CN111976246B - High-flame-retardant intelligent coating high-frequency copper-clad plate and preparation method thereof - Google Patents

High-flame-retardant intelligent coating high-frequency copper-clad plate and preparation method thereof Download PDF

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CN111976246B
CN111976246B CN202010902216.2A CN202010902216A CN111976246B CN 111976246 B CN111976246 B CN 111976246B CN 202010902216 A CN202010902216 A CN 202010902216A CN 111976246 B CN111976246 B CN 111976246B
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resin
clad plate
glass fiber
parts
flame
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CN111976246A (en
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向中荣
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Wuxi Relong New Material Technology Co ltd
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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Abstract

The invention provides a high-flame-retardant function intelligent coating high-frequency copper-clad plate and a preparation method thereof, wherein the high-flame-retardant function intelligent coating high-frequency copper-clad plate comprises a prepreg positioned in the middle, a first resin-coated fiberglass cloth-based copper foil positioned on the upper side of the prepreg and a second resin-coated fiberglass cloth-based copper foil positioned on the lower side of the prepreg; the prepreg is a phosphatized modified polyimide film, and the coating resin is a bio-based dimer acid glycidyl ester modified epoxy resin. The high-frequency copper-clad plate provided by the invention is a double-layer direct metallization without an adhesive layer, meets the requirement of high miniaturization of electronic devices, and has high glass transition temperature, low thermal expansion coefficient and dielectric constant, and further has high flame retardant property and high rigidity. The phosphorization modified polyimide film and the glass fiber cloth coated with the bio-based dimer acid glycidyl ester modified epoxy resin are both not filled with inorganic filler, so that the occurrence of agglomeration phenomenon is reduced, the microstructure of the copper-clad plate is not uniform, and the defects of low transparency and light transmittance reduction are avoided.

Description

High-flame-retardant intelligent coating high-frequency copper-clad plate and preparation method thereof
Technical Field
The invention belongs to the technical field of communication materials, and particularly relates to an intelligent coating high-frequency copper-clad plate with a high flame-retardant function and a preparation method thereof.
Background
In recent years, with national defense war industry, aerospace andthe rapid development of emerging information industries such as 3G communication, Internet of things, mobile internet and the like, the high-frequency signal transmission and high-frequency data processing of electronic circuits face higher and higher requirements, so that new requirements are put forward on the related performance of copper-clad plates, and lower dielectric constants (D) are requiredk) And dielectric loss (D)f) To meet the requirements of increasing the information transmission speed and reducing the signal transmission loss. The official implementation of two instructions (an instruction about limiting the use of certain harmful substances in electric and electronic products and an instruction about scrapping the electric and electronic products) in the european union on 1/7 in 2006 marks that the global electronic industry enters the lead-free welding era. Due to the improvement of the welding temperature, the requirement on the thermal reliability of the copper-clad plate is comprehensively improved.
Meanwhile, the development of the 5G technology is applied to mobile cloud computing, wearable equipment, unmanned driving, smart homes, high-definition video simultaneous shooting transmission and other products, the bonding layer is reduced as much as possible on the high-frequency copper-clad plate to reduce the thickness, the requirement of miniaturized electronic devices is met, the dielectric constant Dk and the dielectric loss Df are reduced to maintain the loss of the 5G signal in the transmission process, however, in the prior art, the Chinese patent 201611268856.2 forms an adhesive layer by adding an inorganic filler and an adhesive to prepare the high-frequency copper-clad plate, an additive is required to be added and the high-frequency copper-clad plate is provided with the adhesive layer, and the thickness and the thermal expansion rate of the high-frequency copper-clad.
Therefore, there is a need for a high-frequency copper-clad plate which is prepared by using an adhesive or has no adhesive layer, has high peel strength, high light transmittance, high glass transition temperature, low thermal expansion coefficient and dielectric constant, and further has high flame retardant property and high rigidity.
Disclosure of Invention
Aiming at the defects, the invention provides a double-layer direct metallization without an adhesive layer, which meets the requirement of high miniaturization of electronic devices, has high peel strength, high light transmittance, high glass transition temperature, low thermal expansion coefficient and dielectric constant, further has a middle layer with high flame retardant property and high rigidity, and is a phosphatized modified polyimide film prepreg, and the upper side and the lower side of the middle layer are high-frequency copper clad plates coated with bio-based dimer acid glycidyl ester modified epoxy resin glass fiber cloth base.
