene oxide has large molecular weight, high symmetry and few polar groups on a molecular chain, so that the polyphenylene oxide has poor compatibility with epoxy resin, and is easy to have a sea-island structure and the like after blending and curing.
Therefore, the development of a novel thermosetting resin with lower dielectric constant and dielectric loss has positive significance for the development of millimeter wave circuit substrates.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a thermosetting resin composition, which has low dielectric constant and low dielectric loss, excellent heat resistance and mechanical property, and can be used for preparing millimeter wave circuit substrate materials;
the second technical problem to be solved by the present invention is to provide the application of the thermosetting resin composition for preparing millimeter wave circuit substrates.
In order to solve the above technical problems, the thermosetting resin composition of the present invention comprises an epoxy resin base material and a filler;
the epoxy resin base material comprises 50-75 parts by weight of epoxy resin, 10-25 parts by weight of polyphenyl ether resin and 10-25 parts by weight of cyanate ester resin;
the filler comprises 10-25 parts by weight of polybutadiene liquid rubber, 3-12 parts by weight of aluminum hydroxide and 1-4 parts by weight of ammonium polyphosphate.
Specifically, the thermosetting resin composition:
the epoxy resin comprises brominated epoxy resin, preferably with a bromine content of 30-50%;
the polyphenylene ether resin comprises an allylated polyphenylene ether resin;
the cyanate resin comprises a cyanate resin containing an aromatic heterocyclic structure;
the polybutadiene liquid rubber comprises hydroxyl-terminated polybutadiene, carboxyl-terminated polybutadiene and isocyanate-terminated polybutadiene liquid rubber.
Preferably, in the filler, the particle sizes of the aluminum hydroxide and the ammonium polyphosphate are micron-sized, preferably 5-20 μm, the micron-sized filler can be mixed with the base material more ideally, and the obtained material has more ideal heat resistance and flame retardance.
The invention also discloses a thermosetting resin material prepared from the thermosetting resin composition.
The invention also discloses a method for preparing the thermosetting resin material, which comprises the following steps:
(1) taking a selected amount of epoxy resin, respectively adding part of the fillers, and stirring at a low speed; then all the rest fillers are added into the mixed material stirred at a low speed, and vacuum high-speed stirring is carried out;
(2) after stirring, standing the sample and carrying out three-roller grinding treatment; sequentially adding selected amounts of the polyphenyl ether resin and cyanate ester resin into the treated material, and carrying out ultrasonic crushing to obtain a thermosetting resin precursor;
(3) and sequentially adding a curing agent and a catalyst into the thermosetting resin precursor, reacting at the temperature of 110-125 ℃, and performing vacuum pumping until all bubbles disappear to obtain the required thermosetting resin material.
Specifically, in the step (1), the adding amount of each filler accounts for 40-60 wt% of the total amount of each filler.
Specifically, in the step (1):
the conditions of the low-speed stirring step are as follows: stirring at the temperature of 75-85 ℃ for 1-1.5h at the speed of 1000r/min, and stirring at the speed of 1500-2000r/min for 2-2.5 h.
In the step (2), the conditions of the high-speed stirring step are as follows: stirring at the temperature of 75-85 ℃ for 1-1.5h at the speed of 1000r/min for 500-.
Specifically, in the step (2), the vacuum degree is preferably controlled to be-0.08 to-0.1 MPa.
Specifically, in the step (2), the standing step is standing for 24-48h at room temperature.
Specifically, in the step (2), in the three-roll grinding step:
the spacing pattern is: the interval 1 is 90-75 μm, the interval 2 is 45-30 μm, the rotating speed is 85-100r/min, and the cycle times are 3-5 times;
the pressure mode is as follows:
the first step is as follows: the interval 1 is 60-45 μm, the interval 2 is 20-15 μm, the rotating speed is 60-75r/min, and the cycle times are 3-5 times;
the second step is that: the interval 1 is 30-25 μm, the interval 2 is 10-5 μm, the rotating speed is 60-75r/min, and the cycle times are 3-5 times;
the third step: the interval 1 is 15-10 μm, the interval 2 is 5-1 μm, the rotating speed is 60-75r/min, and the cycle times are 3-5 times.
