CN101786354A - Two-layer-process double-sided flexible copper-clad laminate (CCL) and manufacture method thereof - Google Patents
Two-layer-process double-sided flexible copper-clad laminate (CCL) and manufacture method thereof Download PDFInfo
- Publication number
- CN101786354A CN101786354A CN200910189365A CN200910189365A CN101786354A CN 101786354 A CN101786354 A CN 101786354A CN 200910189365 A CN200910189365 A CN 200910189365A CN 200910189365 A CN200910189365 A CN 200910189365A CN 101786354 A CN101786354 A CN 101786354A
- Authority
- CN
- China
- Prior art keywords
- polyimide resin
- resin layer
- expansion
- coefficient
- thermoset
- 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.)
- Granted
Links
Images
Landscapes
- Laminated Bodies (AREA)
Abstract
The invention relates to a two-layer-process double-sided flexible copper-clad laminate (CCL) and a manufacture method thereof. The two-layer-process double-sided flexible CCL comprises an upper copper foil, a lower copper foil and three polyimide resin layers sequentially clamped between the two copper foils, i.e. a thermoplastic polyimide resin layer with a thermal expansion coefficient larger than 40 ppm/DEG C, a thermoset polyimide resin layer with a low thermal expansion coefficient of 0-20 ppm/DEG C and a thermoset polyimide resin layer with a high thermal expansion coefficient of 20-40 ppm/DEG C. The two-layer-process double-sided flexible provided by the invention has higher thermal stability and high moisture fastness and can still have excellent high thermal stability, favorable size stability and high stripping strength under the harsh environment of high temperature, high moisture, and the like, thereby having favorable industrial prosperities. The double-sided flexible CCL manufactured by the invention has practically improved size stability under the condition of heavy moisture. When being applied to the environment of high temperature, high moisture, and the like, the double-sided flexible CCL and printing circuits made by the same have excellent thermal stability, high temperature reliability and moisture fastness stability.
Description
Technical field
The present invention relates to the flexibility coat copper plate field, relate in particular to a kind of two layers of method double-faced flexible copper coated foil plate and preparation method thereof with high-fire resistance and high moisture-proof.
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 flexibility coat copper 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 method that adopts as Zhong Yuan company is to carry out suitable surface treatment on the Kapton 3 that has prepared, and then at its two sided coatings thermoplastic polyimide resin 2 (TPI), carry out the high temperature pressing with two Copper Foils 1 again after the imidization, obtain flexible copper-clad dual platen (US P 20070178323A1, US P 20040063900A1, WO 2007083526A1), its copper-clad plate resin structure is seen Fig. 1.Company of Nippon Steel then adopts three coatings earlier, and then the method for lamination is made the two-layer method flexibility coat copper plate method: successively be coated with one deck thermoplastic polyimide resin 22 (TPI), one deck low thermal coefficient of expansion thermoset polyimide resin (PI) 33 and one deck thermoplastic polyimide resin 44 (TPI) on Copper Foil 11 continuously, last plays imidization, the high temperature pressing obtains having concurrently flexible copper-clad dual platen (the US P 20030012882 of good dimensional stability and high-peeling strength, US P20070149758, CN 1527763A), this copper-clad plate resin structure as shown in Figure 2.Mitsui Chemicals company then has two layers of method dual platen of above two kinds of resin structures simultaneously, and has obtained corresponding patent right (CN1750927A, CN 101189287A).Although the concrete manufacture method of above product is different, but total resin bed structure is the TPI/PI/TPI type, the glass transition temperature (Tg) of the thermoplastic polyimide resin in the copper-clad plate of this resin bed structure (TPI layer) all is lower than 300 ℃, its hear resistance and polyimide layer (the PI layer that mediates, glass transition temperature is higher than 300 ℃) compare lower, its TPI layer is in high temperature viscoelastic attitude when scolding tin is handled, and performances such as the peel strength of copper-clad plate and dimensional stability all have decline by a relatively large margin.Simultaneously, because the hygroscopicity of TPI is bigger than thermosetting polyimide resin, therefore the copper-clad plate of this resin structure is under super-humid conditions, and its dimensional stability also has part to descend.
Summary of the invention
The object of the present invention is to provide a kind of two layers of method double side flexible copper coated board, these two layers of method double side flexible copper coated boards have high-fire resistance and high moisture-proof, thereby make copper-clad plate and the printed circuit board made has good property retention rate under harsh conditions such as high temperature, high humidity;
Another object of the present invention is to, a kind of preparation method of above-mentioned two layers of method double side flexible copper coated board is provided, two layers of method double side flexible copper coated board that this preparation method obtains have good high-fire resistance, good dimensional stability and high-peeling strength, have excellent industrial application foreground.
To achieve these goals, the invention provides a kind of two layers of method double side flexible copper coated board, these two layers of method double side flexible copper coated boards comprise: up and down two Copper Foils, successively be located between this two Copper Foil thermal coefficient of expansion greater than 40ppm/ ℃ thermoplastic polyimide resin layer, low thermal coefficient of expansion thermoset polyimide resin layer that thermal coefficient of expansion is 0～20ppm/ ℃, and thermal coefficient of expansion be the high thermal expansion coefficient thermoset polyimide resin layer of 20ppm/ ℃～40ppm/ ℃.
