CN109880133A - A kind of fluorine resin mixture film and copper-clad plate preparation method - Google Patents
A kind of fluorine resin mixture film and copper-clad plate preparation method Download PDFInfo
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Abstract
The invention discloses a kind of fluorine resin mixture film and copper-clad plate preparation methods, the evenly dispersed solution including configuring fluorine resin mixture；And the fluorine resin mixture solution is dispersed on PTFE, toasted drying, obtain the fluorine resin mixture film of PTFE, then copper-clad plate is made with the fluorine resin mixture film of above-mentioned PTFE, it is an object of the invention to the PTFEs poor using self performance, using unique film preparing technology, it overcomes and above-mentioned copper-clad plate thermal stability is caused due to PTFE built-in problem, mechanicalness, caking property, the poor problem of the performances such as intensity, enable to finally obtained copper-clad plate that there is agent of low hygroscopicity, stable dielectric constant, low transmission loss, and the peel strength of product, adhesiveness is in higher level, the utilization of resource is realized simultaneously, it avoids wasting.
Description
Technical field
The invention belongs to communicate Material Field, and in particular to a kind of fluorine resin mixture film and copper-clad plate preparation side
Method.
Background technique
Nowadays, information electronic industries are in the high speed development stage, just gradually become one of the pillar industry of various countries.As
The copper-clad plate of one of the critical material of information electronic industries is widely used in communication base station, satellite, automatic vending machine, computer, hand
The fields such as machine, wearable device, pilotless automobile, unmanned plane, intelligent robot.
The high frequency of circuit signal transmission, baseplate material will be main key, especially copper clad foil substrate material technology,
The DK and Df of existing copper-clad plate are relatively high, even if by improving the signal that can not be fully met under all high frequencies route design
The application demand of high-speed transfer and signal integrity, because high DK can make signal delivery rate slack-off, high Df can be such that signal section turns
Heat energy loss is turned in baseplate material, and material in plate factory manufacturing process be easy moisture absorption and influence electrical property, at leisure without
Method meets the needs of manufacturer terminal.Although PTFE has excellent electric property, since its glass transition temperature (Tg) is very low,
Rigidity is very poor, mechanical strength is inadequate, this just determines its harsh processing conditions, seriously affects the use reliability of copper-clad plate.
The resin overwhelming majority used in copper-clad plate is thermosetting resin, the matrix tree using thermoplastic resin as copper-clad plate
Rouge, PTFE are most typical representatives, macromolecule of the polyflon as full symmetric unbranched linear ultra-high molar mass,
With low dielectric constant and dielectric loss, since fluorine atom has high electronegativity, so that C-F key becomes very short, bond energy
Very strong, fluorine atom volume is big in addition, makes the spiral close-packed arrays of macromolecular chain, thus have excellent chemical resistance,
The characteristics such as resistance to acid and alkali, wet-heat resisting.
But a variety of uncertain factors can be generated in the production process of present PTFE, so that finally obtained
The granular size of PTFE product is inconsistent, form is coarse, surface and internal state are unstable, polymer stability difference compared with
Greatly, the performances such as thermal stability, mechanicalness, intensity are poor, the PTFE poor for these performance itself, general waste treatment,
Or it is only used for processing and obtains the poor copper-clad plate of performance.Therefore, above-mentioned PTFE of problems can be utilized by inventing one kind,
The wasting of resources is avoided, and the fluorine resin that the copper-clad plate mechanical performance enabled to is high, breaking strength is high, dielectric constant is stable
Mixture and its film, become the task of top priority.
Summary of the invention
The present invention provides a kind of fluorine resin mixture film and copper-clad plate preparation method, and it is poor to solve self performance
PTFE is difficult to be utilized, and using its copper-clad plate bad mechanical property obtained, breaking strength is low, dielectric constant is unstable, glue
The poor problem of knot property.
Specific technical solution is as follows:
A kind of fluorine resin mixture film preparation method, comprising the following steps:
(1) the evenly dispersed solution of fluorine resin mixture is configured；
(2) the fluorine resin mixture solution is dispersed on PTFE, toasted drying obtains the fluorine-containing of PTFE
Resin compound film.
Preferably, the fluorine resin mixture includes the raw material of following parts by weight: 30-60 parts of fluorine-containing resin emulsion,
70-90 parts of inorganic fillers, 10-15 parts of coupling agent, 5-15 parts of modifier.
