CN109266262B - Method for preparing low dielectric loss composite adhesive - Google Patents

Method for preparing low dielectric loss composite adhesive Download PDF

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Publication number
CN109266262B
CN109266262B CN201810840158.8A CN201810840158A CN109266262B CN 109266262 B CN109266262 B CN 109266262B CN 201810840158 A CN201810840158 A CN 201810840158A CN 109266262 B CN109266262 B CN 109266262B
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polybutadiene
styrene
dielectric loss
low dielectric
silicon dioxide
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CN109266262A (en
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郭少云
张先龙
张旋
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Sichuan University
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Sichuan University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J147/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

Abstract

The invention relates to a low dielectric loss composite adhesive and a preparation method thereof, wherein the composite adhesive is prepared by taking 1, 2-polybutadiene with different vinyl contents as a substrate and adding two types of silica, tackifiers, curing agents and the like with different particle diameters, wherein the content of the two types of silica with different particle diameters is 50-100% of the weight of the 1, 2-polybutadiene, the content of the tackifiers is 9-53.8% of the weight of the 1, 2-polybutadiene, and the content of the curing agents is 2.7-7.6% of the weight of the 1, 2-polybutadiene. The low dielectric loss composite adhesive has low dielectric loss, low expansion coefficient, high adhesive strength and good processing fluidity, can be applied to spray forming processing, can meet the requirements of the high-frequency circuit field on various functions of high polymer materials such as low expansion coefficient, low dielectric loss, high adhesive strength, high fluidity and the like, has good application prospect, simple production process, convenient operation and control, stable quality, high production efficiency and wide industrialization and market prospect.

Description

Method for preparing low dielectric loss composite adhesive
Technical Field
The invention relates to a method for preparing a low dielectric loss composite adhesive, belonging to the technical field of functional composite materials.
Background
With the rapid development of high-frequency communication information technology, the development of high-frequency microwave communication technology to integrated, multifunctional, high-frequency and low-loss microwave systems is a great trend. High integration, lower power consumption, and higher performance integrated circuits place more stringent demands on high frequency dielectric substrate materials. In order to reduce capacitance-Resistance (RC) time delay and crosstalk interference brought by an integrated circuit and simultaneously meet characteristic impedance requirements of different transmission conditions so as to achieve high-fidelity low-loss high-frequency information transmission, development of low-dielectric-loss dielectric materials and adjustment and control of dielectric properties thereof are paid attention by more and more researchers. However, this material is required to have a low dielectric loss and also to have good adhesion to a copper foil and a substrate. In order to reduce the dielectric loss of polymer materials, on one hand, the dielectric loss of polymers is reduced through molecular structure design, but the method generally needs special equipment, has complex process and strict process condition control, so that the method for reducing the dielectric loss of polymers and improving the bonding strength through molecular structure design is difficult to industrialize. On the other hand, the composition of the polymer material and the low dielectric loss filler is usually selected, so that the composite material has the advantages of easy processing, good adhesion and easy regulation of dielectric constant and dielectric loss of the polymer. Improving the adhesion of composite materials generally requires that the matrix has polar groups, reducing the dielectric loss generally requires that the matrix has non-polarity, reducing the dielectric loss as much as possible, and simultaneously keeping the composite materials have excellent adhesion, good fluidity, processability, curing temperature and substrate matching regulation and control, which has become a great problem restricting the development of low dielectric loss composite adhesive materials.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a method for preparing a low dielectric loss adhesive material, which has low dielectric loss and strong adhesion, and maintains good fluidity, toughness and processability under the condition of higher filler filling.
The technical principle of the invention is that the adhesive strength and toughness of the composite material are adjusted by the vinyl content of the resin, the processability, film-forming property and viscosity chirality of the low dielectric loss composite material are adjusted by the styrene-butadiene-styrene triblock copolymer, the dielectric constant and thermal expansion coefficient of the composite material are adjusted by compounding of silicon dioxide with different particle sizes, and the functional composite material with low dielectric loss and high adhesive strength can be developed based on the adjustment and balance of the three aspects.
Based on the technical principle, the invention adopts the technical scheme that:
the invention discloses a method for preparing low-loss functional composite material, which takes resin with high vinyl content as a matrix and is characterized in that the method comprises the following steps:
firstly, preparing the following components in parts by weight:
(1) 1, 2-polybutadiene A: 50 (vinyl content is more than or equal to 90)
(2) 1, 2-polybutadiene B: 5 to 15 (80 is not less than 40 of vinyl content)
(3) Styrene-butadiene-styrene triblock copolymer: 5 to 35
(4) Silica A: 25 to 70 (particle size 1 to 5 μm)
(5) Silicon dioxide B: 10 to 50 (particle size 100 to 600 nm)
(6) Cumene hydroperoxide: 1.5 to 5
(7) Vinyl silane coupling agent: 0.6 to 1.5
Secondly, drying the silicon dioxide A and the silicon dioxide B, cooling to room temperature, then treating with a vinyl silane coupling agent, and drying;
thirdly, dissolving the 1, 2-polybutadiene A, 1, 2-polybutadiene B and styrene-butadiene-styrene triblock copolymer solvent in a good solvent by stirring to obtain a uniform solution of the 1, 2-polybutadiene A, 1, 2-polybutadiene B and styrene-butadiene-styrene triblock copolymer;
and fourthly, adding cumene hydroperoxide and silicon dioxide A and silicon dioxide B which are treated by the vinyl silane coupling agent and dried in the second step into the uniform solution of the triblock copolymer of the 1, 2-polybutadiene A, the 1, 2-polybutadiene B and the styrene-butadiene-styrene in the third step, stirring and mixing to obtain the low dielectric loss composite adhesive.
In the first step, the weight ratio of 1, 2-polybutadiene a, 1, 2-polybutadiene B, styrene-butadiene-styrene triblock copolymer, silica a, silica B, cumene hydroperoxide, vinylsilane coupling agent may be preferably selected to be 50: 10: 15: 70: 10: 2: 0.8.
the main purpose of adding two kinds of polybutadiene in the first step, namely 1, 2-polybutadiene A (the vinyl content is more than or equal to 90%) and 1, 2-polybutadiene B (the vinyl content is more than or equal to 40%) is to adjust the sizing degree of the composite material through the vinyl content, so that the bonding strength and the toughness are balanced to a certain extent.
The styrene-butadiene-styrene triblock copolymer is added in the first step mainly for adjusting the viscosity of the composite material, namely that the composite adhesive has a certain shape after a solvent is volatilized and can keep certain fluidity.