Specifically, in the step (2), the conditions of the ultrasonic step are as follows: controlling the temperature at 110-.
Specifically, in the step (3):
the curing agent comprises methyl tetrahydrophthalic anhydride and/or tetrahydrophthalic anhydride; the addition amount of the methyl tetrahydrophthalic anhydride is 30-45 parts by weight and the addition amount of the tetrahydrophthalic anhydride is 25-40 parts by weight based on 100 parts by weight of the addition amount of the epoxy resin;
the catalyst comprises N, N-dimethylbenzylamine, and the addition amount of the catalyst is 0.75-1.5 parts by weight based on 100 parts by weight of the addition amount of the curing agent.
The invention also discloses a prepreg prepared from the thermosetting resin material, which is obtained by coating the glue solution consisting of the thermosetting resin material and the solvent according to claim 3 on a base material and drying the glue solution.
Specifically, the preparation method of the prepreg comprises the following steps:
(1) adding a solvent into the thermosetting resin material, mixing, and stirring for 30-40min under the reflux condition of 50-80 ℃ to obtain a resin glue solution;
(2) soaking the selected base material into the resin glue solution, and performing vacuum pumping at 50-80 ℃ for 20-30min until bubbles in the sample completely disappear to obtain a prepreg;
(3) drying the obtained prepreg at the temperature of 110-125 ℃ for 20-40min to obtain the prepreg.
Preferably, the base material is glass fiber cloth, more specifically comprises E glass fiber, D glass fiber and quartz glass fiber, and the solvent comprises butanone and trichloromethane.
The invention also discloses a millimeter wave circuit substrate prepared by laminating the prepreg.
The invention also discloses a method for preparing the millimeter wave circuit substrate, which comprises the following steps:
(1) stacking selected prepreg, matching with copper foil, filling the prepreg into a mold, placing the mold into a hot press, and pressing the prepreg according to a formulated lamination flow;
(2) naturally cooling the pressed substrate to room temperature under the pressure of 15-30MPa, demolding, and standing at 160 ℃ for 2-3h to obtain the material.
Specifically, the lamination process specifically comprises:
(1) preheating and prepressing: melting the resin at the temperature of 110-;
(2) and (3) maintaining the pressure at medium temperature: pre-curing the resin for 150-240min at the temperature of 155 ℃ and the pressure of 15-30 MPa;
(3) and (3) high-temperature pressure maintaining: fully curing the resin for 60-90min at the temperature of 155-160 ℃ and under the pressure of 15-30 MPa.
It should be noted that the "millimeter wave" in the present invention means a frequency in the range of 20-43.5 GHz.
According to the thermosetting resin material, the cyanate ester resin is introduced into the polyphenyl ether modified epoxy system, so that the problem of compatibility between the polyphenyl ether and the epoxy resin can be solved, the dielectric constant of the resin system is reduced, and the thermosetting resin material is more favorable for application in the field of high-frequency and high-speed substrates; furthermore, a weak polar group is introduced into the epoxy resin by a chemical modification method, so that the content of the polar group in the cured material is reduced, and the dielectric constant and the loss factor of the cured material can be effectively reduced; the epoxy resin system modified by the nonpolar liquid rubber (such as the weak polar polybutadiene) has mature preparation process and stable comprehensive performance, and is widely concerned by more researchers. The thermosetting resin material disclosed by the invention has lower dielectric constant and dielectric loss performance, can meet the performance requirements of a millimeter wave circuit substrate, and is suitable for preparing the millimeter wave circuit substrate.
The millimeter wave circuit substrate prepared by the thermosetting resin material has lower dielectric constant (2.3-3.0) and dielectric loss (0.001-0.004) in the range of 20-43.5GHz, has excellent heat resistance (the thermal decomposition temperature is 400-465 ℃) and mechanical properties (the bending strength is 380-420MPa), and is suitable for the application fields of high-frequency and high-speed PCB substrate materials and the like under 5G communication.
Detailed Description
In the following embodiments of the invention, the raw materials respectively comprise the following components in types:
brominated epoxy resin, Lanxing EX 27-D;
allylated polyphenylene ether resin, asahi chemical S2100;
the cyanate resin is cyanate resin containing aromatic heterocyclic structure, Xu71787 of Dow company;
the polybutadiene liquid rubber is hydroxyl-terminated polybutadiene liquid rubber, and K100203 of D & B company;
the other fillers are selected from conventional commercial products, the particle size is selected from micron grade, and the particle size of the preferred aluminum hydroxide and ammonium polyphosphate is 5-20 μm.
