CN113897015A - Preparation method of thermosetting polyolefin copper-clad plate with high thermal stability and low water absorption - Google Patents
Preparation method of thermosetting polyolefin copper-clad plate with high thermal stability and low water absorption Download PDFInfo
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Abstract
The invention relates to a preparation method of a thermosetting polyolefin copper-clad plate with high thermal stability and low water absorption, which comprises the steps of respectively carrying out surface chemical treatment on an inorganic filler and a short-cut quartz fiber by using a coupling agent; uniformly dispersing thermosetting polyolefin, inorganic filler, chopped quartz fiber, flame retardant and curing agent in an organic solvent to form polyolefin composite glue solution; removing the organic solvent in the polyolefin composite glue solution through vacuum drying, pouring the organic solvent into a mold, and performing mold pressing forming under the conditions of the temperature of 80-160 ℃ and the pressure of 5-30MPa to obtain a prepreg; and covering copper foils on the upper surface and the lower surface of the cut prepreg, and then hot-pressing and sintering for 2-5h at the temperature of 200-280 ℃ and under the pressure of 8-30MPa to enable thermosetting polyolefin to be crosslinked and cured and finally shaped, thus preparing the thermosetting polyolefin copper-clad plate.
Description
Technical Field
The invention relates to the field of copper-clad plates and preparation methods thereof, in particular to a preparation method of a thermosetting polyolefin copper-clad plate with high thermal stability and low water absorption.
Background
Copper-clad plates have been developed for over half a century and are becoming one of the most important basic materials in electronic information products. With the development of electronic information technology, the conventional copper-clad plate cannot meet the requirement of electronic installation high-density interconnection developed at a high speed in recent years, and a microwave substrate with high performance receives more and more attention.
The copper-clad plate is prepared by using glass fiber cloth, fiber paper or glass fiber non-woven fabric and the like as reinforcing materials, soaking the reinforcing materials in resin, coating copper foil on one side or two sides of the reinforcing materials, and performing hot pressing. Chinese patent application publication No. CN104647868A describes a method for manufacturing a polytetrafluoroethylene copper-clad plate, which adopts a dipping lamination process. Because PTFE has good chemical stability, thermal stability and excellent dielectric property, PTFE is widely applied to the fields of satellite communication and the like. However, PTFE has a large coefficient of thermal expansion and poor dimensional stability, which can cause serious quality problems in the alignment of microwave substrates and the subsequent mounting of electronic components, thereby restricting the development of PTFE substrates.
Chinese patent application publication No. CN108127994A proposes a thermosetting resin composition copper-clad plate and a preparation method thereof, which is prepared from a thermosetting resin composition, glass fiber cloth and copper foil, wherein the adopted thermosetting resin is high bromine epoxy resin, novolac epoxy resin, bisphenol F type epoxy resin and styrene maleic anhydride copolymer. Although the thermosetting epoxy resin has excellent performances such as heat resistance, adhesiveness and electrical insulation, the dielectric loss factor is large, and a large number of polar groups such as hydroxyl groups are generated after curing, so that the water absorption rate of the board is large.
Therefore, the copper-clad plate used as a component carrier needs to have stable dielectric constant and dielectric loss factor, high thermal stability and low water absorption rate so as to ensure the processing reliability and the use stability of the plate.
Disclosure of Invention
The invention aims to provide a preparation method of a thermosetting polyolefin copper-clad plate with high thermal stability and low water absorption aiming at the problems and the defects of the prior art, and the prepared microwave substrate has the advantages of low dielectric loss factor, low water absorption, high thermal stability, simple processing technology and the like; the preparation method has simple process and is beneficial to industrial mass production.
The technical scheme of the invention is as follows: a thermosetting polyolefin copper-clad plate with high thermal stability and low water absorption rate comprises the following raw material components in parts by weight: 20-50 parts of thermosetting polyolefin, 25-50 parts of inorganic filler, 1-10 parts of chopped quartz fiber, 10-20 parts of flame retardant, 0.5-5 parts of curing agent and 20-40 parts of organic solvent.
The raw material components are as follows according to the weight portion: 23-46 parts of thermosetting polyolefin, 28-47 parts of inorganic filler, 2-7 parts of chopped quartz fiber, 12-18 parts of flame retardant, 1-4.5 parts of curing agent and 24-38 parts of organic solvent.