It is worth pointing out that the low dielectric loss composite adhesive can be sprayed and molded on a substrate, and after the solvent is volatilized, the low dielectric loss composite adhesive can be hot-pressed with copper foil, so that the bonding function of the low dielectric loss composite adhesive can be fully exerted. Because the composite adhesive has good fluidity, the composite adhesive can fill the grooves of the copper foil different-row circuit, so that the whole circuit substrate is more compact, no air bubbles exist between the copper foil and the substrate, and the signal transmission performance of the whole high-frequency circuit is influenced if the air bubbles exist.
Compared with the prior art, the invention has the following advantages:
the invention firstly adjusts the density of a crosslinking point through the content of vinyl, realizes the balance of toughness and rigidity, can fully play the bonding function of the low dielectric loss composite adhesive through the addition of butadiene, and then adjusts the hand-sticking property of a composite material through the addition of a styrene-butadiene-styrene triblock copolymer, namely, the composite adhesive has a certain shape after a solvent is volatilized and can keep certain fluidity, the main principle is that the physical crosslinking point characteristic of the styrene-butadiene-styrene triblock copolymer, namely the styrene-butadiene-styrene triblock copolymer can flow at high temperature and presents a crosslinking state at low temperature, and simultaneously crosslinkable double bonds and polybutadiene perform crosslinking reaction, aiming at the current dielectric composite adhesive, the bonding strength is low, the dielectric loss is large, and the thermal expansion coefficient is high, the invention adopts the methods of polymer interface structure design and composite material aggregation state structure design, the bonding strength of the prepared low dielectric loss composite adhesive and a copper foil reaches 0.89N/m (Newton/m), the dielectric loss is as low as 0.0015, and the linear thermal expansion coefficient reaches 2.90 × 10-5℃-1And simultaneously, the requirements of spray forming on the processing rheological property of the polymer can be met.
The low dielectric loss composite adhesive provided by the invention has good adhesive property and low thermal expansion coefficient while reducing the dielectric loss of the composite material, keeps good high fluidity of the polymer composite material, has good toughness after curing, improves the added value of the polymer product, widens the application range of the polymer product, and has important significance in the aspects of theoretical research, application development and the like of the polymer composite material. Meanwhile, the production process is simple, the operation and the control are convenient, the quality is stable, the production efficiency is high, the production cost is low, the application range is wide, and the method has wide industrialization and market prospects.
The specific implementation method comprises the following steps:
the present invention is further specifically described below by way of examples. In the following examples, the amounts of the components are given by mass. It is to be noted that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention, and that the skilled person in the art may make modifications and adaptations of the present invention in view of the above disclosure.
Example 1
The preparation of the low dielectric loss composite adhesive in this embodiment, which uses 1, 2-polybutadiene as a main matrix and silica as a filler, includes the following steps:
firstly, preparing the following components by weight (unit is gram):
(1) 1, 2-polybutadiene A: 50
(2) 1, 2-polybutadiene B: 5
(3) Styrene-butadiene-styrene triblock copolymer: 20
(4) Silica A: 60
(5) Silicon dioxide B: 30
(6) Cumene hydroperoxide: 1.5
(7) Vinyl silane coupling agent: 1.5
Taking 60 g of silicon dioxide A (with the particle size range being normal distribution and the particle size range being 1-5 microns) and 30 g of silicon dioxide B (with the particle size range being normal distribution and the particle size range being 100-600 nanometers), drying at 120 ℃, cooling to room temperature (here, 25 ℃), putting the dried silicon dioxide A and the dried silicon dioxide B into a high-speed mixer together, mixing for 5 minutes at the speed of 600 revolutions per minute, putting 1.5 g of vinyl silane coupling agent, mixing for 5 minutes at the speed of 800 revolutions per minute, controlling the temperature of materials in the whole process at 80 ℃, and cooling to the room temperature for later use;
thirdly, 50 g of 1, 2-polybutadiene A (with the vinyl content of 91 percent), 5 g of 1, 2-polybutadiene B (with the vinyl content of 45 percent) and 20 g of styrene-butadiene-styrene triblock copolymer are taken and dissolved in 336 g of dimethylbenzene under stirring at room temperature to obtain a uniform solution of the 1, 2-polybutadiene A, the 1, 2-polybutadiene B and the styrene-butadiene-styrene triblock copolymer for later use;
fourthly, adding 1.5 g of cumene hydroperoxide and the silicon dioxide C and the silicon dioxide D treated by the vinyl silane coupling agent in the second step into the solution of the triblock copolymer of the 1, 2-polybutadiene A, the 1, 2-polybutadiene B and the styrene-butadiene-styrene in the third step, stirring and mixing to obtain the low dielectric loss composite adhesive;
and fifthly, spraying the low dielectric loss composite adhesive on an epoxy resin substrate, drying at 80 ℃, controlling the thickness of an adhesive layer by controlling the spraying dosage, controlling the thickness of the adhesive layer to be 20 microns after drying in the embodiment, and then carrying out hot pressing on the adhesive layer and a 50 micron copper foil together at the hot pressing temperature of 200 ℃ under the pressure of 1 MPa to test the peeling strength. Spraying the low dielectric loss composite adhesive on the polytetrafluoroethylene film, covering another polytetrafluoroethylene film, and hot-pressing together at 200 ℃ under 1 MPa to obtain a sample, wherein the sample can be subjected to thermal expansion coefficient and dielectric property tests.
The low dielectric loss composite adhesive prepared in the example has a dielectric peel strength of 0.78 newtons/meter (N/m) with copper foil, a dielectric loss of 0.0018, and a linear expansion coefficient of 3.21 × 10-5℃-1The obtained composite adhesive has good fluidity and can well fill the grooves left after the copper foil is corroded (the copper foil can be corroded into various complex shapes according to the circuit design requirement).
Comparative examples 1 to 1
The contents of the components in the comparative example were the same as those in example 1, except that only silica A was used as in the comparative example.
