CN115339191A - Para-aramid paper composite base halogen-free low-dielectric copper-clad plate and preparation method thereof - Google Patents

Para-aramid paper composite base halogen-free low-dielectric copper-clad plate and preparation method thereof Download PDF

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Publication number
CN115339191A
CN115339191A CN202210974350.2A CN202210974350A CN115339191A CN 115339191 A CN115339191 A CN 115339191A CN 202210974350 A CN202210974350 A CN 202210974350A CN 115339191 A CN115339191 A CN 115339191A
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China
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para
aramid paper
halogen
copper
preparation
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Inventor
范翠玲
高晓佳
庄锐
李双昌
王先利
魏楠
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Chambroad Chemical Industry Research Institute Co Ltd
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Chambroad Chemical Industry Research Institute Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/06—Layered products comprising a layer of paper or cardboard specially treated, e.g. surfaced, parchmentised
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B15/12—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 paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/002—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/04—Addition to the pulp; After-treatment of added substances in the pulp
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/04—Physical treatment, e.g. heating, irradiating
    • D21H25/06—Physical treatment, e.g. heating, irradiating of impregnated or coated paper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • B32B2262/0269—Aromatic polyamide fibres

Abstract

The invention provides a para-aramid paper composite base halogen-free low-dielectric copper-clad plate and a preparation method thereof; the preparation method comprises the following steps: a) Sequentially carrying out high-temperature pretreatment, coupling agent treatment and drying on the para-aramid paper to obtain the treated para-aramid paper; b) Impregnating the treated para-aramid paper obtained in the step a) in a halogen-free resin system glue solution, taking out the para-aramid paper, and baking to obtain a prepreg; c) Covering copper foils on two surfaces of the prepreg obtained in the step b), and compounding to obtain the para-aramid paper composite base halogen-free low-dielectric copper clad laminate. Compared with the prior art, the preparation method provided by the invention adopts the para-aramid paper as the raw material, and the specific process steps are matched to realize better overall interaction, so that the prepared para-aramid paper composite-based halogen-free low-dielectric copper-clad plate has good peel strength, smaller density and water absorption, better dielectric property and heat resistance, and good flame retardance, and the application scenes of the para-aramid paper composite-based halogen-free low-dielectric copper-clad plate can be greatly widened.

Description

Para-aramid paper composite base halogen-free low-dielectric copper-clad plate and preparation method thereof
Technical Field
The invention relates to the technical field of copper-clad plate manufacturing, in particular to a para-aramid paper composite base halogen-free low-dielectric copper-clad plate and a preparation method thereof.
Background
With the development of scientific information technology in various countries, various electronic products are produced and used worldwide, and the most core part of electronic equipment is the circuit board, but the circuit board and components generate a lot of harmful substances in the manufacturing process. At present, a large number of flame-retardant copper-clad plates contain halides, antimonides and the like, the copper-clad plates of the type have unpleasant smell and release hydrogen halide gas with high toxicity and strong corrosivity when being ignited and combusted, and bromine flame retardants can generate dioxin with carcinogenic effect when being combusted, so that the bromine flame retardants harm human health and pollute the environment. Internationally, it is clearly required that all electronic manufacturers should not use brominated flame retardants and polyvinyl chloride in electronic products, but should manufacture lead-free and halogen-free green electronic devices. The substrate material for high-speed digital circuits, which is specially used for communication, internet equipment and server PCBs with low transmission loss requirements, has become the mainstream trend of the current market, and the number of copper clad laminate substrates which can be applied to 5G communication servers and can meet the requirements in the prior art is small, so that the environment is protected, the high-frequency and high-speed characteristics can be met, and the development of a halogen-free low-dielectric compatible high-frequency copper clad laminate is imperative.
The aramid fiber is one of three high-performance fibers (carbon fiber, aramid fiber and ultra-high molecular weight polyethylene fiber), and is an organic fiber with a molecular configuration axis extending, a molecular arrangement order, high crystallization degree and high orientation degree; the material has the characteristics of high specific strength, high specific modulus, low density, low thermal expansion coefficient, good dimensional stability, shock absorption, impact resistance, fatigue resistance, shearing resistance, abrasion resistance, electrical insulation, flame retardance, thermal stability, low heat conduction, chemical corrosion resistance, elasticity resistance, radiation resistance and the like. The glass fiber cloth for multiple selection in the conventional copper-clad plate prepreg preparation has the dielectric constant of 6.6, the dielectric constant of a printed circuit board substrate made of glass fiber impregnated epoxy resin is 4.5-4.7, the dielectric constant of a printed circuit board substrate made of aramid fiber paper impregnated epoxy resin is 3.4-3.5, and the dielectric constant of a printed circuit board substrate made of aramid fiber paper impregnated polyimide resin is below 3.5. Meanwhile, the para-aramid paper resin-based composite material has high specific strength and modulus, good toughness, excellent point insulation property, wave permeability and other properties, and is widely applied to the field of aerospace. The para-aramid prepreg is used as a novel high-insulation special material, and has higher research value when being used as a base material of a circuit board substrate.
