CN102378561B - Covering membrance with electromagnetic shielding function and manufacturing method of covering membrance - Google Patents
Covering membrance with electromagnetic shielding function and manufacturing method of covering membrance Download PDFInfo
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- CN102378561B CN102378561B CN201010257292.9A CN201010257292A CN102378561B CN 102378561 B CN102378561 B CN 102378561B CN 201010257292 A CN201010257292 A CN 201010257292A CN 102378561 B CN102378561 B CN 102378561B
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- epoxy resin
- composite material
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Abstract
The invention relates to a covering membrance, which comprises an insulation base material layer, an epoxy resin composite material layer and an adhesive layer which are stacked in sequence, wherein the epoxy resin composite material layer is positioned between the insulation base material layer and the adhesive layer and is formed by an epoxy resin composite material, the epoxy resin composite material comprises carboxy terminal polymer modified epoxy resin, a carbon nanometer tube and inorganic dispersion materials, and the mass percentage of the carbon nanometer tube in the epoxy resin composite material is 4.6-16. The invention also provides a manufacturing method of the covering membrance.
Description
Technical field
The present invention relates to circuit board technology field, particularly relate to and be a kind ofly applied to board production and coverlay with electromagnetic shielding action and preparation method thereof.
Background technology
Along with the progress of science and technology, the application widely that printed circuit board (PCB) obtains at electronic applications.Application about circuit board refers to document Takahashi, A.Ooki, N.Nagai, A.Akahoshi, H.Mukoh, A.Wajima, M.Res.Lab, High densitymultilayer printed circuit board for HITAC M-880, IEEE Trans.onComponents, Packaging, and Manufacturing Technology, 1992,15 (4): 418-425.
Along with the circuit board product number of plies increases, circuit board product, when real work, often produces electromagnetic interference phenomenon, affects circuit board signal transmission.Like this, need to arrange electro-magnetic screen layer in circuit board product.At present, the stainless steel substrates that the electro-magnetic screen layer of employing adopts thickness less usually makes, and is arranged at by stainless steel substrates on the coverlay on the surface of circuit board product, thus plays the effect of electromagnetic shielding.But the weight of stainless steel substrates is comparatively large, thus adds the weight of circuit board product.And the flexility of stainless steel substrates is poor, the electro-magnetic screen layer adopting stainless steel substrates to make affects flexible PCB and to destroy or force to yield performance.Further, due to circuit board is fitted coverlay and stainless steel substrates simultaneously, the thickness of circuit board is increased.
Summary of the invention
Therefore, be necessary to provide a kind of coverlay and preparation method thereof, described coverlay can be applied to circuit board to play electromagnetic shielding action.
By with embodiment, a kind of coverlay with electromagnetic shielding action and preparation method thereof is described below.
A kind of coverlay, it comprises the insulated base material layer, epoxy resin composite material layer and the glue-line that stack gradually.Described epoxy resin composite material layer is between insulated base material layer and glue-line.Described epoxy resin composite material layer is made up of epoxy resin composite material.Described epoxy resin composite material comprises the epoxy resin of end carboxyl polymer modification, carbon nano-tube and inorganic dispersion, and the mass percent of described carbon nano-tube shared by described epoxy resin composite material is 4.6% to 16%.
A manufacture method for coverlay, comprises step: adopt end carboxyl polymer to carry out modification to obtain the epoxy resin of end carboxyl polymer modification to epoxy resin; Even carbon nanotube is scattered in inorganic dispersion, to obtain nanotube dispersion; The epoxy resin of described end carboxyl polymer modification and nanotube dispersion are carried out mixing and grinding distribution, to obtain epoxy resin composite material; Insulated base material layer is provided; The surface described epoxy resin composite material being coated insulated base material layer forms epoxy resin composite material layer; By described epoxy resin composite material layer solidification; And glue-line is formed on the epoxy resin composite material layer of solidification.
Compared to prior art, the coverlay that the technical program provides, it comprises insulated base material layer and epoxy resin composite material layer, owing to having finely dispersed carbon nano-tube, there is electromagnetic shielding action in described epoxy resin composite material layer, described coverlay can directly be fitted in the surface being formed with conducting wire, this coverlay can play the effect by conducting wire and external insulation, also to the effect playing electromagnetic shielding, and can reduce the thickness of circuit board.The manufacture method of the coverlay that the technical program provides, can simply produce the coverlay with electromagnetic shielding action.
Accompanying drawing explanation
Fig. 1 is the cutaway view of the coverlay that the technical program execution mode provides.
Fig. 2 is the cutaway view of the insulating substrate that the technical program embodiment provides.
