CN115610045A - Preparation method of low-loss and low-water-absorption copper-clad plate containing core-shell structure powder - Google Patents
Preparation method of low-loss and low-water-absorption copper-clad plate containing core-shell structure powder Download PDFInfo
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Abstract
The invention discloses a preparation method of a low-loss and low-water absorption copper-clad plate containing core-shell structure powder, which comprises the following steps of firstly, carrying out surface modification on inorganic powder; secondly, uniformly mixing the modified powder, the polyolefin resin, the medium-temperature initiator and the solvent, and then preparing core-shell structure powder of the inorganic powder coated by the polyolefin resin by adopting free radical precipitation polymerization; then uniformly dispersing the core-shell structure powder, polyolefin resin, a flame retardant, an antioxidant and a high-temperature initiator in a solvent to form a polyolefin composite glue solution; then soaking the glass fiber cloth in the polyolefin composite glue solution at a constant speed, and drying to obtain a prepreg; and finally, laminating the prepregs, and carrying out hot-pressing sintering on the copper foils coated on the two sides to enable the polyolefin resin to be crosslinked and cured, so as to finish final setting to obtain the low-loss and low-water-absorption copper-clad plate. The loss of the copper-clad plate prepared by the method is lower than 0.0025, and the water absorption is lower than 0.055%, so that the method is beneficial to low-delay and low-loss transmission of high-frequency signals.
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 low-loss and low-water-absorption copper-clad plate containing core-shell structure powder.
Background
The copper-clad plate is the circuit bearing foundation of the printed circuit board, and gradually becomes one of the most important basic materials in the electronic industry after development of more than half a century. With the continuous development of multilayer, high density and high reliability of printed circuit boards, higher requirements are put forward on the dielectric property, mechanical property, moisture and heat resistance and the like of copper clad laminates.
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 composite glue solution of organic resin, inorganic powder and various additives, drying the composite glue solution, coating copper foil on the composite glue solution, and finally performing hot pressing. Because the organic resin and the inorganic powder have distinct physical and chemical properties, the bonding force between the organic resin and the inorganic powder is poor, and a large number of pores exist at the interface. The pores can easily absorb water in a humid environment, so that the dielectric constant, the loss and the water absorption of the copper-clad plate are increased, and the problem of plate delamination and plate explosion caused by water evaporation in a high-temperature environment is solved. The method generally adopts the steps of modifying inorganic powder, and compounding the inorganic powder with organic resin, glass fiber cloth and the like to prepare the copper-clad plate. Chinese patent application publication No. CN110039852A introduces a preparation method of a PTFE copper-clad plate, which comprises the steps of uniformly mixing ceramic powder modified by a silane coupling agent and PTFE emulsion to form PTFE glue solution, and then adopting a dipping, laminating and hot-pressing process. After the ceramic powder is modified by a silane coupling agent, the surface of the ceramic powder is bonded with coupling agent molecules containing specific groups, and the compatibility of the ceramic powder and PTFE resin can be improved to a certain extent. However, a chemical bond is difficult to form between a specific group of the coupling agent and the PTFE resin, and only by weak interaction between molecules, more pores still exist at the interface of the ceramic powder and the resin, so that the performance and subsequent application of the copper-clad plate are influenced.
Chinese patent application publication No. CN106674602A proposes a preparation method of a coated filler slurry composition, and a prepreg, a laminate and a printed circuit board comprising the slurry composition, that is, a sol-gel method is used to coat nano-scale silica or nano-scale alumina on the surface of a mother particle filler, so as to improve the dispersibility and fluidity of the composite slurry. However, since the inorganic coating layer is hydrophilic and the polyolefin resin is hydrophobic, the compatibility between the filler and the resin is not improved, and the problems of large loss and high water absorption of the laminate are not solved.
Disclosure of Invention
The invention aims to solve the problems and defects of high loss and high water absorption of the copper-clad plate filled with inorganic powder in the prior art, and provides a preparation method of the low-loss and low-water absorption copper-clad plate containing core-shell structure powder.
