CN111605267B - Flame-retardant olefin substrate and preparation method thereof - Google Patents

Flame-retardant olefin substrate and preparation method thereof Download PDF

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CN111605267B
CN111605267B CN202010471131.3A CN202010471131A CN111605267B CN 111605267 B CN111605267 B CN 111605267B CN 202010471131 A CN202010471131 A CN 202010471131A CN 111605267 B CN111605267 B CN 111605267B
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copper foil
flame
weight
olefin substrate
flame retardant
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CN111605267A (en
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周学琴
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Zhuhai Guoneng New Material Co ltd
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Zhuhai Guoneng New Material 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
    • 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
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
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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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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D153/02—Vinyl aromatic monomers and conjugated dienes
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/69—Particle size larger than 1000 nm
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/06—Coating on the layer surface on metal 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B32B2262/10—Inorganic fibres
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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Abstract

The invention relates to a flame-retardant olefin substrate and a preparation method thereof, and the flame-retardant olefin substrate comprises the following steps: adding double-bond hydrocarbon and filler into a solvent to form a mixed solution, coating the mixed solution on the rough surface of the copper foil, and removing the solvent to obtain the surface-treated copper foil; soaking the glass cloth in the glue solution and then heating to obtain a prepreg; the glue solution comprises olefin polymer, solvent, filler, curing agent and additive flame retardant; and laminating the surface-treated copper foil and the prepreg and then carrying out hot pressing to obtain the flame-retardant olefin substrate. The product has excellent dielectric property and flame retardant capability, and can be industrially applied to high-frequency circuit boards.