Firstly, preparing the following components by weight (unit is gram):
(1) 1, 2-polybutadiene A: 50
(2) 1, 2-polybutadiene B: 5
(3) Styrene-butadiene-styrene triblock copolymer: 20
(4) Silica A: 90
(5) Cumene hydroperoxide: 1.5
(6) Vinyl silane coupling agent: 1.5
The method comprises the following specific steps:
taking 90 g of silicon dioxide A (the particle size range is in normal distribution and is 1-5 microns), drying at 120 ℃, cooling to room temperature (25 ℃), putting the dried silicon dioxide A into a high-speed mixer, mixing for 5 minutes at a speed of 600 revolutions per minute, putting 1.5 g of vinyl silane coupling agent, mixing for 5 minutes at a speed of 800 revolutions per minute, controlling the temperature of the materials in the whole process at 80 ℃, and cooling to room temperature for later use;
thirdly, 50 g of 1, 2-polybutadiene A (with the vinyl content of 91 percent), 5 g of 1, 2-polybutadiene B (with the vinyl content of 45 percent) and 20 g of styrene-butadiene-styrene triblock copolymer are taken and dissolved in 336 g of dimethylbenzene under stirring at room temperature to obtain a uniform solution of the 1, 2-polybutadiene A, the 1, 2-polybutadiene B and the styrene-butadiene-styrene triblock copolymer for later use;
fourthly, adding 1.5 g of cumene hydroperoxide and the silicon dioxide A treated by the vinyl silane coupling agent in the second step into the solution of the triblock copolymer of the 1, 2-polybutadiene A, the 1, 2-polybutadiene B and the styrene-butadiene-styrene in the third step, stirring and mixing to obtain the low dielectric loss composite adhesive;
and fifthly, spraying the low dielectric loss composite adhesive on an epoxy resin substrate, drying at 80 ℃, controlling the thickness of an adhesive layer by controlling the spraying dosage, controlling the thickness of the adhesive layer to be 20 microns after drying in the embodiment, and then carrying out hot pressing on the adhesive layer and a 50 micron copper foil together at the hot pressing temperature of 200 ℃ under the pressure of 1 MPa to test the peeling strength. Spraying the low dielectric loss composite adhesive on the polytetrafluoroethylene film, covering another polytetrafluoroethylene film, and hot-pressing together at 200 ℃ under 1 MPa to obtain a sample, wherein the sample can be subjected to thermal expansion coefficient and dielectric property tests.
The dielectric peel strength of the low dielectric loss composite adhesive prepared by the embodiment and the copper foil is 0.73N/m (Newton/m), the dielectric loss is 0.0022, and the linear thermal expansion coefficient reaches 3.44 × 10-5℃-1The obtained composite adhesive has good fluidity and can well fill the grooves left after the copper foil is corroded (the copper foil can be corroded into various complex shapes according to the circuit design requirement).
Comparative examples 1 to 2
The contents of the components in the comparative example were the same as those in example 1, except that only silica B was used as in the comparative example.
Firstly, preparing the following components by weight (unit is gram):
(1) 1, 2-polybutadiene A: 50
(2) 1, 2-polybutadiene B: 5
(3) Styrene-butadiene-styrene triblock copolymer: 20
(4) Silicon dioxide B: 90
(5) Cumene hydroperoxide: 1.5
(6) Vinyl silane coupling agent: 1.5
The method comprises the following specific steps:
taking 90 g of silicon dioxide B (the particle size range is normal distribution and is 100-600 nanometers), drying at 120 ℃, cooling to room temperature (25 ℃), putting the dried silicon dioxide B into a high-speed mixer, mixing for 5 minutes at a speed of 600 revolutions per minute, putting 1.5 g of vinyl silane coupling agent, mixing for 5 minutes at a speed of 800 revolutions per minute, controlling the temperature of the materials in the whole process at 80 ℃, and cooling to room temperature for later use;
thirdly, 50 g of 1, 2-polybutadiene A (with the vinyl content of 91 percent), 5 g of 1, 2-polybutadiene B (with the vinyl content of 45 percent) and 20 g of styrene-butadiene-styrene triblock copolymer are taken and dissolved in 336 g of dimethylbenzene under stirring at room temperature to obtain a uniform solution of the 1, 2-polybutadiene A, the 1, 2-polybutadiene B and the styrene-butadiene-styrene triblock copolymer for later use;
fourthly, adding 1.5 g of cumene hydroperoxide and the silicon dioxide B treated by the vinyl silane coupling agent in the second step into the solution of the triblock copolymer of the 1, 2-polybutadiene A, the 1, 2-polybutadiene B and the styrene-butadiene-styrene in the third step, stirring and mixing to obtain the low dielectric loss composite adhesive;
and fifthly, spraying the low dielectric loss composite adhesive on an epoxy resin substrate, drying at 80 ℃, controlling the thickness of an adhesive layer by controlling the spraying dosage, controlling the thickness of the adhesive layer to be 20 microns after drying in the embodiment, and then carrying out hot pressing on the adhesive layer and a 50 micron copper foil together at the hot pressing temperature of 200 ℃ under the pressure of 1 MPa to test the peeling strength. Spraying the low dielectric loss composite adhesive on the polytetrafluoroethylene film, covering another polytetrafluoroethylene film, and hot-pressing together at 200 ℃ under 1 MPa to obtain a sample, wherein the sample can be subjected to thermal expansion coefficient and dielectric property tests.
The dielectric peel strength of the low dielectric loss composite adhesive prepared by the embodiment and the copper foil is 0.68N/m (Newton/m), the dielectric loss is 0.0024, and the linear thermal expansion coefficient reaches 3.31 × 10-5℃-1The obtained composite adhesive has good fluidity and can well fill the grooves left after the copper foil is corroded (the copper foil can be corroded into various complex shapes according to the circuit design requirement).
Comparative examples 1 to 3
The contents of the components in the comparative example were identical to those in example 1, except that the components in the comparative example were all added together, instead of the implementation step in the present invention.