The technical scheme of the invention is as follows: a preparation method of a low-loss and low-water absorption copper-clad plate containing core-shell structure powder comprises the following steps: step 1: firstly, 0.5 to 1.5 parts of silane coupling agent is added into 50 to 70 parts of ethanol to form ethanol solution of the silane coupling agent, then 25 to 50 parts of inorganic powder is immersed into the ethanol solution of the silane coupling agent, dispersed and stirred for 60 to 90min to form modified inorganic powder solution, and finally the modified inorganic powder solution is dried in an oven at the temperature of between 90 and 120 ℃ for 2 to 5h to obtain modified powder;
step 2: sequentially adding 30-50 parts of modified powder, 10-25 parts of polyolefin resin and 0.5-1.5 parts of medium-temperature initiator into 50-70 parts of solvent, uniformly mixing, and carrying out free radical precipitation polymerization at 90-140 ℃ for 1-3 h to obtain core-shell structure powder of polyolefin resin coated inorganic powder;
and 3, step 3: sequentially adding 25-50 parts of core-shell structure powder of polyolefin resin coated inorganic powder, 20-50 parts of polyolefin resin, 10-20 parts of flame retardant, 0.2-1 part of antioxidant and 0.5-3 parts of high-temperature initiator into 20-40 parts of solvent, and fully stirring for 60-120 min at a stirring speed of 600-1200 r/min to form polyolefin composite glue solution;
and 4, step 4: soaking the glass fiber cloth in the polyolefin composite glue solution at a constant speed, and drying at the temperature of 80-120 ℃ for 10-30 min to obtain a prepreg;
and 5: laminating the prepregs according to the required thickness, covering copper foils on the two sides, and hot-pressing and sintering at the temperature of 180-250 ℃ and the pressure of 6-25 MPa for 2-5 h to enable the polyolefin resin to be crosslinked and cured, thus finishing final shaping and preparing the low-loss and low-water-absorption copper-clad plate.
The inorganic powder is one or more of silicon dioxide, titanium dioxide, aluminum oxide, magnesium oxide and barium titanate.
The silane coupling agent is one or more of vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tri (2-methoxyethoxy) silane and gamma-methacryloxypropyl trimethoxy silane.
The polyolefin resin is one or more of polybutadiene, polyisoprene, styrene-isoprene copolymer, styrene-butadiene block copolymer and ethylene-propylene-dicyclopentadiene copolymer.
The medium-temperature initiator is one or more of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, tert-butyl peroxybenzoate and persulfate.
The solvent is one of acetonitrile, cyclohexane, butanone, cyclohexanone and xylene.
The flame retardant is one or more of decabromodiphenyl ether, ethylene bistetrabromophthalimide, tricresyl phosphate, diphenyl cresyl phosphate and trioctyl phosphate.
The antioxidant is one or more of 4, 4-di (alpha, alpha-dimethylbenzyl) diphenylamine, [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester and tris (2, 4-di-tert-butylphenyl) phosphite.
The high-temperature initiator is one or more of dicumyl peroxide, di-tert-butylperoxy diisopropylbenzene, 2, 3-dimethyl-2, 3-diphenyl butane and cumyl hydroperoxide.
The beneficial effects produced by the invention are as follows: the copper-clad plate prepared by the invention is filled with core-shell structure powder which takes polyolefin resin as a matrix, is reinforced by glass fiber cloth and is coated with inorganic powder by the polyolefin resin, has the characteristics of loss lower than 0.0025, water absorption lower than 0.055 percent and the like, and is beneficial to low-delay and low-loss transmission of high-frequency signals. 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 method is favorable for realizing industrial production.
The polyolefin resin of the present invention is a polymerization product of butadiene, styrene, isoprene, ethylene and propylene, such as polybutadiene, styrene-butadiene block copolymer. The polyolefin resin is a weak polar polymer only consisting of carbon and hydrogen, and the molecular structure has higher symmetry, so that the material has low loss and low 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 free radical initiator, so that the thermal stability and the rigidity of the material are improved.
