CN116162342A - Prepreg, circuit substrate and printed circuit board - Google Patents
Prepreg, circuit substrate and printed circuit board Download PDFInfo
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- CN116162342A CN116162342A CN202111415359.1A CN202111415359A CN116162342A CN 116162342 A CN116162342 A CN 116162342A CN 202111415359 A CN202111415359 A CN 202111415359A CN 116162342 A CN116162342 A CN 116162342A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- Microelectronics & Electronic Packaging (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to a prepreg, which comprises glass fiber cloth and a resin composition attached to the glass fiber cloth, wherein the resin composition comprises polyphenyl ether resin, dielectric filler and a curing agent, wherein the tail end of a molecular chain of the polyphenyl ether resin is replaced by carbon-carbon unsaturated double bonds, more than 2 unsaturated double bonds are arranged in the molecular chain of the curing agent, the dielectric filler is selected from inorganic nonmetallic oxides, the purity is greater than or equal to 99.98%, and the mass fraction of the inorganic nonmetallic oxides in the glass fiber cloth is greater than or equal to 67%; the mass fraction of the resin composition in the prepreg is 30% or more, and the dielectric filler is used in an amount of 30 to 250 parts by weight based on 100 parts by weight of the polyphenylene ether resin. The invention also relates to a circuit substrate and a printed circuit board. The Dk=2.5-4.0 and Df < 0.002 of the circuit board prepared by the prepreg of the invention are simple in processing and low in cost when being used for preparing the printed circuit board.
Description
Technical Field
The invention relates to the technical field of electronic industry, in particular to a prepreg, a circuit substrate and a printed circuit board.
Background
In order to make the circuit substrate have low dielectric loss and stable dielectric constant, and meet the use requirement of the 5G field, the conventional technology generally uses a fluorine-containing resin with low dielectric loss as a resin base material of the dielectric layer. However, the circuit board has problems in that drilling and copper plating are difficult in manufacturing a Printed Circuit Board (PCB) due to the characteristics of the fluorine-containing resin itself, and in that a special manufacturing apparatus is required, there is also a problem in that the cost is excessively high. Therefore, the application field of the circuit substrate is limited.
Disclosure of Invention
Based on this, it is necessary to provide a prepreg, a circuit board and a printed circuit board in order to solve the above-mentioned problems; the circuit substrate prepared from the prepreg has low dielectric loss and stable dielectric constant, and is simple to process and low in cost when used for preparing a printed circuit board.
A prepreg comprising a glass fiber cloth and a resin composition attached to the glass fiber cloth, the resin composition comprising a polyphenylene ether resin, a dielectric filler and a curing agent, wherein the terminal of the molecular chain of the polyphenylene ether resin is substituted by a carbon-carbon unsaturated double bond, the molecular chain of the curing agent has more than 2 unsaturated double bonds, the dielectric filler is selected from inorganic nonmetallic oxides, the purity is greater than or equal to 99.98%, and the mass fraction of the inorganic nonmetallic oxides in the glass fiber cloth is greater than or equal to 67%;
the mass fraction of the resin composition in the prepreg is greater than or equal to 30%, and the dielectric filler is used in an amount of 30 to 250 parts by weight based on 100 parts by weight of the polyphenylene ether resin in the resin composition.
In one embodiment, the mass fraction of the resin composition in the prepreg is 40% -80%.
In one embodiment, the polyphenylene ether resin has a weight average molecular weight of 1000 to 4000.
In one embodiment, the molecular chain of the curing agent further comprises an aromatic ring or an aromatic heterocyclic ring, and the weight average molecular weight of the curing agent is 100-4000.
In one embodiment, the dielectric filler comprises at least one of silica, boron oxide.
In one embodiment, the dielectric filler has a spheroidization rate of 95% or more, an average particle size of 0.1 μm to 8 μm, and a specific surface area of 6.0m or less 2 /g。
In one embodiment, the glass fiber cloth has a dielectric constant of less than or equal to 5.0 at 10GHz and a dielectric loss of less than or equal to 0.004.
In one embodiment, the surface of the dielectric filler is modified with a first coupling agent;
and/or the surface of the glass fiber cloth is modified with a second coupling agent.