Firstly, preparing the following components by weight (unit is gram):
(1) 1, 2-polybutadiene A: 50
(2) 1, 2-polybutadiene B: 5
(3) Styrene-butadiene-styrene triblock copolymer: 20
(4) Silica A: 60
(5) Silicon dioxide B: 30
(6) Cumene hydroperoxide: 1.5
(7) Vinyl silane coupling agent: 1.5
Taking 60 g of silicon dioxide A (with the particle size range being normal distribution and the particle size range being 1-5 microns) and 30 g of silicon dioxide B (with the particle size range being normal distribution and the particle size range being 100-600 nanometers), drying at 120 ℃, cooling to room temperature (here, 25 ℃), putting the dried silicon dioxide A and the dried silicon dioxide B into a high-speed mixer together, mixing for 5 minutes at the speed of 600 revolutions per minute, putting 1.5 g of vinyl silane coupling agent, mixing for 5 minutes at the speed of 800 revolutions per minute, controlling the temperature of materials in the whole process at 80 ℃, and cooling to the room temperature for later use;
thirdly, dissolving 1.5 g of cumene hydroperoxide, 50 g of silicon dioxide C, silicon dioxide D, 1, 2-polybutadiene A (the vinyl content is 91 percent), 5 g of 1, 2-polybutadiene B (the vinyl content is 45 percent) and 20 g of styrene-butadiene-styrene triblock copolymer in 336 g of dimethylbenzene by stirring at room temperature and mixing to obtain the low dielectric loss composite adhesive;
and fourthly, spraying the low dielectric loss composite adhesive on an epoxy resin substrate, drying at 80 ℃, controlling the thickness of the adhesive layer by controlling the spraying dosage, controlling the thickness of the adhesive layer to be 20 microns after drying in the embodiment, and then carrying out hot pressing on the adhesive layer and 50 microns of copper foil together, wherein the hot pressing temperature is 200 ℃, and the pressure is 1 MPa, so that the peeling strength can be tested. Spraying the low dielectric loss composite adhesive on the polytetrafluoroethylene film, covering another polytetrafluoroethylene film, and hot-pressing together at 200 ℃ under 1 MPa to obtain a sample, wherein the sample can be subjected to thermal expansion coefficient and dielectric property tests.
The dielectric peel strength of the low dielectric loss composite adhesive prepared in this example from copper foil was 0.64N/m (Newton/m), and the dielectric loss wasThe linear thermal expansion coefficient reaches 3.67 × 10 by 0.0023-5℃-1The obtained composite adhesive has good fluidity and can well fill the grooves left after the copper foil is corroded (the copper foil can be corroded into various complex shapes according to the circuit design requirement).
Example 2
The preparation of the low dielectric loss composite adhesive in this embodiment, which uses 1, 2-polybutadiene as a main matrix and silica as a filler, includes the following steps:
firstly, preparing the following components by weight (unit is gram):
(1) 1, 2-polybutadiene A: 50
(2) 1, 2-polybutadiene B: 10
(3) Styrene-butadiene-styrene triblock copolymer: 15
(4) Silica A: 70
(5) Silicon dioxide B: 10
(6) Cumene hydroperoxide: 2
(7) Vinyl silane coupling agent: 0.8
Taking 70 g of silicon dioxide A (with the particle size range being normal distribution and the particle size range being 1-5 microns) and 10 g of silicon dioxide B (with the particle size range being normal distribution and the particle size range being 100-600 nanometers), drying at 120 ℃, cooling to room temperature (here, 25 ℃), putting the dried silicon dioxide A and the dried silicon dioxide B into a high-speed mixer together, mixing for 5 minutes at the speed of 600 revolutions per minute, putting 0.8 g of vinyl silane coupling agent, mixing for 5 minutes at the speed of 800 revolutions per minute, controlling the temperature of materials in the whole process at 80 ℃, and cooling to the room temperature for later use;
thirdly, 50 g of 1, 2-polybutadiene A (with the vinyl content of 91 percent), 10 g of 1, 2-polybutadiene B (with the vinyl content of 45 percent) and 15 g of styrene-butadiene-styrene triblock copolymer are taken and dissolved in 336 g of dimethylbenzene under stirring at room temperature to obtain a uniform solution of the 1, 2-polybutadiene A, the 1, 2-polybutadiene B and the styrene-butadiene-styrene triblock copolymer for later use;
fourthly, adding 2 g of cumene hydroperoxide and the silicon dioxide C and the silicon dioxide D treated by the vinyl silane coupling agent in the second step into the solution of the triblock copolymer of the 1, 2-polybutadiene A, the 1, 2-polybutadiene B and the styrene-butadiene-styrene in the third step, stirring and mixing to obtain the low dielectric loss composite adhesive;
and fifthly, spraying the low dielectric loss composite adhesive on an epoxy resin substrate, drying at 80 ℃, controlling the thickness of an adhesive layer by controlling the spraying dosage, controlling the thickness of the adhesive layer to be 20 microns after drying in the embodiment, and then carrying out hot pressing on the adhesive layer and a 50 micron copper foil together at the hot pressing temperature of 200 ℃ under the pressure of 1 MPa to test the peeling strength. Spraying the low dielectric loss composite adhesive on the polytetrafluoroethylene film, covering another polytetrafluoroethylene film, and hot-pressing together at 200 ℃ under 1 MPa to obtain a sample, wherein the sample can be subjected to thermal expansion coefficient and dielectric property tests.
The dielectric peel strength of the low dielectric loss composite adhesive prepared by the embodiment and the copper foil is 0.89N/m (Newton/m), the dielectric loss is 0.0015, and the linear thermal expansion coefficient reaches 2.90 × 10-5℃-1The obtained composite adhesive has good fluidity and can well fill the grooves left after the copper foil is corroded (the copper foil can be corroded into various complex shapes according to the circuit design requirement).
Comparative example 2-1
The contents of the components in the comparative example were the same as those in example 2, except that only silica A was used as in the comparative example.
Firstly, preparing the following components by weight (unit is gram):
(1) 1, 2-polybutadiene A: 50
(2) 1, 2-polybutadiene B: 10
(3) Styrene-butadiene-styrene triblock copolymer: 15
(4) Silica A: 80
(5) Cumene hydroperoxide: 2
(6) Vinyl silane coupling agent: 0.8
The method comprises the following specific steps:
step two, taking 80 g of silicon dioxide A (the particle size range is in normal distribution and is 1-5 microns), respectively drying at 120 ℃, cooling to room temperature (here, 25 ℃), putting the dried silicon dioxide A into a high-speed mixer, mixing for 5 minutes at a speed of 600 revolutions per minute, putting 1.5 g of vinyl silane coupling agent, mixing for 5 minutes at a speed of 800 revolutions per minute, controlling the temperature of the materials in the whole process at 80 ℃, and cooling to room temperature for later use;
thirdly, 50 g of 1, 2-polybutadiene A (with the vinyl content of 91 percent), 5 g of 1, 2-polybutadiene B (with the vinyl content of 45 percent) and 20 g of styrene-butadiene-styrene triblock copolymer are taken and dissolved in 336 g of dimethylbenzene under stirring at room temperature to obtain a uniform solution of the 1, 2-polybutadiene A, the 1, 2-polybutadiene B and the styrene-butadiene-styrene triblock copolymer for later use;
fourthly, adding 1.5 g of cumene hydroperoxide and the silicon dioxide A treated by the vinyl silane coupling agent in the second step into the solution of the triblock copolymer of the 1, 2-polybutadiene A, the 1, 2-polybutadiene B and the styrene-butadiene-styrene in the third step, stirring and mixing to obtain the low dielectric loss composite adhesive;
and fifthly, spraying the low dielectric loss composite adhesive on an epoxy resin substrate, drying at 80 ℃, controlling the thickness of an adhesive layer by controlling the spraying dosage, controlling the thickness of the adhesive layer to be 20 microns after drying in the embodiment, and then carrying out hot pressing on the adhesive layer and a 50 micron copper foil together at the hot pressing temperature of 200 ℃ under the pressure of 1 MPa to test the peeling strength. Spraying the low dielectric loss composite adhesive on the polytetrafluoroethylene film, covering another polytetrafluoroethylene film, and hot-pressing together at 200 ℃ under 1 MPa to obtain a sample, wherein the sample can be subjected to thermal expansion coefficient and dielectric property tests.