Disclosure of Invention
In view of the above, the invention aims to provide a para-aramid paper composite-based halogen-free low-dielectric copper-clad plate and a preparation method thereof, and the para-aramid paper composite-based halogen-free low-dielectric copper-clad plate obtained by the preparation method provided by the invention has high heat resistance, high toughness, high ion migration resistance, good dimensional stability, low thermal expansion coefficient, low dielectric constant, low dielectric loss and other excellent performances, and particularly has better applicability in the fields of stable high-temperature mechanical characteristics (mainly including bending strength characteristic at high temperature, elastic modulus, copper foil bonding strength characteristic, surface hardness and the like) and high-frequency copper-clad plates of 5G communication servers.
The invention provides a preparation method of a para-aramid paper composite-based halogen-free low-dielectric copper-clad plate, which comprises the following steps:
a) Sequentially carrying out high-temperature pretreatment, coupling agent treatment and drying on the para-aramid paper to obtain the treated para-aramid paper;
b) Dipping the treated para-aramid paper obtained in the step a) in a halogen-free resin system glue solution, taking out the para-aramid paper, and baking to obtain a prepreg;
c) Covering copper foils on two surfaces of the prepreg obtained in the step b), and compounding to obtain the para-aramid paper composite base halogen-free low-dielectric copper clad laminate.
Preferably, the standard weight of the para-aramid paper in the step a) is 40g/m 2 ～60g/m 2 The thickness is 50-150 μm.
Preferably, the temperature of the high-temperature pretreatment in the step a) is 80-120 ℃.
Preferably, aminosilane coupling agent solution is adopted for the coupling agent treatment in the step a), and the concentration is 0.1-1 wt%; the coupling agent is treated by soaking for 1-5 min, and then the product is taken out and naturally dried for 10-60 min.
Preferably, the drying temperature in the step a) is 110-130 ℃, and the drying time is 30-50 min.
Preferably, the halogen-free resin system glue solution in the step b) is prepared from the following raw materials:
30-50 parts by weight of polyfunctional alicyclic epoxy resin;
30-40 parts of curing agent;
20-25 parts of flame retardant;
90 to 100 parts by weight of filler.
Preferably, the time of the dipping treatment in the step b) is 30s to 200s; the baking temperature is 170-190 ℃ and the baking time is 5-15 min.
Preferably, the content of the rubber in the prepreg in the step b) is 40-70 wt%.
Preferably, the compounding process in step c) specifically comprises:
and (3) carrying out hot pressing for 0.5 to 5 hours in a vacuum press under the pressure of 0.8 to 10MPa and at the temperature of 120 to 210 ℃, and then removing the pressure to keep the temperature for 0.5 to 2.5 hours to obtain the para-aramid paper composite-based halogen-free low-dielectric copper-clad plate.
The invention also provides a para-aramid paper composite base halogen-free low-dielectric copper-clad plate prepared by the preparation method of the technical scheme.
The invention provides a para-aramid paper composite base halogen-free low-dielectric copper-clad plate and a preparation method thereof; the preparation method comprises the following steps: a) Sequentially carrying out high-temperature pretreatment, coupling agent treatment and drying on the para-aramid paper to obtain the treated para-aramid paper; b) Impregnating the treated para-aramid paper obtained in the step a) in a halogen-free resin system glue solution, taking out the para-aramid paper, and baking to obtain a prepreg; c) Covering copper foils on two surfaces of the prepreg obtained in the step b), and compounding to obtain the para-aramid paper composite base halogen-free low-dielectric copper clad laminate. Compared with the prior art, the preparation method provided by the invention adopts the para-aramid paper as the raw material, and the specific process steps are matched to realize better overall interaction, so that the prepared para-aramid paper composite-based halogen-free low-dielectric copper-clad plate has good peel strength, smaller density and water absorption, better dielectric property and heat resistance, and good flame retardance, which can greatly widen the application scene of the copper-clad plate.
Meanwhile, the preparation method provided by the invention has the advantages of simple process, low cost of raw materials, easy realization of operation, good product stability and wide application prospect.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood 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 obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The invention provides a preparation method of a para-aramid paper composite base halogen-free low-dielectric copper-clad plate, which comprises the following steps:
a) Sequentially carrying out high-temperature pretreatment, coupling agent treatment and drying on the para-aramid paper to obtain the treated para-aramid paper;
b) Dipping the treated para-aramid paper obtained in the step a) in a halogen-free resin system glue solution, taking out the para-aramid paper, and baking to obtain a prepreg;
c) Covering copper foils on two surfaces of the prepreg obtained in the step b), and compounding to obtain the para-aramid paper composite base halogen-free low-dielectric copper clad laminate.
