CN113896916A - Preparation method of prepreg and copper-clad plate based on high-Tg ultrahigh molecular weight polyethylene fiber cloth - Google Patents
Preparation method of prepreg and copper-clad plate based on high-Tg ultrahigh molecular weight polyethylene fiber cloth Download PDFInfo
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
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Abstract
The invention provides a preparation method of a prepreg and a copper-clad plate based on high Tg ultrahigh molecular weight polyethylene fiber cloth. The preparation method of the prepreg comprises the following steps: 1) weighing resin, filler, flame retardant and initiator according to a proportion; adding the weighed components into a glue mixing bottle, adding a solvent, stirring until the components are completely dissolved, and then adding a proper amount of a coupling agent; 2) dispersing the uniformly mixed glue solution to obtain a resin composition glue solution; 3) and (3) soaking the high-Tg ultrahigh molecular weight polyethylene fiber cloth in the resin composition glue solution, and then heating and drying the high-Tg ultrahigh molecular weight polyethylene fiber cloth by a glue dipping machine until semi-solidification is carried out to obtain a semi-solidified sheet. Because the high-Tg ultrahigh molecular weight polyethylene fiber has excellent dielectric property, the dielectric constant DK of the prepared high-frequency high-speed copper-clad plate is 2.5-2.8 by compounding with the specific resin, the flammability reaches UL 94V-0 grade, and the high-Tg ultrahigh molecular weight polyethylene fiber has higher glass transition temperature, excellent humidity resistance and lower water absorption property.
Description
Technical Field
The invention relates to a prepreg based on high-Tg ultrahigh molecular weight polyethylene fiber cloth and a preparation method for preparing a copper-clad plate by using the prepreg, belonging to the technical field of electronic materials.
Background
The traditional PTFE substrate has low dielectric constant and low dielectric loss, and is widely applied to the field of radio frequency microwaves. However, burrs are generated in a drilling process of the base material in the PCB processing process, naphthalene sodium treatment is needed in a glue removing process, copper is not easy to be added to the hole wall in a copper deposition process, the multilayer board is in contraposition offset and the like, and the traditional PTFE base material is low in modulus and large in thermal expansion coefficient, so that the phase fluctuation of the PCB is large. These factors have resulted in PTFE materials that have failed to meet most of the 5G era antenna product design requirements.
The Chinese patent application CN109836631A discloses a prepreg and a copper-clad plate prepared by adopting a hydrocarbon resin composition and hollow glass microspheres and matching with electronic-grade glass fiber cloth, wherein the copper-clad plate has lower dielectric property, water absorption, better heat resistance and subsequent excellent PCB processing property, but compared with a PTFE copper-clad plate, the copper-clad plate has the defects of higher dielectric property, water absorption and the like.
The Chinese invention patent application CN110039852A discloses that electronic grade glass fiber cloth is soaked in PTFE emulsion to prepare a PTFE bonding sheet and a PTFE copper-clad plate is prepared at a high temperature of more than 380 ℃, the copper-clad plate has excellent dielectric property, lower water absorption and better heat resistance, but the plate needs to be pressed and molded at a higher temperature, and the base material has the problems that burrs occur in a drilling process in a PCB processing process, a glue removing process needs to be treated by sodium naphthalene, the hole wall of a copper precipitation process is not easy to be copper, a multilayer plate is in contraposition offset and the like, and the PTFE material cannot meet the design requirements of most antenna products in the 5G era due to the factors.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a prepreg based on high-Tg ultrahigh molecular weight polyethylene fiber cloth and a preparation method for preparing a copper-clad plate by using the prepreg.
The first invention aims to provide a preparation method of a prepreg based on high Tg ultrahigh molecular weight polyethylene fiber cloth.
