CN113881171A - Resin composition, adhesive sheet, circuit board, and printed wiring board - Google Patents

Resin composition, adhesive sheet, circuit board, and printed wiring board Download PDF

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Publication number
CN113881171A
CN113881171A CN202111155535.2A CN202111155535A CN113881171A CN 113881171 A CN113881171 A CN 113881171A CN 202111155535 A CN202111155535 A CN 202111155535A CN 113881171 A CN113881171 A CN 113881171A
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dielectric filler
modified
dielectric
resin composition
filler
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何亮
董辉
任英杰
卢悦群
韩梦娜
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Hangzhou Wazam New Materials Co ltd
Zhuhai Huazheng New Material Co ltd
Zhejiang Huazheng New Material Group Co ltd
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Hangzhou Wazam New Materials Co ltd
Zhuhai Huazheng New Material Co ltd
Zhejiang Huazheng New Material Group Co ltd
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Priority to CN202111155535.2A priority Critical patent/CN113881171A/en
Publication of CN113881171A publication Critical patent/CN113881171A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • 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
    • H05K1/036—Multilayers with layers of different types
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a resin composition, which comprises fluorine-containing resin, a dielectric filler, a dispersant and water, wherein the dielectric filler comprises a modified first dielectric filler and a modified second dielectric filler, the mass fraction of the modified first dielectric filler in the dielectric filler is more than or equal to 50%, the dielectric constant of the first dielectric filler is less than or equal to 10, the dielectric constant of the first dielectric filler is less than that of the second dielectric filler, the difference value is more than 80, the oleophilic degrees of the modified first dielectric filler and the modified second dielectric filler are respectively and independently selected from 25-45%, and the absolute value of Zeta potential of the resin composition is 20mV-40 mV. The invention also relates to the film, the circuit substrate and the printed circuit board. The circuit substrate made of the resin composition has a dielectric constant of 3-12 at 10GHz, the absolute value of TCDk of the circuit substrate is less than or equal to 50 ppm/DEG C, and the range difference of TCDk is less than or equal to 10%, so that the circuit substrate can meet the use requirements under extreme conditions of high temperature, high humidity and the like.

Description

Resin composition, adhesive sheet, circuit board, and printed wiring board
Technical Field
The present invention relates to the technical field of electronic industry, and more particularly, to a resin composition, a film, a circuit board, and a printed circuit board.
Background
In the dielectric layer of the conventional high frequency circuit board, the fluorine-containing resin with excellent performance and low loss is generally used as the polymer base material, but the Dk of the fluorine-containing resin is low, and in order to meet various special use requirements, a large amount of dielectric filler needs to be added so as to enable the circuit board to have a high dielectric constant (Dk). However, the dielectric fillers have a relatively high temperature coefficient of dielectric constant (TCDk), so that when the circuit substrate meets the requirement of high Dk, the Dk varies greatly with temperature, usually reaching 200 ppm/deg.c or even higher, which results in unstable performance of the circuit substrate at a wide operating temperature and a wide operating humidity, and thus cannot meet higher application requirements.
Disclosure of Invention
In view of this, it is necessary to provide a resin composition, a prepreg, a circuit substrate and a printed circuit board, the circuit substrate made of the resin composition having a dielectric constant of 3 to 12 at 10GHz, the absolute value of TCDk of the circuit substrate being 50 ppm/deg.c or less, the range of TCDk being 10% or less.
A resin composition comprises a fluorine-containing resin, a dielectric filler, a dispersant and water, wherein the dielectric filler comprises a modified first dielectric filler and a modified second dielectric filler, the mass fraction of the modified first dielectric filler in the dielectric filler is greater than or equal to 50%, the dielectric constant of the first dielectric filler is less than or equal to 10, the dielectric constant of the first dielectric filler is less than that of the second dielectric filler, the difference value is more than 80, the oleophilic degrees of the modified first dielectric filler and the modified second dielectric filler are respectively and independently selected from 25% -45%, and the absolute value of Zeta potential of the resin composition is 20mV-40 mV.
In one embodiment, the dielectric constant of the second dielectric filler is greater than 80.
In one embodiment, the modified first dielectric filler is present in an amount of 10 to 100 parts by weight and the modified second dielectric filler is present in an amount of 10 to 100 parts by weight, based on 100 parts by weight of the fluorine-containing resin.