Firstly, the para-aramid paper is sequentially subjected to high-temperature pretreatment, coupling agent treatment and drying to obtain the treated para-aramid paper. In the invention, the standard weight of the para-aramid paper is preferably 40g/m 2 ～60g/m 2 More preferably 45g/m 2 The thickness is preferably 50 μm to 150 μm, and more preferably 100 μm. The source of the para-aramid paper is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. In the present invention, the para-aramid paper is preferably cut into a size of 100mm × 100mm by a cutter, which facilitates the subsequent steps.
In the invention, the temperature of the high-temperature pretreatment is preferably 80-120 ℃, and more preferably 100 ℃; the aim is to remove the moisture in the para-aramid paper.
In the invention, the coupling agent treatment preferably adopts aminosilane coupling agent solution, and the concentration is preferably 0.1-1 wt%, more preferably 0.2-0.6 wt%; the amino silane coupling agent is used as an adhesion promoter, and can effectively improve the adhesion of the surface of the para-aramid paper material. The source of the aminosilane coupling agent is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the coupling agent is preferably treated by soaking, and the soaking time is preferably 1min to 5min, and more preferably 3min; taking out and naturally drying for preferably 10 min-60 min, more preferably 30min.
In the present invention, the drying temperature is preferably 110 to 130 ℃, more preferably 120 ℃, and the time is preferably 30 to 50min, more preferably 40min.
After the treated para-aramid paper is obtained, the treated para-aramid paper is soaked in a halogen-free resin system glue solution, and is taken out and baked to obtain the prepreg.
In the invention, the halogen-free resin system glue solution is preferably prepared from the following raw materials:
30-50 parts by weight of polyfunctional alicyclic epoxy resin;
30-40 parts of curing agent;
20-25 parts of flame retardant;
90 to 100 parts by weight of filler.
In the present invention, the source of each of the above raw materials is not particularly limited, and commercially available products known to those skilled in the art may be used.
In the present invention, the multifunctional cycloaliphatic epoxy resin is preferably a bio-based dimer acid glycidyl ester modified multifunctional cycloaliphatic epoxy resin.
In the present invention, the curing agent is preferably one or more selected from the group consisting of a phosphorus-containing phenol resin, a benzoxazine resin, and a styrene-maleic anhydride resin, and more preferably two or more selected from the group consisting of a phosphorus-containing phenol resin, a benzoxazine resin, and a styrene-maleic anhydride resin. In a preferred embodiment of the present invention, the curing agent is a mixture of 10:9:9, phosphorus-containing phenolic resin, benzoxazine resin and styrene-maleic anhydride resin, or the mass ratio of 10:9, phosphorus-containing phenolic resin and benzoxazine resin, or the mass ratio of 10:9, phosphorus-containing phenolic resin and styrene-maleic anhydride resin, or the mass ratio of 1:1 of benzoxazine resin and styrene-maleic anhydride resin, or 1:1 phosphorus-containing phenolic resin and benzoxazine resin.
In the invention, the flame retardant is preferably a composite flame retardant system formed by mixing a phosphate flame retardant and a phosphazene flame retardant.
In the invention, the filler is preferably selected from spherical aluminum hydroxide and/or spherical silica; the particle size of the filler is preferably 0.5 to 5.0. Mu.m, more preferably 0.7 to 2.0. Mu.m.
The preparation method of the halogen-free resin system glue solution is not particularly limited, and the technical scheme that the raw materials are added into a container and stirred to be fully dissolved, which is well known to a person skilled in the art, is adopted.
In the present invention, the time for the immersion treatment is preferably 30s to 200s, and more preferably 60s to 180s. In the invention, the baking temperature is preferably 170-190 ℃, more preferably 180 ℃, and the time is preferably 5-15 min, more preferably 10min; baking may be carried out using an oven known to those skilled in the art.
In the present invention, the prepreg is uniform in appearance, and the content of the rubber is preferably 40wt% to 70wt%, and more preferably 50wt% to 65wt%. The para-aramid paper-based prepreg is obtained by using the excellent properties of the para-aramid paper-based composite material, such as high specific strength, high specific modulus, good toughness, good point insulation property, good wave permeability and the like, as a base material of a circuit substrate to replace glass fiber cloth required by prepreg manufacturing in the traditional copper-clad plate.
After the prepreg is obtained, copper foils are covered on two sides of the obtained prepreg, and the obtained prepreg is compounded to obtain the para-aramid paper composite base halogen-free low-dielectric copper-clad plate. The source of the copper foil is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the compounding process preferably includes:
hot pressing for 0.5 to 5 hours at the temperature of 120 to 210 ℃ and under the pressure of 0.8 to 10MPa in a vacuum press, and then removing the pressure to keep the temperature and keeping the temperature for 0.5 to 2.5 hours to obtain the para-aramid paper composite-based halogen-free low-dielectric copper-clad plate;
more preferably:
and (3) carrying out hot pressing for 1h in a vacuum press under the pressure of 1-6 MPa and at the temperature of 140-200 ℃, and then removing the pressure to keep the temperature for 1 h-2 h to obtain the para-aramid paper composite-based halogen-free low-dielectric copper-clad plate.
