CN102009515A - Two-layer-method double-sided flexible CCL (Copper-Clad Laminate) and manufacture method thereof - Google Patents
Two-layer-method double-sided flexible CCL (Copper-Clad Laminate) and manufacture method thereof Download PDFInfo
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Abstract
The invention relates to a two-layer-method double-sided flexible CCL (Copper-Clad Laminate) and a manufacture method thereof. The manufacture method comprises the following steps of: providing a copper foil and preparing a thermoplastic polyimide resin precursor solution; coating the prepared thermoplastic polyimide resin precursor solution on the copper foil to manufacture a single-sided plate; providing a polyimide film and carrying out surface treatment; and taking two manufactured single-sided plates, respectively sticking the two manufactured single-sided plates to both sides of the polyimide film in the way that the resin coatings on the two manufactured single-sided plates are opposite to each other, and laminating at a high temperature to obtain a two-layer-method double-sided flexible CCL. The two-layer-method double-sided flexible CCL comprises the polyimide film and the single-sided plates which are attached to both sides of the polyimide film, and each single-sided plate comprises a copper foil and a thermoplastic polyimide resin coating coated on the copper foil. The manufacture method of the two-layer-method double-sided flexible CCL only needs coating once, thereby remarkably lowering the complexity and the difficulty of traditional process flows and improving the production efficiency and the yield. The two-layer-method double-sided flexible CCL manufactured by the method has high size stability.
Description
Technical field
The present invention relates to the flexibility coat copper plate field, relate in particular to preparation method and this two layers of method double side flexible copper coated boards of a kind of two layers of method double-faced flexible copper coated foil plate.
Background technology
Flexible printed-circuit board has been widely used in 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, requires corresponding flexibility coat copper plate lighter and thinner and have high-fire resistance and a high reliability day by day.Two-layer method flexibility coat copper plate has obtained to develop fast in recent years owing to adopt mechanical property, electrical property and all very good polyimide resin of hear resistance.
As everyone knows, the employed polyimide resin of two-layer method flexibility coat copper plate is divided into two kinds of thermoset polyimide resin (PI) and thermoplastic polyimide resins (TPI).The thermoset polyimide resin of low thermal coefficient of expansion can make copper-clad plate have good dimensional stability, and has high-fire resistance, but the peel strength of itself and Copper Foil is lower, is difficult to independent use.And the hear resistance of thermoplastic polyimide resin is not so good as thermoset polyimide resin, and thermal coefficient of expansion is also very high, and the copper-clad plate dimensional stability shrinkage factor of making is excessive, but its fusion pressing at high temperature.So existing commercial two layers of method double side flexible copper coated board all adopt the processing method of thermoset polyimide resin and thermoplastic polyimide resin and usefulness, to obtain good dimensional stability and high-peeling strength simultaneously.(the US P 20030012882 of company of Nippon Steel, US P20070149758, CN 1527763A) adopt three rubbing methods to make the two-layer method flexibility coat copper plate method: on Copper Foil, successively to be coated with one deck thermoplastic polyimide resin (TPI), one deck low thermal coefficient of expansion thermoset polyimide resin (PI) and one deck thermoplastic polyimide resin (TPI) continuously, last plays imidization, and the high temperature pressing obtains having concurrently the flexible copper-clad dual platen of good dimensional stability and high-peeling strength.(the US P 20070178323A1 of Zhong Yuan company, US P 20040063900A1, WO 2007083526A1) method of Cai Yonging has two kinds: the first is carried out suitable surface treatment on the Kapton that has prepared, and then at its two sides difference coating thermoplastic polyimide resin (TPI), high temperature pressing again after the imidization obtains the flexible copper-clad dual platen; It two is repeatedly coating thermoplastic polyimides glue and Thermocurable polyimide glues on stainless steel T type band, after baking forms self-supporter, peel off out from just being with again, carry out hot setting separately, be covered with Copper Foil on this multilayer complex films two sides at last, the high temperature pressing obtains flexibility coat copper plate.Mitsui (CN 101151304A) adopts a kind of etching solution of uniqueness, the finished product Kapton is through after the effect of this etching solution, coating thermoplastic polyimides glue thereon again, hot setting together, last and Copper Foil high temperature pressing can obtain and the double face copper of peel strength up to 1.0N/mm-2.0N/mm.Chemistry (the CN1672920A of SHIN-ETSU HANTOTAI, CN1744344A) then adopt another kind of method to make flexibility coat copper plate, it is coated with one deck polyimides glue on Copper Foil, baking is also controlled its not curing fully, and then with the pressing of finished product Kapton, at high temperature handle afterwards again, the polyimides glue of failing to solidify is solidified fully, little molecules such as solvent are wherein then overflowed by Kapton.