Preferably, the inorganic fillers are Al2O3、SiO2、TiO2、MgO、Bi2O3、AlN、Si3N4、SiC、AL(OH)3、
Mg(OH)2、BaxSr(1-x)TiO3、Mg2TiO4、Bi2(TiO3)3、PbTiO3、NiTiO3、CaTiO3、ZnTiO3、Zn2TiO4、
BaSnO3、Bi2(SnO3)3、CaSnO3、PbSnO3、MgSnO3、SrSnO3、ZnSnO3、BaZrO3、PbZrO3、MgZrO3、SrZrO3、
ZnZrO3, graphite, graphite oxide, fluorographite, talcum powder, mica powder, kaolin, one or more of clay.
Preferably, the coupling agent is silane coupling agent, titanate coupling agent, aluminate coupling agent, borate coupling
Agent, zirconium ester coupling agent, rare-earth coupling agent, phosphate coupling agent and one of sulfonyl azide coupling agent and its derivative or more
The mixture of kind.
Preferably, the method for dispersion solution is configured in the step (1) are as follows: inorganic fillers are put into high-pressure unit
Reason, then through air-flow crushing, obtains pulverulent solids, then utilizes Radio-frequency plasma torch by oxygen at 2600-2800 DEG C
At a temperature of plasma is made, then in plasma reactor by gained pulverulent solids at 2000-2500 DEG C, the residence time
It is to be decomposed into ultrafine particle under conditions of 0.7-1.0 seconds；Take corresponding number fluorine-containing resin emulsion and inorganic fillers it is ultra-fine
Heating particulates mixing, then cools down in a water bath, and coupling agent is added under nitrogen flowing, and control reaction temperature is 45-50 DEG C, continues
Stirring is reacted for 8 hours, is eventually adding modifier and is mixed.
Preferably, PTFE is first modified processing, PTFE is immersed into modifying agent 90-120s, taking-up is put into 55-60 DEG C
Baking oven dries 8-12min, seals after taking-up spare.
Preferably, the modifying agent is pyromellitic acid anhydride, 4,4 '-diaminodiphenyl ethers, nano silica, fourth
Diamines, polyamic acid；The method for preparing modifying agent are as follows: mix pyromellitic acid anhydride and nano silica, machinery stirs
Certain time is mixed, weighs a certain amount of 4,4 '-diaminodiphenyl ethers, classify in three categories part, in the case where helium protects environment, controls water-bath
Temperature is 35-40 DEG C, and 4,4 '-diaminodiphenyl ethers are added while stirring in batches, and then butanediamine, polyamic acid are added
Into above-mentioned system, modifying agent is obtained.
A kind of fluorine resin mixture copper-clad plate preparation method, making step are as follows: by prepreg, the fluorine resin of PTFE
Mixture film is symmetrically superimposed together with copper foil, laminated to obtain copper-clad plate；Wherein number >=1 of prepreg, PTFE film
Number >=0, number >=0 of the fluorine resin film containing inorganic filler, the number of copper foil is 1 or 2, and laminating temperature is in 150-430
DEG C, lamination pressure 50-150kg/cm2, lamination times 24-60h.
The utility model has the advantages that
1. the present invention is using the poor PTFE of self performance, the granular size of product is inconsistent, form is coarse, surface and
Internal state is unstable, polymer stability difference is larger, and present invention employs unique film preparing technologies, overcome
It states due to PTFE built-in problem and causes the performances such as copper-clad plate thermal stability, mechanicalness, caking property, intensity are poor to ask
Topic enables to finally obtained copper-clad plate to have agent of low hygroscopicity, stable dielectric constant, low transmission loss, and the stripping of product
It is in higher level from intensity, adhesiveness, while realizing the utilization of resource, avoids wasting.
It is handled 2. inorganic fillers are put into high-pressure unit in the present invention, then through air-flow crushing, obtains pulverulent solids, so
Plasma is made in oxygen using Radio-frequency plasma torch afterwards, it is then in plasma reactor that gained is powdered solid
Body is decomposed into ultrafine particle, and ultrafine particle obtained can be made to have rock-steady structure, enhances surface energy, arrives in subsequent coated
When on PTFE, avoiding cannot abundant infiltrating material since contact angle is larger, it is difficult to be formed caused by dipole-dipole force and induction force
The problem of bad adhesion.
3. fluorine-containing resin emulsion is mixed with the heating of the ultrafine particle of inorganic fillers in the present invention, it is then cold in a water bath
But, the interaction force enhancing in the solution system that water-bath cooling enables between molecule, improves inorganic filler system
Interior dispersibility is conducive to subsequent be bonded in the surface PTFE.