The preparation method provided by the invention uses para-aramid paper, and the para-aramid paper is pretreated at high temperature to remove moisture in the aramid paper; soaking the pretreated para-aramid paper in a coupling agent solution for 1-5 min, naturally drying, soaking the prepared halogen-free resin system glue solution to prepare a prepreg, covering copper foils on two surfaces of the prepreg, and obtaining the halogen-free low-dielectric compatible high-frequency copper-clad plate by using a vacuum press. The preparation method provided by the invention has the advantages of simple process, low cost of raw materials, easy realization of operation, good product stability and wide application prospect.
The invention also provides a para-aramid paper composite base halogen-free low-dielectric copper-clad plate which is prepared by the preparation method of the technical scheme. The preparation method provided by the invention adopts the para-aramid paper as a raw material, and realizes better overall interaction by matching with specific process steps, and the prepared para-aramid paper composite-based halogen-free low-dielectric copper-clad plate has good peel strength, smaller density and water absorption, better dielectric property and heat resistance, and good flame retardance, so that the application scene of the copper-clad plate can be greatly widened.
Compared with the prior art, the invention has the following beneficial effects:
(1) The weight is light, the temperature resistance is high, the temperature resistance of the para-aramid can reach 500 ℃, and the para-aramid can completely meet various use environments of the circuit board.
(2) The dielectric constant (Dk) is low, the transmission speed of high-frequency signals is directly influenced by the dielectric constant of the printed circuit board, the dielectric constant of glass fiber is 6.6, the dielectric constant of the printed circuit board substrate made of glass fiber impregnated epoxy resin is 4.5-4.7, the dielectric constant of the printed circuit board substrate made of aramid fiber paper impregnated epoxy resin is 3.4-3.5, and the dielectric constant of the printed circuit board substrate made of aramid fiber paper impregnated polyimide resin is less than 3.5.
(3) The substrate made of aramid paper can be perforated by laser, and the processing performance is good.
(4) The heat cycle impact resistance of the substrate made of aramid paper can reach more than 1 ten thousand times (the international standard is 4800 times), so that the aramid paper can be widely used on aerospace engines; the thermal stability is good, and the linear thermal expansion Coefficient (CTE) of the substrate made of aramid paper in the plane directions of x and y axes is 4-9 ppm/DEG C, so that the packaging sheet of the hand integrated circuit can be used in large quantities.
(5) According to the invention, the bio-based dimer acid glycidyl ester modified polyfunctional alicyclic epoxy resin is used as the main body resin, and the phosphorus-containing phenolic resin, the benzoxazine resin and the styrene-maleic anhydride resin are compounded to form the curing agent, so that the thermosetting property is increased, and the dielectric loss is reduced.
(6) The invention is different from the components of the existing halogen-free low-dielectric compatible high-frequency copper-clad plate on the market in the glue solution component of the copper-clad plate, adopts a novel resin, a novel coupling agent, a catalyst bonding solvent and a filler for proportioning, and provides another possibility for the preparation of the halogen-free low-dielectric compatible high-frequency copper-clad plate.
(7) The resin glue liquid filler is a mixture of spherical alumina and spherical silica with relatively consistent particle size, and has excellent characteristics of high heat resistance, low thermal expansion coefficient, low dielectric constant, low dielectric loss and the like, so that the electrical property of the high-speed copper-clad plate for the halogen-free high-TG communication server is greatly improved.
In conclusion, the preparation method provided by the invention selects para-aramid paper as a raw material, and is matched with specific process steps to realize better overall interaction, so that the copper-clad plate obtained by the preparation method provided by the invention has high heat resistance, high toughness, high ion migration resistance, good dimensional stability, low thermal expansion coefficient, low dielectric constant, low dielectric loss and other excellent performances, and particularly has better applicability in the fields of stable high-temperature mechanical properties (mainly comprising bending strength property at high temperature, elastic modulus, copper foil bonding strength property, surface hardness and the like) and high-frequency copper-clad plates of 5G communication servers and the like.
The invention provides a para-aramid paper composite base halogen-free low-dielectric copper-clad plate and a preparation method thereof; the preparation method comprises the following steps: a) Sequentially carrying out high-temperature pretreatment, coupling agent treatment and drying on the para-aramid paper to obtain the treated para-aramid paper; b) Impregnating the treated para-aramid paper obtained in the step a) in a halogen-free resin system glue solution, taking out the para-aramid paper, and baking to obtain a prepreg; c) Covering copper foils on two surfaces of the prepreg obtained in the step b), and compounding to obtain the para-aramid paper composite base halogen-free low-dielectric copper clad laminate. Compared with the prior art, the preparation method provided by the invention adopts the para-aramid paper as the raw material, and the specific process steps are matched to realize better overall interaction, so that the prepared para-aramid paper composite-based halogen-free low-dielectric copper-clad plate has good peel strength, smaller density and water absorption, better dielectric property and heat resistance, and good flame retardance, and the application scene of the copper-clad plate can be greatly widened.