And the said method operation is comparatively complicated, is unfavorable for the raising of production efficiency and the raising of production yields.The manufacture method of company of Nippon Steel adopts three coatings, and production efficiency and product yields are all lower; In the manufacture method of Zhong Yuan company, in coating, also need in baking oven, dry behind the thermoplastic polyimide resin and heat treated such as hot setting, this heat treated especially applies the processing meeting of tension force to the non-response deformation of Kapton generation part itself under the high temperature, may cause the dimensional stability of copper-clad plate very great fluctuation process to occur, so must pass through tension force in production process, the precision of each technological parameter such as temperature is controlled and is compensated or eliminate this effect, so the operation of whole processing procedure is many, technology difficulty is big, and potential substandard products risk is also bigger; And the preparation method of the preparation method of Mitsui and clock deep pool chemistry is similar, to carry out the upper and lower surface coating to Kapton equally, promptly be equivalent to carry out twice coating, Kapton will stand the high-temperature process of long period equally, can exert an influence to yields and production efficiency equally; The limitation part of SHIN-ETSU HANTOTAI chemistry preparation method is, because little molecules such as solvent fail to overflow fully before pressing, thus can not prepare dual platen, otherwise little molecule such as solvent is difficult to pass through Copper Foil, causes forming bubble, destroys goods.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of two layers of method double side flexible copper coated board, process is simplified, and enhances productivity and yields, thereby improves property of fine qualities, hear resistance and the dimensional stability of its two layers of method double side flexible copper coated boards that make.
Two layers of method double side flexible copper coated board providing a kind of said method to make are provided, and these two layers of method double side flexible copper coated boards have high-fire resistance and high-dimensional stability.
To achieve these goals, the invention provides a kind of preparation method of two layers of method double side flexible copper coated board, this method comprises the steps:
Step 1, provide Copper Foil, preparation thermoplastic polyimide resin precursor aqueous solution;
Step 3, provide Kapton, carry out surface treatment;
Step 4, get two above-mentioned single sided boards that make, two single sided boards are fitted in relatively respectively with resinous coat on it on two sides of Kapton, pressing at high temperature obtains two layers of method double side flexible copper coated board.
Wherein said Copper Foil is an electrolytic copper foil, and thickness is 9-70 μ m; The dried thickness of thermoplastic polyimide resin coating is 1-10 μ m.
In the step 2 Copper Foil-thermoplastic polyimide resin coating of obtaining of coating in high temperature oven with 160 ℃, 200 ℃, 250 ℃, 300 ℃, handled respectively 1-30 minute for 350 ℃, finish the imidization process, make the single sided board that gross thickness is 15 μ m.
The surface treatment method of Kapton described in the step 3 comprises alkali lye etching, plasma treatment, sided corona treatment; Described alkali lye etching is that Kapton is immersed in the alkali lye fully, stops 30s and carries out etching, take out water then and rinse well, again in baking oven with its oven dry; Described plasma treatment is to use N
2As handling gas, Kapton is handled 1-120s in the plasma treatment device, the employing radio-frequency power is 1-10kW, voltage is 250V.
Described alkali lye is mixed and made into by monoethanolamine, KOH and water, and alkali liquid temperature is 5-25 ℃.
Two single sided boards are fitted in relatively respectively with the resinous coat on it on two sides of Kapton in the step 4, adopt vacuum press to press 15MPa to carry out hot pressing in 20 minutes in pressurization more than 300 ℃ with face, make two layers of method double side flexible copper coated board.
Simultaneously, two layers of method double side flexible copper coated board that the present invention also provides above-mentioned preparation method to make, these two layers of method double side flexible copper coated boards comprise: Kapton and fit in single sided board on this Kapton two sides; Described single sided board comprises a Copper Foil, coats the thermoplastic polyimide resin coating on this Copper Foil.
