CN113088032A - Linear phenolic resin and method for manufacturing high-performance halogen-free environment-friendly paper-based copper-clad plate by using same - Google Patents
Linear phenolic resin and method for manufacturing high-performance halogen-free environment-friendly paper-based copper-clad plate by using same Download PDFInfo
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- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
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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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- 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 discloses a high-performance halogen-free linear phenolic resin glue solution and a production method for preparing a high-performance halogen-free environment-friendly paper-based copper-clad plate by curing the same. The feed comprises the following raw materials in parts by weight: 8-10 parts of basic epoxy resin, 3-5 parts of o-cresol epoxy resin, 6-10 parts of modified linear phenolic resin, 55-60 parts of modified flame-retardant thermosetting phenolic resin, 13-15 parts of polymeric phosphate and 5-8 parts of aluminum hydroxide. According to the invention, through the implementation of the development and technical innovation, the problems of poor curing and the like of the environment-friendly V0 board are solved, the high-performance environment-friendly V0 board cured by the halogen-free novolac phenolic resin is manufactured in a mode of blending and curing the halogen-free novolac phenolic and the basic epoxy, the quality problem in the production process of the environment-friendly V0 board can be solved, the performance of the board is obviously improved, continuous batch production can be carried out in a workshop, and the production cost is greatly reduced.
Description
Technical Field
The invention relates to a linear phenolic resin and a production method for preparing a high-performance halogen-free environment-friendly paper-based copper-clad plate by curing the same.
Background
The development of the electronic industry also drives the development of the printed circuit industry closely related to the electronic industry, and the development of the printed circuit industry promotes the progress of the new material technology of the copper-clad plate. The copper-clad plates used by common electronic products mostly adopt halogen flame retardants, and the copper-clad plates containing halogen can emit toxic gases when burning, thereby affecting the health of human bodies.
With the enhancement of environmental awareness of people, the concept of green electronic products is gradually popularized, copper-clad plates have become a new development trend without halogenation, and in order to seize the opportunity for commercialization, various copper-clad plate manufacturers have vigorously researched and developed application technologies of halogen-free flame retardants, and the research on halogen-free environment-friendly copper-clad plates is a necessary development trend in the current society.
With the development of electronic and electric products towards the direction of high power, miniaturization and environmental protection, higher requirements are put forward on the performance of the copper-clad plate. Most of the prior halogen-free environment-friendly paperboards use basic epoxy, the molecular weight of the epoxy resin is low, the thermosetting phenolic resin is slow to cure, and the dimethyl imidazole accelerator is too fast to cure, so that the quality problems of aging and the like are caused. According to the project, melamine modified linear phenolic aldehyde is added, heating reflux is matched, effective curing of epoxy resin is promoted, and high-heat-resistance o-cresol epoxy resin is added, so that the heat resistance of the epoxy resin is improved; the flame-retardant phenolic resin and the phosphorus-containing flame retardant of the polymer are added, so that the flame retardant performance of the copper-clad plate reaches 94V0 level, the process formula is suitable for the requirements of high-speed and high-performance development of paper-based copper-clad plate products, and the process formula not only meets the requirement of strategic development of the copper-clad plate products in China, but also meets the urgent requirements of pulling the development of the copper-clad plate industry in China, accelerating the manufacturing pace of high and new technology in the industry and promoting the rapid.
Disclosure of Invention
According to the invention, through the implementation of the development and technical innovation, the problems of poor curing and the like of the environment-friendly V0 board are solved, the high-performance environment-friendly V0 board cured by the halogen-free novolac phenolic resin is manufactured in a mode of blending and curing the halogen-free novolac phenolic and the basic epoxy, the quality problem in the production process of the environment-friendly V0 board can be solved, continuous batch production in a workshop can be realized, and the production cost is greatly reduced.
Specifically, the application provides a high-performance halogen-free linear phenolic resin glue solution which is characterized by comprising melamine modified linear phenolic resin and modified flame-retardant thermosetting phenolic resin.
Further, the feed comprises the following raw materials in parts by weight: 8-10 parts of basic epoxy resin, 3-5 parts of o-cresol epoxy resin, 6-10 parts of modified linear phenolic resin, 55-60 parts of modified flame-retardant thermosetting phenolic resin, 13-15 parts of polymeric phosphate and 5-8 parts of aluminum hydroxide.