Description

Flame-retardant olefin substrate and preparation method thereof
Technical Field
The invention relates to a thermosetting flame-retardant olefin substrate which has flame-retardant property and can be used for preparing materials in the field of high-frequency and high-speed communication.
Background
The flame retardant is widely varied, can be connected to a polymer chain in a chemical bond form and is called a reactive flame retardant, and if the flame retardant is mixed in a polymer, the flame retardant is called an additive flame retardant, and is also divided into an inorganic flame retardant and an organic flame retardant.
The prior art discloses a polyphenyl ether adhesive which is formed by mixing a resin composition, a flame retardant, a powder material, a curing accelerator and a solvent. The modified polyphenylene ether resin is prepared by the steps of preparing modified low molecular weight polyphenylene ether resin, preparing a resin composition, preparing a polyphenylene ether adhesive and the like; coating the prepreg by a gluing machine to prepare a polyphenylene oxide glass fiber cloth prepreg, and preparing a copper-clad plate by a vacuum press; the prepared copper-clad plate has good dielectric property. The prior art also discloses a halogen-free epoxy resin composition for a copper-clad plate and application thereof, and the prepared copper-clad plate can meet the requirements of high heat resistance, low water absorption, good toughness and good cohesiveness and can be widely applied to high-performance electronic materials.
The frequency band in the period of 5G is higher than that in the period of 4G, so that higher loss is caused in the transmission process. In order to solve the problem, materials with lower loss (lower dielectric constant and dielectric loss) are needed, the olefin substrate has become a key direction for researching high-frequency substrates, the research is carried out on resin matrix in the prior art, the technology related to copper foil treatment is not updated, and the interface effect of the copper foil and a dielectric layer is very critical to the application of the copper-clad plate, especially the peeling strength is concerned.
Disclosure of Invention
The invention aims to solve the technical problem of providing a flame-retardant olefin substrate, the composite material substrate has low loss factor, high peel strength and good thermal property under the condition of low copper foil roughness Rz, and particularly, on the basis of olefin resin, an additive flame retardant is used for obtaining excellent flame-retardant property, so that the flame-retardant olefin substrate is suitable for application of antennas, base stations and the like which require high frequency.
The invention adopts the following technical scheme:
a flame-retardant olefin substrate and a preparation method thereof comprise the following steps:
(1) adding double-bond hydrocarbon and filler into a solvent to form a mixed solution, coating the mixed solution on the rough surface of the copper foil, and removing the solvent to obtain the surface-treated copper foil;
(2) soaking the glass cloth in the glue solution and then heating to obtain a prepreg; the glue solution comprises olefin polymer, solvent, filler, curing agent and additive flame retardant;
(3) and laminating the surface-treated copper foil and the prepreg and then carrying out hot pressing to obtain the flame-retardant olefin substrate.
In the present invention, the double bond-containing hydrocarbon is a double bond-containing material consisting of only hydrocarbon, such as butadiene, styrene, polybutadiene, polystyrene, or a copolymer of butadiene and styrene; the matte roughness Rz of the copper foil is 1-10 microns; the thickness of the copper foil is 5-70 microns, for example, the copper foil is a 1 ounce copper foil or a half ounce copper foil, the matte surface roughness Rz of the copper foil is preferably 1-5 microns, and the matte surface roughness Rz of the copper foil is further preferably 1-3 microns; the copper foil is RTF copper foil or HVLP copper foil.
In the invention, in the step (1), the amount of the filler is 8-10% of the mass of the double-bond hydrocarbon; the particle size of the filler is 1-10 micrometers; the filler comprises barium titanate or alumina.
In the invention, in the step (2), the mass ratio of the olefin polymer, the filler, the curing agent and the additive-type flame retardant is 100: 50-300: 2-4: 10-12; the glass cloth is 2116 glass cloth or 1080 glass cloth; the particle size of the filler is 30-50 micrometers; the curing agent comprises one or more of dicumyl peroxide, tert-butyl peroxybenzoate and 2, 5-di (2-ethylhexanoylperoxy) -2, 5-dimethylhexane; the solid content of the glue solution is 80-85%.
In the present invention, in the step (2), the filler includes one or more of silica, titanium dioxide, barium titanate, boron nitride, and alumina.
In the invention, the prepreg is positioned between two pieces of surface-treated copper foil; the number of the prepregs is 5-10.
In the invention, the hot pressing temperature is 200-250 ℃, the time is 30-45 minutes, and the pressure is 65kg/cm2～90kg/cm2。
The invention discloses application of the flame-retardant olefin substrate in preparation of high-frequency materials; the high frequency material includes a circuit board.
In the invention, the additive flame retardant is phenoxy cyclophosphazene and zinc borate, preferably, the mass ratio of the phenoxy cyclophosphazene to the zinc borate is 0.3: 1.
The invention has the following advantages:
the olefin polymer of the present invention may be a polymerization product of butadiene and styrene, such as butadiene styrene copolymer and styrene butadiene styrene copolymer, and can increase the crosslinking density during curing and thus improve the excellent high temperature resistance and rigidity of the material, since the resin has a benzene ring with good rigidity and a high vinyl content to provide a large amount of unsaturated vinyl groups required for curing crosslinking, such as D1101(Kraton company) and FG1901(Kraton company).
The granular filler for the prepreg is one or more of crystalline silica, amorphous silica, spherical silica, fumed silica, titanium dioxide, barium titanate, boron nitride, alumina, glass fiber and the like, and the granular filler plays the roles of improving the solid content of a glue solution, improving the dimensional stability of a material, reducing the CTE and the like; preferred particulate fillers are silica having a particle size of 30 to 50 microns, and silica fillers such as FB-35(Denka corporation), 525 (Sibelco corporation) may be used.
The fiber glass cloth of the invention has the functions of improving the dimensional stability of the substrate and reducing the material shrinkage in the curing process, and the specification of the fiber glass cloth is as follows:
Figure DEST_PATH_IMAGE001
the curing agent is dicumyl peroxide (DCP), tert-butyl peroxybenzoate and 2, 5-di (2-ethyl hexanoyl peroxy) -2, 5-dimethyl hexane, and has the effect of accelerating reaction.
The resin adopted in the thermosetting electronic composite material is not epoxy resin, but is a low-dielectric double-bond polymer material, and a filling technology is matched, so that the low-loss factor substrate can be prepared, particularly, the defect that high copper foil copper nodules are needed to improve the peeling strength of a resin system in the prior art is overcome, the peeling strength close to 1N/mm can be obtained under the condition of lower roughness Rz of a rough surface (rough surface), and the transmission loss of the obtained substrate is extremely low; meanwhile, the flame retardant property of the substrate is improved by adopting the additive flame retardant.
Drawings
FIG. 1 is a photograph of a surface-treated copper foil of the present invention.
Detailed Description
The preparation method of the flame-retardant olefin substrate comprises the following steps:
(1) adding double-bond hydrocarbon and filler into a solvent to form a mixed solution, coating the mixed solution on the rough surface of the copper foil, and removing the solvent to obtain the surface-treated copper foil;