The invention adopts free radical precipitation polymerization to prepare the core-shell structure powder of polyolefin resin coated inorganic powder, and the polyolefin resin and the inorganic powder are connected by chemical bonds and have close combination and good compatibility. And the coating layer of the polyolefin resin still contains residual double bonds, and can be further crosslinked and cured with the polyolefin resin during hot-pressing sintering to finish final shaping. The introduction of the core-shell structure powder greatly improves the compatibility of inorganic powder and organic resin, so that the prepared substrate has low loss and water absorption, and also has excellent heat-conducting property, and is beneficial to the processing of a board into a microwave circuit and the assembly of subsequent electronic components.
The invention can be widely applied to the relevant fields of communication, radar, high-speed rail and the like.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1, step 1: according to the weight portion, 1 portion of vinyl triethoxysilane is added into 60 portions of ethanol, then 40 portions of silicon dioxide powder are immersed into the ethanol solution of the vinyl triethoxysilane, dispersed and stirred for 80min, and finally the modified inorganic powder is dried in an oven at 110 ℃ for 2.5h to obtain the modified silicon dioxide powder.
And 2, step: according to the weight portion, 45 portions of modified silicon dioxide powder, 10 portions of polybutadiene, 5 portions of ethylene-propylene-dicyclopentadiene copolymer and 1 portion of azodiisobutyronitrile are sequentially added with 60 portions of acetonitrile, uniformly mixed and subjected to free radical polymerization at 120 ℃ for 1.5h to obtain the core-shell structure powder of polyolefin resin coated silicon dioxide. The inorganic powder core and the polyolefin resin coating layer of the core-shell structure powder are connected by chemical bonds, and the combination of the inorganic powder core and the polyolefin resin coating layer is tight and has good compatibility.
And step 3: according to the weight portion, 30 portions of polybutadiene, 10 portions of ethylene-propylene-dicyclopentadiene copolymer, 30 portions of core-shell structure powder, 15 portions of ethylene bis tetrabromophthalimide, 0.5 portion of [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1.5 portions of bis-tert-butylperoxy diisopropylbenzene are sequentially added into 35 portions of dimethylbenzene and fully stirred for 90min under the condition of 1000r/min to form polyolefin composite glue solution, and the polyolefin resin coating layer of the core-shell structure powder of the polyolefin composite glue solution has the same property with the polyolefin resin, so that the core-shell structure powder can be uniformly dispersed in the polyolefin composite glue solution.
And 4, step 4: and infiltrating the glass fiber cloth into the polyolefin composite glue solution at a constant speed, and drying for 25min at 110 ℃ to obtain the prepreg.
And 5: laminating prepregs according to the required thickness, covering copper foils on two sides, and hot-pressing and sintering at the temperature of 230 ℃ and the pressure of 20MPa for 2.5h, wherein in the hot-pressing and sintering process, the polyolefin resin coating layer of the core-shell structure powder still contains residual double bonds, and can be further crosslinked and cured with polyolefin resin in the composite glue solution to finish final shaping to obtain the low-loss and low-water-absorption copper-clad plate.
Example 2, step 1: according to the weight portion, 1 portion of vinyl triethoxysilane is added into 60 portions of ethanol, then 40 portions of silicon dioxide powder are immersed into the ethanol solution of the vinyl triethoxysilane, dispersed and stirred for 80min, and finally the modified inorganic powder is dried in an oven at 110 ℃ for 2.5h to obtain the modified silicon dioxide powder.
Step 2: according to parts by weight, sequentially adding 60 parts of acetonitrile into 45 parts of modified silicon dioxide powder, 10 parts of polybutadiene, 5 parts of ethylene-propylene-dicyclopentadiene copolymer and 1 part of azodiisobutyronitrile, uniformly mixing, and carrying out free radical polymerization at 120 ℃ for 1.5 hours to obtain the core-shell structure powder of polyolefin resin coated silicon dioxide. The inorganic powder core and the polyolefin resin coating layer of the core-shell structure powder are connected by chemical bonds, and the combination of the inorganic powder core and the polyolefin resin coating layer is tight and has good compatibility.
And step 3: according to parts by weight, 30 parts of polybutadiene, 10 parts of ethylene-propylene-dicyclopentadiene copolymer, 45 parts of core-shell structure powder, 15 parts of ethylene bis-tetrabromophthalimide, 0.5 part of [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1.5 parts of bis-tert-butylperoxy-diisopropylbenzene are sequentially added into 35 parts of dimethylbenzene and fully stirred for 90min under the condition of 1000r/min to form the polyolefin composite glue solution. The polyolefin resin coating layer of the core-shell structure powder of the polyolefin composite glue solution has the same property with the polyolefin resin, so that the core-shell structure powder can be uniformly dispersed in the polyolefin composite glue solution.