In the preparation method, the raw materials comprise the following components in parts by weight: 20-40 parts of resin, 10-40 parts of filler, 0-15 parts of flame retardant, 1.5-3 parts of coupling agent and 0.5-1 part of initiator; preferably, the raw materials comprise the following components in parts by weight: 24-27 parts of resin, 15 parts of filler, 3.5 parts of flame retardant, 1.5 parts of coupling agent and 1 part of initiator;
the resin is selected from one or more of modified polyphenyl ether resin with a multi-hydrocarbon structure, polydiene polymer resin, cyanate resin or benzocyclobutene resin. Wherein, the modified polyphenylene ether resin is low molecular weight polyphenylene ether capped by a reactive functional group, and the molecular weight of the modified polyphenylene ether resin is 800-5000, preferably 1000-4000. The polydiene hydrocarbon polymer resin comprises one or more of isoprene, styrene, butadiene copolymer, styrene/divinyl copolymer, polydivinylbenzene, and dicyclopentadiene polymer. Preferably, the resin is a composition of polyphenylene oxide resin PPO (SA9000), styrene-butadiene resin (R100) and polybutadiene resin (B3000), the weight ratio of the polyphenylene oxide resin (SA9000) to the styrene-butadiene resin (R100) to the polybutadiene resin (B3000) in the composition is 10-50: 10-30: 2-20; more preferably, the weight ratio of the polyphenylene ether resin (SA9000), the styrene-butadiene resin (R100) and the polybutadiene resin (B3000) in the composition is 12-15: 10: 2.
the filler is selected from one or more of silicon dioxide, silicon carbide, aluminum nitride, titanium dioxide and hollow glass microspheres. The filler is preferably modified fused silica, more preferably the combination of the modified fused silica and hollow glass microspheres, and the weight ratio of the modified fused silica to the hollow glass microspheres is 2: 1; the hollow glass microspheres can be selected from one or more of K37, S38, S38HS, K42HS, S60, S60HS, IM30K and the like of 3M company.
The flame retardant is one or two selected from phosphorus-containing flame retardants, nitrogen-containing flame retardants, decabromodiphenyl ether, decabromodiphenylethane, tetrabromobisphenol A and decabromocyclododecane. Preferably, the flame retardant is decabromodiphenyl ether.
The coupling agent is any one selected from vinyl trimethyl siloxane, 3-aminopropyl trimethyl siloxane, (2, 3-epoxypropoxy) propyl trimethyl siloxane and phenyl trimethyl siloxane. Preferably, the coupling agent is vinyl trimethicone.
The initiator is selected from peroxy radical initiators, and is selected from one or more of dibenzoyl peroxide, tert-butyl peroxybenzoate, di-tert-butyl peroxide, tert-butyl hydroperoxide, diisopropylbenzene hydroperoxide, methyl ethyl ketone peroxide, 1, 1, 3, 3-tetramethylbutyl hydroperoxide, tert-amyl hydroperoxide and the like. Preferably, the initiator is di-tert-butyl peroxide.
The preparation method comprises the following steps:
1) weighing resin, filler, flame retardant and initiator according to a proportion; adding the weighed components into a glue mixing bottle, adding a solvent, stirring until the components are completely dissolved, and then adding a proper amount of a coupling agent;
2) dispersing the uniformly mixed glue solution by adopting a sand mill, a ball mill or a high-speed emulsifying machine to obtain a resin composition glue solution; preferably a ball mill;
3) and (3) soaking the high-Tg ultrahigh molecular weight polyethylene fiber cloth in the resin composition glue solution, and then heating and drying the high-Tg ultrahigh molecular weight polyethylene fiber cloth by a glue dipping machine until semi-solidification is carried out to obtain a semi-solidified sheet.
In the step 1), the solvent is toluene, xylene or chloroform, and preferably the solvent is toluene.
In the step 3), the clearance of the impregnator is 0.25mm, the heating and drying temperature is 120 ℃, and the time is 5 min.
In the step 3), the weight of the high Tg ultrahigh molecular weight polyethylene fiber cloth accounts for 40% of the total weight of the fiber cloth and the glue solution.