In one embodiment, the modified first dielectric filler is present in the dielectric filler in an amount greater than or equal to 60% by weight.
In one embodiment, the modified first dielectric filler is present in the dielectric filler in an amount greater than or equal to 70% by weight.
In one embodiment, the modified first dielectric filler is present in the dielectric filler in an amount greater than or equal to 75% by weight.
In one embodiment, the first dielectric filler comprises at least one of silicon dioxide, aluminum oxide, magnesium oxide, boron oxide, aluminum nitride, and silicon carbide.
In one embodiment, the second dielectric filler includes at least one of titanium dioxide, strontium titanate, barium titanate, and barium strontium titanate.
In one embodiment, the mass of the dispersant is 0.1% -1% of the sum of the mass of the modified first dielectric filler and the mass of the modified second dielectric filler, and the hydrophilic-lipophilic balance value of the dispersant is 5-15.
A film is made of the resin composition.
A circuit substrate comprises a dielectric layer and a conductive layer arranged on at least one surface of the dielectric layer, wherein the dielectric layer is formed by pressing one or at least two overlapped films.
A printed circuit board is manufactured by the circuit substrate.
In the resin composition, the first dielectric filler and the second dielectric filler are compounded and used through different dielectric constant ranges and the difference value of the first dielectric filler and the second dielectric filler reaches more than 30, the first dielectric filler and the second dielectric filler are simultaneously oleophilic modified, the range of the oleophilic degree of the first dielectric filler and the second dielectric filler is limited, and the dispersant is used for assisting dispersion, so that the absolute value of the Zeta potential of the resin composition is stabilized to be 20mV-40mV, the modified first dielectric filler and the modified second dielectric filler can be uniformly and stably dispersed in the resin composition, the density of a circuit substrate is improved, and the use of the second dielectric filler can be reduced.
Furthermore, the circuit substrate made of the resin composition has a dielectric constant of 3-12 at 10GHz, the absolute value of TCDk of the circuit substrate is less than or equal to 50 ppm/DEG C, and the range difference of TCDk is less than or equal to 10%, so that the circuit substrate has high Dk and is adjustable, the performance is stable under wide working temperature and wide working humidity, and the use requirements under extreme conditions of high temperature, high humidity and the like can be met.
Detailed Description
The resin composition, the prepreg, the circuit board and the printed wiring board according to the present invention will be further described below.
The resin composition provided by the invention is mainly used for preparing a film and then preparing a dielectric layer in a circuit substrate based on the film.
Specifically, the resin composition mainly includes a fluorine-containing resin, a dielectric filler, a dispersant, and water.
In one embodiment, the fluorine-containing resin includes at least one of a polytetrafluoroethylene resin, a tetrafluoroethylene-hexafluoropropylene copolymer resin, a tetrafluoroethylene-ethylene copolymer resin, a copolymer resin of tetrafluoroethylene and perfluoro (alkyl vinyl) ether, a vinylidene fluoride and ethylene-ethylene tetrafluoroethylene copolymer resin, and a polyvinylidene fluoride resin.
In one embodiment, the fluorine-containing resin is preferably a polytetrafluoroethylene resin, because the polytetrafluoroethylene resin has the most symmetrical molecular structure, non-polar molecules, and the most excellent dielectric properties, i.e., the least dielectric constant and dielectric loss.
Since the Dk of the fluorine-containing resin is low, the Dk of the circuit substrate needs to be improved by adding high Dk dielectric fillers, and the absolute value of TCDk of the dielectric fillers is high, so that the addition of too much dielectric fillers can cause great difference of TCDk characteristics of the circuit substrate, and the performance stability of the circuit substrate is influenced.
Therefore, in order to stabilize the performance of the circuit substrate under a wide operating temperature and a wide operating humidity, the dielectric filler of the present invention includes a modified first dielectric filler and a modified second dielectric filler. Wherein the first dielectric filler has a Dk of 10 or less, more preferably 5 or less, and a TCDk of between 10 ppm/deg.c and 100 ppm/deg.c; the Dk of the second dielectric filler is greater than the Dk of the first dielectric filler by a difference of 80 or more, preferably 90 or more, more preferably 100 or more, specifically, the Dk of the second dielectric filler is preferably greater than 80, more preferably greater than or equal to 90, more preferably greater than or equal to 100, and the TCDk of the second dielectric filler in the Dk range is less than 0 ppm/deg.c. Therefore, the absolute value of TCDk and the range of the TCDk of the circuit substrate made of the resin composition can be effectively reduced by compounding the first dielectric filler and the second dielectric filler which have different dielectric constant ranges and have a difference value of more than 30.
