CN104149420A - Preparation for non-sintered forming of high-performance polytetrafluoroethylene copper-clad laminate for high-frequency communication - Google Patents
Preparation for non-sintered forming of high-performance polytetrafluoroethylene copper-clad laminate for high-frequency communication Download PDFInfo
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- CN104149420A CN104149420A CN201410196744.5A CN201410196744A CN104149420A CN 104149420 A CN104149420 A CN 104149420A CN 201410196744 A CN201410196744 A CN 201410196744A CN 104149420 A CN104149420 A CN 104149420A
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- frequency communication
- polytetrafluoroethylene
- ptfe
- copper coated
- coated foil
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Abstract
The invention discloses preparation for non-sintered forming of a high-performance polytetrafluoroethylene copper-clad laminate for high-frequency communication. The preparation adopts polytetrafluoroethylene as a main material and aims at simplifying a preparation process on the basis of maintaining excellent dielectric property (dielectric constant is less than 2.8 and dielectric loss is less than 0.005) and high heat resistance of the copper-clad laminate for high-frequency communication and enabling the copper-clad laminate to be pressed and formed under the temperature lower than 250 DEG C; the thickness of the copper-clad laminate is 0.05-3.2mm. The preparation process comprises the following steps: carrying out surface treatment on polytetrafluoroethylene, mixing with a bonding agent to prepare a prepreg and finally pressing to be formed. The polytetrafluoroethylene copper-clad laminate prepared by the method is simple in process, low in cost and wide in application range and lays a foundation for fast development of communication in future.
Description
Technical field
The invention belongs to high-performance copper coated foil plate technical field, specifically, the present invention relates to the surface treatment of polytetrafluoroethylene (PTFE) and technical field prepared by high-performance copper coated foil plate.
Background technology
Along with the revolution of information technology, digital circuit gradually stepped into information is processed high speed, signal carry high frequency stage.Along with ever-increasing data, the frequency of electronic equipment becomes more and more higher, and at this moment the electrical property of substrate, by having a strong impact on the characteristic of digital circuit, is therefore had higher requirement to the performance of PCB substrate.Traditional FR-4 product can not meet the requirement of this series products at side signal transmission face.The square root of signaling rate and dielectric constant (Dk) is inversely proportional to, and what dielectric loss (Df) and signal passed is worn to direct ratio, and Dk and the Df value of traditional FR-4 product are bigger than normal, can hinder like this speed of signal transmission, affects the integrality of signal transmission.
Just because of there is such demand, on market, constantly emerge various types of sheet material, can be divided into haply following three class by the dielectric constant of its insulating barrier and application: (1) Dk<3.0, taking PTFE material as main, as RT5880, AR522 etc.; (2) PTFE substitute: Dk is in 3.5 left and right, mainly taking thermosetting compound as main, and as PPE, alkene, CE and compound thereof etc., as GML2000, RO4350, AR25FR etc.; (3) high-speed figure application: Dk, in 3.9 left and right, mainly taking epoxy resin modification as main, has the processing technology that approaches traditional F R-4, and price is relatively cheap, as GETEK, and FR408 etc.
At present, only having PTFE material is that main copper-clad plate can meet Dk<3.0, but its complicated process of preparation (needing high temperature sintering), softening point is low, therefore cause yield rate low, and its price is high, has limited its application, for the fast development of 4G, be therefore badly in need of the copper coated foil plate of the simple high-performance poly tetrafluoroethene of preparation technology.
Summary of the invention
The deficiency of the polytetrafluoroethylene (PTFE) metal clad board of producing for prior art, the present invention aims to provide a kind of new preparation method of high-performance poly tetrafluoroethene copper coated foil plate, this kind of polytetrafluoroethylene (PTFE) copper coated foil plate preparation technology is simple, function admirable, and is applicable to multiple application.
This kind of polytetrafluoroethylene (PTFE) copper coated foil plate, is made by the raw material of following parts by weight:
100 parts of polytetrafluoroethylene (PTFE)
Bonding agent 50.0-100 part
Filler 10-50 part
Catalyst is a small amount of
Material modified 10-50 part
Reinforcing material (fiber) 150-200 part
2 of Copper Foils (half ounce or 1 ounce)
The preparation of above-mentioned polytetrafluoroethylene (PTFE) copper coated foil plate, comprises following steps:
1. utilize surface treatment method to comprise chemical corrosion method, high temperature surface fusion method, low temperature plasma method, air heat oxidizing process and radiation method etc., ptfe surface is processed.
