阅读说明：本技术 一种高导热碳氢组合物及其制备的高频覆铜板和制备方法 (High-thermal-conductivity hydrocarbon composition, high-frequency copper-clad plate prepared from same and preparation method of high-frequency copper-clad plate ) 是由 向中荣 刘永成 于 2021-07-29 设计创作，主要内容包括：本发明提供一种高导热碳氢组合物及其制备的高频覆铜板和制备方法,高导热碳氢组合物,按重量组份计,包括复合树脂20-50份；导热填料10-40份；阻燃剂10-40份；无机填料5-30份；抗氧剂0.1-5份；交联剂2-10份；复合树脂为树脂为聚丁二烯聚合物,聚丁二烯-苯乙烯共聚物,苯乙烯-丁二烯-苯乙烯共聚物,改性聚苯醚,丁二烯-丙烯腈共聚物中的两种或两种以上的复合物。本发明采用高导热碳氢组合物浸渍以电子级E级玻璃纤维布制得胶片,两面覆铜压合制得高频覆铜板,此覆铜板具有低介电常数,低介质损耗,高导热系数,吸水率极低,铜箔玻璃强度高,综合性能稳定,能充分满足5G高频通信领域的对材料的性能要求。(The invention provides a high-thermal-conductivity hydrocarbon composition, a high-frequency copper-clad plate prepared from the same and a preparation method of the high-thermal-conductivity hydrocarbon composition, wherein the high-thermal-conductivity hydrocarbon composition comprises 20-50 parts by weight of composite resin; 10-40 parts of heat-conducting filler; 10-40 parts of a flame retardant; 5-30 parts of inorganic filler; 0.1-5 parts of antioxidant; 2-10 parts of a cross-linking agent; the composite resin is a composite of two or more of polybutadiene polymer, polybutadiene-styrene copolymer, styrene-butadiene-styrene copolymer, modified polyphenyl ether and butadiene-acrylonitrile copolymer. The high-frequency copper-clad plate is prepared by dipping the high-heat-conductivity hydrocarbon composition into an electronic grade E-grade glass fiber cloth to prepare a film, and laminating two sides of the film to prepare the high-frequency copper-clad plate.)

1. The high-thermal-conductivity hydrocarbon composition is characterized by comprising the following components in parts by weight:

2. the highly thermally conductive hydrocarbon composition as claimed in claim 1, wherein the composite resin is a composite of two or more of polybutadiene polymer, polybutadiene-styrene copolymer, styrene-butadiene-styrene copolymer, modified polyphenylene ether and butadiene-acrylonitrile copolymer.

3. The hydrocarbon composition as claimed in claim 2, wherein the polybutadiene polymer has a molecular weight of 1000-10000, the polybutadiene-styrene copolymer has a molecular weight of 10000-50000, the styrene-butadiene-styrene copolymer has a molecular weight of 20000-100000, the modified polyphenylene ether has a molecular weight of 2000-20000, and the butadiene-acrylonitrile copolymer has a molecular weight of 10000-50000.

4. The highly heat-conductive hydrocarbon composition as claimed in claim 1, wherein the heat-conductive filler is a mixture of one or more of alumina, silicon carbide, silicon nitride and boron nitride.

5. The highly heat-conductive hydrocarbon composition as claimed in claim 1, wherein the flame retardant is one or more of phosphorus flame retardant, nitrogen flame retardant, bromine flame retardant, aluminum flame retardant, magnesium flame retardant, silicone flame retardant and boron flame retardant.

6. The hydrocarbon composition with high thermal conductivity as claimed in claim 1, wherein the inorganic filler is a mixture of one or more of silica powder, fumed silica, tin dioxide, wollastonite, alumina and titanium dioxide.

7. The highly thermally conductive hydrocarbon composition as claimed in claim 1, wherein the antioxidant is pentaerythritol tetrakis [ β -propionate ], tris (2, 4-di-t-butylphenyl) phosphite, 4' -thiobis (6-t-butyl-3-methylphenol), 2, 4-bis (n-octylthiomethylene) -6-methylphenol, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-t-butyl-4-hydroxybenzyl) benzene, 2, 6-di-t-butyl-p-cresol, ethyleneglycol bis-3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate, bis (2, 4-di-t-butylphenol) pentaerythritol diphosphite and 2, one or more of 2' -methylene bis (4-methyl-6-tert-butylphenol).

8. The highly thermally conductive hydrocarbon composition as claimed in claim 1, wherein the cross-linking agent is one or a mixture of at least two of divinylbenzene, triallylisocyanurate, diallyl bisphenol a, 2, 5-dimethyl-2, 5-di-tert-butyl-hexane peroxide, di-tert-butyl peroxide, benzoyl peroxide and dicumyl peroxide.

