CN115302885B - High-heat-resistance high-heat-conductivity copper-clad plate and preparation method thereof - Google Patents

High-heat-resistance high-heat-conductivity copper-clad plate and preparation method thereof Download PDF

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CN115302885B
CN115302885B CN202210954783.1A CN202210954783A CN115302885B CN 115302885 B CN115302885 B CN 115302885B CN 202210954783 A CN202210954783 A CN 202210954783A CN 115302885 B CN115302885 B CN 115302885B
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heat
epoxy resin
fibers
conductivity
copper
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CN115302885A (en
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周培峰
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Jiangmen Kingboard Laminates Holdings Ltd
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Jiangmen Kingboard Laminates Holdings Ltd
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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Abstract

The invention belongs to the technical field of printed circuit boards, and discloses a high-heat-resistance high-heat-conductivity copper-clad plate and a preparation method thereof. The preparation method comprises the following steps: uniformly stirring and mixing the paper-based fiber slurry, the heat-conducting filler and the emulsion adhesive, and then adding the silica sol to uniformly stir and mix to obtain mixed slurry; adding the obtained mixed slurry into a mould, and performing hot pressing, curing and forming to obtain a high-heat-resistance high-heat-conductivity reinforced material; then, carrying out gum dipping and semi-curing treatment on the epoxy resin glue solution to obtain a prepreg; and laminating the obtained prepreg through or without multiple layers, then coating copper foil on one side or both sides, and performing hot pressing curing treatment to obtain the high-heat-resistance high-heat-conductivity copper-clad plate. According to the invention, the heat conducting filler is added into the paper-based fiber reinforced material, and under the bonding effect of the emulsion adhesive and the reinforcing effect of the silica sol, the obtained paper-based fiber reinforced material has good strength, toughness, heat resistance and heat conductivity, and the service performance of the copper-clad plate can be greatly improved.

Description

High-heat-resistance high-heat-conductivity copper-clad plate and preparation method thereof
Technical Field
The invention belongs to the technical field of printed circuit boards, and particularly relates to a high-heat-resistance high-heat-conductivity copper-clad plate and a preparation method thereof.
Background
The copper clad laminate (Copper Clad Laminate, CCL), referred to as copper clad laminate for short, is a plate-like material obtained by impregnating a reinforcing material with a resin, and hot-pressing one or both sides of the reinforcing material with copper foil.
Copper-clad plates can be divided into paper substrates (FR-1, FR-2, FR-3), epoxy glass fiber cloth substrates (FR-4, FR-5), composite substrates (CEM-1, CEM-3), HDI boards (RCC) and special substrates (metal substrates, ceramic substrates, thermoplastic substrates and the like) according to different reinforcing materials.
The paper-based copper-clad plate has low cost and good performance; the epoxy glass fiber cloth copper-clad plate has high strength, good heat resistance and good dielectric property. Among various copper-clad plates in the world, a paper-based copper-clad plate and an epoxy glass fiber cloth copper-clad plate are the two types with the most wide application and the greatest use amount, and are widely used in products such as mobile communication, digital televisions, satellites, radars and the like. However, the reinforced material has low heat conductivity, and the heat conduction performance of the whole copper-clad plate is restricted from being improved.
Patent CN 107097508A discloses a preparation method of a copper-clad plate with high heat resistance and high heat conductivity. By adding graphene into the prepreg glue solution, the heat resistance of the obtained copper-clad plate can reach 288 ℃ and the floating welding is not layered or foamed for more than 60 minutes, so that the heat resistance is obviously improved; the heat conductivity of the copper-clad plate reaches more than 30W/m.K. Patent CN 110317432A discloses a high heat conduction metal-based copper-clad plate glue coating, which comprises the following components in parts by weight: 5-18 parts of low molecular epoxy resin, 5-15 parts of flexible film-forming resin, 5-15 parts of multifunctional epoxy, 3-10 parts of flexibilizer, 0-4 parts of curing agent A, 5-15 parts of curing agent B, 50-80 parts of heat conducting filler, 20-40 parts of solvent, 0.25-0.4 part of silane coupling agent and 0.01-0.1 part of accelerator. The metal-based copper-clad plate prepared by using the high-heat-conductivity metal-based copper-clad plate glue coating has higher heat resistance, better heat conductivity and high pressure resistance.
