CN102166853B - Manufacturing method of two-layer single-sided flexible copper clad laminate - Google Patents
Manufacturing method of two-layer single-sided flexible copper clad laminate Download PDFInfo
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Abstract
The invention relates to a manufacturing method of a two-layer single-sided flexible copper clad laminate. The method comprises the following steps: providing copper foil and preparing a polyamic acid solution with filling materials and a polyamic acid solution without filling materials; coating the copper foil with the polyamic acid solution without filling materials and pre-baking the copper foil at a temperature of 100 to 200 DEG C to form a polyamic acid coating without filling materials; coating the polyamic acid coating without filling materials with the polyamic acid solution with filling materials and pre-baking at a temperature of 100 to 200 DEG C to form a polyamic acid coating with filling materials; placing the copper foil successively coated with the polyamic acid coating without filling materials and the polyamic acid coating with filling materials into a nitrogen high-temperature baking oven for high-temperature imidization and finally to obtain the two-layer single-sided flexible copper clad laminate. The invention is simple in operation. The two-layer single-sided flexible copper clad laminate prepared by two times of coating is flat and smooth instead of warping before and after etching.
Description
Technical field
The present invention relates to the copper-clad plate field, particularly a kind of preparation method of two layers of method single-face flexibility copper-clad board.
Background technology
Flexible printed-circuit board has been widely used in the consumption electronic products such as notebook computer, mobile phone, personal digital assistant and digital camera, because improving constantly of electron trade specification requirement, it is compact that consumption electronic products move towards just fast, day by day requires corresponding flexibility coat copper plate lighter and thinner and have high-fire resistance and a high reliability.Two-layer method flexibility coat copper plate is owing to adopting all very good polyimide resins and obtained fast development in recent years of mechanical property, electrical property and heat resistance.
The problem of bow warping after the etching easily occurs in two layers of method single-face flexibility copper-clad board in application process, affect the passing rate of processing of FPC.And when being applied in the demixing plate field, the intermembranous problem that fits together mutually and can't separate of PI easily occurs at demixing zone behind the pressing coverlay, affect the resistance to deflection of demixing zone circuit.
At Chinese patent: among the CN 1733473A, set forth and repeatedly be coated with the method for preparing two-layer method flexibility coat copper plate, namely be coated with first one deck high resiliency resin bed, be coated with again one deck low thermal coefficient of expansion resin bed, can selectively be coated with again on this basis one deck high resiliency resin bed close with the ground floor resin property.And in order to solve the problem of copper-clad plate warpage after the etching, just be to be coated with the 3rd layer can obtain smooth copper-clad plate to form symmetrical structure.And this patent does not relate to the problem that the mutual applying of demixing zone PI film can't layering that how to solve yet.
In TOHKEMY 2001-177201 communique, proposed in the polyimides of high glass-transition temperature, low hotline expansion coefficient, to sneak into the flexibility coat copper plate of making at the additive of temperature required lower plasticizing.The plastication of additive has reduced internal stress, thereby has improved curling problem, yet but exists employed additive in heat treated, can disperse the problem that pollutes in stove.
Find through further investigation, the intermembranous reason that is easily fit together mutually by pressing of demixing zone PI is that PI film surface is too smooth, causes easy absorption to stick together, and the surface roughness that increases the PI film can head it off.In prescription, add the roughness that filler can increase the PI film, but also can reduce the breakdown voltage resistant of PI film simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of two layers of method single-face flexibility copper-clad board, be simple and easy to implement, all very smooth before and after prepared two layers of method single-face flexibility copper-clad board etching, can warpage.