Example 1
The thermosetting resin composition of this example includes the following raw materials:
Figure BDA0002456321500000061
the preparation method of the thermosetting resin in this embodiment includes the following steps:
(1) sequentially adding various filler components which are all 50 percent of the total mass of various fillers into the epoxy resin, and stirring at a low speed in a stirrer, wherein the stirring flow is controlled as follows: stirring at the temperature of 85 ℃ for 1h at 600r/min and stirring at 1800r/min for 2 h; then all the rest various fillers are added into the mixture which is stirred at a low speed, and the mixture is stirred at a vacuum degree of-0.1 MPa at a high speed, and the stirring process is controlled as follows: stirring at 85 ℃ for 1h at 500r/min, stirring at 2500r/min for 2h, and stirring at 5000r/min for 3 h;
(2) after stirring, standing the sample for 24h at room temperature, and then carrying out three-roll grinding to enable the particles to reach an optimal dispersion state, wherein the three-roll grinding process is controlled as follows:
a pitch mode, wherein the pitch 1 is 75 micrometers, the pitch 2 is 30 micrometers, the rotating speed is 100r/min, and the cycle time is 5 times;
pressure mode, first step: the interval 1 is 45 μm, the interval 2 is 15 μm, the rotating speed is 60r/min, and the cycle times are 3 times; the second step is that: the interval 1 is 25 μm, the interval 2 is 10 μm, the rotating speed is 60r/min, and the cycle times are 3 times; thirdly, the interval 1 is 15 microns, the interval 2 is 5 microns, the rotating speed is 60r/min, and the cycle times are 5 times;
sequentially adding selected amounts of the polyphenyl ether resin and cyanate ester resin into the modified material for ultrasonic treatment, controlling the ultrasonic temperature to be 110 ℃ and the power to be 350W, and carrying out ultrasonic crushing for 20min to obtain a thermosetting resin prepolymer;
(3) and (2) sequentially adding 24g of curing agent methyltetrahydrophthalic anhydride and 2.4g of catalyst N, N-dimethylbenzylamine into the thermosetting resin prepolymer, reacting at the temperature of 110 ℃, stirring for 30min under the condition of controlling the speed at 500r/min, and then performing vacuum pumping at the temperature of 110 ℃ until all bubbles disappear to obtain the required thermosetting resin material.
The prepreg and the millimeter wave circuit substrate are prepared from the following raw materials:
100g of thermosetting resin system;
35g of trichloromethane;
and 80g of D-type glass fiber cloth.
The preparation process of the prepreg comprises the following steps:
(1) adding chloroform into thermosetting resin material, mixing, and stirring at 50 deg.C under reflux for 30min to obtain resin glue solution;
(2) soaking selected glass fiber cloth into the resin glue solution, and performing vacuum air suction at the temperature of 50 ℃ for 30min until bubbles in the sample completely disappear to obtain a prepreg;
(3) and fully drying the obtained prepreg at the temperature of 110 ℃ for 30min to obtain the required prepreg.
The preparation process of the millimeter wave circuit substrate comprises the following steps:
(1) stacking the prepared prepregs, matching with copper foils, placing the prepregs into a hot press after mould filling, and pressing according to a lamination flow (110 ℃, 8MPa, 120 min; 150 ℃, 20MPa, 180 min; 160 ℃, 20MPa, 80 min);
(2) naturally cooling the obtained substrate to room temperature, controlling the pressure at the stage to be 20MPa, demolding, and standing at 155 ℃ for 3h to obtain the substrate.
Example 2
The thermosetting resin composition described in this embodiment includes the following raw materials:
Figure BDA0002456321500000081
the thermosetting resin described in this example was prepared in the same manner as in example 1.
The materials and preparation methods of the prepreg and the millimeter wave circuit substrate in this embodiment are the same as those in embodiment 1.
Example 3
The thermosetting resin composition described in this embodiment includes the following raw materials:
Figure BDA0002456321500000082
the thermosetting resin described in this example was prepared in the same manner as in example 1.