(2) soaking the glass cloth in the glue solution and then heating to obtain a prepreg; the glue solution comprises olefin polymer, solvent, filler, curing agent and additive flame retardant;
(3) and laminating the surface-treated copper foil and the prepreg and then carrying out hot pressing to obtain the flame-retardant olefin substrate.
The raw materials used in the invention are conventional raw materials in the field of copper-clad plates, and the related test method is a conventional standard test method of the copper-clad plates; the copper foil is generally a rolled copper foil or an electrolytic copper foil (the selection of the rolled copper foil or the electrolytic copper foil does not influence the realization of the technical effect of the invention, generally the electrolytic copper foil is an RTF copper foil or an HVLP copper foil according to the roughness), one surface of the copper foil is prepared with a copper nodule forming rough surface, and then the rough surface is treated by hydrocarbon containing double bonds to obtain the copper foil; the prior art adopts high copper nodule height to improve the peeling strength, and the invention adopts double bond-containing hydrocarbon to treat the low-roughness copper foil for the first time, thereby solving the problems of high residual copper rate and improving the peeling strength.
The invention adopts an additive flame retardant which does not participate in olefin curing, the additive flame retardant is phenoxy cyclophosphazene and zinc borate, and the mass ratio of the phenoxy cyclophosphazene (CAS #: 1184-10-7) to the zinc borate is 0.3: 1; the additive flame retardant is a conventional product sold in the market.
Example 1
Adding a block copolymer (D1101 SBS) of styrene and butadiene and alumina (the particle size is 1-10 microns) into dimethylbenzene to form a mixed solution, coating the mixed solution on a rough surface of a copper foil, naturally airing, volatilizing to remove a solvent to obtain a surface-treated copper foil, forming a copolymer film layer on the rough surface of the copper foil, wherein the thickness of the copolymer film layer is 20 microns, and a physical photograph is shown in figure 1; the amount of alumina used was 10% by weight of the block copolymer of styrene and butadiene (D1101 SBS).
Dissolving 100 parts by weight of styrene-butadiene block copolymer (D1101) in toluene, adding 90 parts by weight of silicon dioxide (525), 3 parts by weight of curing agent DCP and 10 parts by weight of additive flame retardant under stirring to obtain a glue solution (solid content is 80%), impregnating 1080 fiber glass cloth into the glue solution to obtain a prepreg, drying to remove the solvent to obtain the prepreg, wherein the glue content is (weight of the prepreg-weight of the corresponding glass cloth)/weight of the prepreg) is 66%; and (3) overlapping 8 prepregs, covering surface-treated copper foils on two sides of the prepregs, and performing high-temperature hot-pressing curing in a press to prepare the flame-retardant olefin substrate.
The drying temperature is 90 deg.C, the drying time is 4 min, the hot pressing temperature is 220 deg.C, the hot pressing time is 60 min, and the pressure is 70kg/cm2(ii) a The physical property data are shown in Table 1.
In the embodiment, the particle size of the filler is 30-40 microns; the copper foil was a 1 oz copper foil, and the matte roughness Rz of the copper foil was 2.9 μm.
Example 2
Adding a styrene-butadiene block copolymer (D1101 SBS) and aluminum oxide (the particle size is 1-10 micrometers) into xylene to form a mixed solution, coating the mixed solution on the rough surface of the copper foil, naturally airing, volatilizing to remove a solvent to obtain a surface-treated copper foil, and forming a copolymer film layer on the rough surface of the copper foil, wherein the thickness of the copolymer film layer is 25 micrometers; the amount of alumina used was 10% by weight of the block copolymer of styrene and butadiene (D1101 SBS).
Dissolving 100 parts by weight of styrene-butadiene block copolymer (D1101) in toluene, adding 250 parts by weight of silicon dioxide (525), 3.8 parts by weight of curing agent DCP and 10 parts by weight of additive flame retardant under stirring to obtain a glue solution (solid content is 80%), soaking the resin solution in 1080 fiber glass cloth, drying and removing the solvent to obtain a prepreg, wherein the glue content is 67% (weight of prepreg-weight of corresponding glass cloth)/weight of prepreg); then overlapping 8 prepregs, covering surface treatment copper foils on two sides of the prepregs, and performing high-temperature hot-pressing curing in a press to prepare a flame-retardant olefin substrate; the drying temperature is 95 deg.C, the drying time is 3 min, the hot-pressing temperature is 230 deg.C, the hot-pressing time is 40 min, and the pressure is 85kg/cm2(ii) a The physical property data are shown in Table 1.
In the embodiment, the particle size of the filler is 30-40 microns; the copper foil was a 0.5 ounce copper foil, and the matte-surface roughness Rz of the copper foil was 2.2 microns.
Comparative example 1
The preparation process was the same as in example 1, except that no additive flame retardant was added, the physical property data are shown in Table 1.
Comparative example 2
The same procedure as in example 1 was followed, except that a 1 oz copper foil having a matte surface roughness Rz of 10 μm was used and subjected to the same surface treatment with a block copolymer of styrene and butadiene (D1101 SBS) and alumina.
All the raw materials are commercially available products, the performance test method of the obtained product is a conventional method, and on the basis of the first embodiment, the silicon dioxide is replaced by the barium titanate, the aluminum oxide and other fillers, so that the performance is close to that of the first embodiment.
TABLE 1 examples and comparative product Properties
Figure 684094DEST_PATH_IMAGE002
Dielectric properties were tested according to IPC TM-6502.5.5 method; the moisture absorption rate is tested according to the IPC TM-6502.6.2.1 method, and the examples are all less than 0.1%; peel strength was tested according to IPC TM-6502.4.8 method; the flame retardant properties were tested according to the UL94 vertical burning method.
The invention effectively improves the flame retardant performance based on the application of the olefin-based copper-clad plate, and some comparative information can be referred to the application, and a PIM tester is adopted to test the PIM performance; as shown in the physical property analysis, compared with the common composite material, the olefin copper-clad plate disclosed by the invention has the advantages of more excellent dielectric constant and loss factor and good high-frequency and high-speed performance, and completely meets the requirements of the future 5G market.
The above examples are not intended to limit the electronic composite material of the composition of the present invention, and all the minor modifications, equivalent variations and modifications made to the above examples according to the technical implementation or composition or content of the present invention are within the scope of the technical solution of the present invention. The prior art discloses an electronic composite material substrate, the thermosetting electronic composite material comprises butadiene, styrene, butadiene styrene copolymer or styrene butadiene styrene copolymer, a low-loss factor substrate can be prepared, and the performances of heat resistance, water resistance, peeling and the like are excellent, but a copper foil adopted for improving the peeling strength is an STD copper foil, high roughness is required and reaches 10 micrometers, a rough surface of the copper foil is treated by a vinyl coupling agent, so that the prepared substrate PIM has poor performance, and the prior art uses a bromine-containing flame retardant for flame retardation; the invention adopts a new technical scheme, obtains the peeling strength similar to that of the prior art under the condition of low roughness, particularly greatly improves the PIM performance, reduces the signal distortion and realizes flame retardance through an environment-friendly flame retardant.

