CN102673047A - Fabricating method of thermal conducting halogen-free binderless copper clad foil - Google Patents
Fabricating method of thermal conducting halogen-free binderless copper clad foil Download PDFInfo
- Publication number
- CN102673047A CN102673047A CN201210168329XA CN201210168329A CN102673047A CN 102673047 A CN102673047 A CN 102673047A CN 201210168329X A CN201210168329X A CN 201210168329XA CN 201210168329 A CN201210168329 A CN 201210168329A CN 102673047 A CN102673047 A CN 102673047A
- Authority
- CN
- China
- Prior art keywords
- copper foil
- thermal conductivity
- hours
- halogen
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses and provides a fabricating method of a thermal conducting halogen-free binderless copper clad foil. The method mainly comprises the following steps of enabling aromatic diamine to react with aromatic dianhydride, adding different thermal conducting fillers with proper amount to the reactants, and then performing polyreaction to produce high temperature resistant polyamic acid; and then coating the polyamic acid on a copper foil, carrying out high temperature cyclization to form polymide with excellent performance on the copper foil surface, thereby obtaining the halogen-free plastic-free covering copper plate with excellent heat conducting performance. The copper foil produced by the method provided by the invention can ensure the best radiation effect of electron products, and the application performances of electron products are ensured. Moreover, the method can be widely used in the fabrication field of copper clad foils.
Description
Technical field
The present invention relates to a kind of thermal conductivity, no halogen and do not have the preparation method that glue covers Copper Foil.
Background technology
Along with the development of mechanics of communication, the personal electric product is tending towards slimming gradually in recent years.And electronic devices and components and circuit in the electronic product mainly are to be substrate with flexibility coat copper plate FPC, and this requires flexibility coat copper plate FPC circuit granular, densification day by day.Along with the high speed of information processing, can the production great amount of heat in the equipment.Heat dissipation problem in the electronic product equipment causes people's attention and attention.So various heat conduction products arise at the historic moment, like aluminium base copper-clad plate etc.Though electronics heat conduction products such as aluminium base copper-clad plate have in the market been obtained certain effect in the application of electronic product; But; On those high-power jumbo electronic product fuselages; Heat dissipation problem still is distinct issues, and this problem has had influence on the serviceability of electronic product itself even cause electronic product to crash.The copper-clad plate of research and the better excellence of exploitation heat dispersion just seems very necessary under such form.
Summary of the invention
Technical problem to be solved by this invention is the deficiency that overcomes prior art, and the thermal conductivity, no halogen that provides a kind of making to have high-termal conductivity does not have the preparation method that glue covers Copper Foil.
The technical scheme that the present invention adopted is: the present invention is that a kind of thermal conductivity, no halogen does not have the preparation method that glue covers Copper Foil, and this method may further comprise the steps:
(1) in the container that is loaded with aprotic polar solvent, adds a certain amount of heat filling, and on dispersion machine, be uniformly dispersed, obtain heat filling solution;
(2) taking by weighing the certain amount of diamine monomer is dissolved in the aprotic polar solvent; Under the state of high-speed stirred, add the heat filling solution that obtains in the step (1) and stirred 1.5～2.5 hours; Adding and the equimolar dianhydride monomer of said diamine monomer also stirred 2.5～3.5 hours; Obtain polyamic acid solution, the apparent viscosity of said polyamic acid solution is 18000～20000cps;
(3) Copper Foil is laid on the coating machine; On said copper foil surface, apply the polyamic acid solution that one deck above-mentioned steps (2) makes equably with special-purpose scraper; Put into oven for baking a period of time to coated Copper Foil then, take out and place a period of time;
(4) put into the baking box that is full of nitrogen to the Copper Foil of handling through above-mentioned steps (3) and carry out the imidization processing, the thermal conductivity, no halogen that obtains single face does not at last have glue and covers Copper Foil.