4. coupling agent is added under nitrogen flowing, control reaction temperature is 45-50 DEG C, persistently stirs 8 hours and is reacted, energy
Other impurities molecule is enough avoided for the influence of evenly dispersed solution, makes the evenly dispersed solution of fluorine resin mixture obtained
Purity is higher, has good breaking strength and modulus, improves mechanical performance.
5. PTFE is first modified processing by the present invention, PTFE is immersed into modifying agent 90-120s, taking-up is put into 55-60
DEG C baking oven dries 8-12min, seals spare after taking-up, and aforesaid operations method reduces the crystallinity of PTFE itself, is conducive to height
Phase counterdiffusion between polymer molecular chain, while one layer of fluorine atom layer that the helical conformation surface of PTFE is surrounded generates
Slight void, to be conducive to the immersion of fluorine resin mixed solution.
6. modifying agent of the invention, by reasonably selecting, collaboration plays a role, the modifying agent is Pyromellitic Acid
Dianhydride, 4,4 '-diaminodiphenyl ethers, nano silica, butanediamine, polyamic acid；The method for preparing modifying agent are as follows: will be equal
Pyromellitic dianhydride and nano silica mixing, mechanical stirring certain time weigh a certain amount of 4,4 '-diamino hexichol
Ether, classify in three categories part, and in the case where helium protects environment, control bath temperature is 35-40 DEG C, in batches by 4,4 '-diaminodiphenyl ethers
It is added, butanediamine, polyamic acid is added in above-mentioned system while stirring then, obtain modifying agent, above-mentioned modifying agent
Modifying agent be can be improved for the modifying function of PTFE, fluorine effect is gone on its surface, surface carbonation can be made, in addition,
The harm for avoiding unstable end-group, avoids double bond from being further oxidized, and makes it have good mechanical performance and dielectric properties
And higher peel strength, reduce loss of the signal energy in transmission process.
Specific embodiment
PTFE used in the present invention is the poor material of self performance, and each performance parameter is as shown in the table.
| Performance | Numerical value |
| Dielectric constant (10GHz) | 3.8 |
| Dielectric loss (10GHz) | 0.095-0.185 |
| Volume resistivity (Ω cm) | >1014 |
| Surface resistivity (Ω cm) | >1012 |
As can be seen from the above table, the PTFE material that the present invention uses, dielectric properties are poor, and dielectric constant is high, dielectric loss
Height, insulating property (properties) is poor, and material itself is unstable.
Goal of the invention of the invention is that the poor PTFE of the self performance that can be processed using plant produced is obtained
To a kind of copper-clad plate of good performance, the reasonable utilization of resource is realized, solving the problems, such as can not since PTFE itself exists
Obtain the problem of the preferable copper-clad plate of quality.
The modifier that the present invention uses is aryl tertiary amine and the mixture of N- alkyl.
Embodiment: clearly narration in detail is carried out to the solution of the present invention below with reference to embodiment.
Embodiment 1:
The number of prepreg used is 5, model prepreg 2116, the prepreg of the prepreg of use
7628, the number of copper foil is that 2 a combination thereof sequences are from top to bottom followed successively by copper foil, the fluorine resin mixture film of PTFE, half
Cured sheets 2116, the fluorine resin mixture film of PTFE, prepreg 7628, prepreg 2116, prepreg 7628,
The fluorine resin mixture film of PTFE, prepreg 2116, PTFE fluorine resin mixture film, copper foil.Pressing-in temp
At 150 DEG C, pressure 150kg/cm2, pressing time 52h.
The fluorine resin mixture includes the raw material of following parts by weight: 30 parts of fluorine-containing resin emulsion, inorganic fillers
70 parts, 15 parts of coupling agent, 15 parts of modifier.