Described Kapton is through surface treatment, and its surface treatment method comprises alkali lye etching, plasma treatment, sided corona treatment.
The thickness of described Kapton is 5-100 μ m.
Thermoplastic polyimide resin thermal coefficient of expansion in the described thermoplastic polyimide resin coating is greater than 50ppm/ ℃, and glass transition temperature is 200-280 ℃.
The dried thickness of described thermoplastic polyimide resin coating is 1-10 μ m, preferred 1-3 μ m.
Beneficial effect of the present invention: the preparation method of two layers of method double side flexible copper coated board of the present invention is simple, only need take once to be coated with, significantly reduced the complexity and the difficulty of technological process in existing commercial two layers of method double side flexible copper coated board production, can substance enhance productivity and yields; Two layers of method double side flexible copper coated board that this method makes, wherein employed Kapton without crossing high-temperature baking, can not produce non-response deformation in process of production, therefore also have high-dimensional stability.
Description of drawings
Below in conjunction with accompanying drawing,, will make technical scheme of the present invention and other beneficial effect apparent by the specific embodiment of the present invention is described in detail.
In the accompanying drawing,
Fig. 1 is the preparation method flow chart of two layers of method double side flexible copper coated board of the present invention;
Fig. 2 is the structural representation of two layers of method double side flexible copper coated board of the present invention.
The specific embodiment
As shown in Figure 1, the making flow process of two layers of method double side flexible copper coated board of the present invention comprises the steps: step 1, and Copper Foil is provided, preparation thermoplastic polyimide resin precursor aqueous solution; Step 2, the preparation single sided board: coating thermoplastic polyimide resin precursor aqueous solution on Copper Foil, form the thermoplastic polyimide resin coating, after super-dry, high-temperature sub amination, form single sided board; Step 3 provides Kapton, carries out surface treatment; Step 4, get two above-mentioned single sided boards that make, two single sided boards are fitted in relatively respectively with the resinous coat on it on two sides of Kapton, pressing at high temperature obtains double side flexible copper coated board.
As shown in Figure 2, two layers of method double side flexible copper coated board 10 of the present invention comprise Kapton 3 and fit in single sided board on these Kapton 3 two sides; Described single sided board comprises a Copper Foil 1, coats the thermoplastic polyimide resin coating 2 on this Copper Foil 1.
The dried thickness of thermoplastic polyimide resin coating that described thermoplastic polyimide resin precursor aqueous solution coating forms is 1-10 μ m.The thickness of used Kapton is 5-100 μ m, and Copper Foil is an electrolytic copper foil, and thickness is 9-70 μ m.
The molecular structure of described thermoplastic polyimide resin can have multiple choices, the monomer that synthesizes it also can have multiple choices, but the thermal coefficient of expansion behind its coating and the hot setting must be at least greater than 50ppm/ ℃, glass transition temperature must be in 200-280 ℃ of scope, could guarantee that like this it has good fusion pressing under 300-380 ℃ high temperature, thereby has good peel strength with Kapton, as adopt monomers B APP (2,2 '-two [4-(4-amino-benzene oxygen phenyl)] propane) and BPDA (bibenzene tetracarboxylic dianhydride).
Kapton of the present invention can adopt commercially available various Kaptons, as the Kapton series Kapton of E.I.Du Pont Company, and the EN series Kapton of E.I.Du Pont Company, the NPI series thin film of Zhong Yuan company etc.Preferentially select for use water absorption rate own lower, the Kapton that dimensional stability is good, the water absorption rate of the dual platen of Huo Deing and dimensional stability are also better corresponding like this.But because the technology difference of each manufacturer, the dimensionally stable sex expression of its Kapton is also different.
Described Kapton must carry out suitable surface treatment before pressing, to increase the bonding force of itself and thermoplastic polyimide resin.Surface treatment comprises methods such as alkali lye etching, sided corona treatment, plasma treatment.Plasma treatment can activate the polarity of Kapton surface molecular, makes the intermolecular bonding more chemical b ` that has, and obtains higher peel strength.In addition, the alkali lye etching also can make the molecular polarity on Kapton surface increase.But because the structure difference of each producer's polyimides, they are also different to the surface-treated reaction, so the surface treatment method that each polyimides is fit to is also different.