A circuit substrate comprises a dielectric layer and a conductive layer which is laminated on at least one surface of the dielectric layer, wherein the dielectric layer is formed by pressing one or at least two overlapped prepregs.
A printed circuit board, said printed circuit board being made of said circuit substrate.
In the prepreg, the Df of the circuit substrate manufactured by the prepreg is less than 0.002, dk=2.5-4.0 and can be regulated, the dielectric constant is low, and the use requirement of the 5G field is met by combining modification of the polyphenyl ether resin, matching selection of the curing agent, limitation of the content of inorganic nonmetallic oxides in the dielectric filler and the glass fiber cloth, limitation of the mass ratio of the polyphenyl ether resin to the dielectric filler and limitation of the mass fraction of the resin composition in the prepreg.
Therefore, when the circuit substrate is used for preparing the printed circuit board, universal equipment can be used for processing, and the process is simple and low in cost.
Detailed Description
The prepreg, the circuit board and the printed circuit board provided by the invention are further described below.
The prepreg provided by the invention comprises glass fiber cloth and a resin composition attached to the glass fiber cloth, wherein the resin composition comprises polyphenyl ether resin, dielectric filler and curing agent. Thus, by using a polyphenylene ether resin having low dielectric properties and high heat resistance as a resin base material, problems caused by the use of a fluorine-containing resin can be effectively avoided, while the circuit substrate is made to have a low dielectric constant and a low dielectric loss.
In order to provide the circuit substrate with excellent heat resistance and meet the use requirement of the 5G field, the tail end of the molecular chain of the polyphenyl ether resin is further substituted by a carbon-carbon unsaturated double bond. Further, in order to satisfy good processability and good electrical properties of the material, in one embodiment, the polyphenylene ether resin has a weight average molecular weight of 1000 to 4000.
Meanwhile, in order to enable the polyphenylene ether resin to be cured to obtain a circuit substrate having excellent heat resistance and stable dielectric constant and low dielectric loss, the curing agent has 2 or more unsaturated double bonds in a molecular chain, and the unsaturated double bonds are at least one selected from vinyl, vinylbenzyl, acryl, and methacryl.
In one embodiment, the curing agent is selected from trialkenyl isocyanurate compounds such as triallyl isocyanurate (TAIC), polyfunctional methacrylate compounds having 2 or more methacryloyl groups in the molecule, polyfunctional acrylate compounds having 2 or more acryloyl groups in the molecule, vinyl compounds (polyfunctional vinyl compounds) having 2 or more vinyl groups in the molecule such as polybutadiene, and the like, and vinylbenzyl compounds such as styrene and divinylbenzene having vinylbenzyl groups in the molecule. Among them, compounds having 2 or more carbon-carbon double bonds in the molecule, such as at least one of a trialkenyl isocyanurate compound, a polyfunctional acrylate compound, a polyfunctional methacrylate compound, and a polyfunctional vinyl compound, are preferable.
In one embodiment, the mass ratio of the polyphenylene ether resin to the curing agent is 30:70 to 90:10, more preferably 50:50 to 90:10.
Further, in order to ensure good heat resistance of the material, in one embodiment, the molecular chain of the curing agent further comprises an aromatic ring or an aromatic heterocyclic ring, and the weight average molecular weight of the curing agent is 100-4000. The curing agent is at least one selected from trialkenyl isocyanurate compounds such as triallyl isocyanurate and polyfunctional maleimide compounds having 2 or more imide groups in the molecule.
The dielectric constant of the circuit substrate can be controlled by the dielectric filler, but the dielectric properties exhibited by different dielectric fillers are different. The applicant has long and intensive research to find that: when the composition atoms of the dielectric filler mainly exist in a covalent bond form, the polarity is lower, so that the dielectric loss is lower, and the dielectric property is excellent, such as inorganic nonmetallic oxides and the like; the dielectric filler has strong polarity when the constituent atoms mainly exist in the form of ionic bonds, so that the dielectric filler has high dielectric loss and poor dielectric performance, such as metal oxide and the like. Therefore, in order to provide a circuit board with a stable dielectric constant and a low dielectric loss, the resin composition of the present invention is characterized in that the dielectric filler is selected from a covalent bond compound such as an inorganic nonmetallic oxide, specifically, at least one of silica and boron oxide.