The materials and preparation methods of the prepreg and the millimeter wave circuit substrate in this embodiment are the same as those in embodiment 1.
Example 4
The thermosetting resin composition described in this embodiment includes the following raw materials:
Figure BDA0002456321500000091
the thermosetting resin described in this example was prepared in the same manner as in example 1.
The materials and preparation methods of the prepreg and the millimeter wave circuit substrate in this embodiment are the same as those in embodiment 1.
Example 5
The thermosetting resin composition described in this embodiment includes the following raw materials:
Figure BDA0002456321500000092
the thermosetting resin described in this example was prepared in the same manner as in example 1.
The materials and preparation methods of the prepreg and the millimeter wave circuit substrate in this embodiment are the same as those in embodiment 1.
Example 6
The thermosetting resin composition described in this embodiment includes the following raw materials:
Figure BDA0002456321500000101
the thermosetting resin described in this example was prepared in the same manner as in example 1.
The materials and preparation methods of the prepreg and the millimeter wave circuit substrate in this embodiment are the same as those in embodiment 1.
Example 7
The thermosetting resin composition described in this embodiment includes the following raw materials:
Figure BDA0002456321500000102
the thermosetting resin described in this example was prepared in the same manner as in example 1.
The materials and preparation methods of the prepreg and the millimeter wave circuit substrate in this embodiment are the same as those in embodiment 1.
Example 8
The thermosetting resin composition described in this embodiment includes the following raw materials:
Figure BDA0002456321500000111
the thermosetting resin described in this example was prepared in the same manner as in example 1.
The materials and preparation methods of the prepreg and the millimeter wave circuit substrate in this embodiment are the same as those in embodiment 1.
Comparative example 1
The raw material composition of the thermosetting resin composition of this comparative example was the same as that of example 1 except that the cyanate ester resin and the polybutadiene liquid rubber were not added.
The preparation of the thermosetting resin described in this comparative example was the same as in example 1.
The materials and preparation methods of the prepreg and the millimeter wave circuit substrate in the comparative example are the same as those in example 1.
Comparative example 2
The raw material composition of the thermosetting resin composition of this comparative example was the same as that of example 1 except that the cyanate ester resin was not added.
The preparation of the thermosetting resin described in this comparative example was the same as in example 1.
The materials and preparation methods of the prepreg and the millimeter wave circuit substrate in the comparative example are the same as those in example 1.
Comparative example 3
The raw material composition of the thermosetting resin composition of this comparative example was the same as that of example 1 except that the polybutadiene liquid rubber was not added.
The preparation of the thermosetting resin described in this comparative example was the same as in example 1.
The materials and preparation methods of the prepreg and the millimeter wave circuit substrate in the comparative example are the same as those in example 1.
Comparative example 4
The raw material composition of the thermosetting resin composition of this comparative example was the same as that of example 2 except that the cyanate ester resin was not added.
The preparation of the thermosetting resin described in this comparative example was the same as in example 1.
The materials and preparation methods of the prepreg and the millimeter wave circuit substrate in the comparative example are the same as those in example 1.
Comparative example 5
The raw material composition of the thermosetting resin composition of this comparative example was the same as that of example 2 except that the polybutadiene liquid rubber was not added.
The preparation of the thermosetting resin described in this comparative example was the same as in example 1.
The materials and preparation methods of the prepreg and the millimeter wave circuit substrate in the comparative example are the same as those in example 1.
Comparative example 6
The raw materials of the thermosetting resin composition, the materials of the prepreg and the millimeter wave circuit board, and the preparation method of the composition in this comparative example are the same as those in example 2, but the difference is that in the preparation method of the thermosetting resin, the low-speed stirring step is omitted, and the corresponding high-speed stirring treatment is directly performed.
Comparative example 7
The raw materials of the thermosetting resin composition, the materials of the prepreg and the millimeter wave circuit board, and the preparation method of the composition in this comparative example are the same as those in example 4, but the difference is that in the preparation method of the thermosetting resin, the low-speed stirring step is omitted, and the corresponding high-speed stirring treatment is directly performed.