In the prior art, in order to enhance the heat resistance and the heat conductivity of the rigid copper clad laminate, a heat conductive filler component is often added to the prepreg glue solution, and the conventional filler component is generally an inorganic filler component, such as graphene, alumina, silicon carbide, boron nitride, zirconia, aluminum nitride, silicon dioxide, magnesium oxide or zinc oxide, and the like. However, it still does not solve the problem of low thermal conductivity of the reinforcing material. And the addition of the inorganic heat-conducting filler component tends to reduce the toughness of the rigid copper-clad plate, resulting in the reduction of the service performance.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the primary purpose of the invention is to provide a preparation method of a high-heat-resistance high-heat-conductivity copper-clad plate.
The invention further aims to provide the high-heat-resistance high-heat-conductivity copper-clad plate prepared by the method.
The invention aims at realizing the following technical scheme:
a preparation method of a high heat-resistant high-heat-conductivity copper-clad plate comprises the following preparation steps:
(1) Preparation of a high heat-resistant high-heat-conductivity reinforcing material: uniformly stirring and mixing the paper-based fiber slurry, the heat-conducting filler and the emulsion adhesive, and then adding the silica sol to uniformly stir and mix to obtain mixed slurry; adding the obtained mixed slurry into a mould, and performing hot pressing, curing and forming to obtain a high-heat-resistance high-heat-conductivity reinforced material;
(2) Performing gum dipping and semi-curing treatment on the high-heat-conductivity reinforced material obtained in the step (1) by adopting epoxy resin glue solution to obtain a prepreg;
(3) And (3) laminating the prepreg obtained in the step (2) through or without multiple layers, then coating copper foil on one side or both sides, and performing hot pressing curing treatment to obtain the high-heat-resistance high-heat-conductivity copper-clad plate.
Further, the paper-based fiber in the step (1) is at least one of a plant fiber, a carbon fiber, a glass fiber, a ceramic fiber, a polyester fiber, a polyamide fiber, a polyaramid fiber, a polyacrylonitrile fiber, a polyvinyl chloride fiber, a polypropylene fiber, a viscose fiber, a polyurethane fiber, a polyvinyl alcohol fiber, a polyhydroxyalkanoate fiber, a polybutylene succinate fiber, a terephthalate fiber, and a polycaprolactone fiber.
Further, the heat conductive filler in the step (1) is at least one of graphene, silver oxide, aluminum oxide, silicon carbide, boron nitride, zirconium oxide, aluminum nitride, silicon dioxide, magnesium oxide or zinc oxide.
Further preferably, the addition amount of the heat conducting filler is 5% -20% of the mass of the paper-based fiber.
Further, the emulsion adhesive in the step (1) is at least one of polyvinyl acetate emulsion, poly (methyl) acrylate emulsion, polyurethane emulsion, epoxy resin emulsion, phenolic resin emulsion, polyvinyl chloride resin emulsion and organic silicon resin emulsion.
Further preferably, the addition amount of the emulsion adhesive is 10-60% of the total mass of the high heat-resistant high-heat-conductivity reinforcing material in terms of solid content.
Further, the addition amount of the silica sol in the step (1) is 2-10% of the total mass of the high heat-resistant high-heat-conductivity reinforcing material in terms of solid content.
Further, the epoxy resin in the step (2) is bisphenol a type epoxy resin, bisphenol F type epoxy resin, phenolic aldehyde modified epoxy resin, isocyanate modified epoxy resin or polysiloxane-polyurethane elastomer powder reinforced epoxy resin.