The thickness of the high-Tg ultrahigh molecular weight polyethylene fiber cloth used in the invention is similar to that of the traditional electronic grade glass fiber cloth, but the dielectric property under high frequency is greatly improved, the traditional electronic grade glass fiber cloth is Dk 6.13 and Df 0.0035, while the high-Tg ultrahigh molecular weight polyethylene fiber cloth is Dk 2.3 and Df 0.0004, and the heat distortion temperature of the treated high-Tg ultrahigh molecular weight polyethylene fiber cloth is between 100 ℃ and 120 ℃, which is greatly improved compared with the traditional ultrahigh molecular weight polyethylene fiber cloth (the heat distortion temperature is 80-90 ℃). The surface of the used high-Tg ultrahigh molecular weight polyethylene fiber cloth is modified by vinyl trimethyl siloxane so as to improve the wettability of the polyethylene fiber cloth and a resin system. The treated ultrahigh molecular weight polyethylene is modified by chemical crosslinking, namely peroxide is used as a crosslinking agent to generate free radicals under the action of the peroxide, so that the ultrahigh molecular weight polyethylene has higher crosslinking density, namely the thermal deformation temperature is increased, or fillers such as hollow ceramic powder or white carbon black are added to increase the thermal deformation temperature.
The high-Tg ultrahigh molecular weight polyethylene fiber cloth is adopted to replace the traditional glass fiber cloth to prepare the copper-clad plate, the advantages of low dielectric property of resin and reinforced fiber cloth in the copper-clad plate can be simultaneously exerted, the dielectric property which is difficult to achieve by the traditional thermosetting copper-clad plate can be achieved, and the high-Tg ultrahigh molecular weight polyethylene fiber cloth is used as a reinforcing material, so that the mechanical property, the heat resistance and certain dimensional stability of the copper-clad plate are ensured.
The second invention aims to provide a method for preparing a laminated copper-clad plate by using the prepreg.
The preparation method of the laminated copper-clad plate comprises the following steps: taking 4 prepregs, stacking the prepregs in order, covering 18 mu m of electrolytic copper foil on two sides, and placing the prepregs in a vacuum hot oil press, wherein the pressing procedure is as follows: the heating rate of lamination is controlled below 3 ℃/min; the laminating pressure is kept at 2MPa all the time; controlling the temperature of the prepreg at 180 ℃, and keeping the temperature for 60-100min, preferably 90 min.
The dielectric constant of the low-dielectric copper-clad plate is 2.5-2.7(@10 GHz).
The third purpose of the invention is to provide the application of the laminated copper-clad plate on a circuit board of 5G communication equipment.
The invention has the following technical effects:
1) the invention provides a prepreg based on high-Tg ultra-high molecular weight polyethylene fiber cloth and a preparation method for preparing a copper-clad plate by using the prepreg, wherein the high-Tg ultra-high molecular weight polyethylene fiber has excellent dielectric properties (Dk 2.3 and Df 0.0004@10GHz), and the high-frequency high-speed copper-clad plate prepared by compounding the prepreg with the specific resin has the dielectric constant DK of 2.5-2.8, the flammability reaches UL 94V-0 grade, and simultaneously has higher glass transition temperature, excellent moisture and heat resistance and lower water absorption performance, so that the performance of the PTFE copper-clad plate is achieved, the prepreg has excellent processing performance of the thermosetting copper-clad plate, and the design requirements of antenna products in most 5G times can be met.
2) As can be seen from the examples 1-2 of the invention, the dielectric properties DK and Df of the copper-clad plate prepared by the high Tg ultra-high molecular weight polyethylene fiber cloth are obviously reduced, the dielectric property requirements of the PTFE-grade copper-clad plate are met, and the properties of other copper-clad plates are basically consistent with those of the traditional thermosetting hydrocarbon copper-clad plate.
3) As can be seen from the embodiment 2 of the invention, the hollow glass microspheres with lower dielectric property are added in the embodiment 2, so that the dielectric property of the copper-clad plate can be reduced on the premise of not influencing other properties of the copper-clad plate.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
The purchase sources of the raw materials involved in example 1 of the present invention and the comparative examples are as follows:
polyphenylene oxide resin PPO (SA9000) resin was obtained from Saudi Industrial Foundation Co., Ltd;
the styrene-butadiene resin R100 is purchased from Kleavery chemical Co., Ltd;
polybutadiene resin B3000 was purchased from Nippon soda;
modified fused silica was purchased from brocade, suzhou, model Q1005.