For achieving the above object, the invention provides a kind of preparation method of two layers of method single-face flexibility copper-clad board, comprise that step is as follows:
Step 1, provide Copper Foil, and preparation contains the polyamic acid solution of filler and does not contain the polyamic acid solution of filler;
Step 2, do not contain the polyamic acid solution of filler in Copper Foil coating, afterwards 100-200 ℃ of lower prebake conditions, form the polyamic acid coating that does not contain filler;
Step 4, will be coated with successively the polyamic acid coating that does not contain filler and the Copper Foil of the polyamic acid coating that contains filler places the nitrogen high temperature oven to carry out the high temperature imidization, namely make two layers of method single-face flexibility copper-clad board.
Form the polyimide layer that does not contain filler after the described polyamic acid coating high-temp imidization that does not contain filler, this thermal linear expansion coefficient that does not contain the polyimide layer of filler is 10-20 * 10
-6/ K, glass transition temperature are 330-370 ℃; Form the polyimide layer that contains filler after the described polyamic acid coating high-temp imidization that contains filler, this thermal linear expansion coefficient of polyimide layer that contains filler is than the large 4-10 of thermal linear expansion coefficient of the polyimide layer that does not contain filler * 10
-6/ K, glass transition temperature are 300-350 ℃.
To account for the mass percent of the total solid component of polyamic acid solution be 3-20% to the content of filler in the described polyamic acid solution that contains filler.
Described filler is one or more in aluminium hydroxide, silica, aluminium oxide, magnesium hydroxide, mica powder, silicon powder, talcum powder, kaolin, calcium carbonate, the talcum powder etc.
Described Copper Foil is electrolytic copper foil or rolled copper foil, and thickness is 9-70 μ m.
The invention provides the preparation method of another kind of two layers of method single-face flexibility copper-clad board, comprise that step is as follows:
Step 1, provide Copper Foil, and preparation contains the polyamic acid solution of filler and does not contain the polyamic acid solution of filler;
Step 2, coating does not contain the polyamic acid solution of filler and contains the polyamic acid solution of filler successively on Copper Foil;
Step 4, will be coated with the polyamic acid coating that does not contain filler and the Copper Foil of the polyamic acid coating that contains filler places the nitrogen high temperature oven to carry out the high temperature imidization, namely make two layers of method single-face flexibility copper-clad board.
Form the polyimide layer that does not contain filler after the described polyamic acid coating high-temp imidization that does not contain filler, this thermal linear expansion coefficient that does not contain the polyimide layer of filler is 10-20 * 10
-6/ K, glass transition temperature are 330-370 ℃; Form the polyimide layer that contains filler after the described polyamic acid coating high-temp imidization that contains filler, this thermal linear expansion coefficient of polyimide layer that contains filler is than the large 4-10 of thermal linear expansion coefficient of the polyimide layer that does not contain filler * 10
-6/ K, glass transition temperature are 300-350 ℃.
To account for the mass percent of the total solid component of polyamic acid solution be 3-20% to the content of filler in the described polyamic acid solution that contains filler.
Described filler is one or more in aluminium hydroxide, silica, aluminium oxide, magnesium hydroxide, mica powder, silicon powder, talcum powder, kaolin, calcium carbonate, the talcum powder etc.
Described Copper Foil is electrolytic copper foil or rolled copper foil, and thickness is 9-70 μ m.
The invention has the beneficial effects as follows: the preparation method of two layers of method single-face flexibility copper-clad board of the present invention, simple to operate, take twice coating, form respectively the polyamic acid coating that does not contain the polyamic acid coating of filler and contain filler, thereby all very smooth before and after prepared two layers of method single-face flexibility copper-clad board etching, can warpage, and wherein a coating is by the adding of filler, increased the surface roughness of the polyimide layer that forms, the problem that the polyimides interlayer is fitted mutually can not occur behind the pressing coverlay when being applied to demixing plate, and do not contain filler in another polyimide layer, kept the breakdown voltage resistant of overall polyimide layer.
Description of drawings
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail, so that technical scheme of the present invention and other beneficial effects are apparent.