Further preferably, the epoxy resin is a polysiloxane-polyurethane elastomer powder reinforced epoxy resin, which is prepared by the following method:
reacting double-end hydroxypropyl silicone oil with a polyisocyanate compound in an organic solvent to obtain a hydroxyl-terminated polyurethane prepolymer, adding isocyanic acid propyl trialkoxysilane for end-capping reaction to obtain the polyurethane prepolymer, adding water for hydrolysis and crosslinking reaction to gelation, and crushing and vacuum drying the obtained gel product to remove the organic solvent to obtain polysiloxane-polyurethane elastomer powder; and adding the obtained polysiloxane-polyurethane elastomer powder into the epoxy resin glue solution, and stirring and dispersing uniformly to obtain the polysiloxane-polyurethane elastomer powder reinforced epoxy resin.
The synthetic reaction route of the polysiloxane-polyurethane elastomer powder is shown in the following formula:
wherein R is 1 Represents an isocyanate chain, R 2 And represents a polysiloxane chain, and R represents a polysiloxane-polyurethane chain.
The compatibility of polysiloxane chain and epoxy resin can be obviously improved by carrying out copolymerization reaction on double-end hydroxypropyl silicone oil and polyisocyanate compound, so that the improvement effect of toughness and high temperature resistance can be better exerted; meanwhile, a large number of repeated carbamate structures in the polymer can participate in the subsequent curing reaction of the epoxy resin to a certain extent, so that the strength and the high temperature resistance of the cured epoxy resin are obviously enhanced. The hydroxyl-terminated polyurethane prepolymer is prepared in advance, and then the isocyanic acid propyl trialkoxysilane is added for end capping, so that the crosslinking density and the crosslinking uniformity of the subsequent hydrolysis crosslinking reaction can be well controlled, and the reinforcing performance is better. The effect of simultaneously enhancing the strength, toughness and heat resistance of the composite substrate can be achieved.
In the preparation process of the polysiloxane-polyurethane elastomer powder reinforced epoxy resin, the molecular formula of the double-end hydroxypropyl silicone oil is HOC 3 H 6 (CH 3 ) 2 SiO[Si(CH 3 ) 2 O] n Si(CH 3 ) 2 C 3 H 6 OH with molecular weight of 500-5000. Which is commercially available. The polyisocyanate compound is at least one selected from Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI), diphenylmethane diisocyanate (MDI) and dicyclohexylmethane diisocyanate (HMDI). The molar ratio of the double-end hydroxypropyl silicone oil to the polyisocyanate compound is 1.05-1.2:1; the molar ratio of the isocyanatopropyl trialkoxy silane to the polyisocyanate compound is 0.05-0.2:1. The organic solvent is at least one of benzene, toluene, cyclohexane, dimethyl sulfoxide, N-dimethylformamide and acetone; the reaction temperature in the organic solvent is 65-85 ℃.
Further preferably, the addition amount of the polysiloxane-polyurethane elastomer powder is 3% -20% of the mass of the epoxy resin glue solution.
Further, the gum dipping and semi-curing treatment in the step (2) is performed in a gum dipping machine, the temperature of the gum dipping and semi-curing treatment is 80-150 ℃, and the time of the gum dipping and semi-curing treatment is 5-20 min.
Further, the hot press curing treatment in the step (3) is performed in a hot press, the temperature of the hot press curing treatment is 120-180 ℃, the pressure of the hot press curing treatment is 10-20 MPa, and the time of the hot press curing treatment is 2-8 h.
The copper-clad plate with high heat resistance and high heat conductivity is prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, the heat conducting filler is added into the paper-based fiber reinforced material, and under the bonding effect of the emulsion adhesive and the reinforcing effect of the silica sol, the obtained paper-based fiber reinforced material has good strength, toughness, heat resistance and heat conductivity, and the service performance of the copper-clad plate can be greatly improved.