2. prepare and select suitable bonding agent, this kind of bonding agent can be epoxy resin, phenolic resins, cyanate ester resin, bimaleimide resin, polyphenylene oxide resin, aralkyl-phenol resin, silicones, fluorine resin etc.; Or two or three blend.
3. preparation contains the copper coated foil plate of polytetrafluoroethylene (PTFE): first prepare prepreg, then the prepreg of prepreg and modification is stacked up, be placed in 160 DEG C of press, slowly pressurization, control gummosis degree, the maximum pressure that goes directly was then warmed up to 180-200 DEG C in 10 minutes, suppressed 40 minutes-120 minutes.
4. cooling, temperature, lower than 100 DEG C, is got plate.
The multiple embodiment products that prepare according to the present invention are tested its performance as follows:
1. glass transition temperature: see IPC-TM-650 test methods manual-2.4.25 differential scanning calorimetry glass transition temperature and solidification temperature (DSC).
2. heat decomposition temperature: adopt TGA to test, weightless 5% temperature (T
5%) be heat decomposition temperature Td (10 DEG C/min of heating rate, nitrogen atmosphere).
3. thermal stress: the thermal stress of seeing IPC-TM-650 test methods manual-2.4.13.1 laminate.
4. thermal coefficient of expansion: see IPC-TM-650 test methods manual-2.4.24 glass transition temperature and Z axis thermal expansion (TMA method).
5. PCT: concrete steps are shown in the integrity (pressure vessel method) of IPC-TM-650 test methods manual-2.6.16 epoxy glass cloth laminated board.
6. water absorption rate: obtain in PCT process of the test.
7. T288: key step is shown in IPC-TM-650 test methods manual-2.4.24.1 layering (cracking) time (thermomechanical analyzer method), and fixing temperature is 288 DEG C.
8. dielectric properties: see the dielectric constant (parallel plate method) under IPC-TM-650 test methods manual-2.5.5.9 1GHz.
9. fire resistance: see ASTM D 3801 methods.
10. peel strength: the peel strength of seeing IPC-TM-650 test methods manual-2.4.8 clad with metal foil plate.
Detailed description of the invention
Below by embodiment, the present invention is specifically described; be necessary to be pointed out that at this embodiment is only for the present invention is further described; can not be interpreted as limiting the scope of the invention, person skilled in art can make according to the present invention some nonessential improvement and adjustment.
Embodiment mono-:
Select epoxy resin as bonding agent
Get 100g epoxy resin, 0.8g methylimidazole, 100g surface-treated polytetrafluoroethylene powder, 30g silicon powder and appropriate acetone solvent, preparation forms prepreg, then prepreg is placed on the Copper Foil of 1 ounce,, finally place the Copper Foil of 1 ounce topmost.This is placed in the press of 160 DEG C, gets to contact, make it gel, then pressure is made, be warmed up to 190 DEG C, compacting 40min, cools to below 100 DEG C, gets plate.Performance test data is shown in Fig. 1.
Embodiment bis-:
Select epoxy resin as bonding agent
Get 100g epoxy resin, 100g surface-treated polytetrafluoroethylene powder, 10g crosslinked polystyrene micro mist, 0.8g methylimidazole and appropriate acetone, preparation forms prepreg; Then prepreg is placed on successively on the Copper Foil of 1 ounce, places the Copper Foil of 1 ounce topmost.Be pressed into plate according to suitable technique, measure the performance of copper coated foil plate, its test data is shown in Fig. 2.
Embodiment tri-:
Select epoxy resin as bonding agent
Get 100g epoxy resin, 0.8g methylimidazole,, 100g surface-treated polytetrafluoroethylene powder, 10g silicon powder and appropriate acetone, also added that some are material modified; Preparation forms prepreg; Then prepreg is placed on successively on the Copper Foil of 1 ounce, finally places the Copper Foil of 1 ounce topmost.Be pressed into plate, the performance of its copper coated foil plate is as Fig. 3.