In the accompanying drawing,
Fig. 1 is the preparation method flow chart of two layers of method single-face flexibility copper-clad board of one embodiment of the invention;
Fig. 2 is the preparation method flow chart of two layers of method single-face flexibility copper-clad board of another embodiment of the present invention.
The specific embodiment
The preparation method of two layers of method single-face flexibility copper-clad board of one embodiment of the invention, as shown in Figure 1, it comprises that step is as follows:
Step 1 S1, provide Copper Foil, and preparation contains the polyamic acid solution of filler and does not contain the polyamic acid solution of filler.Described Copper Foil is electrolytic copper foil or rolled copper foil, and thickness is 9-70 μ m; Contain filler in the polyamic acid solution of filler and can be in aluminium hydroxide, silica, aluminium oxide, magnesium hydroxide, mica powder, silicon powder, talcum powder, kaolin, calcium carbonate, the talcum powder etc. one or more.The mass percent that the content of filler accounts for the total solid component of polyamic acid solution is 3-20%, when filer content was too low, the surface roughness of the polyimide layer of preparation was inadequate, when being applied to demixing plate, the polyimides interlayer of demixing zone is easily fitted, and flexural property is descended; And content is when too high, and the mechanical performance of polyimide layer can reduce by a relatively large margin, and flexural property is descended.
Step 2 S2, do not contain the polyamic acid solution of filler in Copper Foil coating, then 100-200 ℃ of lower prebake conditions, make wherein partial solvent volatilization, form the polyamic acid coating that does not contain filler;
Step 4 S4, will be coated with successively the polyamic acid coating that does not contain filler and the Copper Foil of the polyamic acid coating that contains filler places the nitrogen high temperature oven to carry out the high temperature imidization, namely make two layers of method single-face flexibility copper-clad board.Wherein, form polyimides (PI) layer that does not contain filler after the described polyamic acid coating high-temp imidization that does not contain filler, this thermal linear expansion coefficient that does not contain the polyimide layer of filler is 10-20 * 10
- 6/ K, glass transition temperature are 330-370 ℃; Form the polyimide layer that contains filler after the described polyamic acid coating high-temp imidization that contains filler, this thermal linear expansion coefficient of polyimide layer that contains filler is than the large 4-10 of thermal linear expansion coefficient of the polyimide layer that does not contain filler * 10
-6/ K, glass transition temperature is 300-350 ℃, when two layers of method single-face flexibility copper-clad board making of guarantee have good peel strength like this, keep very little size breathing, and utilize the polyimide layer that does not contain filler when lowering the temperature in the imidization process different from the contraction of the polyimide layer that contains filler, guarantee that copper-clad plate before and after etching warpage does not occur, and very smooth.
The preparation method of two layers of method single-face flexibility copper-clad board of another embodiment of the present invention, as shown in Figure 2, it comprises that step is as follows:
Step 1 S1 ', provide Copper Foil, and preparation contains the polyamic acid solution of filler and does not contain the polyamic acid solution of filler.Described Copper Foil is electrolytic copper foil or rolled copper foil, and thickness is 9-70 μ m; Contain filler in the polyamic acid solution of filler and can be in aluminium hydroxide, silica, aluminium oxide, magnesium hydroxide, mica powder, silicon powder, talcum powder, kaolin, calcium carbonate, the talcum powder etc. one or more.The mass percent that the content of filler accounts for the total solid component of polyamic acid solution is 3-20%, when filer content was too low, the surface roughness of the polyimide layer of preparation was inadequate, when being applied to demixing plate, the polyimides interlayer of demixing zone is easily fitted, and flexural property is descended; And content is when too high, and the mechanical performance of polyimide layer can reduce by a relatively large margin, and flexural property is descended.
Step 2 S2 ', coating does not contain the polyamic acid solution of filler and contains the polyamic acid solution of filler successively on Copper Foil.