Hollow glass microspheres were purchased from 3M, model K37.
High Tg ultra high molecular weight polyethylene fiber cloth was purchased from ritong.
Electronic grade glass fiber cloth was purchased from Ridong, model 2116.
Example 1
Firstly, preparing a prepreg
The raw materials are as follows: 12g of PPO resin, 10g of styrene-butadiene resin, 2g of polybutadiene resin, 15g of filler modified fused silica, 3.5g of decabromodiphenyl ether serving as a flame retardant, 1.5g of vinyl trimethylsiloxane serving as a coupling agent, 1g of di-tert-butyl peroxide serving as an initiator, 32g of toluene and 17g of Methyl Ethyl Ketone (MEK).
The preparation method of the prepreg comprises the following steps:
1) respectively weighing each component;
2) placing the PPO resin into a rubber mixing bottle, adding solvents toluene and MEK into the rubber mixing bottle, and stirring until the resin is completely dissolved;
3) then adding styrene-butadiene resin and polybutadiene resin into the rubber mixing bottle, and stirring until the styrene-butadiene resin and the polybutadiene resin are uniformly mixed;
4) adding the filler, the flame retardant, the coupling agent and the initiator into the rubber mixing bottle, and stirring until the mixture is uniformly mixed;
5) emulsifying and dispersing the mixed mixture at a rotating speed of 3000/min to obtain a resin composition, then adjusting the solid content of the system to 60%, and mixing to obtain a glue solution;
6) after 40g of high Tg ultrahigh molecular weight polyethylene fiber cloth is soaked in 60g of the resin composition glue solution, the high Tg ultrahigh molecular weight polyethylene fiber cloth passes through a 0.25mm gap width impregnator and is baked for 5min in a high-temperature oven at 120 ℃, and a prepreg can be prepared.
Secondly, preparing the copper-clad laminate
Taking 4 prepregs to stack up, covering copper foils with the thickness of 18 mu m on two sides, and placing the prepregs in a vacuum hot oil press, wherein the pressing procedure is as follows: the heating rate of lamination is controlled below 3 ℃/min; the laminating pressure is kept at 2MPa all the time; controlling the temperature of the prepreg at 180 ℃ and keeping the temperature for 90 min. The properties of the resulting copper clad laminate are shown in table 1.
Example 2
Firstly, preparing a prepreg
The raw materials are as follows: 15g of PPO resin, 10g of styrene-butadiene resin, 2g of polybutadiene resin and 10g of filler modified fused silica; 5g of filler hollow glass microspheres and 3.5g of flame retardant decabromodiphenyl ether; 1.5g of coupling agent vinyl trimethyl siloxane, 1g of initiator di-tert-butyl peroxide, 32g of toluene and 17g of Methyl Ethyl Ketone (MEK).
The prepreg was prepared in the same manner as in example 1.
Secondly, preparing the copper-clad laminate
The preparation method is the same as example 1. The properties of the resulting copper clad laminate are shown in table 1.
Comparative example 1
Firstly, preparing a prepreg
The raw materials are as follows: 15g of PPO resin, 10g of styrene-butadiene resin, 2g of polybutadiene resin, 10g of filler modified fused silica, 5g of filler hollow glass microspheres, 3.5g of flame retardant decabromodiphenyl ether, 1.5g of coupling agent vinyl trimethyl siloxane, 1g of initiator di-tert-butyl peroxide, 32g of toluene and 17g of butanone (MEK).