Said heat filling is the mixture of boron nitride or aluminium oxide or boron nitride and aluminium oxide.
Aprotic polar solvent in said step (1) and step (2) is dimethyl formamide, dimethylacetylamide, N-methyl pyrrolidone or dimethyl sulfoxide (DMSO).
Imidization processing procedure in the said step (4) is: under the room temperature situation, in 30 minutes, be warming up to 170 ℃, constant temperature 2 hours was warming up to 360 ℃ then in 2 hours, and constant temperature 10 minutes was cooled to room temperature at last in 2 hours.
In said step (1), said aprotic polar solvent and the jitter time of said heat filling on dispersion machine are 6 hours.
In the said step (2), having added the mixing time that stirs behind the heat filling is 2 hours, is 3 hours adding the mixing time that stirs behind the dianhydride monomer.
In said step (3), the time of putting into the Copper Foil that coats oven for baking is 5 minutes, and the temperature of baking box remains on 180 ℃.
In said step (1), when in container, adding aprotic polar solvent, add some beades.
The invention has the beneficial effects as follows: because the present invention adds equimolar diamine monomer and dianhydride monomer in the aprotic polar solvent; Add the superpolyamide acid solution that a certain proportion of heat filling makes it to obtain to have high-termal conductivity; Utilize this solution to carry out Copper Foil then and smear processing, after solvent was removed in baking, hot imidization was handled the last copolyimide that forms heat conduction under certain high temperature; It has high adhesion force, makes it to strengthen with the Copper Foil adhesion and have high-termal conductivity; So the Halogen that the inventive method is made does not have the glue Copper Foil and has high-termal conductivity, can guarantee that in application the radiating effect of electronic product reaches best, guaranteed the application performance of electronic product.
Description of drawings
Fig. 1 is a flow chart of the present invention.
The specific embodiment
The present invention as shown in Figure 1 is that a kind of thermal conductivity, no halogen does not have the preparation method that glue covers Copper Foil, and this method may further comprise the steps, and is specially:
(1) in the container that is loaded with aprotic polar solvent, add a certain amount of heat filling, add the bead of some quantity simultaneously, and on dispersion machine, be uniformly dispersed, jitter time is 6 hours, obtains the heat filling solution for standby.Wherein, said aprotic polar solvent is dimethyl formamide, dimethylacetylamide, N-methyl pyrrolidone or dimethyl sulfoxide (DMSO).Said heat filling is the mixture of boron nitride or aluminium oxide or boron nitride and aluminium oxide.
(2) taking by weighing the certain amount of diamine monomer is dissolved in the aprotic polar solvent; Under the state of high-speed stirred, add the heat filling solution that obtains in the step (1) and stirred 1.5～2.5 hours; Be specially 2 hours, adding and the equimolar dianhydride monomer of said diamine monomer also stirred 2.5～3.5 hours, were specially 3 hours; Obtain polyamic acid solution, the apparent viscosity of said polyamic acid solution is 18000～20000cps.
(3) Copper Foil is laid on the hand coatings machine; On said copper foil surface, apply the polyamic acid solution that one deck above-mentioned steps (2) makes equably with special-purpose scraper; Put into coated Copper Foil 5 fens clock times of oven for baking of 180 ℃ then; Take out and place a period of time, dry until said copper foil surface.
(4) be fixed on the Copper Foil of handling through above-mentioned steps (3) with high temperature gummed tape and put into the high temperature baking box that is full of nitrogen on the corrosion resistant plate and carry out imidization and handle, the thermal conductivity, no halogen that obtains single face does not at last have glue and covers Copper Foil.Said imidization process is: under the room temperature situation, in 30 minutes, be warming up to 170 ℃, constant temperature 2 hours was warming up to 360 ℃ then in 2 hours, and constant temperature 10 minutes was cooled to room temperature at last in 2 hours.Practical implementation of the present invention is following:
The concrete specification requirement of covering Copper Foil that present embodiment is made is: polyimides thickness (PI thickness) is 13 ± 3um (micron), copper thickness 12 um (micron), peel strength >=0.8 N/mm; Soldering resistance is good, and dimensional stability is good, and chemical-resistant is good; Surface resistivity >=1.0*1013 Ω; Specific insulation >=1.0*1015 Ω .cm, induction motor >=1.0*1011 Ω, shelf life of products 12 months.