(2) According to the invention, the epoxy resin glue solution reinforced by the specific polysiloxane-polyurethane elastomer powder is further adopted to carry out glue dipping treatment on the high-heat-conductivity reinforced material, so that the strength, toughness and heat resistance of the copper-clad plate can be further enhanced.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto.
Example 1
The preparation method of the high-heat-resistance high-heat-conductivity copper-clad plate comprises the following preparation steps:
(1) According to parts by weight, stirring and mixing 80 parts by dry weight of wood pulp, 20 parts by glass fiber, 8 parts by alumina, 2 parts by graphene, 40 parts by solid content of epoxy resin emulsion and 10 parts by phenolic resin emulsion uniformly, adding 10 parts by solid content of silica sol, and stirring and mixing uniformly to obtain mixed slurry; and adding the obtained mixed slurry into a mould, and performing hot pressing, curing and forming to obtain the high-heat-resistance high-heat-conductivity reinforced material.
(2) And (3) dipping and semi-curing the high heat conduction reinforcing material obtained in the step (1) at the temperature of 100 ℃ by adopting bisphenol A type epoxy resin glue solution for 15min to obtain a prepreg.
(3) And (3) laminating the prepreg obtained in the step (2) by two layers, then coating copper foil on one side, and carrying out hot press curing treatment for 3 hours at 160 ℃ and 10MPa pressure to obtain the high-heat-resistance high-heat-conductivity copper-clad plate.
Example 2
The preparation method of the high-heat-resistance high-heat-conductivity copper-clad plate comprises the following preparation steps:
(1) According to parts by weight, uniformly stirring and mixing 90 parts by dry weight of cotton pulp, 10 parts by glass fiber, 8 parts by alumina, 2 parts by silicon carbide, 20 parts by solid content of epoxy resin emulsion and 20 parts by phenolic resin emulsion, and then adding 10 parts by solid content of silica sol, and uniformly stirring and mixing to obtain mixed slurry; and adding the obtained mixed slurry into a mould, and performing hot pressing, curing and forming to obtain the high-heat-resistance high-heat-conductivity reinforced material.
(2) And (3) dipping and semi-curing the high heat conduction reinforcing material obtained in the step (1) at 130 ℃ by adopting bisphenol A type epoxy resin glue solution for 5min to obtain a prepreg.
(3) And (3) carrying out hot press curing treatment on the single-sided copper clad laminate obtained in the step (2) for 4 hours at the temperature of 150 ℃ and the pressure of 10MPa to obtain the high-heat-resistance high-heat-conductivity copper clad laminate.
Example 3
The preparation method of the high-heat-resistance high-heat-conductivity copper-clad plate comprises the following preparation steps:
(1) According to parts by weight, stirring and mixing 70 parts by dry weight of wood pulp, 20 parts by carbon fiber, 10 parts by glass fiber, 5 parts by silver oxide, 5 parts by silicon carbide, 10 parts by epoxy resin emulsion with solid content and 40 parts by phenolic resin emulsion uniformly, adding 10 parts by solid content of silica sol, and stirring and mixing uniformly to obtain mixed slurry; and adding the obtained mixed slurry into a mould, and performing hot pressing, curing and forming to obtain the high-heat-resistance high-heat-conductivity reinforced material.
(2) And (3) dipping and semi-curing the high heat conduction reinforced material obtained in the step (1) at the temperature of 90 ℃ by adopting bisphenol A epoxy resin glue solution for 20min to obtain a prepreg.
(3) And (3) laminating the prepregs obtained in the step (2) through three layers, then coating copper foil on one side, and carrying out hot press curing treatment for 2 hours at the temperature of 180 ℃ and the pressure of 10MPa to obtain the high-heat-resistance high-heat-conductivity copper-clad plate.