Meanwhile, the preparation method provided by the invention has the advantages of simple process, low cost of raw materials, easy realization of operation, good product stability and wide application prospect.
In order to further illustrate the present invention, the following examples are provided for illustrative purposes. The raw materials used in the following examples of the invention are all commercially available sources; wherein the para-aramid paper is provided by Shandong aromatic new material Co., ltd, and has a standard weight of 45g/m 2 The thickness was 100. Mu.m.
Example 1
(1) Cutting the para-aramid paper into pieces with the size of 100mm multiplied by 100mm by a cutter, pretreating at the high temperature of 100 ℃, removing water in the aramid paper, and obtaining the pretreated para-aramid paper;
(2) Soaking the pretreated para-aramid paper in 0.3wt% KH550 aminosilane coupling agent (919-30-2 Guangdong high-purity coupling agent) solution for 3min, taking out, naturally drying for 30min, and drying at 120 ℃ for 40min for later use to obtain the para-aramid paper treated by the coupling agent;
(3) Preparing a halogen-free resin system glue solution: adding 40 parts by weight of bio-based dimer acid glycidyl ester modified polyfunctional cycloaliphatic epoxy resin (HXION Hansen (original shell brand) dimer acid diglycidyl ester modifier HELOXY 71), 35 parts by weight of curing agent, 20 parts by weight of flame retardant and 90 parts by weight of filler into a container, and stirring to fully dissolve the mixture to obtain a halogen-free resin system glue solution; wherein the curing agent is prepared from phosphorus-containing phenolic resin (Jiaba electronics science and technology, inc., guangzhou city), benzoxazine resin (high molecular technology suitable for Chengdu science and technology) and styrene-maleic anhydride resin (Shanghai method colorization industry and technology, inc.) according to the mass ratio of 10:9:9, uniformly mixing to obtain the mixture; the flame retardant is a composite flame retardant system formed by mixing phosphate flame retardant (Henan Ruizu chemical products, ltd.) and phosphazene flame retardant (Dalton chemical industry) in equal mass; the filling material is spherical aluminum hydroxide (Clara) and spherical silicon dioxide (Bide medicine) according to the mass ratio of 1:2, the spherical aluminum hydroxide and the spherical silicon dioxide are uniformly mixed, and the particle diameters of the spherical aluminum hydroxide and the spherical silicon dioxide are both 0.7-2.0 mu m;
(4) Completely soaking the para-aramid paper treated by the coupling agent obtained in the step (2) in the halogen-free resin system glue solution prepared in the step (3) for 60s, taking out and baking the para-aramid paper in a 180 ℃ oven for 10min to obtain a prepreg (prepreg), wherein the prepreg is uniform in appearance and has a glue content of 55wt%;
(5) Covering copper foils on two surfaces of the prepreg obtained in the step (4), hot-pressing for 1h at the temperature of 180 ℃ under the pressure of 1MPa in a vacuum press, removing the pressure, and preserving heat for 1h at the temperature of 180 ℃ to obtain the para-aramid paper composite base halogen-free low-dielectric copper clad plate.
Example 2
(1) Cutting the para-aramid paper into pieces with the size of 100mm multiplied by 100mm by a cutter, pretreating at the high temperature of 100 ℃, removing water in the para-aramid paper, and obtaining the pretreated para-aramid paper;
(2) Soaking the pretreated para-aramid paper in 0.4wt% KH550 aminosilane coupling agent (919-30-2 Guangdong high-purity coupling agent) solution for 3min, taking out, naturally drying for 30min, and drying at 120 ℃ for 40min for later use to obtain the para-aramid paper treated by the coupling agent;
(3) Preparing a halogen-free resin system glue solution: adding 45 parts by weight of bio-based dimer acid glycidyl ester modified polyfunctional alicyclic epoxy resin (HXION Vast-Sen (original shell brand) dimer acid diglycidyl ester modifier HELOXY 71), 40 parts by weight of curing agent, 25 parts by weight of flame retardant and 95 parts by weight of filler into a container, and stirring to fully dissolve the mixture to obtain a halogen-free resin system glue solution; wherein the curing agent is prepared from phosphorus-containing phenolic resin (Jiaba electronics science and technology limited, guangzhou city) and benzoxazine resin (high molecular technology suitable for Chengdu science) according to the mass ratio of 10:9, uniformly mixing to obtain the product; the flame retardant is a composite flame retardant system formed by mixing phosphate flame retardant (Henan Ruizu chemical products, ltd.) and phosphazene flame retardant (Dalton chemical industry) in equal mass; the filler is spherical aluminum hydroxide (Clara) with the particle size of 0.7-2.0 μm;
(4) Completely soaking the para-aramid paper treated by the coupling agent obtained in the step (2) in the halogen-free resin system glue solution prepared in the step (3) for 80s, taking out and baking the para-aramid paper in a 180 ℃ oven for 10min to obtain a prepreg (prepreg), wherein the prepreg has a uniform appearance and a glue content of 50wt%;
(5) Covering copper foils on two surfaces of the prepreg obtained in the step (4), carrying out hot pressing for 1h in a vacuum press at the pressure of 2MPa and the temperature of 160 ℃, removing the pressure, and carrying out heat preservation for 2h at the temperature of 160 ℃ to obtain the para-aramid paper composite base halogen-free low-dielectric copper clad plate.