The dielectric peel strength of the low dielectric loss composite adhesive prepared in the embodiment with copper foil is 0.83N/m (Newton/m), the dielectric loss is 0.0027, and the linear thermal expansion coefficient reaches 2.93 × 10-5℃-1The resulting compositeThe adhesive has good fluidity and can well fill the grooves left after the copper foil is corroded (the copper foil can be corroded into various complex shapes according to the circuit design requirement).
Comparative examples 2 to 2
The contents of the components in the comparative example were the same as those in example 2, except that only silica B was used as in the comparative example.
Firstly, preparing the following components by weight (unit is gram):
(1) 1, 2-polybutadiene A: 50
(2) 1, 2-polybutadiene B: 10
(3) Styrene-butadiene-styrene triblock copolymer: 15
(4) Silicon dioxide B: 80
(5) Cumene hydroperoxide: 2
(6) Vinyl silane coupling agent: 0.8
The method comprises the following specific steps:
step two, taking 80 g of silicon dioxide B (the particle size range is in normal distribution and is 1-5 microns), respectively drying at 120 ℃, cooling to room temperature (here, 25 ℃), putting the dried silicon dioxide B into a high-speed mixer, mixing for 5 minutes at a speed of 600 revolutions per minute, putting 1.5 g of vinyl silane coupling agent, mixing for 5 minutes at a speed of 800 revolutions per minute, controlling the temperature of the materials in the whole process at 80 ℃, and cooling to room temperature for later use;
thirdly, 50 g of 1, 2-polybutadiene A (with the vinyl content of 91 percent), 5 g of 1, 2-polybutadiene B (with the vinyl content of 45 percent) and 20 g of styrene-butadiene-styrene triblock copolymer are taken and dissolved in 336 g of dimethylbenzene under stirring at room temperature to obtain a uniform solution of the 1, 2-polybutadiene A, the 1, 2-polybutadiene B and the styrene-butadiene-styrene triblock copolymer for later use;
fourthly, adding 1.5 g of cumene hydroperoxide and the silicon dioxide B treated by the vinyl silane coupling agent in the second step into the solution of the triblock copolymer of the 1, 2-polybutadiene A, the 1, 2-polybutadiene B and the styrene-butadiene-styrene in the third step, stirring and mixing to obtain the low dielectric loss composite adhesive;
and fifthly, spraying the low dielectric loss composite adhesive on an epoxy resin substrate, drying at 80 ℃, controlling the thickness of an adhesive layer by controlling the spraying dosage, controlling the thickness of the adhesive layer to be 20 microns after drying in the embodiment, and then carrying out hot pressing on the adhesive layer and a 50 micron copper foil together at the hot pressing temperature of 200 ℃ under the pressure of 1 MPa to test the peeling strength. Spraying the low dielectric loss composite adhesive on the polytetrafluoroethylene film, covering another polytetrafluoroethylene film, and hot-pressing together at 200 ℃ under 1 MPa to obtain a sample, wherein the sample can be subjected to thermal expansion coefficient and dielectric property tests.
The dielectric peel strength of the low dielectric loss composite adhesive prepared in the embodiment with copper foil is 0.74N/m (Newton/m), the dielectric loss is 0.0023, and the linear thermal expansion coefficient reaches 3.12 × 10-5℃-1The obtained composite adhesive has good fluidity and can well fill the grooves left after the copper foil is corroded (the copper foil can be corroded into various complex shapes according to the circuit design requirement).
Comparative examples 2 to 3
The contents of the components in the comparative example were identical to those in example 2, except that the components in the comparative example were all added together, instead of the implementation step in the present invention.
Firstly, preparing the following components by weight (unit is gram):
(1) 1, 2-polybutadiene A: 50
(2) 1, 2-polybutadiene B: 10
(3) Styrene-butadiene-styrene triblock copolymer: 15
(4) Silica A: 70
(5) Silicon dioxide B: 10
(6) Cumene hydroperoxide: 2
(7) Vinyl silane coupling agent: 0.8
Taking 70 g of silicon dioxide A (with the particle size range being normal distribution and the particle size range being 1-5 microns) and 10 g of silicon dioxide B (with the particle size range being normal distribution and the particle size range being 100-600 nanometers), drying at 120 ℃, cooling to room temperature (here, 25 ℃), putting the dried silicon dioxide A and the dried silicon dioxide B into a high-speed mixer together, mixing for 5 minutes at the speed of 600 revolutions per minute, putting 0.8 g of vinyl silane coupling agent, mixing for 5 minutes at the speed of 800 revolutions per minute, controlling the temperature of materials in the whole process at 80 ℃, and cooling to the room temperature for later use;
thirdly, dissolving 2 g of cumene hydroperoxide, 50 g of silicon dioxide A, silicon dioxide B, 1, 2-polybutadiene A (the vinyl content is 91 percent), 10 g of 1, 2-polybutadiene B (the vinyl content is 45 percent) and 15 g of styrene-butadiene-styrene triblock copolymer in 336 g of dimethylbenzene by stirring at room temperature, and mixing to obtain the low dielectric loss composite adhesive;
and fourthly, spraying the low dielectric loss composite adhesive on an epoxy resin substrate, drying at 80 ℃, controlling the thickness of the adhesive layer by controlling the spraying dosage, controlling the thickness of the adhesive layer to be 20 microns after drying in the embodiment, and then carrying out hot pressing on the adhesive layer and 50 microns of copper foil together, wherein the hot pressing temperature is 200 ℃, and the pressure is 1 MPa, so that the peeling strength can be tested. Spraying the low dielectric loss composite adhesive on the polytetrafluoroethylene film, covering another polytetrafluoroethylene film, and hot-pressing together at 200 ℃ under 1 MPa to obtain a sample, wherein the sample can be subjected to thermal expansion coefficient and dielectric property tests.