It prepares modifying agent: pyromellitic acid anhydride and nano silica is mixed, mechanical stirring certain time weighs
A certain amount of 4,4 '-diaminodiphenyl ethers, classify in three categories part, and in the case where helium protects environment, control bath temperature is 35 DEG C, by 4,
4 '-diaminodiphenyl ethers are added while stirring in batches, and then butanediamine, polyamic acid are added in above-mentioned system, obtained
Modifying agent；PTFE is immersed into modifying agent 100s, taking-up is put into 57 DEG C of baking oven drying 10min, seals after taking-up spare；It weighs
The raw material of above-mentioned corresponding number, inorganic fillers are put into high-pressure unit and are handled, and then through air-flow crushing, obtain pulverulent solids,
Then plasma is made at a temperature of 2650 DEG C in oxygen using Radio-frequency plasma torch, then in plasma reactor
It is interior by gained pulverulent solids at 2100 DEG C, the residence time is to be decomposed into ultrafine particle under conditions of 0.9 second；Take corresponding number
Fluorine-containing resin emulsion heats 75 DEG C with the ultrafine particle of inorganic fillers and mixes, then 39 DEG C of coolings in a water bath, in nitrogen stream
Lower addition coupling agent, control reaction temperature are 47 DEG C, persistently stir 8 hours and are reacted, are eventually adding modifier and are mixed,
Obtain fluorine resin mixture solution；The PTFE fluorine resin mixture solution being dispersed in after modification
On, toasted drying obtains the fluorine resin mixture film of PTFE.
Inorganic fillers in the present embodiment are Al2O3、SiO2、TiO2、MgO、AlN、Si3N4、SiC、Mg(OH)2、BaxSr
(1-x)TiO3、Mg2TiO4、Bi2(TiO3)3、PbTiO3、CaTiO3、ZnTiO3、Zn2TiO4、BaSnO3、Bi2(SnO3)3、
CaSnO3、PbSnO3、MgSnO3、、ZnSnO3、BaZrO3、PbZrO3、MgZrO3、SrZrO3、ZnZrO3, graphite, graphite oxide, fluorine
Graphite, mica powder, kaolinic mixture.
Coupling agent in the present embodiment is silane coupling agent, titanate coupling agent, aluminate coupling agent, borate coupling
Agent, zirconium ester coupling agent, rare-earth coupling agent mixture.
Embodiment 2:
The number of prepreg used is 5, model prepreg 2116, the prepreg of the prepreg of use
7628, the number of copper foil is 2, and a combination thereof sequence is from top to bottom followed successively by copper foil, the fluorine resin mixture film of PTFE, half
Cured sheets 2116, prepreg 7628, prepreg 2116, prepreg 7628, prepreg 2116, PTFE fluorine resin
Mixture film, copper foil.Pressing-in temp is at 150 DEG C, pressure 150kg/cm2, pressing time 52h.
The fluorine resin mixture includes the raw material of following parts by weight: 60 parts of fluorine-containing resin emulsion, inorganic fillers
80 parts, 10 parts of coupling agent, 5 parts of modifier.
It prepares modifying agent: pyromellitic acid anhydride and nano silica is mixed, mechanical stirring certain time weighs
A certain amount of 4,4 '-diaminodiphenyl ethers, classify in three categories part, and in the case where helium protects environment, control bath temperature is 38 DEG C, by 4,
4 '-diaminodiphenyl ethers are added while stirring in batches, and then butanediamine, polyamic acid are added in above-mentioned system, obtained
Modifying agent；PTFE is immersed into modifying agent 120s, taking-up is put into 58 DEG C of baking oven drying 12min, seals after taking-up spare；It weighs
The raw material of above-mentioned corresponding number, inorganic fillers are put into high-pressure unit and are handled, and then through air-flow crushing, obtain pulverulent solids,
Then plasma is made at a temperature of 2700 DEG C in oxygen using Radio-frequency plasma torch, then in plasma reactor
It is interior by gained pulverulent solids at 2500 DEG C, the residence time is to be decomposed into ultrafine particle under conditions of 1.0 seconds；Take corresponding number
Fluorine-containing resin emulsion heats 70 DEG C with the ultrafine particle of inorganic fillers and mixes, then 35 DEG C of coolings in a water bath, in nitrogen stream
Lower addition coupling agent, control reaction temperature are 45 DEG C, persistently stir 8 hours and are reacted, are eventually adding modifier and are mixed,
Obtain fluorine resin mixture solution；The PTFE fluorine resin mixture solution being dispersed in after modification
On, toasted drying obtains the fluorine resin mixture film of PTFE.
Inorganic fillers in the present embodiment are Al2O3、SiO2、TiO2、MgO、Bi2O3、AlN、Si3N4、SiC、AL(OH)3、
Mg(OH)2、BaxSr(1-x)TiO3、Mg2TiO4、Bi2(TiO3)3、PbTiO3、NiTiO3、CaTiO3、ZnTiO3、Zn2TiO4、
BaSnO3、Bi2(SnO3)3、CaSnO3、PbSnO3、MgSnO3、SrSnO3、ZnSnO3、BaZrO3、PbZrO3、MgZrO3、SrZrO3、
ZnZrO3, graphite, graphite oxide, fluorographite, talcum powder, mica powder, kaolin, clay mixture.