Embodiment tetra-:
Using phenolic resins as bonding agent,
Get 100g thermosetting phenolic resin, appropriate ethanol, 100g surface-treated polytetrafluoroethylene powder, 30g silicon powder and some are material modified, preparation forms prepreg; Then prepreg is placed on successively on the Copper Foil of 1 ounce,, finally place the Copper Foil of 1 ounce topmost.Be pressed into plate according to suitable technique, measure the performance of plate, it the results are shown in Figure 4.
Embodiment five:
Using epoxy resin and cyanate ester resin as bonding agent,
Get 100g epoxy resin and cyanate ester resin (epoxy resin: cyanate ester resin=5:5), appropriate acetone solvent, 100g surface-treated polytetrafluoroethylene powder and 30g silicon powder, preparation forms prepreg; Then prepreg is placed on successively on the Copper Foil of 1 ounce, finally places the Copper Foil of 1 ounce in the above.Be pressed into plate according to suitable technique, measure the performance of plate, it the results are shown in Figure 5.
Embodiment six:
Using BT resin as bonding agent,
Get 100g BT resin, appropriate dimethyl formamide, 100g surface-treated polytetrafluoroethylene powder for and 30g silicon powder, preparation forms prepreg; Then prepreg is placed on successively on the Copper Foil of 1 ounce, finally places the Copper Foil of 1 ounce in the above.Be pressed into plate according to suitable technique.
Fig. 1 is the performance test data figure of embodiment mono-;
Fig. 2 is the performance test data figure of embodiment bis-;
Fig. 3 is the performance test data figure of embodiment tri-;
Fig. 4 is the performance test data figure of embodiment tetra-;
Fig. 5 is the performance test data figure of embodiment five.
Claims (12)
1. a non-sinter molding high-performance poly tetrafluoroethene high frequency communication copper coated foil plate, is characterized in that the base stock of preparation is polytetrafluoroethylene (PTFE).
2. according to described in right 1, it is characterized in that using the bonding agent of polytetrafluoroethylene (PTFE); This kind of bonding agent can be the blend of epoxy resin, phenolic resins, cyanate ester resin, bimaleimide resin, diphenyl ether and derivative, aralkyl-phenol resin, silicones, fluorine resin etc. two or three.
3. according to described in right 1, it is characterized in that having used reinforcing material; This kind of reinforcing material can be glass fabric, carbon cloth, nylon fiber cloth, polytetrafluoroethylene (PTFE) and glass fibre blended cloth etc.; Or the common use of two kinds and three kinds.
4. according to the non-sinter molding polytetrafluoroethylene (PTFE) high frequency communication copper coated foil plate described in right 2, it is characterized in that ptfe surface need to carry out surface treatment before using bonding agent
;the surface treatment method using comprises chemical corrosion method, high temperature surface fusion method, low temperature plasma method, air heat oxidizing process and radiation method etc.
5. according to described in right 4, it is characterized in that some polar groups in the grafting of surface treated ptfe surface, thereby promoted the bonding force between bonding agent and polytetrafluoroethylene (PTFE).
6. according to described in right 1, it is characterized by and added filler; The filler using comprises silicon powder, the crosslinked polystyrene micro mist etc. of different size size; The filler adding has passed through surface treatment, is beneficial in mixed process dispersed.
7. according to the non-sinter molding high-performance poly tetrafluoroethene high frequency communication copper coated foil plate described in right 1, it is characterized in that having added material modified, be intended to further reduce dielectric constant and the dielectric loss of material.
8. according to the non-sinter molding high-performance poly tetrafluoroethene high frequency communication copper coated foil plate described in right 1, it is characterized in that moulding process is simple, do not need high temperature sintering.
9. according to the non-sinter molding high-performance poly tetrafluoroethene high frequency communication copper coated foil plate described in right 1-5, it is characterized in that thering is low dielectric constant (being less than 2.8) and low dielectric loss (being less than 0.005).
10. according to the non-sinter molding high-performance poly tetrafluoroethene high frequency communication copper coated foil plate described in right 1-4, there is low water absorption rate.
11. according to the non-sinter molding high-performance poly tetrafluoroethene high frequency communication copper coated foil plate described in right 1-4, has high heat decomposition temperature, exceedes 340 DEG C.
12. according to the non-sinter molding high-performance poly tetrafluoroethene high frequency communication copper coated foil plate described in right 1-4, has reached the fire-retardant requirement of UL94-V0 level.