Comparative example 8
The raw materials of the thermosetting resin composition, the materials of the prepreg and the millimeter wave circuit board, and the preparation method of the thermosetting resin composition in this comparative example are the same as those in example 2, except that in the preparation method of the thermosetting resin, the parameters of the high-speed stirring step are as follows: stirring at 85 ℃ at 500r/min for 1h, stirring at 2500r/min for 2h, and stirring at 5000r/min for 5 h.
Comparative example 9
The raw materials of the thermosetting resin composition, the materials of the prepreg and the millimeter wave circuit board, and the preparation method of the comparative example are the same as those of example 4, but the difference between the raw materials and the materials of the prepreg and the millimeter wave circuit board is that in the preparation method of the thermosetting resin, the parameters of the high-speed stirring step are as follows: stirring at 85 ℃ at 500r/min for 1h, stirring at 2500r/min for 2h, and stirring at 5000r/min for 5 h.
Comparative example 10
The raw materials of the thermosetting resin composition, and the materials and the production methods of the prepreg and the millimeter wave circuit substrate according to this comparative example are the same as those of example 3, except that the ultrasonic treatment step is omitted from the production method of the thermosetting resin.
Comparative example 11
The raw materials of the thermosetting resin composition, and the materials and the production methods of the prepreg and the millimeter wave circuit substrate according to this comparative example are the same as those of example 6 except that the ultrasonic treatment step is omitted from the production method of the thermosetting resin.
Comparative example 12
The raw materials of the thermosetting resin composition, the materials of the prepreg and the millimeter wave circuit substrate, and the preparation method of the thermosetting resin composition in this comparative example are the same as those in example 3, except that in the preparation method of the thermosetting resin, the flow parameters of the ultrasonic treatment step are controlled as follows: crushing at 110 deg.C and 350W for 50 min.
Comparative example 13
The raw materials of the thermosetting resin composition, the materials of the prepreg and the millimeter wave circuit substrate, and the preparation method of the thermosetting resin composition in this comparative example are the same as those in example 6, except that in the preparation method of the thermosetting resin, the flow parameters of the ultrasonic treatment step are controlled as follows: crushing at 110 deg.C and 350W for 50 min.
Comparative example 14
The raw materials of the thermosetting resin composition, and the materials and the manufacturing method of the prepreg and the millimeter wave circuit board according to the present comparative example are different from those of example 3 only in that the step of the three-roll grinding medium pressure mode is omitted from the manufacturing method of the thermosetting resin.
Comparative example 15
The raw materials of the thermosetting resin composition, and the materials and the production methods of the prepreg and the millimeter wave circuit board according to the present comparative example are the same as those of example 6, except that the step of the three-roll grinding medium pressure mode is omitted from the production method of the thermosetting resin.
Examples of the experiments
The dielectric constant and the dielectric loss performance of the circuit substrate materials prepared in the above examples 1-8 and comparative examples 1-15 were tested according to standard Q/0500SGC 001-2019 with a frequency of 40 GHz.
The circuit substrate materials prepared in the above examples 1 to 8 and comparative examples 1 to 15 were subjected to thermal stability tests using a thermogravimetric analyzer (type TA Q500, usa) with a sample weight of 5 to 10mg, a temperature rise rate of 10 ℃/min, and an air atmosphere.
The flexural strength of the circuit substrate materials prepared in examples 1 to 8 and comparative examples 1 to 15, respectively, was measured in accordance with the ASTM D7264 standard.
The results of the above parameter tests are shown in table 1 below.
TABLE 1 Circuit Board Performance test results
Figure BDA0002456321500000141
Figure BDA0002456321500000151
As can be seen from the data in the above table, the cyanate ester resin and the polybutadiene liquid rubber have a synergistic effect on the reduction of the dielectric constant and dielectric loss, the improvement of the thermal decomposition temperature and the improvement of the flexural strength of the prepared substrate by comparing the embodiments 1-2 with the comparative examples 1-5 and the parameters. The reasons mainly include: firstly, the weak polar polybutadiene liquid rubber containing active groups such as terminal hydroxyl or terminal carboxyl can play a role in catalyzing cyanate ester triazine cyclization reaction, enhance the reaction activity of cyanate ester resin and promote the cross-linking polymerization of the blend of cyanate ester resin, polyphenyl ether resin and epoxy resin; secondly, the weak polarity polybutadiene liquid rubber is introduced into a cross-linking network, so that the polarity of the cyanate ester resin can be reduced; meanwhile, the viscosity of the liquid rubber is controllable, the viscosity of the cyanate ester resin can be improved, the defects formed when the resin glue solution soaks the glass fibers are reduced, and the comprehensive performance of the prepared substrate is improved.