Example 4
Compared with the preparation method of the high heat-resistant high-heat-conductivity copper-clad plate in the embodiment 1, the preparation method adopts polysiloxane-polyurethane elastomer powder reinforced bisphenol A type epoxy resin to replace the dipping semi-curing treatment, and the rest steps are the same.
The polysiloxane-polyurethane elastomer powder reinforced bisphenol A type epoxy resin is prepared by the following method:
adding a toluene solvent into a reactor, vacuum dehydrating, introducing nitrogen for protection, adding double-end hydroxypropyl silicone oil with the average molecular weight of 1500 and Hexamethylene Diisocyanate (HDI) according to the molar ratio of 1.1:1, stirring and dissolving uniformly, heating to 75 ℃, stirring and reacting for 2 hours, adding isocyanatopropyl trialkoxysilane, continuing stirring and reacting for 1 hour, and obtaining a polyurethane prepolymer according to the molar ratio of 0.1:1 of the isocyanatopropyl trialkoxysilane to the HDI; then adding water to carry out hydrolysis and crosslinking reaction for 0.5h to gel, keeping the temperature, standing and curing for 4h, and crushing and vacuum drying the obtained gel product to remove the solvent, thus obtaining the polysiloxane-polyurethane elastomer powder. And adding the obtained polysiloxane-polyurethane elastomer powder into bisphenol A epoxy resin glue solution according to the mass percent of 10%, and stirring and dispersing uniformly to obtain the reinforced bisphenol A epoxy resin of the polysiloxane-polyurethane elastomer powder.
Comparative example 1
In this comparative example, no silica sol was added to the reinforcing material, and the remainder was the same.
The copper clad laminates obtained in examples 1 to 4 and comparative example 1 above were subjected to strength (peel strength), heat resistance (resistance to dip soldering, 288 ℃) toughness test (drop impact test, visual inspection evaluation of excellent, good, poor) and thermal conductivity test with reference to GB/T4723-1992 standard, and a CEM-1 board subjected to dip curing treatment with a conventional epoxy resin glue solution was used as a reinforcing material with the conventional semi-glass fiber board (glass fiber cloth on both sides, wood pulp paper in the middle) as a control group, and the results are shown in Table 1 below.
TABLE 1
Peel strength of Heat resistance Impact toughness Thermal conductivity
Example 1 2.19N/mm 42min Good grade (good) 17W/(m·K)
Example 2 2.06N/mm 47min Good grade (good) 11W/(m·K)
Example 3 2.25N/mm 39min Excellent (excellent) 12W/(m·K)
Example 4 2.28N/mm 58min Excellent (excellent) 17W/(m·K)
Comparative example 1 1.82N/mm 33min Good grade (good) 13W/(m·K)
Control group 1.31N/mm 15min Difference of difference 1.8W/(m·K)
As can be seen from the results in Table 1, the copper-clad plate prepared from the paper-based fiber reinforced material has obviously improved strength, toughness, heat resistance and heat conductivity compared with the conventional CEM-1 plate by adding the heat conducting filler into the paper-based fiber reinforced material and under the bonding effect of the emulsion adhesive and the reinforcing effect of the silica sol. And the paper-based fiber reinforced material is further subjected to gum dipping treatment by adopting the epoxy resin gum solution reinforced by the specific polysiloxane-polyurethane elastomer powder, so that the strength, toughness and heat resistance of the copper-clad plate can be further and obviously enhanced.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims (7)

1. The preparation method of the high heat-resistant high-heat-conductivity copper-clad plate is characterized by comprising the following preparation steps:
(1) Preparation of a high heat-resistant high-heat-conductivity reinforcing material: uniformly stirring and mixing the paper-based fiber slurry, the heat-conducting filler and the emulsion adhesive, and then adding the silica sol to uniformly stir and mix to obtain mixed slurry; adding the obtained mixed slurry into a mould, and performing hot pressing, curing and forming to obtain a high-heat-resistance high-heat-conductivity reinforced material;