And 4, step 4: and infiltrating the glass fiber cloth into the polyolefin composite glue solution at a constant speed, and drying for 25min at 110 ℃ to obtain the prepreg.
And 5: and laminating the prepregs according to the required thickness, covering copper foils on two sides, and carrying out hot-pressing sintering for 2.5h at the temperature of 230 ℃ and the pressure of 20MPa, wherein in the hot-pressing sintering process, the polyolefin resin coating layer of the core-shell structure powder still contains residual double bonds and can be further crosslinked and cured with the polyolefin resin in the composite glue solution, and finally shaping is finished to obtain the low-loss and low-water-absorption copper-clad plate.
Comparative example 1, step 1: according to the weight portion, 1 portion of vinyl triethoxysilane is added into 60 portions of ethanol, then 40 portions of silicon dioxide powder are immersed into the ethanol solution of the vinyl triethoxysilane, dispersed and stirred for 80min, and finally the modified inorganic powder is dried in an oven at 110 ℃ for 2.5h to obtain the modified silicon dioxide powder.
Step 2: according to the weight portion, 30 portions of polybutadiene, 10 portions of ethylene-propylene-dicyclopentadiene copolymer, 30 portions of modified silicon dioxide powder, 15 portions of ethylene bis tetrabromophthalimide, 0.5 portion of [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1.5 portions of bis-tert-butylperoxy diisopropylbenzene are sequentially added into 35 portions of dimethylbenzene and fully stirred for 90min under the condition of 1000r/min to form the polyolefin composite glue solution.
And step 3: and infiltrating the glass fiber cloth into the polyolefin composite glue solution at a constant speed, and drying for 25min at 110 ℃ to obtain the prepreg.
And 4, step 4: and laminating the prepregs according to the required thickness, covering copper foils on the two sides, and hot-pressing and sintering at the temperature of 230 ℃ and the pressure of 20MPa for 2.5h to enable the polyolefin resin to be crosslinked and cured, thus finishing final shaping and preparing the copper-clad plate.
Comparative example 2, step 1: according to the weight portion, 1 portion of vinyl triethoxysilane is added into 60 portions of ethanol, then 40 portions of silicon dioxide powder are immersed into the ethanol solution of the vinyl triethoxysilane, dispersed and stirred for 80min, and finally the modified inorganic powder is dried in an oven at 110 ℃ for 2.5h to obtain the modified silicon dioxide powder.
And 2, step: according to parts by weight, 30 parts of polybutadiene, 10 parts of ethylene-propylene-dicyclopentadiene copolymer, 45 parts of modified silicon dioxide powder, 15 parts of ethylene bis-tetrabromophthalimide, 0.5 part of [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1.5 parts of bis-tert-butylperoxy-diisopropylbenzene are sequentially added into 35 parts of dimethylbenzene and fully stirred for 90min under the condition of 1000r/min to form the polyolefin composite glue solution.
And 3, step 3: and infiltrating the glass fiber cloth into the polyolefin composite glue solution at a constant speed, and drying for 25min at 110 ℃ to obtain the prepreg.
And 4, step 4: and laminating the prepregs according to the required thickness, covering copper foils on the two sides, and hot-pressing and sintering at the temperature of 230 ℃ and the pressure of 20MPa for 2.5h to enable the polyolefin resin to be crosslinked and cured, thus finishing final shaping and preparing the copper-clad plate.
The test results for the copper clad laminates prepared in examples 1-2 and comparative examples 1-2 are shown in table 1:
as can be seen from Table 1, the core-shell structure powder of silicon dioxide coated with polyolefin resin improves the compatibility with organic resin. The copper-clad plate prepared by the method has the dielectric constant of less than 3.25, the loss of less than 0.0025 and the water absorption of less than 0.055 percent, meets the requirements of the low-loss and low-water-absorption copper-clad plate, has high processing and application reliability, simple preparation process and convenient raw material source, and is beneficial to realizing industrial production.