Coupling agent in the present embodiment is silane coupling agent, titanate coupling agent, boric acid ester coupler, zirconate coupling
Mixture in agent, phosphate coupling agent and sulfonyl azide coupling agent derivative.
Embodiment 3:
The number of prepreg used is 5, and the number of copper foil is 2, and the model half of the prepreg of use is solid
Change piece 106, prepreg 7628, the number of copper foil is 2, a combination thereof sequence be from top to bottom followed successively by copper foil, PTFE it is fluorine-containing
Resin compound film, prepreg 106, the fluorine resin mixture film of PTFE, prepreg 7628, prepreg 106,
Prepreg 7628, the fluorine resin mixture film of PTFE, prepreg 2116, PTFE fluorine resin mixture film,
Copper foil.For pressing-in temp at 430 DEG C, pressure 100kg/cm2, pressing time is for 24 hours
The fluorine resin mixture includes the raw material of following parts by weight: 40 parts of fluorine-containing resin emulsion, inorganic fillers
90 parts, 12 parts of coupling agent, 10 parts of modifier.
It prepares modifying agent: pyromellitic acid anhydride and nano silica is mixed, mechanical stirring certain time weighs
A certain amount of 4,4 '-diaminodiphenyl ethers, classify in three categories part, and in the case where helium protects environment, control bath temperature is 40 DEG C, by 4,
4 '-diaminodiphenyl ethers are added while stirring in batches, and then butanediamine, polyamic acid are added in above-mentioned system, obtained
Modifying agent；PTFE is immersed into modifying agent 90s, taking-up is put into 60 DEG C of baking oven drying 8min, seals after taking-up spare；It weighs
The raw material for stating corresponding number, inorganic fillers are put into high-pressure unit and are handled, and then through air-flow crushing, obtain pulverulent solids, so
Plasma is made at a temperature of 2600 DEG C in oxygen using Radio-frequency plasma torch afterwards, then in plasma reactor
By gained pulverulent solids at 2000 DEG C, the residence time is to be decomposed into ultrafine particle under conditions of 0.7 second；Take containing for corresponding number
Fluoro-resin emulsion heats 80 DEG C with the ultrafine particle of inorganic fillers and mixes, then 45 DEG C of coolings in a water bath, under nitrogen flowing
Coupling agent is added, control reaction temperature is 50 DEG C, persistently stirs 8 hours and is reacted, is eventually adding modifier and is mixed, obtained
To fluorine resin mixture solution；The fluorine resin mixture solution is dispersed on the PTFE after modification,
Toasted drying obtains the fluorine resin mixture film of PTFE.
Inorganic fillers in the present embodiment are Al2O3、SiO2、TiO2、MgO、Bi2O3、AlN、Si3N4、SiC、AL(OH)3、
Mg2TiO4、Bi2(TiO3)3、PbTiO3、NiTiO3、CaTiO3、ZnTiO3、Zn2TiO4、BaSnO3、Bi2(SnO3)3、CaSnO3、
PbSnO3、MgSnO3、SrSnO3、ZnSnO3、SrZrO3、ZnZrO3, it is graphite, talcum powder, mica powder, kaolin, mixed in clay
Close object.
Coupling agent in the present embodiment is boric acid ester coupler, zirconium ester coupling agent, rare-earth coupling agent, phosphate coupling agent
With the mixture of sulfonyl azide coupling agent.
Embodiment 4:
The number of prepreg used is 6, model prepreg 1080, the prepreg of the prepreg of use
7628, prepreg 2116, the number of copper foil are 2, and a combination thereof sequence is from top to bottom followed successively by the fluorine resin of copper foil, PTFE
Mixture film, prepreg 1080, prepreg 2116, prepreg 7628, the fluorine resin mixture film of PTFE, half
Cured sheets 7628, prepreg 2116, prepreg 1080, PTFE fluorine resin mixture film, copper foil.Pressing-in temp exists
320 DEG C, pressure 70kg/cm2, pressing time 60h.
The fluorine resin mixture includes the raw material of following parts by weight: 50 parts of fluorine-containing resin emulsion, inorganic fillers
85 parts, 13 parts of coupling agent, 7 parts of modifier.
