CN1385467A - Composite material board used as circuit substrate - Google Patents
Composite material board used as circuit substrate Download PDFInfo
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- CN1385467A CN1385467A CN 01116048 CN01116048A CN1385467A CN 1385467 A CN1385467 A CN 1385467A CN 01116048 CN01116048 CN 01116048 CN 01116048 A CN01116048 A CN 01116048A CN 1385467 A CN1385467 A CN 1385467A
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- composite panel
- circuit substrate
- coupling agent
- fep
- base material
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Abstract
The present invention relates to a composite material board applicable to production of circuit base board. It possesses high rigidity and low dielectric constant, and is suitable for making high-frequency circuit base board, and is made by using uniform mixture of teflon and FEP as base material of said composite material board and adding ceramic granule filler, for example silicon dioxide as reinforcing material in the polymer base material, in which the ceramic granule filler content is 55 wt%-85 wt% of total weight of said composite material board, and FEP content is 0.5 wt%-10 wt% of total weight of said composite material board, and its dielectric constant is less than 3.5.
Description
The present invention relates to a kind of composite panel that is used as circuit substrate, particularly a kind of composite panel that is applicable to high-frequency circuit board.
The material category that has been used as circuit substrate (for example, tellite or chip packaging substrate) at present is a lot.With the resene circuit base material, promptly include resol, Resins, epoxy, polyimide resin, polytetrafluoroethylene (PTFE) and bismaleimides-cyanate resin (Bismaleimide Triazine, BT) thermosetting resin of Denging.The circuit substrate purposes that with Resins, epoxy is the base material made in present printed circuit board industry is the most general.This kind Resins, epoxy is a kind of bromated resin, is commonly referred to as " FR-4 " resin.Because the tack of FR-4 resin and Copper Foil is very strong, and combine with the glass fibre enhancing weighting material composite panel of gained of FR-4 resin has flexible, low price, reaction is simple and processibility is good advantage, thereby extensively is used as circuit substrate.But because of FR-4 resin specific inductivity height (the Dk value is about 4.5), the interference that telecommunication is transmitted is bigger, so be used in the circuit substrate of the electronic installation of frequency below 2GHz more.Probably can be divided into BT resin, polyphenylene oxide (PPO) resin and PTFE resin three big series and be used in the high frequency substrate material that satellite connects the very high equipment of distributor, cableless communication, high frequency microwave communication, radar equipment and other precision requirement.Wherein BT resin, PPO resin are used for the circuit substrate of frequency at 2～12GHz more, and PTFE resin then major part is used for the circuit substrate of frequency more than 10GHz.Yet as the base material of high-frequency circuit board following shortcoming is arranged with the PTFE resin: (1) Tg too low (about 19 ℃), material is too soft, and scrath resistance difference and boring property are bad; (2) processing temperature too high (700), tonnage too high (about 1600psi) and molding time long (about 6 hours); (3) unreactiveness height is at plated-through-hole (Plated Through Hole; PTH) in the processing procedure, hole wall difficulty activates; (4) (be about FR-4 10 times) costs an arm and a leg.In order to improve above-mentioned shortcoming, wherein a kind of way be with the PTFE resin be base material and therein uniform distribution strengthen weighting material and form a matrix material.This enhancing weighting material can be stupalith, as SiO2 (United States Patent (USP) 5024871,5061548), or macromolecular material, as PEEK (United States Patent (USP) 5922453); Though can obtain the higher substrate matrix material of rigidity yet in the PTFE resin, add above-mentioned enhancing weighting material, often make the deterioration in dielectric properties of substrate because of the high-k that strengthens weighting material.Another kind of improved mode then is to add porous fiber or tubular fibre strengthening material (as European patent 0160418A2 in the PTFE resin, United States Patent (USP) 4849284,5194326), though this mode can make resulting composite panel have high rigidity and low-k simultaneously concurrently, yet but can make the capillarity that generation hates the sight of when carrying out the plated-through-hole processing procedure of circuit substrate, promptly copper infiltrates phenomenon in the substrate by hole wall.