Step 4 S4 ', will be coated with the polyamic acid coating that does not contain filler and the Copper Foil of the polyamic acid coating that contains filler places the nitrogen high temperature oven to carry out the high temperature imidization, namely make two layers of method single-face flexibility copper-clad board.Wherein, form the polyimide layer that does not contain filler after the described polyamic acid coating high-temp imidization that does not contain filler, this thermal linear expansion coefficient that does not contain the polyimide layer of filler is 10-20 * 10
-6/ K, glass transition temperature are 330-370 ℃; Form the polyimide layer that contains filler after the described polyamic acid coating high-temp imidization that contains filler, this thermal linear expansion coefficient of polyimide layer that contains filler is than the large 4-10 of thermal linear expansion coefficient of the polyimide layer that does not contain filler * 10
-6/ K, glass transition temperature is 300-350 ℃, when two layers of method single-face flexibility copper-clad board making of guarantee have good peel strength like this, keep very little size breathing, and utilize the polyimide layer that does not contain filler when lowering the temperature in the imidization process different from the contraction of the polyimide layer that contains filler, warpage does not occur before and after the copper-clad plate etching, and very smooth.
For the prepared two layers of method single-face flexibility copper-clad board of the preparation method of two layers of above-mentioned method single-face flexibility copper-clad board, survey the crimpness of its peel strength, dimensional stability, mechanical performance, etching front and back, the surface roughness of polyimide layer and the stickiness for preparing the polyimide layer in demixing plate layered district, further give to illustrate in detail and describe such as following embodiment.
Hereby the embodiment of the invention is described in detail as follows, but the present invention is confined to scope of embodiments.
For ease of explanation embodiment, existing synthetic method with polyamic acid solution among the embodiment is described below:
Synthetic (comprise and do not contain filler and contain filler) of polyamic acid solution:
Wherein, 4,4 '-ODA:4,4 '-diaminodiphenyl ether;
PPDA: p-phenylenediamine (PPD);
BPDA: bibenzene tetracarboxylic dianhydride;
PMDA: pyromellitic acid anhydride;
2MZ-A:2,4-diaminourea-6-[2 '-methylimidazole ring-(1 ')]-ethyl-S-triazine;
SiO
2: silica;
The NMP:N-methyl pyrrolidone;
DMAC:N, N '-dimethylacetylamide.
Synthesis example 1:
4 of weighing 6.5058g, 4 '-PPDA of ODA and 16.0058g, in the there-necked flask of 1000ml, be dissolved in while stirring in the mixed solvent of 180g DMAc and 180gNMP, then in the situation that logical nitrogen and stirring, add successively the BPDA of 2MZ-A, 34.3281g of 1.24g and the PMDA of 13.7034g, continue to stir 4 hours, carry out polymerisation, make polyamic acid solution.
Synthesis example 2:
4 of weighing 7.2287g, 4 '-PPDA of ODA and 15.6154g, in the situation that stir, be dissolved in while stirring in the mixed solvent of 180g DMAc and 180gNMP in the there-necked flask of adding 1000ml, behind the dissolve complete, in the situation that logical nitrogen and stirring, the BPDA that adds 52.4447g, continue to stir 4 hours, carry out polymerisation, make polyamic acid solution.
Synthesis example 3:
Weighing 3.99g SiO
2, add in the mixed solvent of 180g NMP and 180gDMAC, disperseed 5 minutes with ultrasonic wave, again this pre-dispersed solution is added in the there-necked flask of 1000ml the PPDA of 4,4 of weighing 7.2287g '-ODA and 15.6154g, in the situation that stir, add in the there-necked flask, behind the dissolve complete, in the situation that logical nitrogen and stirring, the BPDA that adds 52.4447g, continue to stir 4 hours, carry out polymerisation, make SiO
2Content is 5% polyamic acid solution.