Further, the composition and the preparation method of the melamine modified linear phenolic resin are as follows,
(1) the melamine modified linear phenolic resin is prepared from the following raw materials in parts by weight
A: 3-5 parts of phenol
B: 55-58 parts of formaldehyde
C, 25-30 parts of melamine
D, 8-12 parts of solvent
(2) Adding 25-30 parts of melamine into a mixed liquid of formaldehyde and phenol with a formula amount, uniformly stirring, adding a proper amount of NAOH, mixing and heating, heating to 92-95 ℃ within 20-30 minutes, keeping the temperature for 30 minutes, measuring the water mixing degree, adding a proper amount of guanidine carbonate when the water mixing degree reaches 100-150mL, and cooling with methanol to prepare the ammonia-containing phenolic resin;
(3) the nitrogenous phenolic resin is prepared for the first-time dry sizing, and can well swell paper, so that low-molecular resin glue solution occupies fiber spaces of the paper, fiber interiors and fiber cavity walls, fiber inner cavities and gaps are enlarged, the permeability and the compactness of secondary resin are improved, the glue content of primary glue is properly improved, and the water absorption rate can be effectively reduced.
Further, the modified flame-retardant thermosetting phenolic resin is prepared by mixing the following raw materials in parts by weight,
a: 50-60 parts of tung oil and flame-retardant epoxy soybean oil modified mixed resin
B: 15-20 parts of bisphenol A type epoxy resin
3-5 parts of o-cresol epoxy resin
D, 1-2 parts of aluminum hydroxide with the particle size of less than 5um
E, 10 to 15 portions of nitrogenous modified linear phenolic resin
And F, 8-10 parts of a solvent.
Further, the method comprises the following steps:
s1, adding the raw materials into a special reaction kettle, stirring at a rotating speed of 200-400 r/min, heating to 60-80 ℃ for reflux, and stirring and mixing at the temperature for 1-2 hours to obtain mixed epoxy resin A;
and S2, after the gel time of the reflux glue solution meets the process requirements, cooling to below 40 ℃, adding 10 parts of methanol, shearing in a high-speed shearing kettle for 2 hours, and blending to obtain the high-performance halogen-free linear phenolic resin glue solution.
Further, the high-performance halogen-free linear phenolic resin is prepared and used for drying sizing for the second time, the nitrogen-containing modified phenolic resin can effectively promote the ring-opening curing reaction of the epoxy resin, the epoxy value of the o-cresol-formaldehyde epoxy resin is as high as more than 0.5eq/100g, 2.5 times of cross-linking points can be provided when the resin is cured, a three-dimensional structure with high cross-linking density is easily formed, and a cured substance is rich in a phenolic aldehyde framework, so that the excellent thermal stability, the electric insulation performance, the water resistance and the like are shown, and the TD temperature of the copper-clad plate is effectively improved.
Further, the method comprises the following steps:
s1, placing the insulating wood pulp paper or the flame-retardant fiber paper in a gluing machine, performing secondary impregnation, and then placing in a drying oven at 160-180 ℃ for heating and drying to obtain an impregnated semi-finished PP or impregnated flame-retardant fiber paper;
s2, overlapping the impregnated semi-finished PP or impregnated flame-retardant fiber paper according to the process specification requirement to prepare semi-finished adhesive paper;
and S3, compounding the semi-finished adhesive paper prepared in the step S2 with copper foil, feeding the compounded semi-finished adhesive paper and the copper foil into a vacuum compressor, and carrying out hot pressing and curing under the conditions of 28-32 MPa pressure and 180-185 ℃ to obtain the paper-based copper-clad plate.
Detailed Description
The high-performance halogen-free linear phenolic resin glue solution is characterized by comprising the following raw materials in parts by weight: 8-10 parts of basic epoxy resin, 3-5 parts of o-cresol epoxy resin, 6-10 parts of modified linear phenolic resin, 55-60 parts of modified flame-retardant thermosetting phenolic resin, 13-15 parts of polymeric phosphate and 5-8 parts of aluminum hydroxide.