From equipment cost, after the selection Kapton type, can select the surface treatment method of its corresponding coupling.If in the difference of actual production process because of customer requirement, need the Kapton of number of different types is produced, then preferable methods is again it to be carried out plasma treatment after the alkaline solution etching.Can handle various Kapton like this, the pressing bonding force of itself and TPI is improved.The alkaline solution etching can make the Kapton surface present scraggly surface state, and plasma treatment afterwards can produce many new chemical action points on rough and uneven in surface surface, both actings in conjunction can make thermoplastic polyimide resin produce stronger bonding force with Kapton after pressing.
The thickness of thermoplastic polyimide resin coating can influence the dimensional stability of base material after the peel strength of copper-clad plate and the etching in the described copper-clad plate.Because Kapton itself has good heat endurance and dimensional stability, so can demonstrate the superperformance that Kapton itself is had after thermoplastic polyimide resin coating and the Kapton pressing.If but the thermoplastic polyimide resin coating layer thickness is blocked up, it can produce stronger shrinkage under the various working conditions of hot pressing and follow-up printed circuit board, can cause the dimensional stability of whole copper-clad plate to descend, the thickness of described thermoplastic polyimide resin coating is 1-10 μ m, preferred 1-3 μ m.
The preparation method of double side flexible copper coated board provided by the invention, reduced the complexity of prior art operation significantly, improved production efficiency, only need on Copper Foil, once to be coated with one deck thermoplastic polyimide resin in the manufacturing process, because Copper Foil belongs to metal, thermal coefficient of expansion is less, the back size response rate of being heated is very high, can not produce nonvolatil size deformation, so tension force is controlled, technological parameters such as temperature selection are insensitive, high texture is coated with operation fast, simultaneously, because Kapton does not experience heat treated in the coating stage, can keep the good dimensional stability that Kapton itself is had to greatest extent, premium properties such as high-fire resistance, thus the stability of whole technology is improved, and the coating of thermoplastic polyimide resin only is several microns, its internal stress is less, in coating, can not produce curlingly in baking and the solidification process, can fully improve the coating speed of a motor vehicle.
At the preparation method of two layers of above-mentioned method double side flexible copper coated board and two layers of method double side flexible copper coated board of making, survey performances such as its peel strength, dimensional stability, further give to illustrate in detail and describe as following embodiment.
Now 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 surface treatment method synthetic and Kapton with thermoplastic polyimide resin precursor aqueous solution among the embodiment is described below, and the alkali lye proportioning in following examples and plasma treatment condition are all with as described below.
One, the thermoplastic polyimide resin precursor aqueous solution is synthetic:
Synthesis example 1: the BAPP of weighing 93.0g, in the there-necked flask of 500ml, be dissolved in while stirring among DMAc (dimethylacetylamide) 340g, then this solution is cooled off in water-bath, flow down the BPDA that adds 73.7g successively at nitrogen, then solution is returned to room temperature, continue to stir 3 hours, carry out polymerisation, the thermoplastic polyimide resin precursor aqueous solution of the thickness of system.
Two, the surface treatment method of Kapton:
1, alkali lye etching
Take by weighing the 650g monoethanolamine, 200g KOH, water 150g, mixing and stirring makes alkali lye; Kapton is immersed in the alkali lye fully, stops 30s and carry out etching, take out water then and rinse well, again in baking oven with its oven dry.Alkali liquid temperature is 25 ℃.
2, plasma treatment
Use N
2As handling gas, Kapton is handled 30s in the plasma treatment device, the employing radio-frequency power is 10kW, voltage is 250V.
Embodiment 1:
The thermoplastic polyimide resin precursor aqueous solution that uses synthesis example 1 gained is to be coated with on the electrolytic copper foil of 12 μ m at thickness with coating machine, thickness after making it to solidify is 3 μ m, heated-air drying, Copper Foil-polyimide layer that coating is obtained in high temperature oven with 160 ℃, 200 ℃, 250 ℃, 300 ℃, handled respectively 10 minutes for 350 ℃, finish the imidization process, make the single sided board that gross thickness is 15 μ m.