In one embodiment, the first dielectric filler comprises at least one of silicon dioxide (Dk: 2.0), aluminum oxide (Dk: 6.5), magnesium oxide (Dk: 9.7), boron nitride (Dk: 5.1), aluminum nitride (Dk: 8.5), silicon carbide (Dk: 9.8), preferably silicon dioxide; the second dielectric filler includes at least one of titanium dioxide (Dk: 90), strontium titanate (Dk: 100), barium strontium titanate (Dk: 110), preferably titanium dioxide.
The applicant has found through long-term and intensive studies that the second dielectric filler has a greater influence on TCDk of the circuit board than the first dielectric filler, and therefore, if the dispersibility and stability of the first and second dielectric fillers in the resin composition can be improved based on the combined use of the first and second dielectric fillers, the density of the dielectric layer can be increased, the amount of the second dielectric filler used can be reduced, and the absolute value of TCDk and the range difference of TCDk of the circuit board made of the resin composition can be further reduced. Therefore, the first dielectric filler and the second dielectric filler are respectively modified.
In one embodiment, the modified first dielectric filler includes a first dielectric filler and a first coupling agent modified on a surface of the first dielectric filler, and the modified second dielectric filler includes a second dielectric filler and a second coupling agent modified on a surface of the second dielectric filler. Wherein the first coupling agent and the second coupling agent are independently selected from at least one of silane coupling agent, titanate coupling agent and fluorine-containing coupling agent.
Considering that the resin in the resin composition is a fluorine-containing resin, in one embodiment, both the first coupling agent and the second coupling agent are preferably fluorine-containing coupling agents including at least one of (3,3, 3-trifluoropropyl) methyldichlorosilane, (3,3, 3-trifluoropropyl) methyldimethoxysilane, (3,3, 3-trifluoropropyl) methyldiethoxysilane, 1,3, 5-trimethyl-1, 3, 5-tris (3,3, 3-trifluoropropyl) -cyclotrisiloxane, perfluorodecyltrimethoxysilane, perfluorodecanoyltrimethoxysilane, perfluorooctyltrimethoxysilane, and perfluorodecyltriethoxysilane.
It should be noted that Dk and TCDk of the modified first dielectric filler are substantially the same as Dk and TCDk of the first dielectric filler and remain unchanged, and Dk and TCDk of the modified second dielectric filler are substantially the same as Dk and TCDk of the second dielectric filler and remain unchanged.
Specifically, the modified first dielectric filler may be obtained with reference to the following modification method:
firstly, the first dielectric filler is treated by adopting a physical ball milling mode, so that the soft agglomerated first dielectric filler is separated, and the ball milling effect can be controlled by controlling the ball milling time and frequency and the particle size of zirconia beads in the ball milling process.
And secondly, uniformly mixing the first coupling agent and absolute ethyl alcohol to obtain a mixed solution, wherein the mass ratio of the first coupling agent to the absolute ethyl alcohol is 1:1-1:1.5, so as to avoid poor modification effect caused by insufficient quantity of the first coupling agent grafted on the first dielectric filler due to insufficient quantity of the first coupling agent, or avoid agglomeration caused by self condensation of redundant first coupling agent after the first coupling agent grafted on the surface of the first dielectric filler is saturated due to excessive quantity of the first coupling agent.
And thirdly, adding acidic solutions such as formic acid and the like into water to adjust the pH value to 2.5-4, adding the first dielectric filler, stirring, and adding the mixed solution in a dropwise and equally batch manner to avoid self condensation of the first coupling agent without grafting onto the first dielectric filler due to too low pH value, or preventing the first coupling agent from being hydrolyzed at a relatively slow rate but at a fast rate due to too high pH value to form silanol, namely, the silanol undergoes self condensation reaction to form oligomer, and the silanol undergoes little reaction with silicon hydroxyl on the surface of the first dielectric filler, so that the grafting rate is low.