Subordinate list 1 is the tables of data of the content (BN content) of heat filling to the influence of sheet material key property, and by knowing in the subordinate list 1, along with the increase of heat filling, peel strength descends but all greater than 1.0N/mm, satisfies industry requirement; To size impact is little but to influence its crimpness bigger; Modulus increases, and hot strength and percentage elongation have all reduced, and it is crisp slightly that PI (polyimides) becomes.
Subordinate list 1
Subordinate list 2 is the content (BN content) of heat filling data subordinate lists to the influence of sheet material heat conducting rate, can know by shown in the subordinate list 2, along with the increase of heat filling; Thermal conductivity increases gradually; When especially addition was raised to 40% from 30%, its thermal conductivity ascensional range was very big, but when the boron nitride of addition 40%; Dispersion effect is relatively poor and price is more expensive, so adopt the heat filling of mixed type to remedy dispersiveness.
Subordinate list 2
Subordinate list 3 is to adopt the data subordinate list of different Heat Conduction Materials to the influence of thermal conductivity, can know that by shown in the subordinate list 3 mixing of heat filling is used and the heat-conducting effect that also can reach single boron nitride with the particle diameter of different sizes, and cost is more low.
Subordinate list 3
The present invention can be widely used in covering the making field of Copper Foil.
Claims (8)
1. a thermal conductivity, no halogen does not have the preparation method that glue covers Copper Foil, it is characterized in that, this method may further comprise the steps:
(1) in the container that is loaded with aprotic polar solvent, adds a certain amount of heat filling, and on dispersion machine, be uniformly dispersed, obtain heat filling solution;
(2) taking by weighing the certain amount of diamine monomer is dissolved in the aprotic polar solvent; Under the state of high-speed stirred, add the heat filling solution that obtains in the step (1) and stirred 1.5～2.5 hours; Adding and the equimolar dianhydride monomer of said diamine monomer also stirred 2.5～3.5 hours; Obtain polyamic acid solution, the apparent viscosity of said polyamic acid solution is 18000～20000cps;
(3) Copper Foil is laid on the coating machine; On said copper foil surface, apply the polyamic acid solution that one deck above-mentioned steps (2) makes equably with special-purpose scraper; Put into oven for baking a period of time to coated Copper Foil then, take out and place a period of time;
(4) put into the baking box that is full of nitrogen to the Copper Foil of handling through above-mentioned steps (3) and carry out the imidization processing, the thermal conductivity, no halogen that obtains single face does not at last have glue and covers Copper Foil.
2. thermal conductivity, no halogen according to claim 1 does not have the preparation method that glue covers Copper Foil, it is characterized in that: said heat filling is the mixture of boron nitride or aluminium oxide or boron nitride and aluminium oxide.
3. thermal conductivity, no halogen according to claim 1 does not have the preparation method that glue covers Copper Foil, it is characterized in that: the aprotic polar solvent in said step (1) and step (2) is dimethyl formamide, dimethylacetylamide, N-methyl pyrrolidone or dimethyl sulfoxide (DMSO).
4. thermal conductivity, no halogen according to claim 1 does not have the preparation method that glue covers Copper Foil; It is characterized in that the imidization processing procedure in the said step (4) is: under the room temperature situation, in 30 minutes, be warming up to 170 ℃; Constant temperature 2 hours; In 2 hours, be warming up to 360 ℃ then, constant temperature 10 minutes was cooled to room temperature at last in 2 hours.