Fig. 3 is the cutaway view after insulating substrate surface forms epoxy resin composite material layer that the technical program embodiment provides.
Main element symbol description
Coverlay 100
Insulated base material layer 110
First surface 111
Second surface 112
Epoxy resin composite material layer 120
3rd surface 121
Glue-line 130
Embodiment
Below in conjunction with embodiment, coverlay with electromagnetic shielding action that the technical program provides and preparation method thereof is further described in detail.
Refer to Fig. 1, the technical program provides a kind of coverlay 100, and it comprises the insulated base material layer 110, epoxy resin composite material layer 120 and the glue-line 130 that stack gradually.
Insulated base material layer 110 for load-carrying ring epoxy resin composite material layer 120, and plays the effect of electric insulation.In the present embodiment, the material of insulated base material layer 110 is polyimides.The thickness of insulated base material layer 110 can set according to actual needs, and its thickness can be 10 microns to 50 microns, is preferably 25 microns.
Epoxy resin composite material layer 120 is for playing electromagnetic shielding action.The power of the electromagnetic interference that the thickness of epoxy resin composite material layer 120 can shield according to actual needs sets.The thickness of epoxy resin composite material layer 120 is about 2 microns to 20 microns, is preferably 3 microns.Epoxy resin composite material in epoxy resin composite material layer 120 comprises the epoxy resin of end carboxyl polymer modification, carbon nano-tube, inorganic dispersion, curing agent, catalyst, solvent and defoamer.
The epoxy resin of described end carboxyl polymer modification is the product after epoxy resin and end carboxyl polymer generation copolymerization, namely the carboxyl of the epoxy radicals of epoxy resin end and the end of end carboxyl polymer reacts and generates an ester group, thus obtains the polymer of the repetitive comprising epoxy resin repetitive alternately and end carboxyl polymer.Wherein, epoxy resin can be bisphenol A type epoxy resin, and end carboxyl polymer can be liquid polybutadiene acrylonitrile (CTBN).In the present embodiment, the epoxy resin of the employing epoxide equivalent before unmodified is 180 to 195, and be preferably 188, the oxygen equivalent of going back of the epoxy resin that carboxyl polymer is modified is 323 to 352, is preferably 337.The mass percent of epoxy resin in epoxy resin composite material of end carboxyl polymer modification is about 55% to 65%, is preferably about 60%.
Carbon nano-tube is as electric conducting material, and it is dispersed in the epoxy resin of end carboxyl polymer modification, to play electromagnetic shielding action.The shared in the composite mass percent of carbon nano-tube is 4.6% to 16%.The electric conductivity that in composite material, how much content of carbon nano-tube can obtain composite material is according to actual needs determined.In epoxy resin composite material, the content of carbon nano-tube is more, and the resistance of epoxy resin composite material is less, and in composite material, the content of carbon nano-tube is fewer, and the resistance of epoxy resin composite material is larger.
Inorganic dispersion is used for dispersing Nano carbon tubes, can be uniformly distributed in epoxy resin composite material to make carbon nano-tube.Described inorganic dispersion is nanoclay or nano mica powder.Described nanoclay is the phyllosilicate of 2: 1, and it is specifically as follows montmorillonite, and (Montmorillonite, molecular formula is M
x(Al
4-xmg
x) Si
8o
20(OH)
4), (Hectorite, molecular formula is M to hectorite
x(Mg
6-xli
x) Si
8o
20(OH)
4) or saponite (Saponite, molecular formula is M
xmg
6(Si
8-xal
x) O
20(OH)
4) etc.Wherein, carbon nano-tube is 8 to 12 to 1 with the mass ratio of inorganic dispersion.
Described curing agent is used for playing induration to composite material.In the present embodiment, the curing agent of employing is dicyandiamide (Dicyandiamine), and described curing agent is about 5% in the mass percent shared by epoxy resin composite material.The consumption of curing agent should be corresponding with the epoxy resin of end carboxyl polymer modification, and wherein the epoxy resin of end carboxyl polymer modification is about 13 to 14 to 1 with the mass ratio of curing agent.
Described catalyst is 2-undecyl imidazole (2-Undecylimidazole), and the content of catalyst is mutually corresponding with the content of the epoxy resin of end carboxyl polymer modification.The mass percentage of catalyst shared by epoxy resin composite material is about 0.5% to 1%, is preferably 0.65%.Described solvent is diethylene glycol ether acetate alone (Diethylene glycolmonoethyl ether acetate), and the content of described solvent in epoxy resin composite material is about 20% to 25%, is preferably 24%.This solvent for dissolving other components above-mentioned, to form uniform liquid dispersed system.Described defoamer is for eliminating the foam in above-mentioned epoxy resin composite material, and the mass percent of described defoamer in epoxy resin composite material is about 2%.Described defoamer can be the 2183H defoamer that commercially available Taiwan Chun Zheng company produces.