The thermosetting polyolefin is selected from one or more of polybutadiene, polyisoprene, styrene-butadiene block copolymer and ethylene-propylene-butadiene copolymer.
The inorganic filler is selected from one or more of silicon dioxide, titanium dioxide, aluminum oxide, magnesium oxide and barium titanate, and the particle size of the inorganic filler is 10-30 mu m.
The curing agent is selected from one or more of dicumyl peroxide, di-tert-butylperoxy-dicumyl and tert-butyl peroxybenzoate.
The flame retardant is one or two selected from decabromodiphenyl ether and 2,4, 6-tribromophenyl allyl ether.
The organic solvent is selected from one of cyclohexane, butanone and xylene.
A preparation method of a thermosetting polyolefin copper-clad plate with high thermal stability and low water absorption rate comprises the following steps:
(1) respectively carrying out surface chemical treatment on the inorganic filler and the chopped quartz fiber by using a coupling agent: firstly, respectively dissolving 0.5-3% of inorganic filler by weight and 0.5-3% of coupling agent by weight of chopped quartz fiber by weight in absolute ethyl alcohol, respectively immersing the weighed inorganic filler and chopped quartz fiber in the absolute ethyl alcohol solution of the coupling agent, stirring for 60-90min, and finally respectively drying the modified inorganic filler and chopped quartz fiber in an oven to constant weight;
(2) sequentially adding the weighed thermosetting polyolefin, the modified inorganic filler, the chopped quartz fiber, the flame retardant and the curing agent into an organic solvent, and fully stirring for 60-120min at the stirring speed of 300-600r/min to form a polyolefin composite glue solution;
(3) putting the polyolefin composite glue solution into a vacuum oven for drying treatment for 2-5h, removing an organic solvent in the glue solution, pouring into a mold, and performing mold pressing forming under the conditions of the temperature of 80-160 ℃ and the pressure of 5-30MPa to obtain a prepreg;
(4) and covering copper foils on the upper surface and the lower surface of the cut prepreg, and then carrying out hot-pressing sintering for 2-5h at the temperature of 200-280 ℃ and under the pressure of 8-30MPa to enable thermosetting polyolefin to be subjected to crosslinking curing and final setting, thus preparing the thermosetting polyolefin copper-clad plate.
The coupling agent is selected from one or more of silane coupling agent, titanate coupling agent and zirconate coupling agent.
The invention has the following advantages:
the thermosetting polyolefin copper-clad plate with high thermal stability and low water absorption rate, which is manufactured by the invention, has the characteristics of adjustable dielectric constant within the range of 2.55-3.45, high thermal stability, low water absorption rate and the like, and can be widely applied to the related fields of communication, radar, high-speed rail and the like. The dielectric loss of the plate is less than or equal to 0.0035, the thermal expansion coefficient is less than 28 ppm/DEG C, the water absorption is less than 0.05 percent, the reliability in the aspects of plate processing and application is high, the preparation process is simple, the raw material source is convenient, and the realization of industrial production is facilitated.
The thermosetting polyolefin of the present invention is a polymerization product of butadiene, styrene, isoprene, ethylene and propylene, such as polybutadiene, styrene-butadiene block copolymer. On one hand, the molecular structure of the polyolefin has higher symmetry, and the types and the number of the contained polar functional groups are less than those of epoxy resin and cyanate resin, so that the material has lower dielectric loss and water absorption; on the other hand, the molecular structure of the polyolefin is linked with double bond functional groups, and the crosslinking curing reaction can be carried out under the action of a curing agent, so that the thermal stability and the rigidity of the material are improved.
The chopped quartz fiber can play a role in improving the thermal stability of the substrate material, so that the plate has a lower thermal expansion coefficient; the curing agent plays a role in initiating crosslinking curing among unsaturated double bonds, and the invention selects organic peroxide curing agents, such as dicumyl peroxide and di-tert-butylperoxy dicumyl peroxide. The curing agent is heated and decomposed to generate free radicals to initiate resin molecular chains to be crosslinked, and polar groups such as hydroxyl and micromolecular substances are not generated in the curing process, so that the prepared substrate has low water absorption rate and dielectric loss factor, has excellent thermal stability, is beneficial to processing the board into a microwave circuit and assembling subsequent electronic components, and obviously improves the reliability of electronic products.
The invention can be widely applied to the relevant fields of communication, radar, high-speed rail and the like.