By comparing the embodiment and parameters of example 2 with those of comparative example 6 and example 4 with those of example 7, the dielectric constant, dielectric loss and bending strength of the substrate prepared by using the thermosetting resin matrix which is not stirred at a low speed are obviously reduced. The main reason is that, the thermosetting resin matrix which is not stirred at low speed does not have sufficient infiltration of each phase interface, under the action of high-speed shearing, the repulsive force between each phase interface is greater than the attractive force, phase separation is easily promoted, even a discontinuous phase is formed, such as a 'sea-island structure', namely, each phase in the material is distributed unevenly, the orientation of a polar group or a high-molecular chain segment along the direction of an electric field cannot be effectively destroyed, the internal stress cannot be effectively transferred, the growth of microcracks is prevented, and further the comprehensive performance of the prepared substrate is influenced.
By comparing the embodiment and parameters of example 2 with those of comparative example 8, and example 4 with those of example 9, it can be seen that the dielectric property and bending property of the material are also damaged by prolonging the time of high-speed stirring (more than 5000 r/min) in the thermosetting resin preparation step. This is mainly because the surface reactivity of the dispersed phase becomes stronger as the size of the dispersed phase becomes smaller under the high-speed shearing action, and if the reactivity is too strong, spontaneous aggregation of the dispersed phase is also caused, resulting in increase in the size of the local phase and deterioration in continuity, thereby affecting the full exertion of the performance advantages of the thermosetting resin matrix.
Comparing example 3 with comparative example 10, and comparing example 6 with example 11, it can be seen that the dielectric constant, dielectric loss and bending strength of the substrate prepared by using the thermosetting resin matrix without ultrasonic treatment are all reduced. The ultrasonic treatment plays a role in instantaneous crushing, can reduce the apparent viscosity of the thermosetting resin, is beneficial to improving the mixing quality among epoxy resin, polyphenyl ether resin and cyanate ester resin, and can promote the resin glue solution to fully impregnate the fiber reinforcement.
Comparing example 3 with comparative example 12, and comparing example 6 with example 13 with the parameters, it can be seen that prolonging the sonication time in the thermosetting resin preparation step also deteriorates the dielectric and bending properties of the material. This is mainly because, under the action of phonons of ultrasonic waves, due to the local heating phenomenon of the thermosetting resin system, if heat is continuously accumulated, local overheating reaction inside the resin can be caused, so that the resin is pre-cured before the resin glue solution is prepared, a small amount of aggregates are formed, the fluidity and the processability of the resin glue solution are affected, and further, the resin glue solution is inhibited from fully impregnating the fiber reinforcement.
By comparing example 3 with comparative example 14, and comparing the schemes and parameters of example 6 and example 15, it can be seen that the pressure mode of three-roll grinding is not adopted in the mixing process, which results in the remarkable reduction of the dielectric property, heat resistance and bending property of the material. This is mainly because the phases need to be uniformly dispersed throughout the system before the material is sonicated, so that under the action of the ultrasound, the phases can only be effectively fused, further promoting phase separation and reducing the phase size. If the phases are not uniformly dispersed before the ultrasonication, the heat transfer is not uniform in the ultrasonication, and a severe exothermic reaction is caused to form a curing defect of the resin, resulting in a significant decrease in the performance. The resin system is uniformly extruded in all directions in a three-roller grinding pressure mode, so that the aggregate can be effectively opened, the defects are reduced, and all phases reach the optimal dispersion state. The three-roller grinding and ultrasonic processing steps are mutually matched, so that the comprehensive performance of the material is optimized.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (10)

1. A thermosetting resin composition is characterized by comprising an epoxy resin base material and a filler;
the epoxy resin base material comprises 50-75 parts by weight of epoxy resin, 10-25 parts by weight of polyphenyl ether resin and 10-25 parts by weight of cyanate ester resin;
the filler comprises 10-25 parts by weight of polybutadiene liquid rubber, 3-12 parts by weight of aluminum hydroxide and 1-4 parts by weight of ammonium polyphosphate.