However, currently, metal oxide impurities such as alumina, potassium oxide, sodium oxide, calcium oxide, magnesium oxide, ferric oxide and the like exist in commonly used dielectric fillers such as silica, boron oxide and the like, so that covalent bonds and ionic bonds coexist in the dielectric fillers such as silica, boron oxide and the like, which is not beneficial to improving the dielectric constant stability of the circuit substrate and reducing the dielectric loss of the circuit substrate.
Therefore, in order to avoid the influence of metal oxide impurities, the purity of the inorganic nonmetallic oxide dielectric filler such as silica, boron oxide, etc. is required to be 99.98% or more, that is, the mass fraction of the effective components such as silica, boron oxide, etc. is required to be 99.98% or more. It can be understood that the inorganic non-metal oxide dielectric filler with the purity of more than or equal to 99.98 percent can be directly synthesized, and the common inorganic non-metal oxide dielectric filler can be purified to remove impurities such as metal oxide and the like contained in the dielectric filler, so that the purity of the inorganic non-metal oxide dielectric filler reaches more than 99.98 percent.
Further, the dielectric filler has a spheroidization ratio of 95% or more, an average particle diameter of 0.1 μm to 8 μm, preferably 0.5 μm to 5 μm, and a specific surface area of 6.0m or less 2 /g, preferably 3m 2 /g-5.5m 2 And/g. Therefore, the dielectric filler with high spheroidization rate, micro-nano particle size and low specific surface area can ensure that the dielectric filler has good dispersibility in the resin composition, so that the dielectric filler can be uniformly and compactly filled in the dielectric layer, further the uniformity of the dielectric performance of the circuit substrate can be improved, and the dielectric loss of the circuit substrate is reduced. Meanwhile, a high filling rate of the dielectric filler can be achieved, and the adjustable range of the dielectric constant of the circuit substrate is further widened, specifically, the dielectric filler is preferably used in an amount of 30 to 250 parts by weight, more preferably 50 to 250 parts by weight, based on 100 parts by weight of the polyphenylene ether resin.
In an embodiment, the dielectric filler is modified by a first coupling agent, so that the surface of the dielectric filler is modified by the first coupling agent, the first coupling agent comprises at least one of an epoxy silane coupling agent, a silane coupling agent containing carbon-carbon unsaturated double bonds and an amino silane coupling agent, and the mass of the first coupling agent is 0.5% -5%, preferably 0.5% -3% of the mass of the dielectric filler.
After the modification treatment of the first coupling agent, the compatibility of the dielectric filler and the resin composition is better, and the gap in the circuit substrate can be reduced, so that the space charge polarization can be reduced, and the dielectric loss of the circuit substrate is reduced. Furthermore, the dielectric property of the circuit substrate can be improved, the dielectric property degradation of the circuit substrate in the use process can be avoided, the service life of the circuit substrate is prolonged, the use environment of the circuit substrate is expanded, and the circuit substrate can be applied to polar environments such as high humidity, high heat and the like.
In view of substitution of the terminal of the molecular chain of the polyphenylene ether resin with a carbon-carbon unsaturated double bond, the first coupling agent for modifying the dielectric filler is preferably a carbon-carbon unsaturated double bond-containing silane coupling agent, specifically including at least one of a vinyl-based silane coupling agent and a methacrylic-based silane coupling agent, to better improve the dielectric properties of the circuit substrate.
Similarly, by increasing the mass fraction of inorganic nonmetallic oxides such as silicon dioxide, boron oxide and the like in the components of the glass fiber yarn, the overall dielectric property of the glass fiber cloth can be improved, and the dielectric loss of the glass fiber cloth itself can be reduced, so that the content of the inorganic nonmetallic oxides in the glass fiber cloth is required to be greater than or equal to 67%. In order to ensure the mechanical property and dielectric property of the circuit substrate, further, the content of silicon dioxide in the glass fiber cloth is more than or equal to 52%. Specifically, the glass fiber cloth is preferably at least one of a D-glass fiber cloth, an NE-glass fiber cloth and a Q-glass fiber cloth.
In order to further reduce the dielectric loss of the circuit substrate, in an embodiment, the dielectric constant of the glass fiber cloth at 10GHz is less than or equal to 5.0, and the dielectric loss is less than or equal to 0.004, and the glass fiber cloth is further preferably NE-glass fiber cloth or Q-glass fiber cloth.