The invention provides the following technical scheme: the high-flame-retardant function intelligent coating high-frequency copper-clad plate is characterized by comprising a prepreg positioned in the middle, a first resin-coated fiberglass cloth-based copper foil positioned on the upper side of the prepreg and a second resin-coated fiberglass cloth-based copper foil positioned on the lower side of the prepreg; the prepreg is a phosphatized modified polyimide film, and the coating resin is bio-based dimer acid glycidyl ester modified epoxy resin;
the phosphatized modified polyimide film comprises the following components in parts by weight:
Figure GDA0002895177070000021
further, the preparation method of the phosphatized modified polyimide film comprises the following steps:
a1: mixing the aniline in parts by weight, the 4-aminoacetophenone in parts by weight and the diethylamine in parts by weight, stirring for 2 to 3 hours at the rotating speed of 200 to 250rpm under the nitrogen atmosphere at the temperature of between 120 and 150 ℃, filtering the obtained mixture, recrystallizing the obtained precipitate by adopting methanol, and drying at the temperature of between 110 and 120 ℃ in vacuum;
a2: mixing the substance obtained in the step A1 with half of the dimethylformamide in parts by weight, stirring at the rotating speed of 100-150 rpm for 20min at the temperature of 60-80 ℃, then cooling to the temperature of 3-5 ℃ at the speed of 20 ℃/min, adding the 4,4' -diaminodiphenyl ether in parts by weight, stirring at the rotating speed of 80-100 rpm for 20-1 h, then gradually heating to the temperature of 80-100 ℃, preserving the heat for 10-15 min, and stopping the reaction to obtain a polymer;
a3: mixing the 5-methoxy-isobenzofuran-1, 3-dione and the benzhydrol in parts by weight, stirring at 40-50 ℃ for 20-30 min, and centrifuging the obtained mixture at 500-600 rpm for 5-10 min to obtain gelatinous precipitate;
a4: mixing the gelatinous precipitate obtained in the step A3 with the polymer obtained in the step A2, adding the phosphonate and the polyimide in parts by weight, stirring at 80-100 ℃ for 30-40 min, dropwise adding the rest half of the dimethylformamide in the stirring process, standing in the dark at 5-10 ℃ for 40-60 min after stirring, filtering with a filter membrane, and semi-drying the gel obtained by filtering under nitrogen gas flow for 10-20 min to obtain semi-dry gel with the water content of 50-60%, wherein the semi-dry gel is a phosphatized modified polyimide film.
Further, the phosphonate is one or more of tetrasodium amino trimethylene phosphonate, sodium hydroxyethylidene diphosphonate, potassium hydroxyethylidene diphosphonate and sodium diethylenetriamine pentamethyl phosphonate.
Further, the bio-based dimer acid glycidyl ester modified epoxy resin comprises the following components in parts by weight:
Figure GDA0002895177070000031
Figure GDA0002895177070000041
further, the dienoic acid is one or more of arachidienoic acid, aromaticacid, 2, 4-hexadienoic acid, decadienoic acid, octadecadienoic acid or docosadienoic acid.
Further, the curing accelerator is one or more of 2-methylimidazole, 2-ethyl-4-methylimidazole and N-methylimidazole.
The invention also provides a preparation method of the intelligent high-frequency coated copper-clad plate with the high flame-retardant function, which comprises the following steps:
s1: heating the glass fiber cloth at 400-500 ℃ for 30min, removing surface paraffin, soaking the glass fiber cloth after heat treatment in a silane coupling agent for 5-10 min, naturally drying in the air, and baking at 110-120 ℃ for 30 min;
s2, heating the bio-based dimer acid glycidyl ester modified epoxy resin at 50-60 ℃ for 20-30 min;
s3: coating the heated biological-based dimer acid glycidyl ester modified epoxy resin obtained in the step S2 on the glass fiber cloth obtained in the step S1, then drying the glass fiber cloth at the temperature of 30-40 ℃ for 30-40 min, and continuously repeating the coating and the drying for 3-5 times, so that the biological-based dimer acid glycidyl ester modified epoxy resin on the glass fiber cloth reaches more than 60%, and obtaining a resin-coated glass fiber cloth raw substrate;
s4: immersing the phosphorized modified polyimide film in a sulfonated disodium succinate ethanol solution with the volume fraction of 30-40%, ultrasonically oscillating for 20-25 min, taking out, and cleaning for 3 times at intervals by using ethanol and distilled water to obtain a surface activated phosphorized modified polyimide film;
s5: taking two resin-coated glass fiber cloth raw substrates obtained in the step S3, respectively covering the upper surface and the lower surface of the surface activated phosphorized modified polyimide film obtained in the step S4, and drying at 100-150 ℃ for 20min to obtain a prepreg with the middle made of the phosphorized modified polyimide film material and three layers of films of the resin-coated glass fiber cloth raw substrates positioned at two sides of the prepreg;
s6: and (2) overlapping a layer of copper foil on the upper surface of the resin-coated glass fiber cloth raw substrate on the upper side, overlapping a layer of copper foil on the lower surface of the resin-coated glass fiber cloth raw substrate on the lower side, then placing the copper foil between two steel plates, and carrying out vacuum hot pressing for 1.5-2.0 h at 380-420 ℃ under the pressure of 450-1150 PSI to obtain the high-flame-retardant-function intelligent coated high-frequency copper-clad plate.
The invention has the beneficial effects that:
1. compared with non-renewable resources such as petroleum-based resin, the bio-based biological dimer acid glycidyl ester synthesized by the diene acid has the advantages of wide raw material source, strong renewability and the like.