Detailed Description
A thermosetting polyolefin copper-clad plate with high thermal stability and low water absorption rate comprises the following raw material components in parts by weight: 20-50 parts of thermosetting polyolefin, 25-50 parts of inorganic filler, 1-10 parts of chopped quartz fiber, 10-20 parts of flame retardant, 0.5-5 parts of curing agent and 20-40 parts of organic solvent.
The thermosetting polyolefin is one or more selected from polybutadiene, polyisoprene, styrene-butadiene block copolymer and ethylene-propylene-butadiene copolymer.
The inorganic filler is selected from one or more of silicon dioxide, titanium dioxide, aluminum oxide, magnesium oxide and barium titanate, and the particle size of the inorganic filler is 10-30 mu m.
The curing agent is one or more selected from dicumyl peroxide, di-tert-butylperoxy-dicumyl and tert-butyl peroxybenzoate.
The flame retardant is one or two of decabromodiphenyl ether and 2,4, 6-tribromophenyl allyl ether.
The organic solvent is selected from one of cyclohexane, butanone and xylene.
Example 1
The thermosetting polyolefin copper-clad plate with high thermal stability and low water absorption rate comprises the following raw materials in parts by weight:
thermosetting polyolefin: 20 parts of polybutadiene, 5 parts of a styrene-butadiene block copolymer;
inorganic filler: 25 parts of silicon dioxide, 5 parts of titanium dioxide;
short-cut quartz fiber: 5 parts of chopped quartz fibers;
flame retardant: 12 parts of decabromodiphenyl ether;
curing agent: 3 parts of dicumyl peroxide;
organic solvent: 25 parts of butanone.
The preparation method of the thermosetting polyolefin copper-clad plate with high thermal stability and low water absorption comprises the following steps:
(1) respectively carrying out surface chemical treatment on the inorganic filler and the chopped quartz fiber by using a coupling agent: firstly, respectively dissolving 0.5-3% of inorganic filler by weight and 0.5-3% of coupling agent by weight of chopped quartz fiber by weight in absolute ethyl alcohol, respectively immersing the weighed inorganic filler and chopped quartz fiber in the absolute ethyl alcohol solution of the coupling agent, stirring for 80min, and finally respectively placing the modified inorganic filler and chopped quartz fiber in a 100 ℃ drying oven and drying to constant weight.
(2) Sequentially adding the weighed thermosetting polyolefin, the modified inorganic filler, the chopped quartz fiber, the flame retardant and the curing agent into an organic solvent, and fully stirring for 100min at a stirring speed of 500r/min to form a polyolefin composite glue solution;
(3) putting the polyolefin composite glue solution into a vacuum oven for drying treatment for 3.5h, removing a solvent in the glue solution, pouring the glue solution into a mould, and carrying out mould pressing forming under the conditions of the temperature of 140 ℃ and the pressure of 20MPa to obtain a prepreg;
(4) and covering copper foils on the upper surface and the lower surface of the cut prepreg, and then carrying out hot-pressing sintering for 3h under the conditions that the temperature is 250 ℃ and the pressure is 25MPa, so that thermosetting polyolefin is subjected to crosslinking curing and final shaping, and the thermosetting polyolefin copper-clad plate with high thermal stability and low water absorption rate is prepared.
The thermosetting polyolefin copper-clad plate prepared by the steps has the dielectric constant of 2.85, the dielectric loss of 0.0028, the X/Y/Z triaxial thermal expansion coefficient of 11.2/10.8/24.2 ppm/DEG C and the water absorption of 0.032 percent, meets the requirements of low dielectric loss, high thermal stability and low water absorption, has high processing and application reliability, simple preparation process and convenient raw material source, and is beneficial to realizing industrial production.
Example 2
The thermosetting polyolefin copper-clad plate with high thermal stability and low water absorption rate comprises the following raw materials in parts by weight:
thermosetting polyolefin: 25 parts of polybutadiene, 10 parts of a styrene-butadiene block copolymer;
inorganic filler: 25 parts of silicon dioxide, 5 parts of titanium dioxide;
short-cut quartz fiber: 5 parts of chopped quartz fibers;
flame retardant: 12 parts of decabromodiphenyl ether;
curing agent: 3 parts of dicumyl peroxide;
organic solvent: 15 parts of butanone.