In an embodiment, the glass fiber cloth is modified by a second coupling agent, so that the surface of the glass fiber cloth is modified by the second coupling agent, the second coupling agent comprises at least one of an epoxy silane coupling agent, a silane coupling agent containing carbon-carbon unsaturated double bonds and an amino silane coupling agent, and the mass of the second coupling agent is 0.5% -5%, preferably 0.5% -3% of the mass of the glass fiber cloth. Also, the second coupling agent is preferably a silane coupling agent containing a carbon-carbon unsaturated double bond, and specifically includes at least one of a vinyl-based silane coupling agent and a methacrylic-based silane coupling agent.
It can be understood that after the glass fiber cloth is modified by the second coupling agent, the dielectric property of the circuit substrate can be further improved, the deterioration of the dielectric property of the circuit substrate in the use process can be avoided, the service life of the circuit substrate is prolonged, and the use environment of the circuit substrate is expanded.
In order to ensure the impregnation property of the prepreg and the electrical property and reliability of the material, the mass fraction of the resin composition in the prepreg is more than or equal to 30%, and more preferably 40% -80%.
The invention also provides a circuit substrate which comprises a dielectric layer and a conductive layer which is laminated on at least one surface of the dielectric layer, wherein the dielectric layer is formed by pressing one or at least two laminated prepregs.
Specifically, the conductive layer is preferably copper foil, so that a copper-clad plate is obtained.
According to the prepreg, the polyphenyl ether resin is modified, the curing agent is matched and selected, the contents of inorganic nonmetallic oxides in the dielectric filler and the glass fiber cloth are limited, the mass ratio of the polyphenyl ether resin to the dielectric filler is limited, and the mass fraction of the resin composition in the prepreg is limited, so that the Df of a circuit substrate manufactured by the prepreg is less than 0.002, dk=2.5-4.0, the regulation and control can be performed according to the requirement, the dielectric constant is low in dielectric loss and stable, and the use requirement of the 5G field is met.
The invention also provides a printed circuit board which is made of the circuit substrate. Specifically, the process flow comprises the following steps: drilling, hole forming, microetching, presoaking, activating, accelerating, chemical copper and thickening copper.
Because the resin base material of the circuit substrate is polyphenyl ether resin, when the circuit substrate is used for preparing a printed circuit board, universal equipment can be used for processing, and the process is simple and the cost is low.
Hereinafter, the prepreg, the circuit board, and the printed circuit board will be further described by the following specific examples.
In the following examples, the first glass cloth was NE-glass cloth; the second glass fiber cloth is Q-glass fiber cloth; and E-glass fiber cloth is arranged in the third glass fiber cloth.
In the following examples, the first polyphenylene ether resin was a polyphenylene ether resin terminated at the end with a carbon-carbon unsaturated double bond, and had a molecular weight of 2500; the second polyphenyl ether resin is polyphenyl ether resin with the tail end blocked by a carbon-carbon unsaturated double bond, and the molecular weight is 4000; the third polyphenylene ether resin is polyphenylene ether resin with the tail end blocked by a carbon-carbon unsaturated double bond, and the molecular weight is 1000; the fourth polyphenylene ether resin was a hydroxyl-terminated polyphenylene ether having a molecular weight of 2500.
In the following examples, the first curative is melamine isocyanurate and has a molecular weight of 300; the second curing agent is polybutadiene resin with a molecular weight of 3000; the third curing agent is polybutadiene resin with the molecular weight of 1000; the fourth curing agent is a maleimide compound with a molecular weight of 3000; the fifth curing agent is hydroxyl-terminated modified polyphenyl ether.