2. The molecular structure of the bio-based dimer acid glycidyl ester prepared from the diene acid and the 1-chloro-2, 3-epoxypropane has both a long aliphatic chain and an aliphatic ring, and can be used as a reactive epoxy resin toughening agent to toughen cured products and ensure heat resistance. The prepared bio-based dimer acid glycidyl ester is mixed with thermosetting phenolic resin and epoxy resin to prepare the bio-based dimer acid glycidyl ester modified epoxy resin, so that the toughness of the epoxy resin can be further improved, and the solvent leaching resistance is ensured.
Meanwhile, the prepared bio-based dimer acid glycidyl ester modified epoxy resin has good water resistance and high adhesive force, and after the epoxy resin is coated on glass fiber cloth, the prepared bio-based dimer acid glycidyl ester modified epoxy resin coated glass fiber cloth-based copper clad laminate can ensure the water absorption rate of the copper clad laminate and the peel strength of the copper clad laminate.
3. In the process of preparing the phosphorized modified polyimide film, aniline, 4-aminoacetophenone and diethylamine are mixed to prepare condensed ketone with an amino-chain end, and further 4,4' -diaminodiphenyl ether is added and assisted with dimethylformamide for polarity affinity, and the amino end is further added, so that a condensed closed benzene ring cyclic polymer with an amino-chain end is formed; the polyphenylene linear polymer connected by-O-is prepared by mixing 5-methoxy-isobenzofuran-1, 3-diketone and benzhydryl alcohol, the polyphenylene with a characteristic phosphonic acid functional group forming end group is formed by adding phosphonate and the synthesized condensation closed benzene ring cyclic polymer with an amino chain end under the action of the residual dimethyl formamide, the existence of the large volume phosphonate on the main chain improves the bonding strength of the polyimide film, effectively reduces the melt flow after hot pressing, and the surface roughness of the film is met, the adhesion effect of the prepared phosphatized modified polyimide film and copper is facilitated, and under the condition of not using an adhesive, the adhesive can be compounded and attached with glass fiber cloth coated with the bio-based dimer acid glycidyl ester modified epoxy resin, and the requirement of high miniaturization of electronic devices is met.
4. The condensation closed benzene ring cyclic polymer with the amino chain end enhances the rigidity of the phosphorization modified polyimide film, improves the storage modulus and the glass transition temperature of the film, and simultaneously, through the reaction of phosphonate, the thermal expansion coefficient and the dielectric constant of the phosphorization modified polyimide film are also reduced by adding organic phosphonic acid groups.
5. And the two layers are not filled with inorganic filler, so that the agglomeration phenomenon is reduced, the microstructure of the copper-clad plate is not uniform, and the defects of low transparency and light transmittance reduction are avoided.
Drawings
The invention will be described in more detail hereinafter on the basis of embodiments and with reference to the accompanying drawings. Wherein:
fig. 1 is a cross-sectional view of a high-flame-retardant function intelligent coated high-frequency copper-clad plate provided in embodiments 1-3 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
All the raw materials are commercially available, and the CAS number of the adopted 4,4' -diaminodiphenyl ether is 101-80-4.
Example 1
The high-flame-retardant-function intelligent coated high-frequency copper-clad plate provided by the embodiment comprises a prepreg 1 positioned in the middle, a first resin-coated fiberglass cloth-based copper foil 2-1 positioned on the upper side of the prepreg and a second resin-coated fiberglass cloth-based copper foil 2-2 positioned on the lower side of the prepreg; the prepreg 1 is a phosphatized modified polyimide film, and the coating resin is bio-based dimer acid glycidyl ester modified epoxy resin.
The phosphatized modified polyimide film comprises the following components in parts by weight:
Figure GDA0002895177070000071
the preparation method of the phosphatized modified polyimide film comprises the following steps:
a1: mixing 25 parts of aniline, 5 parts of 4-aminoacetophenone and 10 parts of diethylamine, stirring for 2 hours at the rotating speed of 200rpm under the nitrogen atmosphere and at the temperature of 120 ℃, filtering the obtained mixture, recrystallizing the obtained precipitate by adopting methanol, and drying under vacuum and at the temperature of 110 ℃;
a2: mixing the substance obtained in the step A1 with 4 parts of dimethylformamide, stirring at the rotating speed of 100rpm for 20min at the temperature of 60 ℃, then cooling to 3 ℃ at the speed of 20 ℃/min, adding 15 parts of 4,4' -diaminodiphenyl ether, stirring at the rotating speed of 80rpm for 20min, then gradually heating to 80 ℃, preserving heat for 10min, and terminating the reaction to obtain a polymer;
a3: mixing 25 parts of 5-methoxy-isobenzofuran-1, 3-dione and benzhydrol in parts by weight, stirring at 40 ℃ for 20min, and centrifuging the obtained mixture at 500rpm for 5min to obtain gelatinous precipitate;
a4: mixing the gelatinous precipitate obtained in the step A3, the polymer obtained in the step A2 and the gelatinous precipitate obtained in the step A2, adding 12.5 parts of amino trimethylene phosphonic acid tetrasodium and 50 parts of polyimide, stirring for 30min at 80 ℃, dropwise adding the rest 4 parts of dimethylformamide in the stirring process, standing in the dark at 5 ℃ for 40min after stirring, filtering by using a filter membrane, and semi-drying the gel obtained by filtering in nitrogen gas flow for 10min to obtain semi-dry gel with the water content of 50%, wherein the semi-dry gel is a phosphatized modified polyimide film.