Therefore, still need to provide a kind of new composite panel that is applicable to high-frequency circuit board, to address the above problem.
In view of this, the object of the present invention is to provide a kind ofly to have high rigidity, low-k concurrently, and do not have the composite panel that plated-through-hole is oozed the copper phenomenon.
A kind of composite panel proposed by the invention, it is by a fluoro containing polymers base material, and at least a ceramic particle weighting material that intersperses among in this polymer base material is formed, this polymer base material mixes institute by tetrafluoroethylene (hereinafter to be referred as PTFE) at least and forms with ethylene fluoride-propene polymer (hereinafter to be referred as FEP), wherein this FEP accounts for the 0.5%wt-10%wt of composite panel gross weight.
As from the foregoing, a kind of composite panel of the present invention, it is with macromolecular material---PTFE and FEP uniform mixing are with the base material as this composite panel, and in this polymer base material, add the ceramic particle weighting material, as silicon-dioxide, as strongthener, wherein this ceramic particle weighting material accounts for the 55wt%～85wt% of this composite panel gross weight.
The preparation method of described composite panel is according to the precalculated ratio allotment and the mixing that stirred with silicon oxide particle packing material, the emulsion that contains the emulsion of PTFE powder and contain the FEP powder.Also can add an amount of softening agent simultaneously and mix, described softening agent is DPG (dipropylene glycol) or other suitable oils or alcohols for example, and its adding helps follow-up machine-shaping processing procedure.For silicon oxide particle, handled lining with coupling agent in advance, this coupling agent can be siloxane-based coupling agent, as the Z-6124 phenyltrimethoxysila,e; Or zirconium is coupling agent, as NZ12, neo-pentyl (diallyl) oxo, and three (dioctyl) Phosphation zirconate [neopentyl (dially) oxy, tri (dioctyl) phosphate zirconate]; Or titanium is coupling agent, as Lical2 (, neo-pentyl (diallyl) oxo, three (dioctyl) Phosphation titanate [neopentyl (dially) oxy, tri (dioctryl) phosphatetitanate]; Perhaps fluorine is the siloxanes coupler.The effect of above-mentioned coupling agent is in order to promote the bonding force between the silicon oxide particle and base material in this composite panel.Wherein the chemical structural formula of NZ12 and Lical2 is respectively as shown in the formula shown in (I) and the formula (II).
With the mixture of above-mentioned ceramic particle, PTFE powder, FEP powder and softening agent, be shaped to suitable shape with pressuring method then, for example writing board shape toasts this forming mixture then, and its softening agent that contains is vapored away; Then carry out sintering with about 360 ℃ temperature again, PTFE and FEP molecule are spread each other and form PTFE and the mixed uniformly single isotropic phase base material of FEP, described silicon oxide particle then intersperses among in this base material, so can obtain a composite panel.
Because FEP and PTFE are the high sub-material of fluorine class, so FEP can be uniformly mixed to form mutually single with PTFE.In PTFE, add thermoplasticity FEP, can improve the rigidity of this base material and improve, and the low-k of FEP also makes that the composite panel that is obtained can maintain lower overall dielectric constant the insufficient problem of circuit board line sticking power.
For making feature of the present invention and advantage there are clearer understanding, next conjunction with figs. are elaborated.But explanation is that the present invention still can have other embodiment except following embodiment, and the following drawings is not to draw according to substantial proportion fully earlier.
Fig. 1 is the photo of the electron microscope (SEM) according to one of matrix material of the present invention.