In the following examples, the first filler was silica, having a purity of 99.99%, a spheroidization rate of 98%, an average particle diameter of 5.0 μm and a specific surface area of 3.0m 2 /g; the second filler is silicon dioxide with the purity of 99.99%, the spheroidization rate of 97%, the average grain diameter of 3.0 μm and the specific surface area of 4.0m 2 /g; the third filler is silicon dioxide with the purity of 99.99%, the spheroidization rate of 96%, the average grain diameter of 1.0 μm and the specific surface area of 4.8m 2 /g; the fourth filler is silicon dioxide, the purity is 99.99%, the spheroidization rate is 95%, the average grain diameter is 0.5 μm, and the specific surface area is 5.5m 2 /g; the fifth filler is boron oxide with purity of 99.99%, spheroidization rate of 97.5%, average particle size of 0.8 μm and specific surface area of 5.2m 2 /g; the sixth filler is silicon dioxide, the purity is 99.99%, the spheroidization rate is 99%, the average grain diameter is 4.0 μm, and the specific surface area is 3.5m 2 /g; the seventh filler is boron oxide with purity of 99.99%, spheroidization rate of 97%, average grain diameter of 2.5 μm and specific surface area of 4.5m 2 /g; the eighth filler is silicon dioxide, the purity is 80%, the spheroidization rate is 99%, the average grain diameter is 5 μm, and the specific surface area is 3m 2 /g; the ninth filler is silicon dioxide with the purity of 99.99%, the spheroidization rate of 60%, the average grain diameter of 5 μm and the specific surface area of 8m 2 /g。
In the following examples, coupling agent A is a vinyltriethoxysilane coupling agent and coupling agent B is a 3- (trimethoxysilyl) propyl methacrylate coupling agent;
example 1
And (3) regulating 100 parts by weight of the first polyphenyl ether resin, 100 parts by weight of the second curing agent and 100 parts by weight of the first filler to a proper viscosity by using a xylene solvent, and uniformly stirring and mixing to uniformly disperse the dielectric filler in the first polyphenyl ether resin to prepare the glue solution.
Then the glue solution is impregnated by a first glass fiber cloth, and the prepreg which is not sticky is prepared after the solvent is removed by drying, wherein the mass fraction of the resin composition in the prepreg is 65%.
Laminating six prepregs, coating copper foil with thickness of 1oz on two sides, and performing programmed heating solidification in a high-temperature vacuum press under solidification pressure of 60kg/cm 2 The curing temperature is 170 ℃, the curing time is 2 hours, and then the circuit substrate is manufactured by heating to 270 ℃ and then curing for 1 hour.
Example 2
Example 2 differs from example 1 only in that both the first filler and the first glass cloth were modified with 3% of the coupling agent a.
Example 3
Example 3 differs from example 2 only in that a second glass cloth was used instead of the first glass cloth.
Example 4
Example 4 differs from example 3 only in that the first curing agent is used instead of the second curing agent.
Example 5
Example 5 differs from example 3 only in that a fourth curing agent is used instead of the second curing agent.
Example 6
And (3) regulating 100 parts by weight of the first polyphenyl ether resin, 65 parts by weight of the second curing agent and 50 parts by weight of the second filler to a proper viscosity by using a xylene solvent, and uniformly stirring and mixing to uniformly disperse the dielectric filler in the first polyphenyl ether resin to prepare the glue solution. Wherein the second filler is modified by 3% of coupling agent A.
The first glass fiber cloth is modified by 3% of coupling agent A, then the first glass fiber cloth is impregnated with the glue solution, and then the prepreg which is not sticky to hands is prepared after drying and removing the solvent, wherein the mass fraction of the resin composition in the prepreg is 55%.
Laminating six prepregs, coating copper foil with thickness of 1oz on two sides, and performing programmed heating solidification in a high-temperature vacuum press under solidification pressure of 60kg/cm 2 The curing temperature is 170 ℃, the curing time is 2 hours, and then the circuit substrate is manufactured by heating to 270 ℃ and then curing for 1 hour.
Example 7
And (3) regulating 100 parts by weight of the second polyphenyl ether resin, 45 parts by weight of the third curing agent and 30 parts by weight of the third filler to a proper viscosity by using a xylene solvent, and uniformly stirring and mixing to uniformly disperse the dielectric filler in the second polyphenyl ether resin to prepare the glue solution. Wherein the third filler is modified by 3% of coupling agent A.
The first glass fiber cloth is modified by 3% of coupling agent A, then is immersed in the glue solution, and is dried to remove the solvent to obtain the prepreg which is not sticky to hands, wherein the mass fraction of the resin composition in the prepreg is 70%.