9. The method for preparing the high-frequency copper-clad plate by using the high-thermal-conductivity hydrocarbon composition according to any one of claims 1 to 8 is characterized by comprising the following steps:

1) stirring and dispersing the high-thermal-conductivity hydrocarbon composition xylene serving as a solvent at the rotating speed of 1500r/min at 500-;

2) dipping the dispersed suspension by using 1080 electronic grade glass fiber cloth, preparing a film with 65-80% of glue content by adjusting, baking the film in a baking oven at the temperature of 110-;

3) and (3) taking 6 prepared films, attaching copper foils on two sides, and pressing for 80-150 minutes at 200 ℃ under 3Mpa to obtain a final product, namely the high-thermal-conductivity hydrocarbon high-frequency copper-clad plate.

10. The high-frequency copper-clad plate prepared by the preparation method according to claim 9.

Technical Field

The invention belongs to the technical field of high-frequency communication materials, and particularly relates to a high-heat-conductivity hydrocarbon composition, a high-frequency copper-clad plate prepared from the same and a preparation method of the high-heat-conductivity hydrocarbon composition.

Background

Under the condition of high-speed development of 5G, the copper-clad plate is required to have high-speed information processing, high-frequency signal transmission and higher requirements on the performance of the copper-clad plate. The traditional epoxy copper clad laminate has higher dielectric constant and higher dielectric loss, and can not meet the requirements of the high-frequency and high-speed communication field. The modified polyphenylene ether-based copper-clad plate has been widely applied in the field of high-speed signal transmission due to the low dielectric constant and dielectric loss, but the defects of pores and the like in later PCB processing are caused by the high-melting property of the modified polyphenylene ether-based copper-clad plate, and the substrate has high water absorption rate and high thermal expansion coefficient, so that the modified polyphenylene ether-based copper-clad plate cannot be applied to the field of communication antennas with low water absorption rate and low thermal expansion coefficient and the like.

The polytetrafluoroethylene-based high-frequency copper-clad plate has the most excellent dielectric property, and has the advantages of low dielectric temperature drift, low frequency drift and the like, and is widely applied to radars, antennas, filters and the like at present. However, because the processing temperature is higher than 360 ℃, and the processing technology has higher difficulty, the metallization and the electroplating of the PCB processing holes are difficult in the later period, and the size expansion and contraction are obvious, thereby further limiting the application of the PCB processing holes.

The poly-hydrocarbon-based high-frequency copper-clad plate has the properties of low dielectric constant, low dielectric loss, low thermal expansion coefficient, low water absorption and the like, and is widely used as a high-frequency electronic communication material. With the development of high frequency and high speed signal transmission, the thermal management of the PCB is more and more emphasized, so that the heat conductivity coefficient of a PCB core component copper-clad plate has definite requirements in some application occasions, the higher the heat conductivity coefficient is, the faster the heat dissipation of the component is, and the temperature rise of the PCB is relatively smaller. The carbon-hydrogen base polymer or copolymer has very poor heat conduction of 0.01-0.03, so that the carbon-hydrogen copper-clad plate has high heat conduction coefficient through filler selection modification, and the method is one of the common methods for copper-clad plate researchers. The common heat-conducting filler comprises aluminum oxide, boron nitride, silicon nitride and the like, and the high-frequency material has higher requirements on selection matching and the like of various heat-conducting fillers under the limitation of high requirements on dielectric property, water absorption and the like.

Therefore, the development of the hydrocarbon-based high-frequency copper-clad plate with stable performances such as low dielectric constant, low dielectric loss, excellent heat resistance, high thermal conductivity coefficient and the like has important significance.

Disclosure of Invention

Aiming at the defects, the invention provides a component of a high-thermal-conductivity hydrocarbon composition, a hydrocarbon-based high-frequency copper-clad plate which is prepared from the composition and has stable properties such as low dielectric constant, low dielectric loss, excellent heat resistance, high thermal conductivity coefficient and the like, and a preparation method thereof.

The invention provides the following technical scheme: the high-thermal-conductivity hydrocarbon composition comprises the following components in parts by weight:

further, the composite resin is a composite of two or more of polybutadiene polymer, polybutadiene-styrene copolymer, styrene-butadiene-styrene copolymer, modified polyphenylene oxide and butadiene-acrylonitrile copolymer.

Further, the molecular weight of the polybutadiene polymer is 10000-.

Further, the heat conducting filler is a mixture formed by one or more of aluminum oxide, silicon carbide, silicon nitride and boron nitride.

Further, the flame retardant is a mixture formed by one or more of a phosphorus flame retardant, a nitrogen flame retardant, a bromine flame retardant, an aluminum flame retardant, a magnesium flame retardant, an organosilicon flame retardant and a boron flame retardant.

Further, the inorganic filler is a mixture formed by one or more of silica micropowder, fumed silica, tin dioxide, wollastonite, alumina and titanium dioxide.

Further, the antioxidant is pentaerythritol tetrakis [ beta-propionate ], tris (2, 4-di-tert-butylphenyl) phosphite, 4' -thiobis (6-tert-butyl-3-methylphenol), 2, 4-bis (n-octylthiomethylene) -6-methylphenol, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, 2, 6-di-tert-butyl-p-cresol, ethylene glycol bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite and 2,2' -methylene bis (4-methyl-6-tert-butylphenol) to form a blend.