Embodiment
According to the disclosed composite panel of the embodiment of the invention, its microtexture can be with reference to electron microscope shown in Figure 1 (SEM) photo.This composite material base is to be that macromolecular material PTFE and FEP are according to the formed single phase base material of suitable proportion uniform mixing by fluorine.In this base material, then insert the ceramic particle packing material of suitable proportion, for example for accounting for the silicon oxide particle packing material of composite panel gross weight 55wt%-85wt%, the purpose that adds the ceramic particle packing material, on the one hand in order to the reinforced composite material plate, the thermal expansivity of may command composite panel then on the other hand; Because the specific inductivity (being about 6) of ceramic particle packing material is more high than the specific inductivity (being about 2) of PTFE, so need the ratio of control ceramic particle packing material, the overall dielectric constant of the composite panel that is obtained to avoid is too high.Table 1: the commercial composite panel of the composite panel of made and relatively according to the present invention
| The test piece kind | Specific inductivity | Rigidity (MPa) |
| ????RO3003 | ????3.16 | ????1267 |
| ????FEP?1.3％ | ????3.06231 | ????1876 |
| ????FEP?3.4％ | ????3.00643 | ????2325 |
| ????FEP?5％ | ????3.08689 | ????2613 |
Table 1 contains the composite panel (be expressed as FEP 1.3% respectively, FEP 3.4%, and FEP 5%) of different ratios FEP and commercial a kind of composite panel RO3003 on the market for three kinds of making according to the present invention
Specific inductivity and rigidity comparison sheet.RO3003 wherein
Composition contain the PTFE of 43.9wt% (44.5vol%) and the ceramic particle weighting material of 56.1wt% (55.5vol%).And according to three kinds of composite panel FEP 1.3% of the present invention, FEP 3.4%, FEP 5%, then be to contain the PTFE that the FEP that accounts for composite panel gross weight 1.3wt%, 3.4wt%, 5wt% replaces part respectively.Can learn that by table 1 the composite panel rigidity of adding FEP is showing and is increased to 1876-2613 MPa, than the RO3003 of present commercialization ad eundem
(rigidity 1267MPa) is much higher.Aforesaid rigidity records under 30.29 ℃ of temperature with dynamic mechanical analysis test (DMA Test).In addition, also quite good according to the dielectric properties of composite panel of the present invention, overall dielectric constant only is about 3.01-3.08, to be lower than RO3003
3.16, thereby applicable to high-frequency circuit board.
Having high bending modulus simultaneously according to composite panel of the present invention, is example with above-mentioned FEP 1.3% composite panel, and its bending modulus can reach 272 * 10
3Psi; With in the United States Patent (USP) 5922453 in RO3003
The PEEK reinforcing particle of the middle 10vol% of interpolation (6wt%) replaces the composite panel (bending modulus 218 * 10 of PTFE gained
3Psi) compare, the FEP that the present invention has only added 1.3wt% can obtain higher bending modulus.
The present invention adds the FEP that accounts for gross weight 0.5%wt-10%wt in ceramics particle strengthened PTFE composite panel, the composite panel that is obtained has the advantage of high rigidity and low-price electricity constant simultaneously concurrently, and can significantly not increase cost of manufacture or produce the problem that plated-through-hole is oozed copper.
The above is preferred embodiment of the present invention only, is not to be used for limiting practical range of the present invention, is familiar with this operator and is not breaking away from any modification and the retouching of being made under the spirit of the present invention, all within claim of the present invention.
Claims (11)
1. composite panel that is used as circuit substrate, this composite panel is by a fluoro containing polymers base material, and at least a ceramic particle weighting material that intersperses among in this polymer base material is formed, it is characterized in that: this polymer base material mixes institute by PTFE at least and forms with FEP, wherein this FEP accounts for the 0.5%wt-10%wt of composite panel gross weight.
2. the composite panel that is used as circuit substrate as claimed in claim 1, wherein said ceramic particle weighting material is a silicon-dioxide.
3. the composite panel that is used as circuit substrate as claimed in claim 2, wherein said ceramic particle weighting material accounts for the 55wt%-85wt% of composite panel gross weight.
4. the composite panel that is used as circuit substrate as claimed in claim 2, wherein said ceramic particle weighting material is surface-coated coupling agent.
5. the composite panel that is used as circuit substrate as claimed in claim 4, wherein said coupling agent are the siloxane series coupling agent.
6. the composite panel that is used as circuit substrate as claimed in claim 5, wherein said coupling agent are phenyltrimethoxysila,e.