The thermal coefficient of expansion of the thermoplastic polyimide resin of described thermoplastic polyimide resin layer is greater than 40ppm/ ℃.
The thickness sum of described low thermal coefficient of expansion thermoset polyimide resin layer and high thermal expansion coefficient thermoset polyimide resin layer is 2～6: 1 with the thickness ratio of thermoplastic polyimide resin layer.
Another kind of two layers of method double side flexible copper coated board of the present invention, it comprises: comprising: symmetrically arranged two single-side coated copper plates of mirror image, this single-side coated copper plate comprises Copper Foil, is coated on high thermal expansion coefficient thermoset polyimide resin layer on this Copper Foil, low thermal coefficient of expansion thermoset polyimide resin layer, and thermoplastic polyimide resin layer successively, and this two single-side coated copper plate is fitted mutually along this thermoplastic polyimide resin layer and is mirror image and is symmetrical arranged.
The thermal coefficient of expansion of the thermoplastic polyimide resin of described thermoplastic polyimide resin layer is greater than 40ppm/ ℃, the thermal coefficient of expansion of high thermal expansion coefficient thermoset polyimide resin layer is 20ppm/ ℃～40ppm/ ℃, and the thermal coefficient of expansion of low thermal coefficient of expansion thermoset polyimide resin layer is 0～20ppm/ ℃.
The thickness sum of described low thermal coefficient of expansion thermoset polyimide resin layer and high thermal expansion coefficient thermoset polyimide resin layer is 2～6: 1 with the thickness ratio of thermoplastic polyimide resin layer.
Further, the present invention also provides a kind of preparation method of above-mentioned two layers of method double side flexible copper coated board, and it comprises the steps:
Step 6, be coated with on the above-mentioned surface high thermal expansion coefficient thermoset polyimide resin layer, low thermal coefficient of expansion thermoset polyimide resin layer, and the Copper Foil of thermoplastic polyimide resin layer in baking oven, adopts step by step temperature-raising method with temperature to 300～400 ℃, handled 5～30 minutes, and made single-side coated copper plate;
Step 7, get a Copper Foil in addition, this Copper Foil is overlying on the thermoplastic polyimide resin layer of single-side coated copper plate, this Copper Foil and single-side coated copper plate are carried out pressing, make double side flexible copper coated board.
The thermal coefficient of expansion of described thermoplastic polyimide resin is greater than 40ppm/ ℃; The thickness of Copper Foil is 9-70 μ m, the thickness of thermoplastic polyimide resin layer is 5～30 μ m, the thickness of low thermal coefficient of expansion thermoset polyimide resin layer is 10～100 μ m, the thickness of high thermal expansion coefficient thermoset polyimide resin layer is 10～35 μ m, and the thickness sum of this low thermal coefficient of expansion thermoset polyimide resin layer and high thermal expansion coefficient thermoset polyimide resin layer is 2～6: 1 with the thickness ratio of thermoplastic polyimide resin layer.
The preparation method of another kind of two layers of method double side flexible copper coated board of the present invention, it comprises the steps:
The low thermal coefficient of expansion thermoset polyimide resin that step 1, preparation are thermoplastic polyimide resin, thermal coefficient of expansion 0～20ppm/ ℃, and thermal coefficient of expansion be the high thermal expansion coefficient thermoset polyimide resin of 20ppm/ ℃～40ppm/ ℃;
Step 6, be coated with on the above-mentioned surface high thermal expansion coefficient thermoset polyimide resin layer, low thermal coefficient of expansion thermoset polyimide resin layer, and the Copper Foil of thermoplastic polyimide resin layer in baking oven with adopting the substep temperature-raising method with temperature to 300～400 ℃, handled 5～30 minutes, and made single-side coated copper plate;
Step 7, get above-mentioned two single-side coated copper plates, the thermoset polyimide resin layer of two single-side coated copper plates is fitted mutually to be mirror image and to be symmetrical arranged, and this two single-side coated copper plate is carried out pressing make double side flexible copper coated board.
The thermal coefficient of expansion of described thermoplastic polyimide resin is greater than 40ppm/ ℃; The thickness of Copper Foil is 9～70 μ m, the thickness of thermoplastic polyimide resin layer is 5～30 μ m, the thickness of low thermal coefficient of expansion thermoset polyimide resin layer is 10～100 μ m, the thickness of high thermal expansion coefficient thermoset polyimide resin layer is 10～35 μ m, and the thickness sum of this low thermal coefficient of expansion thermoset polyimide resin layer and high thermal expansion coefficient thermoset polyimide resin layer is 2～6: 1 with the thickness ratio of thermoplastic polyimide resin layer.