Further, when the mixed solution is mixed with the first dielectric filler, the first dielectric filler can be fully contacted with the first coupling agent through ball milling, so that the effect that the first coupling agent wraps the first dielectric filler is achieved.
It is understood that the modification method of the second dielectric filler may refer to the modification method of the first dielectric filler, and the first dielectric filler and the second dielectric filler may be modified simultaneously or separately.
Degree of oleophilic transformation
Figure BDA0003288318830000061
The value can be used as the standard for judging the modification effect, and the degree of oleophilicity
Figure BDA0003288318830000062
The larger the value, the better the hydrophobic properties, wherein the degree of oleophilicity
Figure BDA0003288318830000065
The values are calculated as: the degree of oleophilic was determined by placing the modified first dielectric filler or the modified second dielectric filler in 50mL of water at V2, adding a solvent thereto until the modified first dielectric filler or the modified second dielectric filler was completely wetted, and recording the amount of solvent added, V1(mL)
Figure BDA0003288318830000064
The value can be represented by
Figure BDA0003288318830000063
And (6) obtaining.
In the present invention, the degree of oleophilicity of the modified first dielectric filler and the modified second dielectric filler is calculated according to the above formula
Figure BDA0003288318830000066
The values are independently selected from 25% to 45%, further selected from 25% to 40%, and more preferably from 25% to 35%.
In the resin composition, electrostatic repulsion and van der waals force exist between particles, which affects the dispersibility of the particles. Therefore, in the present invention, the dispersant further assists in enhancing the effect of dispersing the modified first dielectric filler and the modified second dielectric filler in the resin composition, so that the absolute value of Zeta potential of the resin composition is 20mV to 40mV, preferably 20mV to 35mV, and more preferably 20mV to 30mV, whereby agglomeration of the dielectric fillers can be effectively prevented by the action of electrostatic repulsion and van der waals force, and further, a resin composition having uniform dispersion and stable system can be obtained.
Therefore, the film prepared from the resin composition with uniform dispersion and stable system has high compactness, the density of the dielectric layer prepared from the film can be effectively improved, and the using amount of the second dielectric filler can be further reduced. Specifically, in the resin composition of the present invention, the mass fraction of the modified first dielectric filler in the dielectric filler is greater than or equal to 50%.
Specifically, the preparation method of the resin composition comprises the following steps: mixing water and a dispersing agent, adding the modified first dielectric filler and the modified second dielectric filler, stirring and ball-milling, and finally adding the fluorine-containing resin.
In order to improve the dispersion effect and control the Zeta potential of the resin composition, in one embodiment, the mass of the dispersant is 0.1% to 1% of the sum of the mass of the modified first dielectric filler and the mass of the modified second dielectric filler, and the hydrophilic-lipophilic balance (HLB) of the dispersant is 5 to 15, and specifically includes at least one of octylphenyl polyoxyethylene ether, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, and dodecylphenol polyoxyethylene ether.
In one embodiment, the modified first dielectric filler is present in an amount of 10 to 100 parts by weight and the modified second dielectric filler is present in an amount of 10 to 100 parts by weight, based on 100 parts by weight of the fluorine-containing resin.
Therefore, through the compound use of the first dielectric filler and the second dielectric filler with different dielectric constant ranges and difference values of more than 30, and the oleophylic modification of the first dielectric filler and the second dielectric filler, the absolute value of the Zeta potential of the resin composition is stabilized to be 20mV-40mV, and the use amount of the second dielectric filler is reduced, finally, the circuit substrate made of the resin composition has a dielectric constant of 3-12 at 10GHz, the absolute value of TCDk of the circuit substrate is less than or equal to 50 ppm/DEG C, and the range of TCDk is less than or equal to 10%, so that the circuit substrate has high Dk and is adjustable, the performance is stable under wide working temperature and wide working humidity, and the use requirements under the conditions of high temperature, high humidity and the like under the extreme end conditions can be met.
In one embodiment, the absolute value of TCDk of the circuit substrate may be further reduced by further reducing the mass of the modified second dielectric filler.
For example, when the modified first dielectric filler is present in an amount of 10 to 100 parts by weight based on 100 parts by weight of the fluorine-containing resin and the mass fraction of the modified first dielectric filler in the dielectric filler is 60% or more, a circuit substrate manufactured using the resin composition has a dielectric constant of 3 to 10 at 10GHz, an absolute value of TCDk of the circuit substrate is 40 ppm/DEG C or less, and a range of TCDk is 10% or less.