Synthesis example 4:
Weighing 8.41g SiO
2, add in the mixed solvent of 180g NMP and 180gDMAC, disperseed 5 minutes with ultrasonic wave, again this pre-dispersed solution is added in the there-necked flask of 1000ml the PPDA of 4,4 of weighing 7.2287g '-ODA and 15.6154g, in the situation that stir, add in the there-necked flask, behind the dissolve complete, in the situation that logical nitrogen and stirring, the BPDA that adds 52.4447g, continue to stir 4 hours, carry out polymerisation, make SiO
2Content is 10% polyamic acid solution.
Synthesis example 5:
Weighing 13.36g SiO
2, add in the mixed solvent of 180g NMP and 180gDMAC, disperseed 5 minutes with ultrasonic wave, again this pre-dispersed solution is added in the there-necked flask of 1000ml the PPDA of 4,4 of weighing 7.2287g '-ODA and 15.6154g, in the situation that stir, add in the there-necked flask, behind the dissolve complete, in the situation that logical nitrogen and stirring, the BPDA that adds 52.4447g, continue to stir 4 hours, carry out polymerisation, make SiO
2Content is 15% polyamic acid solution.
Synthesis example 6:
Weighing 18.93g SiO
2, add in the mixed solvent of 180g NMP and 180gDMAC, disperseed 5 minutes with ultrasonic wave, again this pre-dispersed solution is added in the there-necked flask of 1000ml the PPDA of 4,4 of weighing 7.2287g '-ODA and 15.6154g, in the situation that stir, add in the there-necked flask, behind the dissolve complete, in the situation that logical nitrogen and stirring, the BPDA that adds 52.4447g, continue to stir 4 hours, carry out polymerisation, make SiO
2Content is 20% polyamic acid solution.
Synthesis example 7:
Weighing 4.09g SiO
2, add in the mixed solvent of 180g NMP and 180gDMAC, disperseed 5 minutes with ultrasonic wave, again this pre-dispersed solution is added in the there-necked flask of 1000ml the PPDA of 4,4 of weighing 9.3973g '-ODA and 14.4443g, in the situation that stir, add in the there-necked flask, behind the dissolve complete, in the situation that logical nitrogen and stirring, the BPDA that adds 52.4447g, continue to stir 4 hours, carry out polymerisation, make SiO
2Content is 5% polyamic acid solution.
Synthesis example 8:
Weighing 3.97g SiO
2, add in the mixed solvent of 180g NMP and 180gDMAC, disperseed 5 minutes with ultrasonic wave, again this pre-dispersed solution is added in the there-necked flask of 1000ml the PPDA of 4,4 of weighing 4.3372g '-ODA and 17.177g, in the situation that stir, add in the there-necked flask, behind the dissolve complete, in the situation that logical nitrogen and stirring, the BPDA that adds 52.4447g, continue to stir 4 hours, carry out polymerisation, make SiO
2Content is 5% polyamic acid solution.
Embodiment 1:
The polyamic acid solution that uses synthesis example 1 gained is that the electrolytic copper foil of 12 μ m is coated with at thickness, controlling its thickness is 7 μ m after the imidization, under 100～200 ℃ temperature, carry out prebake conditions, as ground floor coating (the polyamic acid coating that does not contain filler), then the polyamic acid solution with synthesis example 2 gained is coated on the ground floor coating, controlling its thickness is 6 μ m after the imidization, under 100～200 ℃ temperature, carry out prebake conditions, as second layer coating (the polyamic acid coating that contains filler), and then under 360 ℃, carry out the high temperature imidization, make two layers of method single-face flexibility copper-clad board.
Embodiment 2:
Change the used polyamic acid solution of second layer coating into synthesis example 3 prepared polyamic acid solution, all the other processes are with embodiment 1.
Embodiment 3:
Change the used polyamic acid solution of second layer coating into synthesis example 4 prepared polyamic acid solution, all the other processes are with embodiment 1.
Embodiment 4:
Change the used polyamic acid solution of second layer coating into synthesis example 5 prepared polyamic acid solution, all the other processes are with embodiment 1.