Claims (9)
1. A preparation method of a low-loss and low-water absorption copper-clad plate containing core-shell structure powder is characterized by comprising the following steps:
step 1: firstly, 0.5 to 1.5 parts of silane coupling agent is added into 50 to 70 parts of ethanol to form ethanol solution of the silane coupling agent, then 25 to 50 parts of inorganic powder is immersed into the ethanol solution of the silane coupling agent, dispersed and stirred for 60 to 90min to form modified inorganic powder solution, and finally the modified inorganic powder solution is dried in an oven at the temperature of between 90 and 120 ℃ for 2 to 5h to obtain modified powder;
step 2: sequentially adding 30-50 parts of modified powder, 10-25 parts of polyolefin resin and 0.5-1.5 parts of medium-temperature initiator into 50-70 parts of solvent, uniformly mixing, and carrying out free radical precipitation polymerization at 90-140 ℃ for 1-3 h to obtain core-shell structure powder of polyolefin resin coated inorganic powder;
and step 3: sequentially adding 25-50 parts of core-shell structure powder of polyolefin resin coated inorganic powder, 20-50 parts of polyolefin resin, 10-20 parts of flame retardant, 0.2-1 part of antioxidant and 0.5-3 parts of high-temperature initiator into 20-40 parts of solvent, and fully stirring for 60-120 min at a stirring speed of 600-1200 r/min to form polyolefin composite glue solution;
and 4, step 4: soaking the glass fiber cloth into the polyolefin composite glue solution at a constant speed, and drying for 10-30 min at 80-120 ℃ to obtain a prepreg;
and 5: laminating the prepregs according to the required thickness, covering copper foils on the two sides, and hot-pressing and sintering at the temperature of 180-250 ℃ and the pressure of 6-25 MPa for 2-5 h to enable the polyolefin resin to be crosslinked and cured, thus finishing final shaping and preparing the low-loss and low-water-absorption copper-clad plate.
2. The method for preparing the copper-clad plate containing the core-shell structure powder with low loss and low water absorption according to claim 1, wherein the inorganic powder is one or more of silicon dioxide, titanium dioxide, aluminum oxide, magnesium oxide and barium titanate.
3. The method for preparing the copper-clad plate containing the core-shell structure powder with low loss and low water absorption according to claim 1, wherein the silane coupling agent is one or more of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane and gamma-methacryloxypropyltrimethoxysilane.
4. The method for preparing the copper-clad plate containing the core-shell structure powder with low loss and low water absorption according to claim 1, wherein the polyolefin resin is one or more of polybutadiene, polyisoprene, styrene-isoprene copolymer, styrene-butadiene block copolymer and ethylene-propylene-dicyclopentadiene copolymer.
5. The method for preparing the copper-clad plate containing the core-shell structure powder with low loss and low water absorption rate according to claim 1, wherein the medium temperature initiator is one or more of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, tert-butyl peroxybenzoate and persulfate.
6. The method for preparing the copper-clad plate containing the core-shell structure powder with low loss and low water absorption according to claim 1, wherein the solvent is one of acetonitrile, cyclohexane, butanone, cyclohexanone and xylene.
7. The method for preparing the copper-clad plate containing the core-shell structure powder with low loss and low water absorption rate according to claim 1, wherein the flame retardant is one or more of decabromodiphenyl ether, ethylenebistetrabromophthalimide, tricresyl phosphate, cresyl diphenyl phosphate and trioctyl phosphate.
8. The method for preparing the copper-clad plate containing the core-shell structure powder with low loss and low water absorption according to claim 1, wherein the antioxidant is one or more of 4, 4-di (alpha, alpha-dimethylbenzyl) diphenylamine, [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester and tris (2, 4-di-tert-butylphenyl) phosphite.
9. The method for preparing the copper-clad plate containing the core-shell structure powder with low loss and low water absorption according to claim 1, wherein the high-temperature initiator is one or more of dicumyl peroxide, di-tert-butylperoxy-diisopropylbenzene, 2, 3-dimethyl-2, 3-diphenylbutane and cumyl hydroperoxide.
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