7. the composite panel that is used as circuit substrate as claimed in claim 4, wherein said coupling agent are that fluorine is the siloxane series coupling agent.
8. the composite panel that is used as circuit substrate as claimed in claim 4, wherein said coupling agent are titanium series.
9. the composite panel that is used as circuit substrate as claimed in claim 8, wherein said coupling agent are Lical2, neo-pentyl (diallyl) oxo, three (dioctyl) Phosphation titanate.
10. the composite panel that is used as circuit substrate as claimed in claim 4, wherein said coupling agent are zirconium series coupling agent.
11. as the circuit board use composite panel of claim 10, wherein said coupling agent is NZ12, neo-pentyl (diallyl) oxo, three (dioctyl) Phosphation zirconate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011160489A CN1165575C (en) | 2001-05-11 | 2001-05-11 | Composite material board used as circuit substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011160489A CN1165575C (en) | 2001-05-11 | 2001-05-11 | Composite material board used as circuit substrate |
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| Publication Number | Publication Date |
|---|---|
| CN1385467A true CN1385467A (en) | 2002-12-18 |
| CN1165575C CN1165575C (en) | 2004-09-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011160489A Expired - Fee Related CN1165575C (en) | 2001-05-11 | 2001-05-11 | Composite material board used as circuit substrate |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103287015A (en) * | 2012-03-01 | 2013-09-11 | 深圳光启创新技术有限公司 | Multi-polymer ceramic composite substrate and preparation method thereof |
| CN103289158A (en) * | 2012-02-29 | 2013-09-11 | 深圳光启创新技术有限公司 | Substrate and preparation method thereof |
| CN107674349A (en) * | 2016-08-01 | 2018-02-09 | 南京工业大学 | A kind of fluoropolymer composite of low-k and preparation method thereof |
| CN108780674A (en) * | 2016-03-18 | 2018-11-09 | 日东电工株式会社 | Dielectric resin material, the dielectric resin material and circuit board with metal layer using it |
| CN111154206A (en) * | 2020-02-17 | 2020-05-15 | 武汉理工大学 | Modified PTFE composite medium material, preparation method and application thereof |
| CN112164497A (en) * | 2020-09-25 | 2021-01-01 | 安徽龙庵电缆集团有限公司 | Low-loss phase-stable cable for airborne early warning radar and preparation method thereof |
-
2001
- 2001-05-11 CN CNB011160489A patent/CN1165575C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103289158A (en) * | 2012-02-29 | 2013-09-11 | 深圳光启创新技术有限公司 | Substrate and preparation method thereof |
| CN103289158B (en) * | 2012-02-29 | 2016-09-28 | 深圳光启创新技术有限公司 | A kind of substrate and preparation method thereof |
| CN103287015A (en) * | 2012-03-01 | 2013-09-11 | 深圳光启创新技术有限公司 | Multi-polymer ceramic composite substrate and preparation method thereof |
| CN108780674A (en) * | 2016-03-18 | 2018-11-09 | 日东电工株式会社 | Dielectric resin material, the dielectric resin material and circuit board with metal layer using it |
| CN108780674B (en) * | 2016-03-18 | 2020-03-06 | 日东电工株式会社 | Insulating resin material, insulating resin material with metal layer using same, and wiring board |
| CN107674349A (en) * | 2016-08-01 | 2018-02-09 | 南京工业大学 | A kind of fluoropolymer composite of low-k and preparation method thereof |
| CN111154206A (en) * | 2020-02-17 | 2020-05-15 | 武汉理工大学 | Modified PTFE composite medium material, preparation method and application thereof |
| CN112164497A (en) * | 2020-09-25 | 2021-01-01 | 安徽龙庵电缆集团有限公司 | Low-loss phase-stable cable for airborne early warning radar and preparation method thereof |
| CN112164497B (en) * | 2020-09-25 | 2021-11-23 | 安徽龙庵电缆集团有限公司 | Low-loss phase-stable cable for airborne early warning radar and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1165575C (en) | 2004-09-08 |
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Granted publication date: 20040908 Termination date: 20110511 |