It prepares modifying agent: pyromellitic acid anhydride and nano silica is mixed, mechanical stirring certain time weighs
A certain amount of 4,4 '-diaminodiphenyl ethers, classify in three categories part, and in the case where helium protects environment, control bath temperature is 37 DEG C, by 4,
4 '-diaminodiphenyl ethers are added while stirring in batches, and then butanediamine, polyamic acid are added in above-mentioned system, obtained
Modifying agent；PTFE is immersed into modifying agent 110s, taking-up is put into 55 DEG C of baking oven drying 9min, seals after taking-up spare；It weighs
The raw material of above-mentioned corresponding number, inorganic fillers are put into high-pressure unit and are handled, and then through air-flow crushing, obtain pulverulent solids,
Then plasma is made at a temperature of 2800 DEG C in oxygen using Radio-frequency plasma torch, then in plasma reactor
It is interior by gained pulverulent solids at 2200 DEG C, the residence time is to be decomposed into ultrafine particle under conditions of 0.8 second；Take corresponding number
Fluorine-containing resin emulsion heats 90 DEG C with the ultrafine particle of inorganic fillers and mixes, then 42 DEG C of coolings in a water bath, in nitrogen stream
Lower addition coupling agent, control reaction temperature are 48 DEG C, persistently stir 8 hours and are reacted, are eventually adding modifier and are mixed,
Obtain fluorine resin mixture solution；The PTFE fluorine resin mixture solution being dispersed in after modification
On, toasted drying obtains the fluorine resin mixture film of PTFE.
Inorganic fillers in the present embodiment are Al2O3、SiO2、TiO2、MgO、Bi2O3、AlN、Si3N4、SiC、AL(OH)3、
Mg(OH)2、PbSnO3、MgSnO3、SrSnO3、ZnSnO3、BaZrO3、PbZrO3、MgZrO3、SrZrO3、ZnZrO3, graphite, oxidation
Graphite, fluorographite, talcum powder mixture.
Coupling agent in the present embodiment is silane coupling agent, aluminate coupling agent, boric acid ester coupler, zirconate coupling
Agent, rare-earth coupling agent, phosphate coupling agent mixture.
Performance test:
Water absorption rate, peel strength test are carried out to the copper-clad plate that embodiment 1-4 is obtained, and detect its dielectric constant, simultaneously
Be arranged comparative experiments, other preparation conditions of comparative experiments 1 with embodiment 1, the difference is that, select PTFE of good performance
Material, performance parameter are as shown in table 1；The PTFE material used in comparative experiments 2 with embodiment 1, the difference is that, cover
Copper sheet the preparation method is as follows: routinely mix method configuration fluorine resin mixture evenly dispersed solution；Directly by institute
It states fluorine resin mixture solution to be dispersed on PTFE, toasted drying, obtains the fluorine resin mixture film of PTFE,
Using lamination, copper-clad plate is obtained.
One, wherein peel strength according to according to experiment condition is surveyed " after thermal stress " in IPC-TM-6502.4.8 method
Examination, water absorption rate is according to ASTM D570 normative testing, as a result as shown in the table.
Table 1: the parameter of PTFE of good performance
| Performance | Numerical value |
| Dielectric constant (10GHz) | 2.1 |
| Dielectric loss (10GHz) | 0.0003 |
| Volume resistivity (Ω cm) | >1018 |
| Surface resistivity (Ω cm) | >1016 |
Table 2: test result
As can be seen from the above table, by copper-clad plate prepared by the present invention, water absorption rate is lower, and removing with higher is strong
Degree, dielectric constant is between 2.79-2.87, with the copper-clad plate phase for using the preferable PTFE of quality to be prepared in comparative experiments 1
Than, water absorption rate and peel strength difference and little, show the copper-clad plate obtained by raw material proportioning and method and process of the invention
Same transmission rate with higher；Compared with the result of comparative experiments 2, it can be seen that when same poor using self performance
PTFE material when, using conventional preparation copper-clad plate mode, obtained copper-clad plate water absorption rate is increased, and peel strength is extremely low,
Bad mechanical property, dielectric constant is higher, and transmission rate is lower.
Two, insulation performance is tested
Insulation performance test: it is tested by standard Q/GDSY6050-20122.5.1.Specific test result see the table below.
| Project | Resistance to electric arc (Kv) |
| Embodiment 1 | 170 |
| Embodiment 2 | 168 |
| Embodiment 3 | 169 |
| Embodiment 4 | 166 |
As shown above, there is good are-tight property by the copper-clad plate that the present invention obtains, insulation performance is good.