The dielectric peel strength of the low dielectric loss composite adhesive prepared in the embodiment with copper foil is 0.0.74N/m (Newton/m), the dielectric loss is 0.0023, and the linear thermal expansion coefficient reaches 3.12 × 10-5℃-1The obtained composite adhesive has good fluidity and can well fill the grooves left after the copper foil is corroded (the copper foil can be corroded into various complex shapes according to the circuit design requirement).
Comparative examples 2 to 3
The contents of the components in the comparative example were identical to those in example 2, except that the components in the comparative example were all added together, instead of the implementation step in the present invention.
Firstly, preparing the following components by weight (unit is gram):
(1) 1, 2-polybutadiene A: 50
(2) 1, 2-polybutadiene B: 10
(3) Styrene-butadiene-styrene triblock copolymer: 15
(4) Silica A: 70
(5) Silicon dioxide B: 10
(6) Cumene hydroperoxide: 2
(7) Vinyl silane coupling agent: 0.8
Taking 70 g of silicon dioxide A (with the particle size range being normal distribution and the particle size range being 1-5 microns) and 10 g of silicon dioxide B (with the particle size range being normal distribution and the particle size range being 100-600 nanometers), drying at 120 ℃, cooling to room temperature (here, 25 ℃), putting the dried silicon dioxide A and the dried silicon dioxide B into a high-speed mixer together, mixing for 5 minutes at the speed of 600 revolutions per minute, putting 0.8 g of vinyl silane coupling agent, mixing for 5 minutes at the speed of 800 revolutions per minute, controlling the temperature of materials in the whole process at 80 ℃, and cooling to the room temperature for later use;
thirdly, dissolving 2 g of cumene hydroperoxide, 50 g of silicon dioxide A, silicon dioxide B, 1, 2-polybutadiene A (the vinyl content is 91 percent), 10 g of 1, 2-polybutadiene B (the vinyl content is 45 percent) and 15 g of styrene-butadiene-styrene triblock copolymer in 336 g of dimethylbenzene by stirring at room temperature, and mixing to obtain the low dielectric loss composite adhesive;
and fourthly, spraying the low dielectric loss composite adhesive on an epoxy resin substrate, drying at 80 ℃, controlling the thickness of the adhesive layer by controlling the spraying dosage, controlling the thickness of the adhesive layer to be 20 microns after drying in the embodiment, and then carrying out hot pressing on the adhesive layer and 50 microns of copper foil together, wherein the hot pressing temperature is 200 ℃, and the pressure is 1 MPa, so that the peeling strength can be tested. Spraying the low dielectric loss composite adhesive on the polytetrafluoroethylene film, covering another polytetrafluoroethylene film, and hot-pressing together at 200 ℃ under 1 MPa to obtain a sample, wherein the sample can be subjected to thermal expansion coefficient and dielectric property tests.
The dielectric peel strength of the low dielectric loss composite adhesive prepared by the embodiment and the copper foil is 0.70N/m (Newton/m), the dielectric loss is 0.0021, and the linear thermal expansion coefficient reaches 3.01 × 10-5℃-1The obtained composite adhesive has good fluidity and can well fill the grooves left after the copper foil is corroded (the copper foil can be corroded into various complex shapes according to the circuit design requirement).
Example 3
The preparation of the low dielectric loss composite adhesive in this embodiment, which uses 1, 2-polybutadiene as a main matrix and silica as a filler, includes the following steps:
firstly, preparing the following components by weight (unit is gram):
(1) 1, 2-polybutadiene A: 50
(2) 1, 2-polybutadiene B: 15
(3) Styrene-butadiene-styrene triblock copolymer: 25
(4) Silica A: 60
(5) Silicon dioxide B: 30
(6) Cumene hydroperoxide: 1.5
(7) Vinyl silane coupling agent: 1.5
Taking 60 g of silicon dioxide A (with the particle size range being normal distribution and the particle size range being 1-5 microns) and 30 g of silicon dioxide B (with the particle size range being normal distribution and the particle size range being 100-600 nanometers), drying at 120 ℃, cooling to room temperature (here, 25 ℃), putting the dried silicon dioxide A and the dried silicon dioxide B into a high-speed mixer together, mixing for 5 minutes at the speed of 600 revolutions per minute, putting 1.5 g of vinyl silane coupling agent, mixing for 5 minutes at the speed of 800 revolutions per minute, controlling the temperature of materials in the whole process at 80 ℃, and cooling to the room temperature for later use;
thirdly, 50 g of 1, 2-polybutadiene A (with the vinyl content of 91 percent), 15 g of 1, 2-polybutadiene B (with the vinyl content of 45 percent) and 25 g of styrene-butadiene-styrene triblock copolymer are taken and dissolved in 336 g of dimethylbenzene under stirring at room temperature to obtain a uniform solution of the 1, 2-polybutadiene A, the 1, 2-polybutadiene B and the styrene-butadiene-styrene triblock copolymer for later use;
fourthly, adding 1.5 g of cumene hydroperoxide and the silicon dioxide A treated by the vinyl silane coupling agent in the second step into the solution of the triblock copolymer of the 1, 2-polybutadiene A, the 1, 2-polybutadiene B and the styrene-butadiene-styrene in the third step, stirring and mixing to obtain the low dielectric loss composite adhesive;
and fifthly, spraying the low dielectric loss composite adhesive on an epoxy resin substrate, drying at 80 ℃, controlling the thickness of an adhesive layer by controlling the spraying dosage, controlling the thickness of the adhesive layer to be 20 microns after drying in the embodiment, and then carrying out hot pressing on the adhesive layer and a 50 micron copper foil together at the hot pressing temperature of 200 ℃ under the pressure of 1 MPa to test the peeling strength. Spraying the low dielectric loss composite adhesive on the polytetrafluoroethylene film, covering another polytetrafluoroethylene film, and hot-pressing together at 200 ℃ under 1 MPa to obtain a sample, wherein the sample can be subjected to thermal expansion coefficient and dielectric property tests.