The bio-based dimer acid glycidyl ester modified epoxy resin comprises the following components in parts by weight:
Figure GDA0002895177070000081
Figure GDA0002895177070000091
the preparation method of the bio-based dimer acid glycidyl ester modified epoxy resin comprises the following steps:
b1: dissolving 30 parts of NaOH solution in distilled water to form 60% NaOH solution by mass fraction;
b2: mixing 25 parts of peanut dienoic acid and 22.5 parts of 1-chloro-2, 3-epoxypropane, stirring for 2.5 hours at the speed of 150rpm under the condition of 120 ℃ oil bath, then cooling to 55 ℃, preserving heat for 1.5 hours, continuously stirring at 90rpm in the heat preservation process, and dropwise adding one-half volume of NaOH solution obtained in the step B1;
b3: after the heat preservation in the step B2 is finished, heating to 85 ℃, continuing to preserve heat for the second time for 1.5h, continuously stirring at 90rpm in the second heat preservation process, and dropwise adding the remaining half volume of NaOH solution obtained in the step B1 to obtain dimer acid glycidyl ester precursor precipitate;
b4: washing the precipitate of the dimer acid glycidyl ester modified epoxy resin precursor obtained in the step B3 with deionized water for 4 times, then washing with saturated NaCl solution for 3 times, washing with toluene for 2 times after reduced pressure distillation, and filtering with a 1.0-micron filter membrane to obtain the bio-based dimer acid glycidyl ester;
b5: dissolving 25 parts of thermoplastic phenolic resin and 10 parts of 2-ethyl-4-methylimidazole serving as a curing accelerator in a mixed solution of acetone and ethanol in a volume ratio of 1:1, heating at 200rpm and 45 ℃ for 30min, adding 45 parts of epoxy resin, continuously stirring for 30min, and naturally airing to obtain the bio-based dimer acid glycidyl ester modified epoxy resin.
The preparation method of the intelligent coating high-frequency copper-clad plate with the high flame-retardant function provided by the embodiment comprises the following steps:
s1: heating the glass fiber cloth at 400 ℃ for 30min, removing paraffin on the surface, soaking the glass fiber cloth after heat treatment in a silane coupling agent for 5min, naturally drying in the air, and baking at 110 ℃ for 30 min;
s2, heating the bio-based dimer acid glycidyl ester modified epoxy resin at 50 ℃ for 20 min;
s3: coating the heated bio-based dimer acid glycidyl ester modified epoxy resin obtained in the step S2 on the glass fiber cloth obtained in the step S1, then drying the glass fiber cloth at 30 ℃ for 30min, and continuously repeating the coating and drying for 3 times to enable the bio-based dimer acid glycidyl ester modified epoxy resin on the glass fiber cloth to reach 60 percent, so as to obtain a resin-coated glass fiber cloth raw substrate;
s4: immersing the phosphatized modified polyimide film in a sulfonated disodium succinate ethanol solution with the volume fraction of 30%, ultrasonically oscillating for 20min, taking out, and cleaning for 3 times at intervals by using ethanol and distilled water to obtain a surface-activated phosphatized modified polyimide film;
s5: taking two resin-coated glass fiber cloth raw substrates obtained in the step S3, respectively covering the upper surface and the lower surface of the surface-activated phosphorized modified polyimide film obtained in the step S4, and drying at 100 ℃ for 20min to obtain a prepreg 1 with the middle made of the phosphorized modified polyimide film material and three layers of films of the resin-coated glass fiber cloth raw substrates positioned at two sides of the prepreg 1;
s6: and (2) overlapping a layer of copper foil on the upper surface of the resin-coated glass fiber cloth raw substrate on the upper side, overlapping a layer of copper foil on the lower surface of the resin-coated glass fiber cloth raw substrate on the lower side, then placing the copper foil between two steel plates, and carrying out vacuum hot pressing for 1.5h at 380 ℃ under the pressure of 450PSI to form the high-flame-retardant function intelligent coated high-frequency copper-clad plate.
Example 2
The high-flame-retardant-function intelligent coating high-frequency copper-clad plate provided by the embodiment comprises a prepreg 1 positioned in the middle, a first resin-coated fiberglass cloth-based copper foil 2-1 positioned on the upper side of the prepreg, and a second resin-coated fiberglass cloth-based copper foil 2-2 positioned on the lower side of the prepreg; the prepreg 1 is a phosphatized modified polyimide film, and the coating resin is bio-based dimer acid glycidyl ester modified epoxy resin.