Three, the evenly dispersed solution property test of fluorine resin mixture
Three groups of comparative experimentss are arranged in the evenly dispersed solution of fluorine resin mixture, and the fluorine resin that 1 group of comparative experiments is mixed
The evenly dispersed solution preparation condition for closing object is same as Example 1, the difference is that in the equal of configuration fluorine resin mixture
When even dispersion solution, using conventional method, raw material is uniformly mixed；In 2 groups of comparative experiments, fluorine resin mixture it is equal
Even dispersion solution preparation condition are as follows: inorganic fillers are put into high-pressure unit and are handled, then through air-flow crushing, are obtained powdered solid
Body takes the fluorine-containing resin emulsion of corresponding number to mix with pulverulent solids, then cools down in a water bath, is added under nitrogen flowing even
Join agent, persistently stirs 8 hours and reacted, be eventually adding modifier and mixed；Fluorine resin mixture in comparative experiments 3
Evenly dispersed solution preparation condition are as follows: inorganic fillers are put into high-pressure unit and are handled, then through air-flow crushing, are obtained powdered solid
Then plasma is made using Radio-frequency plasma torch in oxygen by body, then by gained powder in plasma reactor
For last shape solid at 2000-2500 DEG C, the residence time is to be decomposed into ultrafine particle under conditions of 0.7-1.0 seconds；Take corresponding number
Fluorine-containing resin emulsion is mixed with the heating of the ultrafine particle of inorganic fillers, and coupling agent is added under nitrogen flowing, controls reaction temperature
It is 45-50 DEG C, persistently stirs 8 hours and reacted, be eventually adding modifier and mixed.
A kind of energetic material particle TATB (1,3,5- triamido -2,4,6- trinitrobenzen) is suspended in using high-speed stirred
In water, according to TATB: embodiment 1 to 4 and right is added in the mass ratio of evenly dispersed solution=95:5 of fluorine resin mixture
Than the evenly dispersed solution for testing the fluorine resin mixture of 1-3 group.TATB particle is gradually bonded into bulky grain, stirs 1 hour
After stop, by obtained particle filtering, drying, by the particle after bonding be pressed into Φ 20mm × 6mm cylinder carry out mechanics
Performance test carries out the evenly dispersed solution of fluorine resin mixture using the measurement that quasi-static Brazilian test carries out mechanical property
Adhesive property test, the experimental results are shown inthe following table.
As can be seen from the above table, quality PTFE material of problems itself is being used to pass through method system of the invention
Standby obtained fluorine resin mixture film, breaking strength is higher, and modulus is higher, has a good adhesive property, and with it is right
Data of 1 group than experiment are compared, and when using the evenly dispersed solution of conventional mixing method configuration fluorine resin mixture, are broken
Resistance to spalling is decreased obviously, and in comparative experiments 2, when configuring the evenly dispersed solution of fluorine resin mixture, do not utilize height
Plasma is made in oxygen by frequency plasma generator, is then decomposed into gained pulverulent solids in plasma reactor
Ultrafine particle, the evenly dispersed solution of finally obtained fluorine resin mixture decline obviously, and caking property reduces；Comparative experiments
In 3, water-bath cooling is not carried out, the evenly dispersed solution of finally obtained fluorine resin mixture declines obviously, caking property
It reduces.
Four, transmission rate performance comparison is tested
The other conditions of the comparative experiments of this group are same as Example 1, the difference is that, PTFE is without at modified
The copper-clad plate finally obtained is carried out water absorption rate, peel strength test, and detects its dielectric constant by reason, and wherein peel strength is pressed
According to according to experiment condition is tested " after thermal stress " in IPC-TM-6502.4.8 method, water absorption rate is standardized according to ASTM D570
Test, as a result as shown in the table.
| Project | Water absorption rate/% | Peel strength (N/mm) | Dielectric constant (5GHz) |
| Embodiment 1 | 0.16 | 1.94 | 2.85 |
| Control group | 0.47 | 1.01 | 4.3 |
As can be seen from the above table, when not being modified processing to PTFE, the water absorption rate of obtained copper-clad plate rises, removing
Intensity decline, dielectric constant is significantly raised, and transmission rate reduces, and signal quality reduces, this shows to be modified PTFE processing
When can go fluorine effect on its surface, surface carbonation can be made, in addition, avoid the harm of unstable end-group, avoided double
Key is further oxidized, and reduces loss of the signal energy in transmission process.