The dielectric peel strength of the low dielectric loss composite adhesive prepared by the embodiment and the copper foil is 0.82N/m (Newton/m), the dielectric loss is 0.0017, and the linear thermal expansion coefficient reaches 3.10 × 10-5℃-1The obtained composite adhesive has good fluidity and can well fill the grooves left after the copper foil is corroded (the copper foil can be corroded into various complex shapes according to the circuit design requirement).
Comparative example 3-1
The contents of the components in the comparative example were the same as those in example 3, except that only silica A was used as in the comparative example.
Firstly, preparing the following components by weight (unit is gram):
(1) 1, 2-polybutadiene A: 50
(2) 1, 2-polybutadiene B: 15
(3) Styrene-butadiene-styrene triblock copolymer: 25
(4) Silica A: 90
(5) Cumene hydroperoxide: 1.5
(6) Vinyl silane coupling agent: 1.5
The method comprises the following specific steps:
step two, taking 90 g of silicon dioxide A (the particle size range is in normal distribution and is 1-5 microns), respectively drying at 120 ℃, cooling to room temperature (here, 25 ℃), putting the dried silicon dioxide A into a high-speed mixer, mixing for 5 minutes at a speed of 600 revolutions per minute, putting 1.5 g of vinyl silane coupling agent, mixing for 5 minutes at a speed of 800 revolutions per minute, controlling the temperature of the materials in the whole process at 80 ℃, and cooling to room temperature for later use;
thirdly, 50 g of 1, 2-polybutadiene A (with the vinyl content of 91 percent), 15 g of 1, 2-polybutadiene B (with the vinyl content of 45 percent) and 25 g of styrene-butadiene-styrene triblock copolymer are taken and dissolved in 336 g of dimethylbenzene under stirring at room temperature to obtain a uniform solution of the 1, 2-polybutadiene A, the 1, 2-polybutadiene B and the styrene-butadiene-styrene triblock copolymer for later use;
fourthly, adding 1.5 g of cumene hydroperoxide and the silicon dioxide A treated by the vinyl silane coupling agent in the second step into the solution of the triblock copolymer of the 1, 2-polybutadiene A, the 1, 2-polybutadiene B and the styrene-butadiene-styrene in the third step, stirring and mixing to obtain the low dielectric loss composite adhesive;
and fifthly, spraying the low dielectric loss composite adhesive on an epoxy resin substrate, drying at 80 ℃, controlling the thickness of an adhesive layer by controlling the spraying dosage, controlling the thickness of the adhesive layer to be 20 microns after drying in the embodiment, and then carrying out hot pressing on the adhesive layer and a 50 micron copper foil together at the hot pressing temperature of 200 ℃ under the pressure of 1 MPa to test the peeling strength. Spraying the low dielectric loss composite adhesive on the polytetrafluoroethylene film, covering another polytetrafluoroethylene film, and hot-pressing together at 200 ℃ under 1 MPa to obtain a sample, wherein the sample can be subjected to thermal expansion coefficient and dielectric property tests.
The dielectric peel strength of the low dielectric loss composite adhesive prepared in the embodiment with copper foil is 0.80N/m (Newton/m), the dielectric loss is 0.0019, and the linear thermal expansion coefficient reaches 3.13 × 10-5℃-1The obtained composite adhesive has good fluidity and can well fill the grooves left after the copper foil is corroded (the copper foil can be corroded into various complex shapes according to the circuit design requirement).
Comparative examples 3 to 2
The contents of the components in the comparative example were the same as those in example 3, except that only silica B was used as in the comparative example.
Firstly, preparing the following components by weight (unit is gram):
(1) 1, 2-polybutadiene A: 50
(2) 1, 2-polybutadiene B: 15
(3) Styrene-butadiene-styrene triblock copolymer: 25
(4) Silicon dioxide B: 90
(5) Cumene hydroperoxide: 1.5
(6) Vinyl silane coupling agent: 1.5
The method comprises the following specific steps:
step two, taking 90 g of silicon dioxide B (the particle size range is in normal distribution and is 1-5 microns), respectively drying at 120 ℃, cooling to room temperature (here, 25 ℃), putting the dried silicon dioxide B into a high-speed mixer, mixing for 5 minutes at a speed of 600 revolutions per minute, putting 1.5 g of vinyl silane coupling agent, mixing for 5 minutes at a speed of 800 revolutions per minute, controlling the temperature of the materials in the whole process at 80 ℃, and cooling to room temperature for later use;
thirdly, 50 g of 1, 2-polybutadiene A (with the vinyl content of 91 percent), 15 g of 1, 2-polybutadiene B (with the vinyl content of 45 percent) and 25 g of styrene-butadiene-styrene triblock copolymer are taken and dissolved in 336 g of dimethylbenzene under stirring at room temperature to obtain a uniform solution of the 1, 2-polybutadiene A, the 1, 2-polybutadiene B and the styrene-butadiene-styrene triblock copolymer for later use;
fourthly, adding 1.5 g of cumene hydroperoxide and the silicon dioxide B treated by the vinyl silane coupling agent in the second step into the solution of the triblock copolymer of the 1, 2-polybutadiene A, the 1, 2-polybutadiene B and the styrene-butadiene-styrene in the third step, stirring and mixing to obtain the low dielectric loss composite adhesive;
and fifthly, spraying the low dielectric loss composite adhesive on an epoxy resin substrate, drying at 80 ℃, controlling the thickness of an adhesive layer by controlling the spraying dosage, controlling the thickness of the adhesive layer to be 20 microns after drying in the embodiment, and then carrying out hot pressing on the adhesive layer and a 50 micron copper foil together at the hot pressing temperature of 200 ℃ under the pressure of 1 MPa to test the peeling strength. Spraying the low dielectric loss composite adhesive on the polytetrafluoroethylene film, covering another polytetrafluoroethylene film, and hot-pressing together at 200 ℃ under 1 MPa to obtain a sample, wherein the sample can be subjected to thermal expansion coefficient and dielectric property tests.
The dielectric peel strength of the low dielectric loss composite adhesive prepared in the embodiment with copper foil is 0.77N/m (Newton/m), the dielectric loss is 0.0024, and the linear thermal expansion coefficient reaches 3.24 × 10-5℃-1The obtained composite adhesive has good fluidity and can well fill the grooves left after the copper foil is corroded (the copper foil can be corroded into various complex shapes according to the circuit design requirement).
Comparative examples 3 to 3
The contents of the components in the comparative example were identical to those in example 3, except that the components in the comparative example were all added together, instead of the implementation step in the present invention.