5. thermal conductivity, no halogen according to claim 1 does not have the preparation method that glue covers Copper Foil, it is characterized in that: in said step (1), said aprotic polar solvent and the jitter time of said heat filling on dispersion machine are 6 hours.
6. thermal conductivity, no halogen according to claim 1 does not have the preparation method that glue covers Copper Foil; It is characterized in that: in the said step (2); Having added the mixing time that stirs behind the heat filling is 2 hours, is 3 hours adding the mixing time that stirs behind the dianhydride monomer.
7. thermal conductivity, no halogen according to claim 1 does not have the production method that glue covers Copper Foil, it is characterized in that: in said step (3), the time of putting into the Copper Foil that coats oven for baking is 5 minutes, and the temperature of baking box remains on 180 ℃.
8. thermal conductivity, no halogen according to claim 1 does not have the preparation method that glue covers Copper Foil, it is characterized in that: in said step (1), when in container, adding aprotic polar solvent, add some beades.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210168329XA CN102673047A (en) | 2012-05-28 | 2012-05-28 | Fabricating method of thermal conducting halogen-free binderless copper clad foil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210168329XA CN102673047A (en) | 2012-05-28 | 2012-05-28 | Fabricating method of thermal conducting halogen-free binderless copper clad foil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102673047A true CN102673047A (en) | 2012-09-19 |
Family
ID=46805908
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210168329XA Pending CN102673047A (en) | 2012-05-28 | 2012-05-28 | Fabricating method of thermal conducting halogen-free binderless copper clad foil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102673047A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104149472A (en) * | 2014-08-04 | 2014-11-19 | 江汉大学 | Preparation method for size-stable glue-free flexible copper-clad plate |
| CN104228211A (en) * | 2014-09-29 | 2014-12-24 | 王定锋 | Adhesive-free polyimide copper-clad plate, and manufacturing method and application thereof |
| CN106380844A (en) * | 2016-10-14 | 2017-02-08 | 黑龙江科技大学 | Preparation method of boron nitride and aluminum nitride co-doped high-heat-conduction and high-insulation polyimide composite thin film |
| CN106380845A (en) * | 2016-10-14 | 2017-02-08 | 黑龙江科技大学 | Preparation method of laminar-boron-nitride/spherical-aluminum-oxide-codoped high-performance sandwich-structure polyimide layer composite film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1672008A1 (en) * | 2004-12-15 | 2006-06-21 | E.I.Du pont de nemours and company | Thermally conductive polyimide film composites having high mechanical elongation useful as a heat conducting portion of an electronic device |
| CN101157077A (en) * | 2007-09-18 | 2008-04-09 | 湖北省化学研究院 | A preparation method of gum-free flexible copper-coating plate |
| US20110165410A1 (en) * | 2008-09-08 | 2011-07-07 | Eijiro Aoyagi | Highly heat conductive polyimide film, highly heat conductive metal-clad laminate, and method for producing the same |
| CN102453325A (en) * | 2010-10-22 | 2012-05-16 | 东丽纤维研究所（中国）有限公司 | Preparation method of polyimide composite material with high heat conductivity |
-
2012
- 2012-05-28 CN CN201210168329XA patent/CN102673047A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1672008A1 (en) * | 2004-12-15 | 2006-06-21 | E.I.Du pont de nemours and company | Thermally conductive polyimide film composites having high mechanical elongation useful as a heat conducting portion of an electronic device |
| CN101157077A (en) * | 2007-09-18 | 2008-04-09 | 湖北省化学研究院 | A preparation method of gum-free flexible copper-coating plate |
| US20110165410A1 (en) * | 2008-09-08 | 2011-07-07 | Eijiro Aoyagi | Highly heat conductive polyimide film, highly heat conductive metal-clad laminate, and method for producing the same |
