阅读说明：本技术 一种阻燃烯烃基板及其制备方法 (Flame-retardant olefin substrate and preparation method thereof ) 是由 周学琴 于 2020-05-28 设计创作，主要内容包括：本发明涉及一种阻燃烯烃基板及其制备方法,包括以下步骤：将双键碳氢物、填料加入溶剂中形成混合液,再将混合液涂在铜箔粗糙面上,去除溶剂,得到表面处理铜箔；将玻璃布浸渍胶液后加热得到半固化片；所述胶液包括烯烃聚合物、溶剂、填料、固化剂、添加型阻燃剂；将表面处理铜箔与半固化片叠合后热压,得到阻燃烯烃基板。本发明产品介电性能优异,具有阻燃能力,可工业化应用于高频电路板。(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.)

1. The preparation method of the flame-retardant olefin substrate is characterized by comprising 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.

2. The method for preparing a flame-retardant olefin substrate according to claim 1, wherein: the hydrocarbon containing double bonds is 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.

3. The method for preparing a flame-retardant olefin substrate according to claim 1, wherein: 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 microns.

4. The method for preparing a flame-retardant olefin substrate according to claim 1, wherein: in the step (2), the mass ratio of the olefin polymer to the filler to the curing agent to the additive-type flame retardant is 100 to (50-300) to (2-4) to (10-12); the glass cloth is 2116 glass cloth or 1080 glass cloth.

5. The method for preparing a flame-retardant olefin substrate according to claim 1, wherein: in the step (2), the particle size of the filler is 30-50 microns; 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%.

6. The method for producing a flame-retardant olefin substrate according to claim 5, characterized in that: in the step (1), the filler comprises barium titanate or aluminum oxide; in the step (2), the filler comprises one or a mixture of more than one of silicon dioxide, titanium dioxide, barium titanate, boron nitride and aluminum oxide.

7. The method for preparing a flame-retardant olefin substrate according to claim 1, wherein: the prepreg is positioned between two pieces of surface treatment copper foil; the number of the prepregs is 5-10.

8. The method for preparing a flame-retardant olefin substrate according to claim 1, wherein: the hot pressing temperature is 200-250 ℃, the time is 30-45 minutes, and the pressure is 65kg/cm²～90kg/cm²。

9. The flame retardant olefin substrate prepared by the method for preparing a flame retardant olefin substrate according to claim 1.

10. Use of the flame retardant olefin substrate according to claim 1 for the preparation of high frequency materials.

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.

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 microns; 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 microns; 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 an application of the flame-retardant olefin substrate in the 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, and the mass ratio of the phenoxy cyclophosphazene to the zinc borate is preferably 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; the preferred particulate filler is silica having a particle size of 30 to 50 microns, and silica fillers such as FB-35(Denka corporation) and 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:

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, wherein 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.