The preparation method of the prepreg comprises the following steps:
1) respectively weighing each component;
2) placing the PPO resin into a rubber mixing bottle, adding solvents toluene and MEK into the rubber mixing bottle, and stirring until the resin is completely dissolved;
3) then adding styrene-butadiene resin and polybutadiene resin into the rubber mixing bottle, and stirring until the styrene-butadiene resin and the polybutadiene resin are uniformly mixed;
4) adding the filler, the flame retardant, the coupling agent and the initiator into the rubber mixing bottle, and stirring until the mixture is uniformly mixed;
5) emulsifying and dispersing the mixed mixture at the rotating speed of 3000r/min to obtain a resin composition, then adjusting the solid content of the system to 60%, and mixing to obtain a glue solution;
6) after 40g of electronic grade glass fiber cloth is soaked in 60g of the resin composition glue solution, the electronic grade glass fiber cloth passes through a roller with a specific gap (the gap width is 0.25 mm), and then the electronic grade glass fiber cloth is baked for 8min in a high-temperature oven at 140 ℃ to obtain a prepreg.
Secondly, preparing the copper-clad laminate
The preparation method is the same as example 1. The properties of the resulting copper clad laminate are shown in table 1.
TABLE 1 copper clad laminate Properties of examples and comparative examples
And (4) conclusion:
from table 1 above it can be seen that: the copper-clad laminates of examples 1-2 achieved superior heat resistance and aging resistance with lower water absorption, superior dielectric properties, and a flame rating of UL 94V-0.
Compared with the copper-clad plate prepared by adopting the electronic-grade glass fiber cloth in the comparative example 1, the following steps can be seen: the dielectric properties DK and Df of the copper-clad plate prepared by the high-Tg ultrahigh molecular weight polyethylene fiber cloth are obviously reduced, the dielectric property requirement of the PTFE-grade copper-clad plate is met, and the properties of other copper-clad plates are basically consistent with those of the traditional thermosetting hydrocarbon copper-clad plate.
Compared with the embodiment 2, the embodiment 1 has the advantage that the hollow glass microspheres with lower dielectric property are added in the embodiment 2, so that the dielectric property of the copper-clad plate can be reduced on the premise of not influencing other properties of the copper-clad plate. Therefore, in examples 1-2, the performance parameters of example 2 were all superior.
Claims (10)
1. A preparation method of a prepreg based on high Tg ultra-high molecular weight polyethylene fiber cloth is characterized in that,
in the preparation method, the raw materials comprise the following components in parts by weight: 20-40 parts of resin, 10-40 parts of filler, 0-15 parts of flame retardant, 1.5-3 parts of coupling agent and 0.5-1 part of initiator;
the preparation method comprises the following steps:
1) weighing resin, filler, flame retardant and initiator according to a proportion; adding the weighed components into a glue mixing bottle, adding a solvent, stirring until the components are completely dissolved, and then adding a proper amount of a coupling agent;
2) dispersing the uniformly mixed glue solution to obtain a resin composition glue solution;
3) and (3) soaking the high-Tg ultrahigh molecular weight polyethylene fiber cloth in the resin composition glue solution, and then heating and drying the high-Tg ultrahigh molecular weight polyethylene fiber cloth by a glue dipping machine until semi-solidification is carried out to obtain a semi-solidified sheet.
2. The method for preparing a prepreg based on high Tg ultra high molecular weight polyethylene fiber cloth according to claim 1,
the resin is selected from one or more of modified polyphenyl ether resin with a multi-hydrocarbon structure, polydiene polymer resin, cyanate resin or benzocyclobutene resin;
the filler is selected from one or more of silicon dioxide, silicon carbide, aluminum nitride, titanium dioxide and hollow glass microspheres;
the flame retardant is one or two selected from phosphorus-containing flame retardants, nitrogen-containing flame retardants, decabromodiphenyl ether, decabromodiphenylethane, tetrabromobisphenol A and decabromocyclododecane;
the coupling agent is any one of vinyl trimethyl siloxane, 3-aminopropyl trimethyl siloxane, (2, 3-epoxypropoxy) propyl trimethyl siloxane and phenyl trimethyl siloxane;
the initiator is selected from peroxy radical initiators, and is selected from one or more of dibenzoyl peroxide, tert-butyl peroxybenzoate, di-tert-butyl peroxide, tert-butyl hydroperoxide, diisopropylbenzene hydroperoxide, methyl ethyl ketone peroxide, 1, 1, 3, 3-tetramethylbutyl hydroperoxide, tert-amyl hydroperoxide and the like.