Embodiment 5:
Change the used polyamic acid solution of second layer coating into synthesis example 6 prepared polyamic acid solution, all the other processes are with embodiment 1.
Embodiment 6:
Change the used polyamic acid solution of second layer coating into synthesis example 7 prepared polyamic acid solution, all the other processes are with embodiment 1.
Comparative example 1:
Change the used polyamic acid solution of second layer coating into synthesis example 8 prepared polyamic acid solution, all the other processes are with embodiment 1.
Comparative example 2:
Change the used polyamic acid solution of ground floor coating into synthesis example 3 prepared polyamic acid solution, change the used polyamic acid solution of second layer coating into synthesis example 4 prepared polyamic acid solution, all the other processes are with embodiment 1.
The performance of two layers of method single-face flexibility copper-clad board of above each embodiment and comparative example sees Table 1.
The performance of two layers of method single-face flexibility copper-clad board of table 1, each embodiment and comparative example
The method of testing of above characteristic is as follows:
(1), peel strength (PS) is according to IPC-TM-650 2.4.9 method, the peel strength that the test metal level is 90 °.Record data are that less value of peel strength in two faces of dual platen in the table.
(2), dimensional stability: press IPC-TM-650 method 2.2.4 test, wherein "+" expression is expanded, and "-" expression is shunk.
(3), crimpness: material is cut into 250mm * 250mm size, and tiling on the table
(4), tensile strength: press the test of Q/DZAD650 method.
(5), percentage elongation: press the test of Q/DZAD365-2007 method.
(6), PI surface roughness: test with roughness tester.
(7), the stickiness of the polyimide layer of demixing zone: the window of pure glue being opened 5 2cm * 5cm, with the pure glue after windowing the PI face of two layers of method single-face flexibility copper-clad board is pressed to together again, etch away the Copper Foil of both sides, then at both sides pressing coverlay, whether the polyimide layer at watch window place fits.
In sum, the preparation method of two layers of method single-face flexibility copper-clad board of the present invention, simple to operate, take twice coating, form respectively the polyamic acid coating that does not contain the polyamic acid coating of filler and contain filler, thereby all very smooth before and after prepared two layers of method single-face flexibility copper-clad board etching, can warpage, and wherein a coating is by the adding of filler, increased the surface roughness of the polyimide layer that forms, the problem that the polyimides interlayer is fitted mutually can not occur behind the pressing coverlay when being applied to demixing plate, and do not contain filler in another polyimide layer, kept the breakdown voltage resistant of overall polyimide layer.
The above; it only is preferred embodiment of the present invention; for the person of ordinary skill of the art, can make other various corresponding changes and distortion according to technical scheme of the present invention and technical conceive, and all these changes and distortion all should belong to the protection domain of claim of the present invention.
Claims (6)
1. the preparation method of two layers of method single-face flexibility copper-clad board is characterized in that, comprises that step is as follows:
Step 1, provide Copper Foil, and preparation contains the polyamic acid solution of filler and does not contain the polyamic acid solution of filler;
Step 2, do not contain the polyamic acid solution of filler in Copper Foil coating, in 100-200 ℃ of lower prebake conditions, form the polyamic acid coating that does not contain filler;
Step 3, coating contains the polyamic acid solution of filler again on the above-mentioned polyamic acid coating that does not contain filler, in 100-200 ℃ of lower prebake conditions, forms the polyamic acid coating that contains filler;
Step 4, will be coated with successively the polyamic acid coating that does not contain filler and the Copper Foil of the polyamic acid coating that contains filler places the nitrogen high temperature oven to carry out the high temperature imidization, namely make two layers of method single-face flexibility copper-clad board;
Form the polyimide layer that does not contain filler after the described polyamic acid coating high-temp imidization that does not contain filler, this thermal linear expansion coefficient that does not contain the polyimide layer of filler is 10-20 * 10
-6/ K, glass transition temperature are 330-370 ℃; Form the polyimide layer that contains filler after the described polyamic acid coating high-temp imidization that contains filler, this thermal linear expansion coefficient of polyimide layer that contains filler is than the large 4-10 of thermal linear expansion coefficient of the polyimide layer that does not contain filler * 10
-6/ K, glass transition temperature are 300-350 ℃;
To account for the mass percent of the total solid component of polyamic acid solution be 3-20% to the content of filler in the described polyamic acid solution that contains filler.