Example 3
(1) Cutting the para-aramid paper into pieces with the size of 100mm multiplied by 100mm by a cutter, pretreating at the high temperature of 100 ℃, removing water in the para-aramid paper, and obtaining the pretreated para-aramid paper;
(2) Soaking the pretreated para-aramid paper in 0.5wt% KH550 aminosilane coupling agent (919-30-2 Guangdong high-purity coupling agent) solution for 3min, taking out, naturally drying for 30min, and drying at 120 ℃ for 40min for later use to obtain the para-aramid paper treated by the coupling agent;
(3) Preparing a halogen-free resin system glue solution: adding 50 parts by weight of bio-based dimer acid glycidyl ester modified polyfunctional cycloaliphatic epoxy resin (HXION Hansen (original shell brand) dimer acid diglycidyl ester modifier HELOXY 71), 30 parts by weight of curing agent, 25 parts by weight of flame retardant and 90 parts by weight of filler into a container, and stirring to fully dissolve the mixture to obtain a halogen-free resin system glue solution; wherein the curing agent is prepared from phosphorus-containing phenolic resin (Jiaba electronic technology, inc., guangzhou city) and styrene-maleic anhydride resin (Shanghai method colorization industrial technology, inc.) according to the mass ratio of 10:9, uniformly mixing to obtain the mixture; the flame retardant is a composite flame retardant system formed by mixing phosphate flame retardant (Henan Ruizu chemical products, ltd.) and phosphazene flame retardant (Dalton chemical industry) in equal mass; the filler is spherical silicon dioxide (Bikuai medicine), and the particle diameter of the spherical silicon dioxide is 0.7-2.0 μm;
(4) Completely soaking the para-aramid paper treated by the coupling agent obtained in the step (2) in the halogen-free resin system glue solution prepared in the step (3) for 120s, taking out and baking the para-aramid paper in a 180 ℃ oven for 10min to obtain a prepreg (prepreg), wherein the prepreg is uniform in appearance and 65wt% in glue content;
(5) Covering copper foils on two surfaces of the prepreg obtained in the step (4), hot-pressing for 1h at the temperature of 150 ℃ under the pressure of 4MPa in a vacuum press, and then removing the pressure and preserving heat for 1h at the temperature of 150 ℃ to obtain the para-aramid paper composite base halogen-free low-dielectric copper clad plate.
Example 4
(1) Cutting the para-aramid paper into pieces with the size of 100mm multiplied by 100mm by a cutter, pretreating at the high temperature of 100 ℃, removing water in the aramid paper, and obtaining the pretreated para-aramid paper;
(2) Soaking the pretreated para-aramid paper in 0.2wt% KH550 aminosilane coupling agent (919-30-2 Guangdong high-purity coupling agent) solution for 3min, taking out, naturally drying for 30min, and drying at 120 ℃ for 40min for later use to obtain the para-aramid paper treated by the coupling agent;
(3) Preparing a halogen-free resin system glue solution: adding 30 parts by weight of bio-based dimer acid glycidyl ester modified polyfunctional alicyclic epoxy resin (HXION Vast-Sen (original shell brand) dimer acid diglycidyl ester modifier HELOXY 71), 35 parts by weight of curing agent, 24 parts by weight of flame retardant and 100 parts by weight of filler into a container, and stirring to fully dissolve the mixture to obtain a halogen-free resin system glue solution; wherein the curing agent is prepared from benzoxazine resin (suitable for high molecular science and technology in Chengdu science) and styrene-maleic anhydride resin (Shanghai method colorization industry and technology Co., ltd.) according to the mass ratio of 1:1, uniformly mixing to obtain the product; the flame retardant is a composite flame retardant system formed by mixing phosphate ester flame retardant (Henan Ruizhou chemical products, ltd.) and phosphazene flame retardant (Dalton chemical industry) in equal mass; the filling material is spherical aluminum hydroxide (Clara) and spherical silicon dioxide (Bide medicine) according to the mass ratio of 1:1, and the particle diameters of the spherical aluminum hydroxide and the spherical silicon dioxide are both 0.7-2.0 μm;
(4) Completely soaking the para-aramid paper treated by the coupling agent obtained in the step (2) in the halogen-free resin system glue solution prepared in the step (3) for 100s, taking out and baking the para-aramid paper in a 180 ℃ oven for 10min to obtain a prepreg (prepreg), wherein the prepreg is uniform in appearance and has a glue content of 55wt%;
(5) Covering copper foils on two surfaces of the prepreg obtained in the step (4), hot-pressing for 1h at the temperature of 200 ℃ and under the pressure of 6MPa in a vacuum press, and then removing the pressure and preserving heat for 1.5h at the temperature of 200 ℃ to obtain the para-aramid paper composite base halogen-free low-dielectric copper clad plate.