When the modified first dielectric filler accounts for 10 to 100 weight parts of the fluorine-containing resin, and the mass fraction of the modified first dielectric filler in the dielectric filler is more than or equal to 70 percent, a circuit substrate made of the resin composition has a dielectric constant of 3 to 8 at 10GHz, the absolute value of TCDk of the circuit substrate is less than or equal to 20 ppm/DEG C, and the range of TCDk is less than or equal to 10 percent.
The modified first dielectric filler accounts for 10-100 parts by weight of the fluorine-containing resin, when the mass fraction of the modified first dielectric filler in the dielectric filler is greater than or equal to 75%, a circuit substrate made of the resin composition has a dielectric constant of 3-6 at 10GHz, the absolute value of TCDk of the circuit substrate is less than or equal to 5 ppm/DEG C and approaches to 0, and the range of TCDk is less than or equal to 10%.
In one embodiment, the resin composition further comprises a third coupling agent, wherein the third coupling agent comprises at least one of a silane coupling agent, a titanate coupling agent and a fluorine-containing coupling agent, preferably a fluorine-containing coupling agent, and the amount of the fluorine-containing coupling agent is 0.1-2% of the sum of the mass of the modified first dielectric filler and the mass of the modified second dielectric filler.
The invention also provides a film made of the resin composition.
Specifically, the method for preparing the film from the resin composition includes various methods, such as: drying, crushing and rolling the resin composition to obtain the film; alternatively, the resin composition is cast and rolled to obtain the film. Wherein the rolling temperature is 100-150 ℃.
The invention also provides a circuit substrate which comprises a dielectric layer and a conducting layer arranged on at least one surface of the dielectric layer, wherein the dielectric layer is formed by pressing one or at least two overlapped films.
In one embodiment, the density of the circuit substrate is 2.0g/cm3-2.6g/cm3。
In one embodiment, the conductive layer is preferably a copper foil, and thus, the circuit substrate is a copper clad laminate.
The invention also provides a printed circuit board which is made of the circuit substrate. The circuit substrate is mainly manufactured by the processes of drilling a plate, finishing a hole, micro-etching, presoaking, activating, accelerating, chemical copper, thickening copper and the like.
Hereinafter, the resin composition, the prepreg, the circuit board and the printed circuit board will be further described by the following specific examples.
In the performance tests of the following examples and comparative examples, the test standard for Dk was IPC-TM-6502.5.5.5, the test standard for TCDk was IPC-TM-6502.5.5.5, and the test standard for TCDk was IPC-TM-6502.5.5.5, which is very poor.
Example 1
In this example, the first dielectric filler modified is KH1732 modified silica, oleophilic
Figure BDA0003288318830000092
The value is 30%, and the modified second dielectric filler is KH1732 modified titanium dioxide, oleophilic degree
Figure BDA0003288318830000091
The value was 30%.
Mixing water and dispersant octyl phenyl polyoxyethylene ether (HLB value is 10) and stirring for 10 minutes, adding the modified first dielectric filler and the modified second dielectric filler, stirring for 20 minutes, performing ball milling for 30 minutes, adding polytetrafluoroethylene resin, and stirring to obtain the resin composition. In this resin composition, the polytetrafluoroethylene resin was 100 parts by weight, the modified first dielectric filler was 80 parts by weight, the modified second dielectric filler was 20 parts by weight, the dispersant was 1 part by weight, and the absolute value of Zeta potential of the resin composition was 30.24 mV.
The resin composition prepared above was subjected to tape casting, baking, and peeling to obtain a preform, which was then rolled in a two-roll blender at a temperature of 110 ℃ to obtain a film.
Then 6 sheets of the above-prepared films are laminated and coated with copper foil on both sides, and hot-pressed to obtain the film with the density of 2.2g/cm3The circuit board of (1).
Example 2
Example 2 differs from example 1 only in that the mass of the modified first dielectric filler was 95 parts by weight, the mass of the modified second dielectric filler was 40 parts by weight, and the absolute value of Zeta potential of the resin composition was 30.19 mV.