2. the preparation method of two layers of method single-face flexibility copper-clad board as claimed in claim 1, it is characterized in that, described filler is one or more in aluminium hydroxide, silica, aluminium oxide, magnesium hydroxide, mica powder, silicon powder, talcum powder, kaolin, calcium carbonate, the talcum powder.
3. the preparation method of two layers of method single-face flexibility copper-clad board as claimed in claim 1 is characterized in that, described Copper Foil is electrolytic copper foil or rolled copper foil, and thickness is 9-70 μ m.
4. the preparation method of two layers of method single-face flexibility copper-clad board is characterized in that, comprises that step is as follows:
Step 1, provide Copper Foil, and preparation contains the polyamic acid solution of filler and does not contain the polyamic acid solution of filler;
Step 2, coating does not contain the polyamic acid solution of filler and contains the polyamic acid solution of filler successively on Copper Foil;
Step 3, with the above-mentioned Copper Foil of polyamic acid solution that is coated with the polyamic acid solution that does not contain filler and contains filler 100-200 ℃ of lower prebake conditions, form respectively the polyamic acid coating that does not contain the polyamic acid coating of filler and contain filler;
Step 4, will be coated with the polyamic acid coating that does not contain filler and the Copper Foil of the polyamic acid coating that contains filler places the nitrogen high temperature oven to carry out the high temperature imidization, namely make two layers of method single-face flexibility copper-clad board;
Form the polyimide layer that does not contain filler after the described polyamic acid coating high-temp imidization that does not contain filler, this thermal linear expansion coefficient that does not contain the polyimide layer of filler is 10-20 * 10
-6/ K, glass transition temperature are 330-370 ℃; Form the polyimide layer that contains filler after the described polyamic acid coating high-temp imidization that contains filler, this thermal linear expansion coefficient of polyimide layer that contains filler is than the large 4-10 of thermal linear expansion coefficient of the polyimide layer that does not contain filler * 10
-6/ K, glass transition temperature are 300-350 ℃;
To account for the mass percent of the total solid component of polyamic acid solution be 3-20% to the content of filler in the described polyamic acid solution that contains filler.
5. the preparation method of two layers of method single-face flexibility copper-clad board as claimed in claim 4, it is characterized in that, described filler is one or more in aluminium hydroxide, silica, aluminium oxide, magnesium hydroxide, mica powder, silicon powder, talcum powder, kaolin, calcium carbonate, the talcum powder.
6. the preparation method of two layers of method single-face flexibility copper-clad board as claimed in claim 4 is characterized in that, described Copper Foil is electrolytic copper foil or rolled copper foil, and thickness is 9-70 μ m.
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| CN103419439B (en) * | 2013-08-19 | 2016-04-13 | 陕西生益科技有限公司 | The manufacture method of a kind of low-k CEM-3 copper-clad plate |
| CN104786627A (en) * | 2015-04-17 | 2015-07-22 | 新高电子材料（中山）有限公司 | Polyamideimide double-sided flexible copper-clad plate and manufacture method thereof |
| CN114679837A (en) * | 2020-12-24 | 2022-06-28 | 广东生益科技股份有限公司 | Black glue-free flexible copper-clad plate and preparation method and application thereof |
| CN115612100A (en) * | 2022-09-27 | 2023-01-17 | 杭州福斯特电子材料有限公司 | Polyimide film, flexible metal-clad plate and preparation method thereof |
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