Laminating six prepregs, coating copper foil with thickness of 1oz on two sides, and performing programmed heating solidification in a high-temperature vacuum press under solidification pressure of 60kg/cm 2 The curing temperature is 170 ℃, the curing time is 2 hours, and then the circuit substrate is manufactured by heating to 270 ℃ and then curing for 1 hour.
Example 8
And (3) regulating 100 parts by weight of the second polyphenyl ether resin, 25 parts by weight of the fourth curing agent and 150 parts by weight of the fourth filler to a proper viscosity by using a xylene solvent, and uniformly stirring and mixing to uniformly disperse the dielectric filler in the second polyphenyl ether resin to prepare the glue solution. Wherein the fourth filler is modified by 3% of coupling agent B.
The first glass fiber cloth is modified by 3% of coupling agent B, then is immersed in the glue solution, and is dried to remove the solvent to obtain the prepreg which is not sticky to hands, wherein the mass fraction of the resin composition in the prepreg is 67%.
Laminating six prepregs, coating copper foil with thickness of 1oz on two sides, and performing programmed heating solidification in a high-temperature vacuum press under solidification pressure of 60kg/cm 2 The curing temperature is 170 ℃, the curing time is 2 hours, and then the circuit substrate is manufactured by heating to 270 ℃ and then curing for 1 hour.
Example 9
And (3) regulating 100 parts by weight of the first polyphenyl ether resin, 50 parts by weight of the second curing agent and 200 parts by weight of the fifth filler to a proper viscosity by using a xylene solvent, and uniformly stirring and mixing to uniformly disperse the dielectric filler in the polyphenyl ether resin to prepare the glue solution. Wherein the fifth filler is modified by 3% of coupling agent B.
The first glass fiber cloth is modified by 3% of a coupling agent B, then the glue solution is soaked, and the prepreg which is not sticky to hands is prepared after drying and removing the solvent, wherein the mass fraction of the resin composition in the prepreg is 62%.
Laminating six prepregs, coating copper foil with thickness of 1oz on two sides, and performing programmed heating solidification in a high-temperature vacuum press under solidification pressure of 60kg/cm 2 The curing temperature is 170 ℃, the curing time is 2 hours, and then the circuit substrate is manufactured by heating to 270 ℃ and then curing for 1 hour.
Example 10
And (3) adjusting 100 parts by weight of third polyphenyl ether resin, 80 parts by weight of second curing agent and 250 parts by weight of sixth filler to a proper viscosity by using a xylene solvent, and uniformly stirring and mixing to uniformly disperse the dielectric filler in the polyphenyl ether resin to prepare the glue solution. Wherein the sixth filler is modified by 3% of coupling agent A.
The first glass fiber cloth is modified by 3% of coupling agent A, then is immersed in the glue solution, and is dried to remove the solvent to obtain the prepreg which is not sticky to hands, wherein the mass fraction of the resin composition in the prepreg is 50%.
Laminating six prepregs, coating copper foil with thickness of 1oz on two sides, and performing programmed heating solidification in a high-temperature vacuum press under solidification pressure of 60kg/cm 2 The curing temperature is 170 ℃, the curing time is 2 hours, and then the circuit substrate is manufactured by heating to 270 ℃ and then curing for 1 hour。
Example 11
And (3) regulating 100 parts by weight of the first polyphenyl ether resin, 70 parts by weight of the second curing agent and 120 parts by weight of the seventh filler to a proper viscosity by using a xylene solvent, and uniformly stirring and mixing to uniformly disperse the dielectric filler in the polyphenyl ether resin to prepare the glue solution. Wherein the seventh filler is modified by 3% of coupling agent A.
The first glass fiber cloth is modified by 3% of coupling agent A, then is immersed in the glue solution, and is dried to remove the solvent to obtain the prepreg which is not sticky to hands, wherein the mass fraction of the resin composition in the prepreg is 65%.
Laminating six prepregs, coating copper foil with thickness of 1oz on two sides, and performing programmed heating solidification in a high-temperature vacuum press under solidification pressure of 60kg/cm 2 The curing temperature is 170 ℃, the curing time is 2 hours, and then the circuit substrate is manufactured by heating to 270 ℃ and then curing for 1 hour.