The phosphatized modified polyimide film comprises the following components in parts by weight:
Figure GDA0002895177070000111
the preparation method of the phosphatized modified polyimide film comprises the following steps:
a1: mixing 27.5 parts of aniline, 7.5 parts of 4-aminoacetophenone and 15 parts of diethylamine, stirring for 2.5 hours at the rotating speed of 225rpm under the atmosphere of nitrogen and at the temperature of 135 ℃, filtering the obtained mixture, recrystallizing the obtained precipitate by adopting methanol, and drying under vacuum and at the temperature of 115 ℃;
a2: mixing the substance obtained in the step A1 with 6 parts of dimethylformamide, stirring at the rotating speed of 125rpm for 20min at 70 ℃, then cooling to 4 ℃ at the speed of 20 ℃/min, adding 17.5 parts of 4,4' -diaminodiphenyl ether, stirring at the rotating speed of 90rpm for 40min, then gradually heating to 90 ℃, preserving heat for 12min, and terminating the reaction to obtain a polymer;
a3: mixing 30 parts of 5-methoxy-isobenzofuran-1, 3-dione and 30 parts of benzhydrol, stirring at 45 ℃ for 25min, and centrifuging the obtained mixture at 550rpm for 8min to obtain gelatinous precipitate;
a4: mixing the gelatinous precipitate obtained in the step A3 with the polymer obtained in the step A2 and the gelatinous precipitate obtained in the step A2, adding 15 parts of sodium diethylenetriamine pentamethylphosphonate and 55 parts of polyimide, stirring for 35min at 90 ℃, dropwise adding the rest 6 parts of dimethylformamide in the stirring process, standing for 50min in the dark at 8 ℃ after stirring, filtering by using a filter membrane, and semi-drying the gel obtained by filtering for 15min under nitrogen airflow to obtain semi-dry gel with the water content of 55%, wherein the semi-dry gel is a phosphatized modified polyimide film.
The bio-based dimer acid glycidyl ester modified epoxy resin comprises the following components in parts by weight:
Figure GDA0002895177070000121
the preparation method of the bio-based dimer acid glycidyl ester modified epoxy resin comprises the following steps:
b1: dissolving 25 parts of NaOH solution in distilled water to form a NaOH solution with the mass fraction of 58%;
b2: mixing 10 parts of hyphenanthadienic acid, 10 parts of 2, 4-hexadienoic acid and the 1-chloro-2, 3-epoxypropane in parts by weight, stirring for 2.25 hours at the speed of 125rpm under 115 ℃ oil bath, then cooling to 52 ℃, keeping the temperature for 1.25 hours, continuously stirring at 85rpm in the heat preservation process, and dropwise adding one-half volume of NaOH solution obtained in the step B1;
b3: after the heat preservation in the step B2 is finished, heating to 80 ℃, continuing to preserve heat for 1.25h for the second time, continuously stirring at 85rpm in the second heat preservation process, and dropwise adding the residual half volume of NaOH solution obtained in the step B1 to obtain dimer acid glycidyl ester precursor precipitate;
b4: washing the precipitate of the dimer acid glycidyl ester modified epoxy resin precursor obtained in the step B3 with deionized water for 3 times, then washing with saturated NaCl solution for 2 times, washing with toluene for 1 time after reduced pressure distillation, and filtering with a 0.75-micron filter membrane to obtain the bio-based dimer acid glycidyl ester;
b5: dissolving 22.5 parts of thermoplastic phenolic resin and 8 parts of 2-methylimidazole serving as a curing accelerator in a mixed solution of acetone and ethanol in a volume ratio of 4:5, heating at 175rpm and 40 ℃ for 30min, adding 40 parts of epoxy resin, continuously stirring for 25min, and naturally airing to obtain the bio-based dimer acid glycidyl ester modified epoxy resin.
The embodiment also provides a preparation method of the intelligent coating high-frequency copper-clad plate with the high flame-retardant function, which comprises the following steps:
s1: heating the glass fiber cloth at 450 ℃ for 30min, removing paraffin on the surface, soaking the glass fiber cloth after heat treatment in a silane coupling agent for 7min, naturally drying in the air, and baking at 115 ℃ for 30 min;
s2, heating the bio-based dimer acid glycidyl ester modified epoxy resin at 55 ℃ for 25 min;
s3: coating the heated bio-based dimer acid glycidyl ester modified epoxy resin obtained in the step S2 on the glass fiber cloth obtained in the step S1, then drying for 35min at 35 ℃, and continuously repeating the coating and drying for 4 times to enable the bio-based dimer acid glycidyl ester modified epoxy resin on the glass fiber cloth to reach 70%, so as to obtain the resin-coated glass fiber cloth raw substrate;
s4: immersing the phosphatized modified polyimide film in a sulfonated disodium succinate ethanol solution with the volume fraction of 35%, ultrasonically oscillating for 23min, taking out, and cleaning for 3 times at intervals by using ethanol and distilled water to obtain a surface-activated phosphatized modified polyimide film;
s5: taking two resin-coated glass fiber cloth raw substrates obtained in the step S3, respectively covering the upper surface and the lower surface of the surface activated phosphorized modified polyimide film obtained in the step S4, and drying at 125 ℃ for 20min to obtain a prepreg 1 with the middle made of the phosphorized modified polyimide film and three layers of films of the resin-coated glass fiber cloth raw substrates positioned at two sides of the prepreg 1;
s6: and (2) overlapping a layer of copper foil on the upper surface of the resin-coated glass fiber cloth raw substrate on the upper side, overlapping a layer of copper foil on the lower surface of the resin-coated glass fiber cloth raw substrate on the lower side, placing the copper foil between two steel plates, and carrying out vacuum hot pressing for 1.75h at 400 ℃ under 800PSI pressure to form the high-flame-retardant function intelligent coated high-frequency copper-clad plate.