Wherein the composition and the preparation method of the melamine modified linear phenolic resin are as follows,
(1) the melamine modified linear phenolic resin is prepared from the following raw materials in parts by weight
A: 3-5 parts of phenol
B: 55-58 parts of formaldehyde
C, 25-30 parts of melamine
D, 8-12 parts of solvent
(2) Adding 25-30 parts of melamine into a mixed liquid of formaldehyde and phenol with a formula amount, uniformly stirring, adding a proper amount of NAOH, mixing and heating, heating to 92-95 ℃ within 20-30 minutes, keeping the temperature for 30 minutes, measuring the water mixing degree, adding a proper amount of guanidine carbonate when the water mixing degree reaches 100-150mL, and cooling with methanol to prepare the ammonia-containing phenolic resin;
(3) the nitrogenous phenolic resin is prepared for the first-time dry sizing, and can well swell paper, so that low-molecular resin glue solution occupies fiber spaces of the paper, fiber interiors and fiber cavity walls, fiber inner cavities and gaps are enlarged, the permeability and the compactness of secondary resin are improved, the glue content of primary glue is properly improved, and the water absorption rate can be effectively reduced.
Wherein the modified flame-retardant thermosetting phenolic resin is prepared by mixing the following raw materials in parts by weight,
a: 50-60 parts of tung oil and flame-retardant epoxy soybean oil modified mixed resin
B: 15-20 parts of bisphenol A type epoxy resin
3-5 parts of o-cresol epoxy resin
D, 1-2 parts of aluminum hydroxide with the particle size of less than 5um
E, 10 to 15 portions of nitrogenous modified linear phenolic resin
And F, 8-10 parts of a solvent.
The method comprises the following steps:
s1, adding the raw materials into a special reaction kettle, stirring at a rotating speed of 200-400 r/min, heating to 60-80 ℃ for reflux, and stirring and mixing at the temperature for 1-2 hours to obtain mixed epoxy resin A;
and S2, after the gel time of the reflux glue solution meets the process requirements, cooling to below 40 ℃, adding 10 parts of methanol, shearing in a high-speed shearing kettle for 2 hours, and blending to obtain the high-performance halogen-free linear phenolic resin glue solution.
The high-performance halogen-free linear phenolic resin is prepared and used for drying sizing for the second time, the nitrogen-containing modified phenolic resin can effectively promote the ring-opening curing reaction of the epoxy resin, the epoxy value of the o-cresol-formaldehyde epoxy resin is up to more than 0.5eq/100g, 2.5 times of cross-linking points can be provided when the resin is cured, a three-dimensional structure with high cross-linking density is easily formed, and a cured substance is rich in a phenolic aldehyde framework, shows excellent thermal stability, electrical insulation performance, water resistance and the like, and effectively improves the TD temperature of the copper-clad plate.
The method comprises the following steps:
s1, placing the insulating wood pulp paper or the flame-retardant fiber paper in a gluing machine, performing secondary impregnation, and then placing in a drying oven at 160-180 ℃ for heating and drying to obtain an impregnated semi-finished PP or impregnated flame-retardant fiber paper;
s2, overlapping the impregnated semi-finished PP or impregnated flame-retardant fiber paper according to the process specification requirement to prepare semi-finished adhesive paper;
and S3, compounding the semi-finished adhesive paper prepared in the step S2 with copper foil, feeding the compounded semi-finished adhesive paper and the copper foil into a vacuum compressor, and carrying out hot pressing and curing under the conditions of 28-32 MPa pressure and 180-185 ℃ to obtain the paper-based copper-clad plate.
Example 1
The high-performance halogen-free linear phenolic resin glue solution is characterized by comprising the following raw materials in parts by weight: 8 parts of basic epoxy resin, 3 parts of o-cresol epoxy resin, 10 parts of modified linear phenolic resin, 60 parts of modified flame-retardant thermosetting phenolic resin, 15 parts of polymeric phosphate and 5 parts of aluminum hydroxide.