Comparative example 1
Comparative example 1 differs from example 1 only in that a fourth polyphenylene ether resin was used instead of the first polyphenylene ether resin.
Comparative example 2
Comparative example 2 differs from example 1 only in that a fifth curing agent was used instead of the second curing agent.
Comparative example 3
Comparative example 3 differs from example 1 only in that an eighth filler was used instead of the first filler.
Comparative example 4
Comparative example 4 differs from example 1 only in that a ninth filler was used instead of the first filler.
Comparative example 5
Comparative example 5 differs from example 1 only in that a third glass fiber cloth was used instead of the first glass fiber cloth.
Comparative example 6
Comparative example 6 differs from example 1 only in that the mass fraction of the resin composition in the prepreg is 25%.
The circuit substrates of examples 1 to 11 and comparative examples 1 to 6 were subjected to performance test, and the results are shown in Table 1.
The dielectric constant and dielectric loss were measured by a network analyzer using a dielectric constant (Dk) and dielectric loss tangent (Df) of a base laminate at 10GHz by a split dielectric resonator method using a laminate obtained by removing copper foil from the above-mentioned circuit board as an evaluation board.
TABLE 1
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The prepreg is characterized by comprising glass fiber cloth and a resin composition attached to the glass fiber cloth, wherein the resin composition comprises polyphenyl ether resin, dielectric filler and curing agent, wherein the tail end of a molecular chain of the polyphenyl ether resin is replaced by carbon-carbon unsaturated double bonds, more than 2 unsaturated double bonds are arranged in the molecular chain of the curing agent, the dielectric filler is selected from inorganic nonmetallic oxides, the purity is greater than or equal to 99.98%, and the mass fraction of the inorganic nonmetallic oxides in the glass fiber cloth is greater than or equal to 67%;
the mass fraction of the resin composition in the prepreg is greater than or equal to 30%, and the dielectric filler is used in an amount of 30 to 250 parts by weight based on 100 parts by weight of the polyphenylene ether resin in the resin composition.
2. The prepreg according to claim 1, wherein the mass fraction of the resin composition in the prepreg is 40-80%.
3. The prepreg according to claim 1, wherein the polyphenylene ether resin has a weight average molecular weight of 1000 to 4000.
4. The prepreg according to claim 1, wherein the curing agent further comprises an aromatic or heteroaromatic ring in the molecular chain, and the weight average molecular weight of the curing agent is 100-4000.
5. The prepreg of claim 1, wherein the dielectric filler comprises at least one of silica, boron oxide.
6. The prepreg according to claim 1, wherein the dielectric filler has a spheroidization ratio of 95% or more, an average particle diameter of 0.1 μm to 8 μm, and a specific surface area of 6.0m or less 2 /g。
7. The prepreg of claim 1, wherein the glass fiber cloth has a dielectric constant of less than or equal to 5.0 at 10GHz and a dielectric loss of less than or equal to 0.004.
8. The prepreg of claim 1, wherein the dielectric filler has a surface modified with a first coupling agent;
and/or the surface of the glass fiber cloth is modified with a second coupling agent.
9. A circuit substrate comprising a dielectric layer and a conductive layer laminated on at least one surface of the dielectric layer, wherein the dielectric layer is formed by pressing one or at least two laminated prepregs according to any one of claims 1 to 8.
10. A printed circuit board, characterized in that the printed circuit board is made of the circuit substrate of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111415359.1A CN116162342A (en) | 2021-11-25 | 2021-11-25 | Prepreg, circuit substrate and printed circuit board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111415359.1A CN116162342A (en) | 2021-11-25 | 2021-11-25 | Prepreg, circuit substrate and printed circuit board |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116162342A true CN116162342A (en) | 2023-05-26 |
Family
ID=86415143
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111415359.1A Pending CN116162342A (en) | 2021-11-25 | 2021-11-25 | Prepreg, circuit substrate and printed circuit board |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116162342A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118955107A (en) * | 2024-10-16 | 2024-11-15 | 浙江华正新材料股份有限公司 | Ceramics and their preparation methods and applications |
-
2021
- 2021-11-25 CN CN202111415359.1A patent/CN116162342A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118955107A (en) * | 2024-10-16 | 2024-11-15 | 浙江华正新材料股份有限公司 | Ceramics and their preparation methods and applications |
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