Example 3
The high-flame-retardant-function intelligent coating high-frequency copper-clad plate provided by the embodiment comprises a prepreg 1 positioned in the middle, a first resin-coated fiberglass cloth-based copper foil 2-1 positioned on the upper side of the prepreg, and a second resin-coated fiberglass cloth-based copper foil 2-2 positioned on the lower side of the prepreg; the prepreg 1 is a phosphatized modified polyimide film, and the coating resin is bio-based dimer acid glycidyl ester modified epoxy resin.
The phosphatized modified polyimide film comprises the following components in parts by weight:
Figure GDA0002895177070000141
Figure GDA0002895177070000151
the preparation method of the phosphatized modified polyimide film comprises the following steps:
a1: mixing 30 parts of aniline, 10 parts of 4-aminoacetophenone and 20 parts of diethylamine, stirring for 3 hours at 150 ℃ and 250rpm in a nitrogen atmosphere, filtering the obtained mixture, recrystallizing the obtained precipitate with methanol, and drying at 120 ℃ in vacuum;
a2: mixing the substance obtained in the step A1 with 8 parts of dimethylformamide, stirring at the rotation speed of 150rpm for 20min at the temperature of 80 ℃, then cooling to 5 ℃ at the speed of 20 ℃/min, adding 20 parts of 4,4' -diaminodiphenyl ether, stirring at the rotation speed of 100rpm for 1h, then gradually heating to 100 ℃, preserving heat for 15min, and terminating the reaction to obtain a polymer;
a3: mixing 35 parts of 5-methoxy-isobenzofuran-1, 3-dione and 35 parts of benzhydrol, stirring at 50 ℃ for 30min, and centrifuging the obtained mixture at 600rpm for 10min to obtain gelatinous precipitate;
a4: mixing the gelatinous precipitate obtained in the step A3, the polymer obtained in the step A2 and the gelatinous precipitate obtained in the step A2, adding 17.5 parts of sodium hydroxy ethylidene diphosphonate and 60 parts of polyimide, stirring for 40min at 100 ℃, dropwise adding the rest 8 parts of dimethylformamide in the stirring process, standing for 60min in the dark at 10 ℃ after stirring, filtering by using a filter membrane, and semi-drying the gel obtained by filtering for 20min under nitrogen gas flow to obtain semi-dry gel with the water content of 60%, wherein the semi-dry gel is a phosphatized modified polyimide film.
The bio-based dimer acid glycidyl ester modified epoxy resin comprises the following components in parts by weight:
Figure GDA0002895177070000152
Figure GDA0002895177070000161
the preparation method of the bio-based dimer acid glycidyl ester modified epoxy resin comprises the following steps:
b1: dissolving 20 parts of NaOH solution in distilled water to form 55% of NaOH solution by mass fraction;
b2: mixing 7.5 parts of octadecadienoic acid, 7.5 parts of docosadienoic acid and 17.5 parts of 1-chloro-2, 3-epoxypropane, stirring for 2 hours at the speed of 100rpm under 110 ℃ oil bath, then cooling to 50 ℃ and preserving heat for 1 hour, continuously stirring at 80rpm in the heat preservation process, and dropwise adding half volume of NaOH solution obtained in the step B1;
b3: after the heat preservation in the step B2 is finished, heating to 75 ℃, continuing to preserve heat for 1h for the second time, continuously stirring at 80rpm in the second heat preservation process, and dropwise adding the residual half volume of NaOH solution obtained in the step B1 to obtain dimer acid glycidyl ester precursor precipitate;
b4: washing the precipitate of the dimer acid glycidyl ester modified epoxy resin precursor obtained in the step B3 with deionized water for 3 times, then washing with saturated NaCl solution for 2 times, washing with toluene for 2 times after reduced pressure distillation, and filtering with a 0.5-micron filter membrane to obtain the bio-based dimer acid glycidyl ester;
b5: dissolving 20 parts of thermoplastic phenolic resin and 5 parts of N-methylimidazole serving as a curing accelerator in a mixed solution of acetone and ethanol with the volume ratio of 3:4, heating at the temperature of 35 ℃ for 30min at 150rpm, then adding 35 parts of epoxy resin, continuously stirring for 20min, and naturally airing to obtain the bio-based dimer acid glycidyl ester modified epoxy resin.