Wherein the composition and the preparation method of the melamine modified linear phenolic resin are as follows,
(1) the melamine modified linear phenolic resin is prepared from the following raw materials in parts by weight
A: 5 parts of phenol
B: 58 portions of formaldehyde
C, 30 parts of melamine
D, 12 parts of solvent
(2) Adding 30 parts of melamine into a mixed liquid of formaldehyde and phenol with a formula amount, uniformly stirring, adding a proper amount of NAOH, mixing and heating, heating to 95 ℃ within 20 minutes, keeping the temperature for 30 minutes, measuring the water mixing degree, adding a proper amount of guanidine carbonate when the water mixing degree reaches 100mL, and cooling with methanol to prepare an ammonia-containing phenolic resin;
(3) the nitrogenous phenolic resin is prepared for the first-time dry sizing, and can well swell paper, so that low-molecular resin glue solution occupies fiber spaces of the paper, fiber interiors and fiber cavity walls, fiber inner cavities and gaps are enlarged, the permeability and the compactness of secondary resin are improved, the glue content of primary glue is properly improved, and the water absorption rate can be effectively reduced.
Wherein the modified flame-retardant thermosetting phenolic resin is prepared by mixing the following raw materials in parts by weight,
a: 60 parts of tung oil and flame-retardant epoxidized soybean oil modified mixed resin
B: bisphenol A type epoxy resin 15 parts
5 portions of o-cresol epoxy resin
D, 1 part of aluminum hydroxide with the particle size of less than 5um
E, 15 parts of nitrogen-containing modified linear phenolic resin
And F, 10 parts of a solvent.
The method comprises the following steps:
s1, adding the raw materials into a special reaction kettle, stirring at a rotating speed of 400r/min, heating to 60 ℃ for reflux, and stirring and mixing at the temperature for 1-2 hours to obtain mixed epoxy resin A;
and S2, after the gel time of the reflux glue solution meets the process requirements, cooling to below 40 ℃, adding 10 parts of methanol, shearing in a high-speed shearing kettle for 2 hours, and blending to obtain the high-performance halogen-free linear phenolic resin glue solution.
Example 2
The high-performance halogen-free linear phenolic resin glue solution is characterized by comprising the following raw materials in parts by weight: 10 parts of basic epoxy resin, 5 parts of o-cresol epoxy resin, 6 parts of modified linear phenolic resin, 55 parts of modified flame-retardant thermosetting phenolic resin, 13 parts of polymeric phosphate and 8 parts of aluminum hydroxide.
Wherein the composition and the preparation method of the melamine modified linear phenolic resin are as follows,
(1) the melamine modified linear phenolic resin is prepared from the following raw materials in parts by weight
A: phenol 3 parts
B: 55 parts of formaldehyde
C, 25 parts of melamine
D, 8 parts of solvent
(2) Adding 25 parts of melamine into a mixed liquid of formaldehyde and phenol with a formula amount, uniformly stirring, adding a proper amount of NAOH, mixing and heating, heating to 92 ℃ within 30 minutes, keeping the temperature for 30 minutes, measuring the water mixing degree, adding a proper amount of guanidine carbonate when the water mixing degree reaches 150mL, and cooling with methanol to prepare an ammonia-containing phenolic resin;
(3) the nitrogenous phenolic resin is prepared for the first-time dry sizing, and can well swell paper, so that low-molecular resin glue solution occupies fiber spaces of the paper, fiber interiors and fiber cavity walls, fiber inner cavities and gaps are enlarged, the permeability and the compactness of secondary resin are improved, the glue content of primary glue is properly improved, and the water absorption rate can be effectively reduced.
Wherein the modified flame-retardant thermosetting phenolic resin is prepared by mixing the following raw materials in parts by weight,
a: 50 parts of tung oil and flame-retardant epoxy soybean oil modified mixed resin
B: bisphenol A type epoxy resin 20 parts
3 portions of o-cresol epoxy resin
D, 2 parts of aluminum hydroxide with the particle size of less than 5um
E, 10 parts of nitrogen-containing modified linear phenolic resin
And F, 8 parts of a solvent.
The method comprises the following steps:
s1, adding the raw materials into a special reaction kettle, stirring at a rotating speed of 350r/min, heating to 80 ℃ for reflux, and stirring and mixing at the temperature for 1.5 hours to obtain mixed epoxy resin A;
and S2, after the gel time of the reflux glue solution meets the process requirements, cooling to below 40 ℃, adding 10 parts of methanol, shearing in a high-speed shearing kettle for 2 hours, and blending to obtain the high-performance halogen-free linear phenolic resin glue solution.