Then, with thickness is that the upper and lower surface " alkali lye is handled the 12.5 μ m Kapton Kaptons of 30s " is applied in the single sided board shop of 15 μ m, the resin bed face of single sided board is towards the Kapton direction, press 15MPa with vacuum press with face then, pressurization was carried out hot pressing in 20 minutes more than 300 ℃, made double side flexible copper coated board.
Embodiment 2:
" alkali lye is handled the 12.5 μ m Kapton Kaptons of 30s " is changed to " the 12.5 μ m Kapton Kaptons of plasma treatment 30s ", and all the other processes are with embodiment 1.
Embodiment 3:
Will " alkali lye handle 30s 12.5 μ m Kapton Kaptons " be changed to " first alkali lye handle behind the 30s the 12.5 μ m Kapton Kaptons of plasma treatment 30s " again, all the other processes are with embodiment 1.
Embodiment 4:
" alkali lye is handled the 12.5 μ m Kapton Kaptons of 30s " is changed to " the 12.5 μ m NPI Kaptons that alkali lye is handled 30s ", and all the other processes are with embodiment 1.
Embodiment 5:
" alkali lye is handled the 12.5 μ m Kapton Kaptons of 30s " is changed to " the 12.5 μ m NPI Kaptons of plasma treatment 30s ", and all the other processes are with embodiment 1.
Embodiment 6:
Will " alkali lye handle 30s 12.5 μ m Kapton Kaptons " be changed to " first alkali lye handle behind the 30s the 12.5 μ m NPI Kaptons of plasma treatment 30s " again, all the other processes are with embodiment 1.
Embodiment 7:
" alkali lye is handled the 12.5 μ m Kapton Kaptons of 30s " is changed to " the 12.5 μ m ENS Kaptons that alkali lye is handled 30s ", and all the other processes are with embodiment 1.
Embodiment 8:
" alkali lye is handled the 12.5 μ m Kapton Kaptons of 30s " is changed to " the 12.5 μ m ENS Kaptons that alkali lye is handled 30s ", and all the other processes are with embodiment 1.
Embodiment 9:
Will " alkali lye handle 30s 12.5 μ m Kapton Kaptons " be changed to " first alkali lye handle behind the 30s the 12.5 μ m ENS Kaptons of plasma treatment 30s " again, all the other processes are with embodiment 1.
Embodiment 10:
" alkali lye is handled the 12.5 μ m Kapton Kaptons of 30s " is changed to " the 12.5 μ m Uptical Kaptons that alkali lye is handled 30s ", and all the other processes are with embodiment 1.
Embodiment 11:
" alkali lye is handled the 12.5 μ m Kapton Kaptons of 30s " is changed to " the 12.5 μ m Uptical Kaptons that erosion alkali lye is handled 30s ", and all the other processes are with embodiment 1.
Embodiment 12:
Will " alkali lye handle 30s 12.5 μ m Kapton Kaptons " be changed to " first alkali lye handle behind the 30s the 12.5 μ m Uptical Kaptons of plasma treatment 30s " again, all the other processes are with embodiment 1.
The performance of two layers of method double side flexible copper coated board that embodiment 1-12 obtains sees Table 1.
Table 1
The method of testing of above characteristic is as follows:
1), peel strength (PS):, test the peel strength of 90 ° of metal levels according to the IPC-TM-6502.4.9 method.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.
In sum, the preparation method of two layers of method double side flexible copper coated board of the present invention is simple, only need take once to be coated with, significantly reduce the complexity and the difficulty of technological process in existing commercial two layers of method double side flexible copper coated board production, can substance enhance productivity and yields; Two layers of method double side flexible copper coated board that this method makes, wherein employed Kapton without crossing high-temperature baking, can not produce non-response deformation in process of production, therefore also have high-dimensional stability.
Above embodiment is not that content to composition of the present invention imposes any restrictions, and every foundation technical spirit of the present invention all still belongs in the scope of technical solution of the present invention any trickle modification, equivalent variations and modification that above embodiment did.
Claims (10)
1. the preparation method of two layers of method double side flexible copper coated board is characterized in that, comprises the steps:
Step 1, provide Copper Foil, preparation thermoplastic polyimide resin precursor aqueous solution;
Step 2, on Copper Foil the above-mentioned thermoplastic polyimide resin precursor aqueous solution that makes of coating, form the thermoplastic polyimide resin coating, behind hot setting, obtain single sided board;
Step 3, provide Kapton, carry out surface treatment;
Step 4, get two above-mentioned single sided boards that make, two single sided boards are fitted in relatively respectively with resinous coat on it on two sides of Kapton, pressing at high temperature obtains two layers of method double side flexible copper coated board.