Obviously present invention specific implementation is not subject to the restrictions described above, as long as using method concept and skill of the invention
The improvement for the various unsubstantialities that art scheme carries out, or not improved the conception and technical scheme of the invention are directly applied to it
Its occasion, within that scope of the present invention.
Claims (8)
1. a kind of fluorine resin mixture film preparation method, which comprises the following steps:
(1) the evenly dispersed solution of fluorine resin mixture is configured；
(2) the fluorine resin mixture solution is dispersed on PTFE, toasted drying obtains the fluorine resin of PTFE
Mixture film.
2. fluorine resin mixture film preparation method as described in claim 1, which is characterized in that the fluorine resin mixing
Object includes the raw material of following parts by weight: 30-60 parts of fluorine-containing resin emulsion, 70-90 parts of inorganic fillers, 10-15 parts of coupling agent,
5-15 parts of modifier.
3. fluorine resin mixture film preparation method as claimed in claim 2, which is characterized in that the inorganic fillers are
Al2O3、SiO2、TiO2 、MgO、Bi2O3、AlN、Si3N4、SiC、AL(OH)3、Mg(OH)2、BaxSr(1-x)TiO3、Mg2TiO4、
Bi2(TiO3)3、PbTiO3、NiTiO3、CaTiO3、ZnTiO3、Zn2TiO4、BaSnO3、Bi2(SnO3)3、CaSnO3、PbSnO3、
MgSnO3、SrSnO3、ZnSnO3、BaZrO3、PbZrO3、MgZrO3、SrZrO3、ZnZrO3, graphite, graphite oxide, fluorographite,
One or more of talcum powder, mica powder, kaolin, clay.
4. fluorine resin mixture film preparation method as claimed in claim 2, which is characterized in that the coupling agent is silicon
Alkane coupling agent, titanate coupling agent, aluminate coupling agent, boric acid ester coupler, zirconium ester coupling agent, rare-earth coupling agent, phosphoric acid
Ester coupling agent and one of sulfonyl azide coupling agent and its derivative or a variety of mixtures.
5. fluorine resin mixture film preparation method as described in claim 1, which is characterized in that match in the step (1)
The method for setting dispersion solution are as follows: inorganic fillers are put into high-pressure unit and are handled, then through air-flow crushing, obtain pulverulent solids,
Then plasma is made at a temperature of 2600-2800 DEG C in oxygen using Radio-frequency plasma torch, then in plasma
By gained pulverulent solids at 2000-2500 DEG C in reacting furnace, the residence time is to be decomposed into superfine granule under conditions of 0.7-1.0 seconds
Son；It takes the fluorine-containing resin emulsion of corresponding number to mix with the heating of the ultrafine particle of inorganic fillers, then cools down in a water bath,
Coupling agent is added under nitrogen stream, control reaction temperature is 45-50 DEG C, persistently stirs 8 hours and is reacted, is eventually adding improvement
Agent is mixed.
6. fluorine resin mixture film preparation method as described in claim 1, which is characterized in that be first modified PTFE
PTFE is immersed modifying agent 90-120s by processing, and taking-up is put into 55-60 DEG C of baking oven and dries
Dry 8-12min, seals spare after taking-up.
7. fluorine resin mixture film preparation method as claimed in claim 6, which is characterized in that the modifying agent is equal
Pyromellitic dianhydride, 4,4 '-diaminodiphenyl ethers, nano silica, butanediamine, polyamic acid；Prepare the side of modifying agent
Method are as follows: mix pyromellitic acid anhydride and nano silica, mechanical stirring certain time weighs a certain amount of 4,4 '-two
Amino-diphenylethers is divided into 3 equal portions, and in the case where helium protects environment, control bath temperature is 35-40 DEG C, by 4,4 '-diamino
Diphenyl ether is added while stirring in batches, and then butanediamine, polyamic acid are added in above-mentioned system, obtain modifying agent.
8. a kind of fluorine resin mixture copper-clad plate preparation method, which is characterized in that making step are as follows: by prepreg, PTFE
Fluorine resin mixture film be symmetrically superimposed together with copper foil, it is laminated to obtain copper-clad plate；The wherein number of prepreg
>=1, number >=0 of PTFE film, number >=0 of the fluorine resin film containing inorganic filler, the number of copper foil is 1 or 2, laminating temperature
At 150-430 DEG C, lamination pressure 50-150kg/cm2, lamination times 24-60h.
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