Example 3
The method for producing the halogen-free high-performance environment-friendly board by curing the linear phenolic resin comprises the following steps:
s1, placing the insulating wood pulp paper or the flame-retardant fiber paper in a gluing machine, performing secondary impregnation, and then placing in a drying oven at 160 ℃ for heating and drying to obtain an impregnated semi-finished product PP or impregnated flame-retardant fiber paper;
s2, overlapping the impregnated semi-finished PP or impregnated flame-retardant fiber paper according to the process specification requirement to prepare semi-finished adhesive paper;
and S3, compounding the semi-finished adhesive paper prepared in the step S2 with copper foil, feeding the compounded semi-finished adhesive paper and the copper foil into a vacuum compressor, and carrying out hot-pressing curing under the conditions of 32MPa pressure and 180 ℃ to obtain the paper-based copper-clad plate.
Example 4
The method for producing the halogen-free high-performance environment-friendly board by curing the linear phenolic resin comprises the following steps:
s1, placing the insulating wood pulp paper or the flame-retardant fiber paper in a gluing machine, performing secondary impregnation, and then placing in a drying oven at 180 ℃ for heating and drying to obtain an impregnated semi-finished product PP or impregnated flame-retardant fiber paper;
s2, overlapping the impregnated semi-finished PP or impregnated flame-retardant fiber paper according to the process specification requirement to prepare semi-finished adhesive paper;
and S3, compounding the semi-finished adhesive paper prepared in the step S2 with copper foil, feeding the compounded semi-finished adhesive paper and the copper foil into a vacuum press, and carrying out hot-pressing curing under the conditions of 28MPa pressure and 185 ℃ to obtain the paper-based copper-clad plate.
The performance of the eco-friendly boards of examples 3 to 4 was measured and compared with the performance of the conventional general boards as follows.
High performance panel performance test comparison data:
therefore, through the implementation of the development and technical innovation, the problems of poor curing and the like of the environment-friendly V0 board are solved, the environment-friendly V0 board cured by the high-performance halogen-free novolac phenolic resin is manufactured in a mode of blending and curing the halogen-free novolac phenolic and the basic epoxy, the quality problem in the production process of the environment-friendly V0 board can be solved, the performance is obviously improved, continuous batch production can be carried out in a workshop, and the production cost is greatly reduced.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any alterations made therein are intended to be included within the spirit and scope of the present invention.
Claims (7)
1. The high-performance halogen-free linear phenolic resin glue solution is characterized by comprising melamine modified linear phenolic resin and modified flame-retardant thermosetting phenolic resin.
2. The high-performance halogen-free linear phenolic resin glue solution of claim 1 is characterized by comprising the following raw materials in parts by weight: 8-10 parts of basic epoxy resin, 3-5 parts of o-cresol epoxy resin, 6-10 parts of modified linear phenolic resin, 55-60 parts of modified flame-retardant thermosetting phenolic resin, 13-15 parts of polymeric phosphate and 5-8 parts of aluminum hydroxide.
3. The high-performance halogen-free linear phenolic resin glue solution of claim 1 or 2, characterized in that: the composition and preparation method of the melamine modified linear phenolic resin are as follows,
(1) the melamine modified linear phenolic resin is prepared from the following raw materials in parts by weight
A: 3-5 parts of phenol
B: 55-58 parts of formaldehyde
C, 25-30 parts of melamine
D, 8-12 parts of solvent
(2) Adding 25-30 parts of melamine into a mixed liquid of formaldehyde and phenol with a formula amount, uniformly stirring, adding a proper amount of NAOH, mixing and heating, heating to 92-95 ℃ within 20-30 minutes, keeping the temperature for 30 minutes, measuring the water mixing degree, adding a proper amount of guanidine carbonate when the water mixing degree reaches 100-150mL, and cooling with methanol to prepare the ammonia-containing phenolic resin;
(3) the nitrogenous phenolic resin is prepared for the first-time dry sizing, and can well swell paper, so that low-molecular resin glue solution occupies fiber spaces of the paper, fiber interiors and fiber cavity walls, fiber inner cavities and gaps are enlarged, the permeability and the compactness of secondary resin are improved, the glue content of primary glue is properly improved, and the water absorption rate can be effectively reduced.