The preparation method of the thermosetting polyolefin copper-clad plate with high thermal stability and low water absorption comprises the following steps:
(1) respectively carrying out surface chemical treatment on the inorganic filler and the chopped quartz fiber by using a coupling agent: firstly, respectively dissolving 0.5-3% of inorganic filler by weight and 0.5-3% of coupling agent by weight of chopped quartz fiber by weight in absolute ethyl alcohol, respectively immersing the weighed inorganic filler and chopped quartz fiber in the absolute ethyl alcohol solution of the coupling agent, stirring for 80min, and finally respectively placing the modified inorganic filler and chopped quartz fiber in a 100 ℃ drying oven and drying to constant weight.
(2) Sequentially adding the weighed thermosetting polyolefin, the modified inorganic filler, the chopped quartz fiber, the flame retardant and the curing agent into an organic solvent, and fully stirring for 100min at a stirring speed of 500r/min to form a polyolefin composite glue solution;
(3) putting the polyolefin composite glue solution into a vacuum oven for drying treatment for 3.5h, removing a solvent in the glue solution, pouring the glue solution into a mould, and carrying out mould pressing forming under the conditions of the temperature of 140 ℃ and the pressure of 20MPa to obtain a prepreg;
(4) and covering copper foils on the upper surface and the lower surface of the cut prepreg, and then carrying out hot-pressing sintering for 3h under the conditions that the temperature is 250 ℃ and the pressure is 25MPa, so that thermosetting polyolefin is subjected to crosslinking curing and final shaping, and the thermosetting polyolefin copper-clad plate with high thermal stability and low water absorption rate is prepared.
The thermosetting polyolefin copper-clad plate prepared by the steps has the dielectric constant of 2.78, the dielectric loss of 0.0025, the X/Y/Z triaxial thermal expansion coefficient of 12.3/11.6/25.6 ppm/DEG C and the water absorption of 0.028, meets the requirements of low dielectric loss, high thermal stability and low water absorption, has high processing and application reliability, simple preparation process and convenient raw material source, and is beneficial to realizing industrial production.
Example 3
The thermosetting polyolefin copper-clad plate with high thermal stability and low water absorption rate comprises the following raw materials in parts by weight:
thermosetting polyolefin: 20 parts of polybutadiene, 5 parts of a styrene-butadiene block copolymer;
inorganic filler: 30 parts of silicon dioxide, 10 parts of titanium dioxide;
short-cut quartz fiber: 5 parts of chopped quartz fibers;
flame retardant: 12 parts of decabromodiphenyl ether;
curing agent: 3 parts of dicumyl peroxide;
organic solvent: 15 parts of butanone.
The preparation method of the thermosetting polyolefin copper-clad plate with high thermal stability and low water absorption comprises the following steps:
(1) and (1) respectively carrying out surface chemical treatment on the inorganic filler and the chopped quartz fibers by using a coupling agent: firstly, respectively dissolving 0.5-3% of inorganic filler by weight and 0.5-3% of coupling agent by weight of chopped quartz fiber by weight in absolute ethyl alcohol, respectively immersing the weighed inorganic filler and chopped quartz fiber in the absolute ethyl alcohol solution of the coupling agent, stirring for 80min, and finally respectively placing the modified inorganic filler and chopped quartz fiber in a 100 ℃ drying oven and drying to constant weight.
(2) Sequentially adding the weighed thermosetting polyolefin, the modified inorganic filler, the chopped quartz fiber, the flame retardant and the curing agent into an organic solvent, and fully stirring for 100min at a stirring speed of 500r/min to form a polyolefin composite glue solution;
(3) putting the polyolefin composite glue solution into a vacuum oven for drying treatment for 3.5h, removing a solvent in the glue solution, pouring the glue solution into a mould, and carrying out mould pressing forming under the conditions of the temperature of 140 ℃ and the pressure of 20MPa to obtain a prepreg;
(4) and covering copper foils on the upper surface and the lower surface of the cut prepreg, and then carrying out hot-pressing sintering for 3h under the conditions that the temperature is 250 ℃ and the pressure is 25MPa, so that thermosetting polyolefin is subjected to crosslinking curing and final shaping, and the thermosetting polyolefin copper-clad plate with high thermal stability and low water absorption rate is prepared.
The thermosetting polyolefin copper-clad plate prepared by the steps has the dielectric constant of 3.24, the dielectric loss of 0.0035, the X/Y/Z triaxial thermal expansion coefficient of 10.7/10.4/23.5 ppm/DEG C and the water absorption of 0.035%, meets the requirements of low dielectric loss, high thermal stability and low water absorption, has high processing and application reliability, simple preparation process and convenient raw material source, and is beneficial to realizing industrial production.