Example 5
(1) Cutting the para-aramid paper into pieces with the size of 100mm multiplied by 100mm by a cutter, pretreating at the high temperature of 100 ℃, removing water in the para-aramid paper, and obtaining the pretreated para-aramid paper;
(2) Soaking the pretreated para-aramid paper in 0.6wt% KH550 aminosilane coupling agent (919-30-2 Guangdong high-purity coupling agent) solution for 3min, taking out, naturally drying for 30min, and drying at 120 ℃ for 40min for later use to obtain the para-aramid paper treated by the coupling agent;
(3) Preparing a halogen-free resin system glue solution: adding 45 parts by weight of bio-based dimer acid glycidyl ester modified polyfunctional alicyclic epoxy resin (HXION Vast-Sen (original shell brand) dimer acid diglycidyl ester modifier HELOXY 71), 33 parts by weight of curing agent, 20 parts by weight of flame retardant and 95 parts by weight of filler into a container, and stirring to fully dissolve the mixture to obtain a halogen-free resin system glue solution; wherein the curing agent is prepared from phosphorus-containing phenolic resin (Jiaba electronics science and technology limited, guangzhou) and benzoxazine resin (high molecular technology suitable for Chengdu science) according to the mass ratio of 1:1, uniformly mixing to obtain the product; the flame retardant is a composite flame retardant system formed by mixing phosphate ester flame retardant (Henan Ruizhou chemical products, ltd.) and phosphazene flame retardant (Dalton chemical industry) in equal mass; the filling material is spherical aluminum hydroxide (Clara) and spherical silicon dioxide (Bide medicine) according to the mass ratio of 2:1, and the particle diameters of the spherical aluminum hydroxide and the spherical silicon dioxide are both 0.7-2.0 μm;
(4) Completely soaking the para-aramid paper treated by the coupling agent obtained in the step (2) in the halogen-free resin system glue solution prepared in the step (3) for 180s, taking out and baking the para-aramid paper in a 180 ℃ oven for 10min to obtain a prepreg (prepreg), wherein the prepreg has uniform appearance and glue content of 60wt%;
(5) Covering copper foils on two surfaces of the prepreg obtained in the step (4), carrying out hot pressing for 1h at the temperature of 140 ℃ under the pressure of 3MPa in a vacuum press, removing the pressure, and carrying out heat preservation for 2h at the temperature of 140 ℃ to obtain the para-aramid paper composite base halogen-free low-dielectric copper clad plate.
Comparative example
(1) 1080 glass fiber cloth (standard weight 47 +/-3 g/m) is cut by a cutter 2 ) Cutting the glass fiber cloth into the size of 100mm multiplied by 100mm, and performing paraffin removal pretreatment at the high temperature of 450 ℃ to obtain pretreated glass fiber cloth;
(2) Soaking the pretreated glass fiber cloth in 0.2wt% KH550 aminosilane coupling agent (919-30-2 Guangdong high-purity coupling agent) solution for 2min, taking out, naturally drying for 30min, and drying at 120 ℃ for 40min for later use to obtain the glass fiber cloth treated by the coupling agent;
(3) Preparing a halogen-free resin system glue solution: adding 45 parts by weight of bio-based dimer acid glycidyl ester modified polyfunctional alicyclic epoxy resin (HXION Vast-Sen (original shell brand) dimer acid diglycidyl ester modifier HELOXY 71), 30 parts by weight of curing agent, 25 parts by weight of flame retardant and 100 parts by weight of filler into a container, and stirring to fully dissolve the mixture to obtain a halogen-free resin system glue solution; wherein the curing agent is prepared from phosphorus-containing phenolic resin (Jiaba electronics science and technology, inc., guangzhou city), benzoxazine resin (high molecular technology suitable for Chengdu science and technology) and styrene-maleic anhydride resin (Shanghai method colorization industry and technology, inc.) according to the mass ratio of 10:9:9, uniformly mixing to obtain the product; the flame retardant is a composite flame retardant system formed by mixing phosphate flame retardant (Henan Ruizu chemical products, ltd.) and phosphazene flame retardant (Dalton chemical industry) in equal mass; the filler is spherical aluminum hydroxide (Clarmar) and spherical silicon dioxide (Bide medicine) according to the mass ratio of 1:1, and the spherical aluminum hydroxide and the spherical silicon dioxide have the grain diameters of 0.7 to 2.0 mu m;
(4) Completely soaking the glass fiber cloth treated by the coupling agent obtained in the step (2) in the halogen-free resin system glue solution prepared in the step (3) for 120s, taking out the glass fiber cloth, and baking the glass fiber cloth in an oven at 180 ℃ for 10min to obtain a prepreg (prepreg), wherein the prepreg is uniform in appearance and has a glue content of 55wt%;
(5) Covering copper foils on two surfaces of the prepreg obtained in the step (4), hot-pressing for 1h at the temperature of 170 ℃ and under the pressure of 4MPa in a vacuum press, and then removing the pressure and preserving heat for 2h at the temperature of 170 ℃ to obtain the halogen-free low-dielectric copper-clad plate.