Preferably, in epoxy resin composite material, the mass percentage of the epoxy resin of end carboxyl polymer modification is about 60.3%, the mass percentage of carbon nano-tube is about 7.8%, the mass percentage of inorganic dispersion is about 0.6%, the mass percentage of curing agent is about 4.5%, the mass percentage of catalyst is about 0.65%, and the mass percentage of solvent is about 24.3%, and the mass percentage of defoamer is about 1.85%.
Glue-line 130 is for fitting in the surface of circuit board by coverlay 100.In the present embodiment, the material that glue-line 130 adopts is thermosetting epoxy resin glue.The thickness of glue-line 130 is about 8 to 15 microns, is preferably 12 microns.
The technical program also provide a kind of described in there is the manufacture method of the coverlay 100 of electromagnetic shielding action, described in there is the coverlay 100 of electromagnetic shielding action manufacture method comprise the steps:
The first step, makes epoxy resin composite material.
Epoxy resin composite material described in the present embodiment can be adopted and make with the following method:
First, adopt end carboxyl polymer modification epoxy resin to obtain the epoxy resin of end carboxyl polymer modification.
End carboxyl polymer and epoxy resin are positioned over and are jointly positioned in reaction vessel, and to maintain reaction temperature be 120 degrees Celsius, under the condition stirred, react about 3 hours, thus epoxy resin after obtaining end carboxyl polymer modification.In the present embodiment, the epoxy resin of employing is bisphenol A type epoxy resin, and its epoxide equivalent is 188.The end carboxyl polymer adopted can be liquid polybutadiene acrylonitrile (CTBN), and the epoxide equivalent of the modified epoxide resin obtained after reaction is 337.Through above-mentioned reaction, an epoxy radicals of epoxy resin end and a carboxyl of end carboxyl polymer ends be combined with each other, and remove the water of a molecule, thus obtain an ester group.Thus compared to not carrying out the epoxy resin of modification, modified epoxy resin has good flexibility.Certainly, the epoxy resin of employing is not limited to the bisphenol A type epoxy resin that the present embodiment provides, and it also can be the epoxy resin of other types.The end carboxyl polymer adopted also is not limited to the liquid polybutadiene acrylonitrile provided in the present embodiment, and it also can be the polymer such as terminal carboxyl polyester.
Then, even carbon nanotube is scattered in inorganic dispersion to form finely dispersed CNT (carbon nano-tube) dispersion.
Adopt physics mode by carbon nanotube dispersed in inorganic dispersion.Described inorganic dispersion can be layered nanoclay or nano mica powder.In the present embodiment, the inorganic dispersion selected is layered nanoclay.The CNT (carbon nano-tube) of configuration quality than 8 to 1 to 12 to 1 and layered nanoclay, and mixed by the mode stirred or shake, even carbon nanotube is scattered in layered nanoclay.The layered nanoclay adopted can be the phyllosilicate of 2: 1, and it is specifically as follows montmorillonite, hectorite or saponite etc.The carbon nano-tube adopted can be Single Walled Carbon Nanotube, also can be multi-walled carbon nano-tubes.
Finally, the epoxy resin of end carboxyl polymer modification, CNT (carbon nano-tube) dispersion, solvent, curing agent, catalyst and defoamer are carried out mixing and grinding distribution, thus obtain epoxy resin composite material.
In the present embodiment, three drum-type grinding distribution machines are adopted to carry out grinding distribution to described end carboxyl polymer modification epoxy resin, CNT (carbon nano-tube) dispersion, solvent, curing agent, catalyst and defoamer.Above-mentioned end carboxyl polymer modification epoxy resin, CNT (carbon nano-tube) dispersion, solvent, curing agent, catalyst and defoamer are devoted in three drum-type grinding distribution machines according to above-mentioned respective content, start three drum-type grinding distribution machines to carry out grinding distribution, thus solid content in above-mentioned each composition is dispersed in liquid component, thus form finely dispersed epoxy resin composite material.In the present embodiment, in above-mentioned each composition, the mass percentage of the epoxy resin of end carboxyl polymer modification is about 60.3%, the mass percentage of carbon nano-tube is about 7.8%, the mass percentage of inorganic dispersion is about 0.6%, the mass percentage of curing agent is about 4.5%, the mass percentage of catalyst is about 0.65%, and the mass percentage of solvent is about 24.3%, and the mass percentage of defoamer is about 1.85%.