In the three embodiments, embodiment 2 is the best embodiment, and the prepared copper-clad plate has the lowest dielectric loss and the lowest water absorption, and the thermal expansion coefficient is less than 28 ppm/DEG C, so that the requirements of the thermosetting polyolefin copper-clad plate with high thermal stability and low water absorption are met.
Claims (9)
1. A thermosetting polyolefin copper-clad plate with high thermal stability and low water absorption is characterized in that the thermosetting polyolefin copper-clad plate comprises the following raw material components in parts by weight: 20-50 parts of thermosetting polyolefin, 25-50 parts of inorganic filler, 1-10 parts of chopped quartz fiber, 10-20 parts of flame retardant, 0.5-5 parts of curing agent and 20-40 parts of organic solvent.
2. The thermosetting polyolefin copper-clad plate with high thermal stability and low water absorption rate according to claim 1, wherein: the raw material components are as follows according to the weight portion: 23-46 parts of thermosetting polyolefin, 28-47 parts of inorganic filler, 2-7 parts of chopped quartz fiber, 12-18 parts of flame retardant, 1-4.5 parts of curing agent and 24-38 parts of organic solvent.
3. The thermosetting polyolefin copper-clad plate with high thermal stability and low water absorption rate according to claim 1, wherein: the thermosetting polyolefin is selected from one or more of polybutadiene, polyisoprene, styrene-butadiene block copolymer and ethylene-propylene-butadiene copolymer.
4. The thermosetting polyolefin copper-clad plate with high thermal stability and low water absorption rate according to claim 1, wherein: the inorganic filler is selected from one or more of silicon dioxide, titanium dioxide, aluminum oxide, magnesium oxide and barium titanate, and the particle size of the inorganic filler is 10-30 mu m.
5. The thermosetting polyolefin copper-clad plate with high thermal stability and low water absorption rate according to claim 1, wherein: the curing agent is selected from one or more of dicumyl peroxide, di-tert-butylperoxy-dicumyl and tert-butyl peroxybenzoate.
6. The thermosetting polyolefin copper-clad plate with high thermal stability and low water absorption rate according to claim 1, wherein: the flame retardant is one or two selected from decabromodiphenyl ether and 2,4, 6-tribromophenyl allyl ether.
7. The thermosetting polyolefin copper-clad plate with high thermal stability and low water absorption rate according to claim 1, wherein: the organic solvent is selected from one of cyclohexane, butanone and xylene.
8. The preparation method of the thermosetting polyolefin copper-clad plate with high thermal stability and low water absorption rate, which is disclosed by claim 1, is characterized by comprising the following steps: comprises the following steps:
(1) respectively carrying out surface chemical treatment on the inorganic filler and the chopped quartz fiber by using a coupling agent: firstly, respectively dissolving 0.5-3% of inorganic filler by weight and 0.5-3% of coupling agent by weight of chopped quartz fiber by weight in absolute ethyl alcohol, respectively immersing the weighed inorganic filler and chopped quartz fiber in the absolute ethyl alcohol solution of the coupling agent, stirring for 60-90min, and finally respectively drying the modified inorganic filler and chopped quartz fiber in an oven to constant weight;
(2) sequentially adding the weighed thermosetting polyolefin, the modified inorganic filler, the chopped quartz fiber, the flame retardant and the curing agent into an organic solvent, and fully stirring for 60-120min at the stirring speed of 300-600r/min to form a polyolefin composite glue solution;
(3) putting the polyolefin composite glue solution into a vacuum oven for drying treatment for 2-5h, removing an organic solvent in the glue solution, pouring into a mold, and performing mold pressing forming under the conditions of the temperature of 80-160 ℃ and the pressure of 5-30MPa to obtain a prepreg;
(4) and covering copper foils on the upper surface and the lower surface of the cut prepreg, and then carrying out hot-pressing sintering for 2-5h at the temperature of 200-280 ℃ and under the pressure of 8-30MPa to enable thermosetting polyolefin to be subjected to crosslinking curing and final setting, thus preparing the thermosetting polyolefin copper-clad plate.
9. The method for preparing the thermosetting polyolefin copper-clad plate with high thermal stability and low water absorption rate according to claim 8, is characterized in that: the coupling agent is selected from one or more of silane coupling agent, titanate coupling agent and zirconate coupling agent.
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