2. the method for two layers of method double side flexible copper coated board as claimed in claim 1 is characterized in that, described Copper Foil is an electrolytic copper foil, and thickness is 9-70 μ m; The dried thickness of thermoplastic polyimide resin coating is 1-10 μ m.
3. the method for two layers of method double side flexible copper coated board as claimed in claim 1, it is characterized in that, in the step 2 Copper Foil-thermoplastic polyimide resin coating of obtaining of coating in high temperature oven with 160 ℃, 200 ℃, 250 ℃, 300 ℃, handled respectively 1-30 minute for 350 ℃, finish the imidization process, make the single sided board that gross thickness is 15 μ m.
4. the method for two layers of method double side flexible copper coated board as claimed in claim 1 is characterized in that, the surface treatment method of Kapton described in the step 3 is one or more in alkali lye etching, plasma treatment, the sided corona treatment; Described alkali lye etching is that Kapton is immersed in the alkali lye fully, stops 1-120s and carries out etching, take out water then and rinse well, again in baking oven with its oven dry; Described plasma treatment is to use N
2As handling gas, Kapton is handled 1-120s in the plasma treatment device, the employing radio-frequency power is 1-10kW, voltage is 250V.
5. the method for two layers of method double side flexible copper coated board as claimed in claim 4 is characterized in that, described alkali lye is mixed and made into by monoethanolamine, KOH and water, and alkali liquid temperature is 5-25 ℃.
6. the method for two layers of method double side flexible copper coated board as claimed in claim 1, it is characterized in that, two single sided boards are fitted on the two sides of Kapton relatively respectively in the step 4 with the resinous coat on it, adopt vacuum press to be pressed in to pressurize under the temperature more than 300 ℃ and carried out hot pressing in 1-20 minute, make two layers of method double side flexible copper coated board with the face more than the 5MPa.
7. two layers of method double side flexible copper coated board that use preparation method according to claim 1 to make is characterized in that these two layers of method double side flexible copper coated boards comprise: Kapton and fit in single sided board on this Kapton two sides; Described single sided board comprises a Copper Foil, coats the thermoplastic polyimide resin coating on this Copper Foil.
8. two layers of method double side flexible copper coated board as claimed in claim 7 is characterized in that, described Kapton is through surface treatment, and its surface treatment method is one or more in alkali lye etching, plasma treatment, the sided corona treatment.
9. two layers of method double side flexible copper coated board as claimed in claim 7 is characterized in that, the thickness of described Kapton is 5-100 μ m.
10. two layers of method double side flexible copper coated board as claimed in claim 7 is characterized in that, the thermoplastic polyimide resin thermal coefficient of expansion in the described thermoplastic polyimide resin coating is greater than 50ppm/ ℃, and glass transition temperature is 200-280 ℃.
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| CN102514353A (en) * | 2011-12-13 | 2012-06-27 | 广东生益科技股份有限公司 | Production method of copper-clad plate and copper-clad plate |
| CN102585222A (en) * | 2012-02-25 | 2012-07-18 | 舟山维特新材料科技有限公司 | Thermoplastic polyimide material and method for preparing flexible copper clad laminate through using material |
| CN102630126A (en) * | 2012-04-01 | 2012-08-08 | 松扬电子材料(昆山)有限公司 | Compound double-side copper clad laminate and manufacturing method thereof |
| CN103739842A (en) * | 2013-12-20 | 2014-04-23 | 深圳瑞华泰薄膜科技有限公司 | Thermoplastic polyimide and method for preparing flexible copper-clad plate from thermoplastic polyimide |
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| CN105398135A (en) * | 2014-09-16 | 2016-03-16 | 昆山雅森电子材料科技有限公司 | PI type ultra-thin double-sided copper foil substrate and manufacturing method thereof |
| CN109503836A (en) * | 2018-09-28 | 2019-03-22 | 广东圣帕新材料股份有限公司 | The preparation method of polyamic acid resin and the preparation method of double-faced flexible copper-clad plate |
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