Example 3
Example 3 differs from example 1 only in that the mass of the modified first dielectric filler was 85 parts by weight, the mass of the modified second dielectric filler was 55 parts by weight, and the absolute value of Zeta potential of the resin composition was 29.87 mV.
Example 4
Example 4 differs from example 1 only in that the mass of the modified first dielectric filler was 90 parts by weight, the mass of the modified second dielectric filler was 80 parts by weight, and the absolute value of Zeta potential of the resin composition was 31.56 mV.
Example 5
Example 5 differs from example 1 only in that the mass of the modified first dielectric filler was 30 parts by weight, the mass of the modified second dielectric filler was 10 parts by weight, and the absolute value of Zeta potential of the resin composition was 28.35 mV.
Example 6
Example 6 differs from example 1 only in that the mass of the modified first dielectric filler was 50 parts by weight, the mass of the modified second dielectric filler was 20 parts by weight, and the absolute value of Zeta potential of the resin composition was 32.15 mV.
Comparative example 1
Comparative example 1 differs from example 1 only in that the mass of the modified first dielectric filler was 20 parts by weight, the mass of the modified second dielectric filler was 80 parts by weight, and the absolute value of Zeta potential of the resin composition was 29.47 mV.
Comparative example 2
Comparative example 2 differs from example 3 only in that the mass of the modified first dielectric filler was 50 parts by weight and the absolute value of Zeta potential of the resin composition was 29.47 mV.
The circuit substrates of examples 1 to 6 and comparative examples 1 to 2 were subjected to performance tests, and the results are shown in Table 1.
TABLE 1
Figure BDA0003288318830000111
Example 7
Example 7 differs from example 1 only in the degree of oleophilicity of the modified first dielectric filler
Figure BDA0003288318830000112
Value of 25%, degree of oleophilic of the modified second dielectric filler
Figure BDA0003288318830000113
The value was 30%, and the absolute value of the Zeta potential of the resin composition was 31.98 mV.
Example 8
Example 8 differs from example 1 only in the degree of oleophilicity of the modified first dielectric filler
Figure BDA0003288318830000124
Value of 30%, degree of oleophilicity of the modified second dielectric filler
Figure BDA0003288318830000123
The value was 25%, and the absolute value of the Zeta potential of the resin composition was 33.24 mV.
Example 9
Example 9 differs from example 1 only in the degree of oleophilicity of the modified first dielectric filler
Figure BDA0003288318830000122
Value of 35%, degree of oleophilicity of the modified second dielectric filler
Figure BDA0003288318830000126
Value 40%, resin groupThe Zeta potential of the compound was 31.5mV absolute.
Example 10
Example 10 differs from example 1 only in the degree of oleophilicity of the modified first dielectric filler
Figure BDA0003288318830000127
Value of 40%, degree of oleophilicity of the modified second dielectric filler
Figure BDA0003288318830000125
The value was 45%, and the absolute value of the Zeta potential of the resin composition was 28.64 mV.
Comparative example 3
Comparative example 3 differs from example 1 only in the degree of oleophilicity of the modified first dielectric filler
Figure BDA0003288318830000128
The value was 20%, and the absolute value of Zeta potential of the resin composition was 42.35V.
Comparative example 4
Comparative example 4 differs from example 1 only in the degree of oleophilicity of the modified first dielectric filler
Figure BDA0003288318830000129
The value was 50%, and the absolute value of the Zeta potential of the resin composition was 15.37 mV.
The circuit substrates of examples 7 to 10 and comparative examples 3 to 4 were subjected to performance tests, and the results are shown in Table 2.
TABLE 2
Figure BDA0003288318830000121
Figure BDA0003288318830000131
Example 11
Example 11 differs from example 1 only in that the dispersant was octylphenyl polyoxyethylene ether (HLB value: 10), the mass of the dispersant was 0.5 part by weight, and the absolute value of Zeta potential of the resin composition was 29.37 mV.
Example 12
Example 12 differs from example 1 only in that the dispersant was octylphenyl polyoxyethylene ether (HLB value: 10), the mass of the dispersant was 0.45 part by weight, and the absolute value of Zeta potential of the resin composition was 28.62 mV.
Example 13
Example 13 differs from example 1 only in that the dispersant was octylphenyl polyoxyethylene ether (HLB value: 10), the mass of the dispersant was 0.4 part by weight, and the absolute value of Zeta potential of the resin composition was 29.54 mV.