3. The method for preparing a prepreg based on high Tg ultra high molecular weight polyethylene fiber cloth according to claim 2,
the resin is a composition of polyphenyl ether resin PPO, styrene-butadiene resin and polybutadiene resin, wherein the weight ratio of the polyphenyl ether resin to the styrene-butadiene resin to the polybutadiene resin in the composition is 10-50: 10-30: 2-20;
the filler is modified fused silica or the combination of the modified fused silica and hollow glass microspheres;
the flame retardant is decabromodiphenyl ether;
the coupling agent is vinyl trimethyl siloxane;
the initiator is di-tert-butyl peroxide.
4. The method for preparing the prepreg based on the high-Tg ultrahigh-molecular-weight polyethylene fiber cloth according to claim 3, wherein the weight ratio of the polyphenylene ether resin, the styrene-butadiene resin and the polybutadiene resin in the resin composition is 12-15: 10: 2.
5. the preparation method of the prepreg based on the high-Tg ultrahigh-molecular-weight polyethylene fiber cloth according to claim 1, wherein the raw materials comprise, by weight: 24-27 parts of resin, 15 parts of filler, 3.5 parts of flame retardant, 1.5 parts of coupling agent and 1 part of initiator.
6. The method for preparing a prepreg based on high-Tg ultra-high molecular weight polyethylene fiber cloth according to claim 1, wherein in the step 1), the solvent is toluene, xylene or chloroform.
7. The method for preparing the prepreg based on the high-Tg ultrahigh-molecular-weight polyethylene fiber cloth according to claim 1, wherein in the step 3), the gap of a impregnator is 0.25mm, the heating and drying temperature is 120 ℃, and the time is 5 min.
8. The method for preparing the prepreg based on the high-Tg ultrahigh-molecular-weight polyethylene fiber cloth according to claim 1, wherein in the step 3), the weight percentage of the high-Tg ultrahigh-molecular-weight polyethylene fiber cloth in the total weight of the fiber cloth and the glue solution is 40%.
9. A method for preparing a laminated copper clad laminate by using the prepreg prepared by any one of the methods of claims 1 to 8, which is characterized by comprising the following steps: and (3) taking the prepregs to be orderly stacked, covering electrolytic copper foils on two sides, placing the prepregs in a vacuum hot oil press, and pressing.
10. The use of the laminated copper clad laminate prepared by the method of claim 9 in a 5G communication equipment circuit board.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115505359A (en) * | 2022-08-17 | 2022-12-23 | 山东金宝电子有限公司 | Copper-clad plate glue solution, preparation method thereof and copper-clad plate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070854A (en) * | 2010-12-18 | 2011-05-25 | 广东生益科技股份有限公司 | Composite material, high-frequency circuit base board made of composite material and manufacture method thereof |
| CN111647247A (en) * | 2020-05-29 | 2020-09-11 | 上海材料研究所 | Resin composition for high-frequency high-speed copper-clad plate and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070854A (en) * | 2010-12-18 | 2011-05-25 | 广东生益科技股份有限公司 | Composite material, high-frequency circuit base board made of composite material and manufacture method thereof |
| CN111647247A (en) * | 2020-05-29 | 2020-09-11 | 上海材料研究所 | Resin composition for high-frequency high-speed copper-clad plate and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115505359A (en) * | 2022-08-17 | 2022-12-23 | 山东金宝电子有限公司 | Copper-clad plate glue solution, preparation method thereof and copper-clad plate |
| CN115505359B (en) * | 2022-08-17 | 2023-11-21 | 山东金宝电子有限公司 | Copper-clad plate glue solution, preparation method thereof and copper-clad plate |
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Application publication date: 20220107 |