2. The thermosetting resin composition according to claim 1, characterized in that:
the epoxy resin comprises a brominated epoxy resin;
the polyphenylene ether resin comprises an allylated polyphenylene ether resin;
the cyanate resin comprises a cyanate resin containing an aromatic heterocyclic structure;
the polybutadiene liquid rubber comprises hydroxyl-terminated polybutadiene, carboxyl-terminated polybutadiene and isocyanate-terminated polybutadiene liquid rubber.
3. A thermosetting resin material prepared from the thermosetting resin composition as claimed in claim 1 or 2.
4. A method of preparing a thermosetting resinous material as claimed in claim 3, comprising the steps of:
(1) taking a selected amount of epoxy resin, respectively adding part of the fillers, and stirring at a low speed; then all the rest fillers are added into the mixed material stirred at a low speed, and vacuum high-speed stirring is carried out;
(2) after stirring, standing the sample and carrying out three-roller grinding treatment; sequentially adding selected amounts of the polyphenyl ether resin and cyanate ester resin into the treated material, and carrying out ultrasonic crushing to obtain a thermosetting resin precursor;
(3) and sequentially adding a curing agent and a catalyst into the thermosetting resin precursor, reacting at the temperature of 110-125 ℃, and performing vacuum pumping until all bubbles disappear to obtain the required thermosetting resin material.
5. The method for preparing a thermosetting resin material as claimed in claim 4, wherein in the step (1):
the conditions of the low-speed stirring step are as follows: stirring at the temperature of 75-85 ℃ for 1-1.5h at the speed of 1000r/min, and stirring at the speed of 1500-2000r/min for 2-2.5 h.
The conditions of the high-speed stirring step are as follows: stirring at the temperature of 75-85 ℃ for 1-1.5h at the speed of 1000r/min for 500-.
6. The method for producing a thermosetting resin material as claimed in claim 4 or 5, wherein in the step (2), in the three-roll grinding step:
the spacing pattern is: the interval 1 is 90-75 μm, the interval 2 is 45-30 μm, the rotating speed is 85-100r/min, and the cycle times are 3-5 times;
the pressure mode is as follows:
the first step is as follows: the interval 1 is 60-45 μm, the interval 2 is 20-15 μm, the rotating speed is 60-75r/min, and the cycle times are 3-5 times;
the second step is that: the interval 1 is 30-25 μm, the interval 2 is 10-5 μm, the rotating speed is 60-75r/min, and the cycle times are 3-5 times;
the third step: the interval 1 is 15-10 μm, the interval 2 is 5-1 μm, the rotating speed is 60-75r/min, and the cycle times are 3-5 times.
7. A process for preparing a thermosetting resin material according to any one of claims 4 to 6, wherein in the step (3):
the curing agent comprises methyl tetrahydrophthalic anhydride and/or tetrahydrophthalic anhydride; the addition amount of the methyl tetrahydrophthalic anhydride is 30-45 parts by weight and the addition amount of the tetrahydrophthalic anhydride is 25-40 parts by weight based on 100 parts by weight of the addition amount of the epoxy resin;
the catalyst comprises N, N-dimethylbenzylamine, and the addition amount of the catalyst is 0.75-1.5 parts by weight based on 100 parts by weight of the addition amount of the curing agent.
8. A prepreg prepared from the thermosetting resin material according to claim 3, wherein the prepreg is obtained by coating a glue solution consisting of the thermosetting resin material according to claim 3 and a solvent on a substrate and drying the coated glue solution.
9. A millimeter wave circuit board produced by laminating the prepreg according to claim 8.
10. A method of manufacturing the millimeter wave circuit substrate according to claim 9, comprising the steps of:
(1) stacking selected prepreg, matching with copper foil, filling the prepreg into a mold, placing the mold into a hot press, and pressing the prepreg according to a formulated lamination flow;
(2) naturally cooling the pressed substrate to room temperature under the pressure of 15-30MPa, demolding, and standing at the temperature of 100-160 ℃ to obtain the material.
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