Further, the crosslinking agent is one or a mixture of at least two of divinylbenzene, triallyl isocyanurate, diallyl bisphenol A, 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide, di-tert-butyl peroxide, benzoyl peroxide and diisopropylbenzene hydroperoxide.

The invention also provides a method for preparing the high-frequency copper-clad plate by adopting the high-thermal-conductivity hydrocarbon composition, which comprises the following steps:

1) stirring and dispersing the high-thermal-conductivity hydrocarbon composition xylene serving as a solvent at the rotating speed of 1500r/min at 500-;

2) dipping the dispersed suspension by using 1080 electronic grade glass fiber cloth, preparing a film with 65-80% of glue content by adjusting, baking the film in a baking oven at the temperature of 110-;

3) and (3) taking 6 prepared films, attaching copper foils on two sides, and pressing for 80-150 minutes at 200 ℃ under 3Mpa to obtain a final product, namely the high-thermal-conductivity hydrocarbon high-frequency copper-clad plate.

The invention also provides the high-frequency copper-clad plate prepared by the preparation method.

The invention has the beneficial effects that:

the high-heat-conductivity hydrocarbon composition has the advantages that the high-heat-conductivity hydrocarbon composition is used for preparing the high-frequency copper clad laminate, the high-frequency copper clad laminate has the excellent characteristics of low dielectric constant, low dielectric loss, excellent heat resistance, high heat conductivity coefficient and stable performance, the xylene dispersion liquid of the high-heat-conductivity hydrocarbon composition is used for dipping the high-frequency copper clad laminate, an electronic grade E grade glass fiber cloth is used for preparing a film, and two sides of the film are coated with copper and pressed to prepare the high-frequency copper clad laminate.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious 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 derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Examples 1 to 3

The following examples 1-3 were prepared as follows: firstly, the composite resin, the heat-conducting filler, the flame retardant, the inorganic filler, the antioxidant and the crosslinking agent are sequentially added into the dimethylbenzene, the mixed materials are fully and uniformly mixed at the rotating speed of 500-2000r/min, the viscosity of the glue solution is adjusted to be 30-60s (Chashi four cups), and the solid content of the glue solution is prepared to be about 65-80% for later use. And (3) dipping the electronic-grade 1080 glass cloth into the prepared glue solution, and baking in an oven at the temperature of 110-. Covering 1OZ (35 μm) copper on two sides of 6 films, and hot-pressing at 180-230 deg.C for 80-150min by a hot press to obtain a double-sided plate, wherein the formula of specific examples 1-3 is shown in Table 1:

TABLE 1

Comparative examples 1 to 3

Comparative examples 1-3 differ from examples 1-3 in that the formulation as in table 2 is used.

TABLE 2

	Comparative example 1	Comparative example 2	Comparative example 3
				Styrene-butadiene-styrene copolymer	15	10	20
Polybutadiene	15	20	10
				Modified polyphenylene ether	3	0	3
Butadiene-acrylonitrile copolymer	0	3	0
				Silicon dioxide	16	21	25
Decabromodiphenylethane	15	0	10
				Intumescent flame retardant	0	30	15
Alumina oxide	30	0	0
				Boron nitride	0	10	0
Silicon nitride	0	0	10
				4,4' -Thiobis (6-tert-butyl-3-methylphenol)	1	1	1
Divinylbenzene	2	1	1
				Triallyl isocyanate TAIC	0	1	2
Dicumyl peroxide	3	3	3

The copper-clad plates prepared in examples 1 to 3 and comparative examples 1 to 3 had the following properties:

as comparative example 1, the heat conductive material uses only alumina as the heat conductive filler, and the heat conductivity is only 0.56w/mk, which is less than the target value of 0.7 w/mk. As comparative example 2, the thermal conductivity coefficient reached 0.70w/mk with the thermal conductive filler being boron nitride and added in 10 parts, but the water absorption was as high as 0.2%, and the peel strength was as low as 3.35 lb/inch. As comparative example 3, when the heat conductive filler was silicon nitride and added in an amount of 10 parts, the thermal conductivity reached 0.69w/mk, but the water absorption was as high as 0.1%, and the peel resistance was 3.92lb/inch, which was relatively small.

As in examples 1 to 3, since alumina has a relatively low thermal conductivity and a relatively high dielectric constant, boron nitride has a relatively high water absorption and a relatively low exfoliation resistance, and silicon nitride has a self-lubricating property similar to boron nitride, two or more compounds are used to minimize the influence of defects of each thermal conductive filler, and to maximize the advantageous properties of the thermal conductive filler, thereby producing a highly reliable and highly stable hydrocarbon compound having a relatively high thermal conductivity, a relatively high exfoliation strength, a relatively low water absorption, and a relatively low water absorption. The crosslinking assistant and different crosslinking agents are added for compounding, so that the mechanical property, the heat resistance and the like are further improved, and the carbon-hydrogen high-frequency copper-clad plate with excellent dielectric property, good heat resistance and uniform material is prepared.

The process is easy to realize, the cost is low, the batch production is easy, and the carbon-hydrogen high-thermal-conductivity copper-clad plate with stable performance can fully meet the application requirement of 5G communication.

The above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.