In order to obtain the epoxy resin composite material of different surfaces resistivity, when can be fed intake by change, the consumption of CNT (carbon nano-tube) dispersion controls.The mass percent accounting for composite material when carbon nano-tube is between 4.6% to 16%, and epoxy resin composite material surface resistivity constant interval is about between 100,000 ohm to ten ohm.Wherein, in epoxy resin composite material, the content of carbon nano-tube is larger, and the surface resistivity that epoxy resin meets material is less.
By the epoxy resin composite material that described method makes, its viscosity can reach 70000 centipoises, and outward appearance presents black, faint reflective.Under microscope amplifies 100 times of observations, without hole.And there is good attachment characteristic and soldering property, and can the corrosion of acid and alkali resistance and solvent.When temperature is 25 degrees Celsius, mass percentage be 10% hydrochloric acid or mass percentage be in the sodium hydroxide solution of 10% soak 0.5 hour, all without peeling phenomenon.Soak in acetone after 17 hours and carry out hundred lattice attachment tests, also without peeling phenomenon.
Refer to Fig. 2, second step, insulated base material layer 110 is provided, and described epoxy resin composite material is coated the first surface 111 of insulated base material layer 110, to form epoxy resin composite material layer 120.
Insulated base material layer 110 is one deck insulating substrate film, and it can be made up of polyimides (PI).The thickness of insulated base material layer 110 is 10 microns to 50 microns.Insulated base material layer 110 has relative first surface 111 and second surface 112.
Refer to Fig. 3, the 3rd step, described epoxy resin composite material is coated the first surface 111 of insulated base material layer 110, to form epoxy resin composite material layer 120.
In the present embodiment, slit type coater is adopted the epoxy resin composite material of liquid state to be coated the first surface 111 of insulated base material layer 110, to form epoxy resin composite material layer 120.Owing to adopting slit type coater to be coated with in the present embodiment, the thickness that can control the epoxy resin composite material layer 120 formed meets the demands and coating uniform.In the present embodiment, the thickness of the epoxy resin composite material layer 120 of formation is 2 microns to 20 microns, is preferably 3 to 10 microns.Epoxy resin composite material layer 120 has the 3rd surface 121 away from insulated base material layer 110.
4th step, is coated with to insulated base material layer 110 the epoxy resin composite material layer 120 formed and processes, solidify to make epoxy resin composite material layer 120.
In the present embodiment, it is prebake conditions and maturation process that epoxy resin composite material layer 120 solidifies the method adopted.
Be about 15 minutes in the time continued of epoxy resin composite material layer 120 being carried out to prebake conditions, the temperature kept during prebake conditions is about 80 degrees Celsius.By carrying out prebake conditions process, make the solvent evaporates in epoxy resin composite material layer 120.
When carrying out maturation process to epoxy resin composite material layer 120, the temperature kept during maturation process is about 180 degrees Celsius, and the time continued is about 120 minutes.After maturation process, make to react between the epoxy resin of the end carboxyl polymer modification in epoxy resin composite material layer 120, inorganic dispersion, curing agent, catalyst and defoamer etc., make epoxy resin composite material layer 120 form solid-state membrane structure.Be understandable that, duration and the temperature of carrying out prebake conditions and slaking can be determined according to the thickness of the epoxy resin composite material layer 120 of reality, when epoxy resin composite material layer 120 thickness is larger, the time proper extension of process or temperature suitably can be heightened, and when epoxy resin composite material layer 120 thickness is less, the time of process suitably can be shortened or temperature suitably reduces, to ensure that epoxy resin composite material layer 120 can form solid film-shaped structure.
See also Fig. 3 and Fig. 1, the 5th step, the 3rd surface 121 of epoxy resin composite material layer 120 forms glue-line 130.
In the present embodiment, slit type coater is adopted the glue line material of liquid state to be coated the surface of epoxy resin composite material layer 120.The liquid glue layer material adopted is thermosetting epoxy resin glue.The thickness controlling the glue-line 130 formed is 5 to 8 microns.
After coating forms glue-line 130, can further include the step that the glue-line 130 formed is toasted, make glue-line 130 semi-cured state formed, to facilitate storage and the application of the coverlay 100 of formation.In the present embodiment, the time of toasting the glue-line 130 formed is 15 minutes, and the time that baking continues is 100 degrees Celsius.
When the coverlay 100 that making is formed directly is not applied, store under coverlay 100 can being positioned over low temperature environment, the temperature of storage can be approximately 5 degrees Celsius.