4. The high-performance halogen-free linear phenolic resin glue solution of claim 1 or 2, characterized in that the modified flame-retardant thermosetting phenolic resin is prepared by mixing the following raw materials in parts by weight,
a: 50-60 parts of tung oil and flame-retardant epoxy soybean oil modified mixed resin
B: 15-20 parts of bisphenol A type epoxy resin
3-5 parts of o-cresol epoxy resin
D, 1-2 parts of aluminum hydroxide with the particle size of less than 5um
E, 10 to 15 portions of nitrogenous modified linear phenolic resin
And F, 8-10 parts of a solvent.
5. The preparation method of the high-performance halogen-free linear phenolic resin glue solution of any one of claims 1 to 4 is characterized by comprising the following steps:
s1, adding the raw materials into a special reaction kettle, stirring at a rotating speed of 200-400 r/min, heating to 60-80 ℃ for reflux, and stirring and mixing at the temperature for 1-2 hours to obtain mixed epoxy resin A;
and S2, after the gel time of the reflux glue solution meets the process requirements, cooling to below 40 ℃, adding 10 parts of methanol, shearing in a high-speed shearing kettle for 2 hours, and blending to obtain the high-performance halogen-free linear phenolic resin glue solution.
6. The high-performance halogen-free linear phenolic resin is prepared and used for drying glue for the second time, the nitrogen-containing modified phenolic resin can effectively promote the ring-opening curing reaction of the epoxy resin, the epoxy value of the o-cresol-formaldehyde epoxy resin is up to more than 0.5eq/100g, 2.5 times of crosslinking points can be provided when the resin is cured, a three-dimensional structure with high crosslinking density is easily formed, and a cured substance is rich in a phenolic aldehyde framework, shows excellent thermal stability, electrical insulation performance, water resistance and the like, and effectively improves the TD temperature of the copper-clad plate.
7. Use according to claim 6, characterized in that it comprises the following steps:
s1, placing the insulating wood pulp paper or the flame-retardant fiber paper in a gluing machine, performing secondary impregnation, and then placing in a drying oven at 160-180 ℃ for heating and drying to obtain an impregnated semi-finished PP or impregnated flame-retardant fiber paper;
s2, overlapping the impregnated semi-finished PP or impregnated flame-retardant fiber paper according to the process specification requirement to prepare semi-finished adhesive paper;
and S3, compounding the semi-finished adhesive paper prepared in the step S2 with copper foil, feeding the compounded semi-finished adhesive paper and the copper foil into a vacuum compressor, and carrying out hot pressing and curing under the conditions of 28-32 MPa pressure and 180-185 ℃ to obtain the paper-based copper-clad plate.
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| CN202110320337.0A CN113088032A (en) | 2021-03-25 | 2021-03-25 | Linear phenolic resin and method for manufacturing high-performance halogen-free environment-friendly paper-based copper-clad plate by using same |
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| CN114589988A (en) * | 2022-03-11 | 2022-06-07 | 建滔(佛冈)积层板有限公司 | CEM-1 copper-clad plate based on multiple curing system and preparation method thereof |
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| CN115489183A (en) * | 2022-07-26 | 2022-12-20 | 江苏耀鸿电子有限公司 | Phenolic resin reinforced high-toughness copper-clad plate and preparation method thereof |
| CN115651366A (en) * | 2022-11-18 | 2023-01-31 | 江苏耀鸿电子有限公司 | Resin glue solution containing alumina for copper-clad plate and preparation method thereof |
| CN117382265A (en) * | 2023-12-12 | 2024-01-12 | 福建利豪电子科技股份有限公司 | Manufacturing method of one-time rubberizing flame-retardant paper-based copper-clad plate |
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| CN117382265A (en) * | 2023-12-12 | 2024-01-12 | 福建利豪电子科技股份有限公司 | Manufacturing method of one-time rubberizing flame-retardant paper-based copper-clad plate |
| CN117382265B (en) * | 2023-12-12 | 2024-02-20 | 福建利豪电子科技股份有限公司 | Manufacturing method of one-time rubberizing flame-retardant paper-based copper-clad plate |
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