Firstly, preparing the following components by weight (unit is gram):
(1) 1, 2-polybutadiene A: 50
(2) 1, 2-polybutadiene B: 15
(3) Styrene-butadiene-styrene triblock copolymer: 25
(4) Silica A: 60
(5) Silicon dioxide B: 30
(6) Cumene hydroperoxide: 1.5
(7) Vinyl silane coupling agent: 1.5
Taking 60 g of silicon dioxide A (with the particle size range being normal distribution and the particle size range being 1-5 microns) and 30 g of silicon dioxide B (with the particle size range being normal distribution and the particle size range being 100-600 nanometers), drying at 120 ℃, cooling to room temperature (here, 25 ℃), putting the dried silicon dioxide A and the dried silicon dioxide B into a high-speed mixer together, mixing for 5 minutes at the speed of 600 revolutions per minute, putting 1.5 g of vinyl silane coupling agent, mixing for 5 minutes at the speed of 800 revolutions per minute, controlling the temperature of materials in the whole process at 80 ℃, and cooling to the room temperature for later use;
thirdly, dissolving 1.5 g of cumene hydroperoxide, 50 g of silicon dioxide a, silicon dioxide B, 1, 2-polybutadiene A (the vinyl content is 91 percent), 15 g of 1, 2-polybutadiene B (the vinyl content is 45 percent) and 25 g of styrene-butadiene-styrene triblock copolymer in 336 g of dimethylbenzene by stirring at room temperature and mixing to obtain the low dielectric loss composite adhesive;
and fourthly, spraying the low dielectric loss composite adhesive on an epoxy resin substrate, drying at 80 ℃, controlling the thickness of the adhesive layer by controlling the spraying dosage, controlling the thickness of the adhesive layer to be 20 microns after drying in the embodiment, and then carrying out hot pressing on the adhesive layer and 50 microns of copper foil together, wherein the hot pressing temperature is 200 ℃, and the pressure is 1 MPa, so that the peeling strength can be tested. Spraying the low dielectric loss composite adhesive on the polytetrafluoroethylene film, covering another polytetrafluoroethylene film, and hot-pressing together at 200 ℃ under 1 MPa to obtain a sample, wherein the sample can be subjected to thermal expansion coefficient and dielectric property tests.
The dielectric peel strength of the low dielectric loss composite adhesive prepared in the embodiment with copper foil is 0.71N/m (Newton/m), the dielectric loss is 0.0022, and the linear thermal expansion coefficient reaches 3.02 × 10-5℃-1The obtained composite adhesive has good fluidity and can be well filled after the copper foil is corroded (due to electricity)The copper foil will corrode into various complex shapes) to leave a recess.

Claims (4)

1. A method for preparing a low dielectric loss composite adhesive is characterized by comprising the following steps:
firstly, preparing the following components in parts by weight:
(1) 1, 2-polybutadiene A having a vinyl content of greater than or equal to 90%: 50
(2) 1, 2-polybutadiene B having a vinyl content of 40% to 80%: 5 to 15
(3) Styrene-butadiene-styrene triblock copolymer: 5 to 35
(4) Silicon dioxide A with the particle size of 1-5 microns: 25 to 70
(5) Silica B with a particle size of 100-600 nm: 10 to 50
(6) Cumene hydroperoxide: 1.5 to 5
(7) Vinyl silane coupling agent: 0.6 to 1.5
Secondly, drying the silicon dioxide A and the silicon dioxide B, cooling to room temperature, then treating with a vinyl silane coupling agent, and drying;
thirdly, dissolving the 1, 2-polybutadiene A, 1, 2-polybutadiene B and the styrene-butadiene-styrene triblock copolymer in a good solvent, and stirring and dissolving to obtain a uniform solution of the 1, 2-polybutadiene A, 1, 2-polybutadiene B and the styrene-butadiene-styrene triblock copolymer;
and fourthly, adding cumene hydroperoxide and silicon dioxide A and silicon dioxide B which are treated by the vinyl silane coupling agent and dried in the second step into the uniform solution of the triblock copolymer of the 1, 2-polybutadiene A, the 1, 2-polybutadiene B and the styrene-butadiene-styrene in the third step, stirring and mixing to obtain the low dielectric loss composite adhesive.
2. The method of claim 1, wherein in the first step, the ratio of 1, 2-polybutadiene a, 1, 2-polybutadiene B, styrene-butadiene-styrene triblock copolymer, silica a, silica B, cumene hydroperoxide, and vinyl silane coupling agent is 50: 5: 20: 60: 30: 1.5: 1.5.
3. the method of claim 1, wherein in the first step, the ratio of 1, 2-polybutadiene a, 1, 2-polybutadiene B, styrene-butadiene-styrene triblock copolymer, silica a, silica B, cumene hydroperoxide, and vinyl silane coupling agent is 50: 10: 15: 70: 10: 2: 0.8.
4. the method of claim 1, wherein in the first step, the ratio of 1, 2-polybutadiene a, 1, 2-polybutadiene B, styrene-butadiene-styrene triblock copolymer, silica a, silica B, cumene hydroperoxide, and vinyl silane coupling agent is 50: 15: 25: 60: 30: 1.5: 1.5.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105130274A (en) * 2015-07-15 2015-12-09 中国电子科技集团公司第四十六研究所 High-thermal-stability microwave composite dielectric substrate and preparation method thereof
CN107090065A (en) * 2017-06-22 2017-08-25 陕西生益科技有限公司 High frequency resin composition and its application in prepreg and metal-clad laminate
CN107964203A (en) * 2017-12-26 2018-04-27 浙江华正新材料股份有限公司 A kind of low dielectric prepreg composition, copper-clad plate and preparation method thereof
JP2018095749A (en) * 2016-12-14 2018-06-21 味の素株式会社 Resin composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105130274A (en) * 2015-07-15 2015-12-09 中国电子科技集团公司第四十六研究所 High-thermal-stability microwave composite dielectric substrate and preparation method thereof
JP2018095749A (en) * 2016-12-14 2018-06-21 味の素株式会社 Resin composition
CN107090065A (en) * 2017-06-22 2017-08-25 陕西生益科技有限公司 High frequency resin composition and its application in prepreg and metal-clad laminate
CN107964203A (en) * 2017-12-26 2018-04-27 浙江华正新材料股份有限公司 A kind of low dielectric prepreg composition, copper-clad plate and preparation method thereof

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