The embodiment also provides a preparation method of the intelligent coating high-frequency copper-clad plate with the high flame-retardant function, which comprises the following steps:
s1: heating the glass fiber cloth at 500 ℃ for 30min, removing paraffin on the surface, soaking the glass fiber cloth after heat treatment in a silane coupling agent for 10min, naturally drying in the air, and baking at 120 ℃ for 30 min;
s2, heating the bio-based dimer acid glycidyl ester modified epoxy resin at 60 ℃ for 30 min;
s3: coating the heated bio-based dimer acid glycidyl ester modified epoxy resin obtained in the step S2 on the glass fiber cloth obtained in the step S1, then drying the glass fiber cloth at 40 ℃ for 40min, and continuously repeating the coating and drying for 5 times to enable the bio-based dimer acid glycidyl ester modified epoxy resin on the glass fiber cloth to reach 75%, so as to obtain a resin-coated glass fiber cloth raw substrate;
s4: immersing the phosphatized modified polyimide film in a sulfonated disodium succinate ethanol solution with the volume fraction of 40%, ultrasonically oscillating for 25min, taking out, and cleaning for 3 times at intervals by using ethanol and distilled water to obtain a surface-activated phosphatized modified polyimide film;
s5: taking two resin-coated glass fiber cloth raw substrates obtained in the step S3, respectively covering the upper surface and the lower surface of the surface activated phosphorized modified polyimide film obtained in the step S4, and drying at 150 ℃ for 20min to obtain a prepreg 1 with the middle made of the phosphorized modified polyimide film and three layers of films of the resin-coated glass fiber cloth raw substrates positioned at two sides of the prepreg 1;
s6: and (2) overlapping a layer of copper foil on the upper surface of the resin-coated glass fiber cloth raw substrate on the upper side, overlapping a layer of copper foil on the lower surface of the resin-coated glass fiber cloth raw substrate on the lower side, placing the copper foil between two steel plates, and carrying out vacuum hot pressing for 2.0h at 420 ℃ under the pressure of 1150PSI for forming to obtain the high-flame-retardant-function intelligent coated high-frequency copper-clad plate.
Comparative example 1
The PCY thermal expansion rate tester of Hunan Tan instrument Co., Ltd is adopted to measure the expansion coefficient values of the high-frequency copper-clad plate in the embodiments 1-3 of the invention and the polytetrafluoroethylene high-frequency microwave copper-clad plate prepared in the embodiment 3 of the Chinese patent 201611268856.2 as the temperature range of 20-150 ℃ in the comparative example 1, and the smaller the thermal expansion coefficient value is, the stronger the thermal shock resistance and the thermal cycle resistance are; the high-frequency copper clad laminate in examples 1 to 3 of the present invention and the polytetrafluoroethylene high-frequency microwave copper clad laminate prepared in example 3 of chinese patent 201611268856.2 were measured for peel strength, solder dip resistance (300 ℃), etching waviness, and light transmittance as comparative example 1. The results are shown in Table 1.
TABLE 1
Figure GDA0002895177070000181
Comparative example 2
The high-frequency copper-clad plate in the embodiments 1-3 of the invention and the polytetrafluoroethylene high-frequency microwave copper-clad plate prepared in the embodiment 3 of the Chinese patent 201611268856.2 are used as the glass transition temperature (Tg value) of the comparative example 2 to be measured by a differential scanning calorimeter with the model of DSC-500C of Shanghai Kanji scientific instruments ltd; electronic limited public with normal incomeDielectric constant (D) of TH2839 precision impedance analyzerk) And dielectric loss (D)f). The results are shown in Table 2.
TABLE 2
Index (I) Example 1 Example 2 Example 3 Comparative example 2
Glass transition temperature (Tg) 37.1℃ 45.6℃ 56.3℃ 12.3℃
Dielectric constant (D)k) 44011 42134 39875 55374
Dielectric loss (D)f) 0.3255％ 0.2987％ 0.2465％ 0.9051％
While the invention has been described with reference to a preferred embodiment, various modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In particular, the technical features mentioned in the embodiments can be combined in any way as long as there is no structural conflict. It is intended that the invention not be limited to the particular embodiments disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.