(2) Performing gum dipping and semi-curing treatment on the high-heat-conductivity reinforced material obtained in the step (1) by adopting epoxy resin glue solution to obtain a prepreg;
(3) Laminating the prepreg obtained in the step (2) through or without multiple layers, then coating copper foil on one side or both sides, and performing hot pressing curing treatment to obtain the high-heat-resistance high-heat-conductivity copper-clad plate;
the heat conducting filler in the step (1) is at least one of graphene, silver oxide, aluminum oxide, silicon carbide, boron nitride, zirconium oxide, aluminum nitride, silicon dioxide, magnesium oxide or zinc oxide; the addition amount of the heat conducting filler is 5% -20% of the mass of the paper-based fiber slurry;
the emulsion adhesive is at least one of polyvinyl acetate emulsion, poly (methyl) acrylate emulsion, polyurethane emulsion, epoxy resin emulsion, phenolic resin emulsion, polyvinyl chloride resin emulsion and organic silicon resin emulsion; the addition amount of the emulsion adhesive is 10-60% of the total mass of the high heat-resistant high-heat-conductivity reinforced material in terms of solid content;
the addition amount of the silica sol is 2-10% of the total mass of the high heat-resistant high-heat-conductivity reinforced material based on the solid content.
2. The method for preparing the high heat-resistant and high heat-conducting copper-clad plate according to claim 1, wherein the paper-based fiber slurry in the step (1) is at least one fiber slurry selected from plant fibers, carbon fibers, glass fibers, ceramic fibers, polyester fibers, polyamide fibers, polyaramid fibers, polyacrylonitrile fibers, polyvinyl chloride fibers, polypropylene fibers, viscose fibers, polyurethane fibers, polyvinyl alcohol fibers, polyhydroxyalkanoate fibers, polybutylene succinate fibers, terephthalate fibers and polycaprolactone fibers.
3. The method for preparing the high heat-resistant and high heat-conducting copper-clad plate according to claim 1, wherein the epoxy resin in the step (2) is bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenolic aldehyde modified epoxy resin, isocyanate modified epoxy resin or polysiloxane-polyurethane elastomer powder reinforced epoxy resin.
4. The method for preparing the high-heat-resistance high-heat-conductivity copper-clad plate according to claim 3, wherein the epoxy resin is polysiloxane-polyurethane elastomer powder reinforced epoxy resin, and is prepared by the following steps:
reacting double-end hydroxypropyl silicone oil with a polyisocyanate compound in an organic solvent to obtain a hydroxyl-terminated polyurethane prepolymer, adding isocyanic acid propyl trialkoxysilane for end-capping reaction to obtain the polyurethane prepolymer, adding water for hydrolysis and crosslinking reaction to gelation, and crushing and vacuum drying the obtained gel product to remove the organic solvent to obtain polysiloxane-polyurethane elastomer powder; and adding the obtained polysiloxane-polyurethane elastomer powder into the epoxy resin glue solution, and stirring and dispersing uniformly to obtain the polysiloxane-polyurethane elastomer powder reinforced epoxy resin.
5. The method for preparing the high heat-resistant high-heat-conductivity copper-clad plate according to claim 4, wherein the addition amount of the polysiloxane-polyurethane elastomer powder is 3-20% of the mass of the epoxy resin glue solution.
6. The method for preparing the high heat-resistant high-heat-conductivity copper-clad plate according to claim 1, wherein the gum dipping semi-curing treatment in the step (2) is performed in a gum dipping machine, the temperature of the gum dipping semi-curing treatment is 80-150 ℃ and the time is 5-20 min; the hot press curing treatment in the step (3) is carried out in a hot press, the temperature of the hot press curing treatment is 120-180 ℃, the pressure is 10-20 MPa, and the time is 2-8 h.
7. A highly heat resistant and highly thermally conductive copper clad laminate characterized by being prepared by the method of any one of claims 1 to 6.
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