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| CN106751711A (en) * | 2017-01-18 | 2017-05-31 | 腾辉电子（苏州）有限公司 | Fluorine substituted ethylene based polyalcohol resin combination, prepreg and laminate |
| CN106827719A (en) * | 2017-01-09 | 2017-06-13 | 三峡大学 | A kind of high-frequency high-speed flexibility coat copper plate and preparation method thereof |
| CN109627374A (en) * | 2018-11-13 | 2019-04-16 | 湖南辰砾新材料有限公司 | A kind of linear expansion coefficient it is low have can viscosity can polytetrafluoroethylene (PTFE) material and preparation method thereof |
| CN110524978A (en) * | 2019-08-07 | 2019-12-03 | 电子科技大学中山学院 | A kind of Copper Clad Laminates Based On Polytetrafluoroethylene and preparation method thereof of long-acting bonding |
| CN112442202A (en) * | 2019-09-04 | 2021-03-05 | 广东生益科技股份有限公司 | Interlayer bonding sheet for multilayer board and preparation method and application thereof |
| CN112538186A (en) * | 2019-09-04 | 2021-03-23 | 广东生益科技股份有限公司 | Interlayer bonding sheet for multilayer board and preparation method and application thereof |
| US11549035B2 (en) | 2020-12-16 | 2023-01-10 | Saint-Gobain Performance Plastics Corporation | Dielectric substrate and method of forming the same |
| US11596064B2 (en) | 2020-07-28 | 2023-02-28 | Saint-Gobain Performance Plastics Corporation | Dielectric substrate and method of forming the same |
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Cited By (13)
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|---|---|---|---|---|
| CN106827719A (en) * | 2017-01-09 | 2017-06-13 | 三峡大学 | A kind of high-frequency high-speed flexibility coat copper plate and preparation method thereof |
| CN106751711B (en) * | 2017-01-18 | 2020-10-09 | 腾辉电子（苏州）有限公司 | Fluorine-substituted vinyl polymer resin composition, prepreg and laminate |
| CN106751711A (en) * | 2017-01-18 | 2017-05-31 | 腾辉电子（苏州）有限公司 | Fluorine substituted ethylene based polyalcohol resin combination, prepreg and laminate |
| CN109627374A (en) * | 2018-11-13 | 2019-04-16 | 湖南辰砾新材料有限公司 | A kind of linear expansion coefficient it is low have can viscosity can polytetrafluoroethylene (PTFE) material and preparation method thereof |
| CN109627374B (en) * | 2018-11-13 | 2021-07-23 | 上海嘉诺密封技术有限公司 | Polytetrafluoroethylene material with low linear expansion coefficient and adhesive property and preparation method thereof |
| CN110524978B (en) * | 2019-08-07 | 2021-06-25 | 电子科技大学中山学院 | Long-acting bonded polytetrafluoroethylene copper-clad plate and preparation method thereof |
| CN110524978A (en) * | 2019-08-07 | 2019-12-03 | 电子科技大学中山学院 | A kind of Copper Clad Laminates Based On Polytetrafluoroethylene and preparation method thereof of long-acting bonding |
| CN112538186A (en) * | 2019-09-04 | 2021-03-23 | 广东生益科技股份有限公司 | Interlayer bonding sheet for multilayer board and preparation method and application thereof |
| CN112442202A (en) * | 2019-09-04 | 2021-03-05 | 广东生益科技股份有限公司 | Interlayer bonding sheet for multilayer board and preparation method and application thereof |
| CN112442202B (en) * | 2019-09-04 | 2022-10-18 | 广东生益科技股份有限公司 | Interlayer bonding sheet for multilayer board and preparation method and application thereof |
| US11596064B2 (en) | 2020-07-28 | 2023-02-28 | Saint-Gobain Performance Plastics Corporation | Dielectric substrate and method of forming the same |
| US11805600B2 (en) | 2020-07-28 | 2023-10-31 | Saint-Gobain Performance Plastics Corporation | Dielectric substrate and method of forming the same |
| US11549035B2 (en) | 2020-12-16 | 2023-01-10 | Saint-Gobain Performance Plastics Corporation | Dielectric substrate and method of forming the same |
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Application publication date: 20141119 |