Example 14
Example 14 differs from example 1 only in that the dispersant was octylphenyl polyoxyethylene ether (HLB value: 10), the mass of the dispersant was 0.3 part by weight, and the absolute value of Zeta potential of the resin composition was 31.27 mV.
Example 15
Example 15 differs from example 1 only in that the dispersant was dodecylphenol polyoxyethylene ether (HLB value: 8), the mass of the dispersant was 1 part by weight, and the absolute value of Zeta potential of the resin composition was 37.76 mV.
Comparative example 5
Comparative example 5 differs from example 1 only in that the absolute value of Zeta potential of the resin composition was 14.35mV without using a dispersant.
The circuit substrates of examples 11 to 14 and comparative example 5 were subjected to performance tests, and the results are shown in Table 3.
TABLE 3
Figure BDA0003288318830000141
Example 16
Example 16 differs from example 1 only in that the modified first dielectric filler is a KH1732 modified silica, oleophilic
Figure BDA0003288318830000146
The value is 30%, the modified second dielectric filler is KH1732 modified strontium titanate with oleophilic degree
Figure BDA0003288318830000145
The value was 30%.
Example 17
Example 17 differs from example 1 only in that the modified first dielectric filler is KH1732 modified alumina, oleophilic
Figure BDA0003288318830000148
The value is 30%, the modified second dielectric filler is KH1732 modified barium titanate with oleophilic degree
Figure BDA0003288318830000143
The value was 30%.
Example 18
Example 18 differs from example 1 only in that the modified first dielectric filler is KH1732 modified magnesium oxide, oleophilic
Figure BDA0003288318830000149
The value is 30%, and the modified second dielectric filler is KH1732 modified titanium dioxide, oleophilic degree
Figure BDA0003288318830000147
The value was 30%.
Example 19
Example 19 differs from example 1 only in that the modified first dielectric filler is KH1732 modified dicaryon silicon, oleophilic
Figure BDA0003288318830000144
The value is 30%, the modified second dielectric filler is KH1732 modified barium strontium titanate with oleophilic degree
Figure BDA0003288318830000142
The value was 30%.
Comparative example 6
Comparative example 6 differs from example 1 only in that,the first dielectric filler is KH1732 modified silica with oleophilic degree
Figure BDA0003288318830000155
The value is 30%, and the modified second dielectric filler is KH1732 modified silica, oleophilic degree
Figure BDA0003288318830000154
The value was 30%.
Comparative example 7
Comparative example 7 differs from example 1 only in that the modified first dielectric filler is a KH1732 modified titanium dioxide, having an oleophilic degree
Figure BDA0003288318830000153
The value is 30%, and the modified second dielectric filler is KH1732 modified titanium dioxide, oleophilic degree
Figure BDA0003288318830000152
The value was 30%.
The circuit substrates of examples 16 to 19 and comparative examples 6 to 7 were subjected to performance tests, and the results are shown in Table 4.
TABLE 4
Figure BDA0003288318830000151
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (12)

1. The resin composition is characterized by comprising a fluorine-containing resin, a dielectric filler, a dispersant and water, wherein the dielectric filler comprises a modified first dielectric filler and a modified second dielectric filler, the mass fraction of the modified first dielectric filler in the dielectric filler is greater than or equal to 50%, the dielectric constant of the first dielectric filler is less than or equal to 10, the dielectric constant of the first dielectric filler is less than that of the second dielectric filler, the difference value is more than 80, the oleophilic degrees of the modified first dielectric filler and the modified second dielectric filler are respectively and independently selected from 25-45%, and the absolute value of the Zeta potential of the resin composition is 20-40 mV.
2. The resin composition of claim 1, wherein the second dielectric filler has a dielectric constant greater than 80.
3. The resin composition according to claim 1, wherein the modified first dielectric filler is 10 to 100 parts by weight and the modified second dielectric filler is 10 to 100 parts by weight based on 100 parts by weight of the fluorine-containing resin.
4. The resin composition of claim 3, wherein the modified first dielectric filler is present in the dielectric filler in an amount greater than or equal to 60% by weight.
5. The resin composition of claim 4, wherein the modified first dielectric filler is present in the dielectric filler in an amount greater than or equal to 70% by weight.