Claims (7)

1. The high-flame-retardant function intelligent coating high-frequency copper-clad plate is characterized by comprising a prepreg (1) positioned in the middle, a first resin-coated fiberglass cloth-based copper foil (2-1) positioned on the upper side of the prepreg and a second resin-coated fiberglass cloth-based copper foil (2-2) positioned on the lower side of the prepreg; the prepreg (1) is a phosphatized modified polyimide film, and the coating resin is bio-based dimer acid glycidyl ester modified epoxy resin;
the phosphatized modified polyimide film comprises the following components in parts by weight:
Figure FDA0002909132270000011
2. the high-flame-retardant function intelligent coating high-frequency copper-clad plate according to claim 1, wherein the preparation method of the phosphatized modified polyimide film comprises the following steps:
a1: mixing the aniline in parts by weight, the 4-aminoacetophenone in parts by weight and the diethylamine in parts by weight, stirring for 2 to 3 hours at the rotating speed of 200 to 250rpm under the nitrogen atmosphere at the temperature of between 120 and 150 ℃, filtering the obtained mixture, recrystallizing the obtained precipitate by adopting methanol, and drying at the temperature of between 110 and 120 ℃ in vacuum;
a2: mixing the substance obtained in the step A1 with half of the dimethylformamide in parts by weight, stirring at the rotating speed of 100-150 rpm for 20min at the temperature of 60-80 ℃, then cooling to the temperature of 3-5 ℃ at the speed of 20 ℃/min, adding the 4,4' -diaminodiphenyl ether in parts by weight, stirring at the rotating speed of 80-100 rpm for 20-1 h, then gradually heating to the temperature of 80-100 ℃, preserving the heat for 10-15 min, and stopping the reaction to obtain a polymer;
a3: mixing the 5-methoxy-isobenzofuran-1, 3-dione and the benzhydrol in parts by weight, stirring at 40-50 ℃ for 20-30 min, and centrifuging the obtained mixture at 500-600 rpm for 5-10 min to obtain gelatinous precipitate;
a4: mixing the gelatinous precipitate obtained in the step A3 with the polymer obtained in the step A2, adding the phosphonate and the polyimide in parts by weight, stirring at 80-100 ℃ for 30-40 min, dropwise adding the rest half of the dimethylformamide in the stirring process, standing in the dark at 5-10 ℃ for 40-60 min after stirring, filtering with a filter membrane, and semi-drying the gel obtained by filtering under nitrogen gas flow for 10-20 min to obtain semi-dry gel with the water content of 50-60%, wherein the semi-dry gel is a phosphatized modified polyimide film.
3. The high-flame-retardant functional intelligent coated high-frequency copper-clad plate according to claim 1, wherein the phosphonate is one or more of tetrasodium amino trimethylene phosphonate, sodium hydroxyethylidene diphosphonate, potassium hydroxyethylidene diphosphonate and sodium diethylenetriamine pentamethyl phosphonate.
4. The high-flame-retardant functional intelligent coated high-frequency copper-clad plate according to claim 1, wherein the bio-based dimer acid glycidyl ester modified epoxy resin comprises the following components in parts by weight:
Figure FDA0002909132270000021
Figure FDA0002909132270000031
5. the high-flame-retardant functional intelligent coated high-frequency copper-clad plate according to claim 4, wherein the dienoic acid is one or more of arachidienic acid, aromatica dienoic acid, 2, 4-hexadienoic acid, decadienoic acid, octadecadienoic acid and docosadienoic acid.
6. The high-flame-retardant functional intelligent coated high-frequency copper-clad plate according to claim 4, wherein the curing accelerator is one or more of 2-methylimidazole, 2-ethyl-4-methylimidazole and N-methylimidazole.
7. The preparation method of the high-flame-retardant function intelligent coating high-frequency copper-clad plate according to any one of claims 1 to 6, which is characterized by comprising the following steps:
s1: heating the glass fiber cloth at 400-500 ℃ for 30min, removing surface paraffin, soaking the glass fiber cloth after heat treatment in a silane coupling agent for 5-10 min, naturally drying in the air, and baking at 110-120 ℃ for 30 min;
s2, heating the bio-based dimer acid glycidyl ester modified epoxy resin at 50-60 ℃ for 20-30 min;
s3: coating the heated biological-based dimer acid glycidyl ester modified epoxy resin obtained in the step S2 on the glass fiber cloth obtained in the step S1, then drying the glass fiber cloth at the temperature of 30-40 ℃ for 30-40 min, and continuously repeating the coating and the drying for 3-5 times, so that the biological-based dimer acid glycidyl ester modified epoxy resin on the glass fiber cloth reaches more than 60%, and obtaining a resin-coated glass fiber cloth raw substrate;
s4: immersing the phosphorized modified polyimide film in a sulfonated disodium succinate ethanol solution with the volume fraction of 30-40%, ultrasonically oscillating for 20-25 min, taking out, and cleaning for 3 times at intervals by using ethanol and distilled water to obtain a surface activated phosphorized modified polyimide film;
s5: taking two resin-coated glass fiber cloth raw substrates obtained in the step S3, respectively covering the upper surface and the lower surface of the surface activated phosphorized modified polyimide film obtained in the step S4, and drying at 100-150 ℃ for 20min to obtain a prepreg (1) with the middle made of the phosphorized modified polyimide film material and three layers of films of the resin-coated glass fiber cloth raw substrates positioned at two sides of the prepreg (1);
s6: and overlapping a layer of copper foil on the upper surface of the resin-coated glass fiber cloth raw substrate on the upper side, overlapping a layer of copper foil on the lower surface of the resin-coated glass fiber cloth raw substrate on the lower side, then placing the copper foil between two steel plates, and carrying out vacuum hot pressing for 1.5-2.0 h at 380-420 ℃ by 450-1150 PSI for forming to obtain the high-flame-retardant function intelligent coated high-frequency copper-clad plate.
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