| CN102453325A (en) * | 2010-10-22 | 2012-05-16 | 东丽纤维研究所（中国）有限公司 | Preparation method of polyimide composite material with high heat conductivity |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104149472A (en) * | 2014-08-04 | 2014-11-19 | 江汉大学 | Preparation method for size-stable glue-free flexible copper-clad plate |
| CN104228211A (en) * | 2014-09-29 | 2014-12-24 | 王定锋 | Adhesive-free polyimide copper-clad plate, and manufacturing method and application thereof |
| CN104228211B (en) * | 2014-09-29 | 2017-05-17 | 王定锋 | Adhesive-free polyimide copper-clad plate, and manufacturing method and application thereof |
| CN106380844A (en) * | 2016-10-14 | 2017-02-08 | 黑龙江科技大学 | Preparation method of boron nitride and aluminum nitride co-doped high-heat-conduction and high-insulation polyimide composite thin film |
| CN106380845A (en) * | 2016-10-14 | 2017-02-08 | 黑龙江科技大学 | Preparation method of laminar-boron-nitride/spherical-aluminum-oxide-codoped high-performance sandwich-structure polyimide layer composite film |
| CN106380845B (en) * | 2016-10-14 | 2018-04-24 | 黑龙江科技大学 | A kind of preparation method of the high-performance sandwich structure polyimide layer laminated film of layered nitride boron and spherical alumina codope |
| CN106380844B (en) * | 2016-10-14 | 2018-04-24 | 黑龙江科技大学 | A kind of preparation method of the high dielectric polyimide laminated film of the high heat conduction of boron nitride and aluminium nitride codope |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI510529B (en) | Polyimide film, method for manufacturing the same and polyimide film laminate including the same | |
| JP6036809B2 (en) | Method for producing polyimide film and polyimide film | |
| TWI609942B (en) | Binder composition with high frequency characteristics and use thereof | |
| JP5665846B2 (en) | Thermally conductive polyimide film and thermal conductive laminate using the same | |
| TW201000306A (en) | Laminate for flexible board and heat conductive polyimide film | |
| WO2010027070A1 (en) | Highly heat conductive polyimide film, highly heat conductive metal-clad laminate and method for producing same | |
| JP2006169533A (en) | Heat conductive polyimide film composite material having large mechanical strength and useful as heat conductive part of electronic device | |
| CN106496611A (en) | A kind of preparation method of high heat conduction Kapton | |
| CN102361753A (en) | Novel ductile metal foil laminate and method for producing the same | |
| CN109808259A (en) | A kind of high frequency double face copper and the preparation method and application thereof | |
| CN102673047A (en) | Fabricating method of thermal conducting halogen-free binderless copper clad foil | |
| CN102964948B (en) | A kind of thermofixation heat-dissipation paint and preparation method thereof | |
| CN105086659B (en) | The preparation method of high heat conducting nano carbon copper foil | |
| TW201927970A (en) | Conductive adhesive composition and isotropic conductive film formed therefrom capable of exhibiting uniform electrical conductivity | |
| JP2010126725A (en) | Paste composition for forming heat-resistant electroconductive pattern on base plate | |
| CN106604535A (en) | Thermal conductive non-plastic single-sided flexible copper clad laminate and the manufacturing method thereof | |
| CN114148048A (en) | High-heat-dissipation aluminum-based copper-clad plate and preparation method thereof | |
| CN104817953A (en) | Insulating heat-dissipating coating and preparation method of same | |
| WO2021068164A1 (en) | Compositely structured insulating film and preparation method therefor | |
| JP4606191B2 (en) | Manufacturing method of laminate | |
| CN107599588A (en) | A kind of preparation method of polyimides flexibility coat copper plate | |
| CN104149472B (en) | The preparation method of a kind of dimensional stability non-gel flexible copper-clad plate | |
| CN103050616B (en) | Composition heat conducting copper foil base plate | |
| JP4693378B2 (en) | Laminated body and method for producing the same | |
| JP4798986B2 (en) | Laminated body and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120919 |