Claims (3)

1. A preparation method of a flame-retardant olefin substrate is characterized in that a block copolymer of styrene and butadiene and alumina are added into dimethylbenzene to form a mixed solution, then the mixed solution is coated on a rough surface of a copper foil, the rough surface is naturally dried, a solvent is removed through volatilization to obtain a surface-treated copper foil, and a copolymer film layer is formed on the rough surface of the copper foil, wherein the thickness of the copolymer film layer is 20 micrometers; 100 parts by weight of a block copolymer of styrene and butadiene were dissolved in toluene, and 90 parts by weight of the solution was added with stirringStirring silicon dioxide, 3 parts by weight of curing agent DCP and 10 parts by weight of additive flame retardant to obtain a glue solution with a solid content of 80%, impregnating the glue solution with 1080 glass fiber cloth to obtain a prepreg, and drying to remove a solvent to obtain a prepreg with a glue content of 66%; superposing 8 prepregs, covering surface treatment copper foils on two sides of the prepregs, and performing high-temperature hot-pressing solidification in a press to prepare a flame-retardant olefin substrate; the drying temperature is 90 deg.C, the drying time is 4 min, the hot-pressing temperature is 220 deg.C, the hot-pressing time is 60 min, and the pressure is 70kg/cm2(ii) a The copper foil is a 1 ounce copper foil, and the rough surface roughness Rz of the copper foil is 2.9 microns; or the preparation method of the flame-retardant olefin substrate comprises the following steps:
adding a block copolymer of styrene and butadiene and alumina into xylene to form a mixed solution, coating the mixed solution on a rough surface of a copper foil, naturally airing, volatilizing to remove a solvent to obtain a surface-treated copper foil, and forming a copolymer film layer with the thickness of 25 micrometers on the rough surface of the copper foil; dissolving 100 parts by weight of styrene-butadiene block copolymer in toluene, adding 250 parts by weight of silicon dioxide, 3.8 parts by weight of curing agent DCP and 10 parts by weight of additive flame retardant under stirring, stirring to obtain a glue solution with a solid content of 80%, impregnating the glue solution with 1080 glass fiber cloth, drying and removing the solvent to obtain a prepreg with a glue content of 67%; then overlapping 8 prepregs, covering surface treatment copper foils on two sides of the prepregs, and performing high-temperature hot-pressing curing in a press to prepare the flame-retardant olefin substrate; the drying temperature is 95 deg.C, the drying time is 3 min, the hot-pressing temperature is 230 deg.C, the hot-pressing time is 40 min, and the pressure is 85kg/cm2(ii) a The copper foil is a 0.5 ounce copper foil, and the matte surface roughness Rz of the copper foil is 2.2 microns;
the block copolymer of styrene and butadiene is D1101; the particle size of the alumina is 1-10 microns; the amount of alumina is 10% of the weight of the block copolymer of styrene and butadiene; the particle size of the silica is 525 and is 30-40 micrometers; the additive flame retardant is phenoxy cyclophosphazene and zinc borate, and the mass ratio of the phenoxy cyclophosphazene to the zinc borate is 0.3: 1.
2. The flame retardant olefin substrate prepared by the method for preparing a flame retardant olefin substrate according to claim 1.
3. Use of the flame retardant olefin substrate according to claim 2 for the preparation of high frequency materials.
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