Respectively carrying out performance tests on the para-aramid paper composite base halogen-free low-dielectric copper clad laminate provided by the embodiments 1-5 and the halogen-free low-dielectric copper clad laminate provided by the comparative example, wherein the test items comprise peel strength, dielectric constant, dielectric loss, heat resistance, flame retardance and water absorption rate; the test results are shown in table 1.
Table 1 performance test results of the para-aramid paper composite based halogen-free low dielectric copper clad laminate provided in examples 1 to 5 and the halogen-free low dielectric copper clad laminate provided in comparative example
Figure BDA0003798137990000121
Figure BDA0003798137990000131
By comparing test experimental data in table 1, it can be seen that the dielectric constant and the dielectric loss can be significantly reduced by selecting the para-aramid paper relative to the glass fiber cloth, the copper-clad plate of the embodiment has a dielectric constant of 2.7-3.3 and a dielectric loss (10G) of 0.0055-0.0067; in addition, the peel strength of the copper-clad plate of the embodiment reaches 2.03N/mm, T288 is more than 120min, the flame retardance reaches FV-0 level, the water absorption rate is less than 0.1%, and the performance is also quite excellent. In conclusion, the invention provides a novel copper-clad plate and a preparation method thereof, and compared with the existing halogen-free copper-clad plate, the novel copper-clad plate can be compatible with high frequency at a lower dielectric constant and low loss, thereby being a halogen-free copper-clad plate with low dielectric constant and high frequency.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A preparation method of a para-aramid paper composite base halogen-free low-dielectric copper clad laminate comprises the following steps:
a) Sequentially carrying out high-temperature pretreatment, coupling agent treatment and drying on the para-aramid paper to obtain the treated para-aramid paper;
b) Dipping the treated para-aramid paper obtained in the step a) in a halogen-free resin system glue solution, taking out the para-aramid paper, and baking to obtain a prepreg;
c) Covering copper foils on two surfaces of the prepreg obtained in the step b), and compounding to obtain the para-aramid paper composite base halogen-free low-dielectric copper clad laminate.
2. The method of claim 1, wherein the para-aramid paper in step a) has a basis weight of 40g/m 2 ～60g/m 2 The thickness is 50-150 μm.
3. The method according to claim 1, wherein the high-temperature pretreatment in step a) is performed at a temperature of 80 to 120 ℃.
4. The method of claim 1, wherein the coupling agent treatment in step a) is performed using an aminosilane coupling agent solution having a concentration of 0.1wt% to 1wt%; the coupling agent is treated by soaking for 1-5 min, and then the product is taken out and naturally dried for 10-60 min.
5. The method according to claim 1, wherein the drying in step a) is carried out at a temperature of 110 ℃ to 130 ℃ for a time of 30min to 50min.
6. The preparation method according to claim 1, wherein the halogen-free resin system glue solution in the step b) is prepared from the following raw materials:
30-50 parts by weight of polyfunctional alicyclic epoxy resin;
30-40 parts of curing agent;
20-25 parts of flame retardant;
90 to 100 parts by weight of filler.
7. The method according to claim 1, wherein the immersion treatment time in step b) is 30 to 200s; the baking temperature is 170-190 ℃ and the baking time is 5-15 min.
8. The method according to claim 1, wherein the prepreg in the step b) has a gel content of 40 to 70wt%.
9. The preparation method according to claim 1, wherein the compounding process in step c) is specifically:
and (3) carrying out hot pressing for 0.5 to 5 hours in a vacuum press under the pressure of 0.8 to 10MPa and at the temperature of 120 to 210 ℃, and then removing the pressure to keep the temperature for 0.5 to 2.5 hours to obtain the para-aramid paper composite-based halogen-free low-dielectric copper-clad plate.
10. A para-aramid paper composite-based halogen-free low-dielectric copper-clad plate is characterized by being prepared by the preparation method of any one of claims 1 to 9.
CN202210974350.2A 2022-08-15 2022-08-15 Para-aramid paper composite base halogen-free low-dielectric copper-clad plate and preparation method thereof Pending CN115339191A (en)

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CN1838855A (en) * 2005-03-23 2006-09-27 安迪克连接科技公司 Circuit substrate and making method and multilayer circuit structure using it and information processing system
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