The coverlay that the technical program provides, it comprises insulated base material layer and epoxy resin composite material layer, in described epoxy resin composite material layer, there is finely dispersed carbon nano-tube and there is electromagnetic shielding action, described coverlay can directly be fitted in the surface being formed with conducting wire, this coverlay can play the effect by conducting wire and external insulation, also to the effect playing electromagnetic shielding, and the thickness of circuit board can be reduced.The manufacture method of the coverlay that the technical program provides, can simply produce the coverlay with electromagnetic shielding action.
Be understandable that, for the person of ordinary skill of the art, other various corresponding change and distortion can be made by technical conceive according to the present invention, and all these change the protection range that all should belong to the claims in the present invention with distortion.
Claims (8)
1. a coverlay, it comprises the insulated base material layer stacked gradually, epoxy resin composite material layer and glue-line, described epoxy resin composite material layer is between insulated base material layer and glue-line, described epoxy resin composite material layer is made up of epoxy resin composite material, described epoxy resin composite material comprises the acrylonitrile modified bisphenol A type epoxy resin of liquid polybutadiene, carbon nano-tube and inorganic dispersion, described carbon nano-tube is 8 to 12 to 1 with the mass ratio of inorganic dispersion, the mass percent of described carbon nano-tube shared by described epoxy resin composite material is 4.6% to 16%.
2. coverlay as claimed in claim 1, is characterized in that, the acrylonitrile modified mass percent of bisphenol A type epoxy resin in epoxy resin composite material of described liquid polybutadiene is 55% to 65%.
3. coverlay as claimed in claim 1, it is characterized in that, described inorganic dispersion is nanoclay.
4. coverlay as claimed in claim 1, it is characterized in that, described epoxy resin composite material also comprises curing agent, solvent, catalyst and defoamer, and described curing agent is dicyandiamide, described solvent is diethylene glycol ether acetate alone, and described catalyst is 2-undecyl imidazole.
5. coverlay as claimed in claim 1, it is characterized in that, the thickness of described epoxy resin composite material layer is 2 microns to 20 microns, and the thickness of described insulated base material layer is 10 microns to 50 microns, and the thickness of described glue-line is 8 to 15 microns.
6. a coverlay manufacture method, comprises step:
Liquid polybutadiene acrylonitrile is adopted to carry out modification to obtain the acrylonitrile modified bisphenol A type epoxy resin of liquid polybutadiene to bisphenol A type epoxy resin;
Even carbon nanotube be scattered in inorganic dispersion, to obtain nanotube dispersion, described carbon nano-tube is 8 to 12 to 1 with the mass ratio of inorganic dispersion;
Bisphenol A type epoxy resin acrylonitrile modified for described liquid polybutadiene and nanotube dispersion are carried out mixing and grinding distribution, to obtain epoxy resin composite material;
Insulated base material layer is provided;
The surface described epoxy resin composite material being coated insulated base material layer forms epoxy resin composite material layer;
By described epoxy resin composite material layer solidification; And
The epoxy resin composite material layer of solidification forms glue-line.
7. coverlay manufacture method as claimed in claim 6, is characterized in that, described epoxy resin composite material adopts slit type coater to coat a surface of insulated base material layer, and the thickness of epoxy resin composite material layer is 2 microns to 20 microns.
8. coverlay manufacture method as claimed in claim 6, it is characterized in that, adopt prebake conditions and maturation process that described epoxy resin composite material layer is solidified to described epoxy resin composite material layer, after coating forms glue-line, also toast to make its semi-solid preparation to described glue-line.
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| CN201010257292.9A CN102378561B (en) | 2010-08-19 | 2010-08-19 | Covering membrance with electromagnetic shielding function and manufacturing method of covering membrance |
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| CN102378561B true CN102378561B (en) | 2015-05-20 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102673070B (en) * | 2012-05-24 | 2015-04-22 | 苏州大学 | Asymmetrical layer-shaped resin matrix composite material and preparation method thereof |
| CN105655014A (en) * | 2016-01-22 | 2016-06-08 | 镇江江南电工器材有限公司 | Thermosetting electromagnetic shielding material, manufacturing method thereof and coil framework pipe material manufactured from thermosetting electromagnetic shielding material |
| CN105744818A (en) * | 2016-02-03 | 2016-07-06 | 中电海康集团有限公司 | Flexible magnetic shielding and anti-irradiation film |
| CN105960157A (en) * | 2016-07-06 | 2016-09-21 | 武汉华星光电技术有限公司 | Electromagnetic shielding protection film and FPC (flexible printed circuit) |
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