6. The resin composition of claim 5, wherein the modified first dielectric filler is present in the dielectric filler in an amount greater than or equal to 75% by weight.
7. The resin composition of any of claims 1-6, wherein the first dielectric filler comprises at least one of silica, alumina, magnesia, boria, aluminum nitride, and silicon carbide.
8. The resin composition of any of claims 1-6, wherein the second dielectric filler comprises at least one of titanium dioxide, strontium titanate, barium titanate, and barium strontium titanate.
9. The resin composition according to any one of claims 1 to 6, wherein the mass of the dispersant is 0.1% to 1% of the sum of the mass of the modified first dielectric filler and the mass of the modified second dielectric filler, and the hydrophilic-lipophilic balance value of the dispersant is 5 to 15.
10. A film, wherein the film is made of the resin composition according to any one of claims 1 to 9.
11. A circuit substrate comprising a dielectric layer and a conductive layer provided on at least one surface of the dielectric layer, wherein the dielectric layer is formed by pressing one or at least two sheets of the prepreg according to claim 10 in a state of being laminated.
12. A printed circuit board, characterized in that it is made of the circuit substrate of claim 11.
CN202111155535.2A 2021-09-29 2021-09-29 Resin composition, adhesive sheet, circuit board, and printed wiring board Pending CN113881171A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114989548A (en) * 2022-06-30 2022-09-02 浙江华正新材料股份有限公司 Glue solution, film and circuit board

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06188529A (en) * 1992-12-18 1994-07-08 Matsushita Electric Works Ltd Circuit board
CN102504332A (en) * 2011-11-02 2012-06-20 台光电子材料(昆山)有限公司 Inorganic filler and electric material containing same
CN105898984A (en) * 2016-05-04 2016-08-24 江苏富仕德科技发展有限公司 Production technology for baseplate made of polytetrafluoroethylene glass fiber composite
CN106480735A (en) * 2015-08-28 2017-03-08 广东生益科技股份有限公司 Circuit substrate and preparation method thereof
CN110423572A (en) * 2019-07-24 2019-11-08 浙江华正新材料股份有限公司 Film and preparation method thereof, copper-clad plate
CN111909476A (en) * 2020-05-29 2020-11-10 浙江华正新材料股份有限公司 Prepreg and circuit board
CN113227245A (en) * 2018-12-27 2021-08-06 株式会社斗山 Resin composition, metal laminate and printed circuit board using same, and method for producing metal laminate
CN113365429A (en) * 2020-04-21 2021-09-07 广州市东泓氟塑料股份有限公司 High-frequency high-speed copper-clad plate with good dielectric constant consistency and preparation and application thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06188529A (en) * 1992-12-18 1994-07-08 Matsushita Electric Works Ltd Circuit board
CN102504332A (en) * 2011-11-02 2012-06-20 台光电子材料(昆山)有限公司 Inorganic filler and electric material containing same
CN106480735A (en) * 2015-08-28 2017-03-08 广东生益科技股份有限公司 Circuit substrate and preparation method thereof
CN105898984A (en) * 2016-05-04 2016-08-24 江苏富仕德科技发展有限公司 Production technology for baseplate made of polytetrafluoroethylene glass fiber composite
CN113227245A (en) * 2018-12-27 2021-08-06 株式会社斗山 Resin composition, metal laminate and printed circuit board using same, and method for producing metal laminate
CN110423572A (en) * 2019-07-24 2019-11-08 浙江华正新材料股份有限公司 Film and preparation method thereof, copper-clad plate
CN113365429A (en) * 2020-04-21 2021-09-07 广州市东泓氟塑料股份有限公司 High-frequency high-speed copper-clad plate with good dielectric constant consistency and preparation and application thereof
CN111909476A (en) * 2020-05-29 2020-11-10 浙江华正新材料股份有限公司 Prepreg and circuit board

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
薛茹君等: "《无机纳米材料的表面修饰改性与物性研究》", 31 October 2009, 合肥工业大学出版社 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114989548A (en) * 2022-06-30 2022-09-02 浙江华正新材料股份有限公司 Glue solution, film and circuit board
CN114989548B (en) * 2022-06-30 2024-01-09 浙江华正新材料股份有限公司 Glue solution, film and circuit substrate

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