Beneficial effect of the present invention: two layers of method double side flexible copper coated board provided by the invention, it has higher hear resistance and high moisture-proof, can under severe rugged environments such as high temperature, high humidity, still have outstanding high-fire resistance and good dimensional stability and high-peeling strength, have excellent industrial application foreground.The double side flexible copper coated board that utilizes the inventive method to make, its dimensional stability under the big condition of humidity has obtained substantial raising, this double side flexible copper coated board and made printed circuit applications thereof have more excellent hear resistance, high temperature reliability and moisture-proof stability when environment such as high temperature, high humidity.
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. 1,2 is the structural representation of the double side flexible copper coated board of two kinds of prior aries;
Fig. 3 is the structural representation of two layers of method double side flexible copper coated board first embodiment of the present invention;
Fig. 4 is the structural representation of two layers of method double side flexible copper coated board second embodiment of the present invention;
Fig. 5 is the preparation method flow chart of two layers of double side flexible copper coated board first embodiment of the present invention;
Fig. 6 is the preparation method flow chart of two layers of double side flexible copper coated board second embodiment of the present invention.
The specific embodiment
As shown in Figure 3, the invention provides a kind of two layers of method double side flexible copper coated board, it comprises: up and down two Copper Foils 10, successively be located between this two Copper Foil 10 thermal coefficient of expansion greater than 40ppm/ ℃ thermoplastic polyimide resin layer 20, low thermal coefficient of expansion thermoset polyimide resin layer 30 that thermal coefficient of expansion (CTE) is 0～20ppm/ ℃, and thermal coefficient of expansion be the high thermal expansion coefficient thermoset polyimide resin layer 40 of 20ppm/ ℃～40ppm/ ℃.
Wherein, the thermal coefficient of expansion of this thermoplastic polyimide resin layer 20 is greater than 40ppm/ ℃, and its CTE is preferably greater than 50ppm/ ℃, and its glass transition temperature has the fusion pressing between 200～260 ℃; The CTE of low thermal coefficient of expansion thermoset polyimide resin layer 30 is preferably less than 15ppm/ ℃, if thermal coefficient of expansion greater than 20ppm/ ℃, can't obtain good dimensional stability, its glass transition temperature is higher than 300 ℃; The CTE of high thermal expansion coefficient thermoset polyimide resin layer 40 is preferably less than 30ppm/ ℃, if thermal coefficient of expansion less than 20ppm/ ℃, will be difficult to guarantee and the peel strength of copper-clad plate that its glass transition temperature is higher than 300 ℃.Further, because the thickness proportion of above-mentioned three kinds of polyimide resin layers has a strong impact on the dimensional stability and the curling situation of base material after the copper-clad plate etching, therefore, among the present invention, the thickness sum of low thermal coefficient of expansion thermoset polyimide resin layer 30 and high thermal expansion coefficient thermoset polyimide resin layer 40 is 2～6: 1 with the thickness ratio of thermoplastic polyimide resin layer 20, more preferably 4～5: 1, otherwise will produce warpage or curling phenomenon.Because the thermoset polyimide resin stratum proportion in these two layers of method double side flexible copper coated boards is bigger, therefore have high-fire resistance and high moisture-proof, can under severe rugged environments such as high temperature, high humidity, still have outstanding high-fire resistance and good dimensional stability, have excellent industrial application foreground.
As shown in Figure 4, structural representation for two layers of method double side flexible copper coated board second embodiment of the present invention, this double side flexible copper coated board comprises: symmetrically arranged two single-side coated copper plates of mirror image, this single-side coated copper plate comprises Copper Foil 10, is coated on high thermal expansion coefficient thermoset polyimide resin layer 40 on this Copper Foil 10, low thermal coefficient of expansion thermoset polyimide resin layer 30, and thermoplastic polyimide resin layer 20 successively, and this two single-side coated copper plate is fitted mutually along this thermoplastic polyimide resin layer 20 and is mirror image and is symmetrical arranged.
Wherein, the thermal coefficient of expansion of the thermoplastic polyimide resin of this thermoplastic polyimide resin layer 20 is greater than 40ppm/ ℃, and its CTE is preferably greater than 50ppm/ ℃, and its glass transition temperature has the fusion pressing between 200～260 ℃.The thermal coefficient of expansion of high thermal expansion coefficient thermoset polyimide resin layer 40 is 20ppm/ ℃～40ppm/ ℃, this CTE is preferably less than 30ppm/ ℃, if thermal coefficient of expansion less than 20ppm/ ℃, will be difficult to guarantee and the peel strength of copper-clad plate that its glass transition temperature is higher than 300 ℃.The thermal coefficient of expansion of low thermal coefficient of expansion thermoset polyimide resin layer is 0～20ppm/ ℃, this CTE is preferably less than 15ppm/ ℃, if thermal coefficient of expansion greater than 20ppm/ ℃, can't obtain good dimensional stability, its glass transition temperature is higher than 300 ℃.Further, because the thickness proportion of above-mentioned three kinds of polyimide resin layers has a strong impact on the dimensional stability and the curling situation of base material after the copper-clad plate etching, therefore, among the present invention, the thickness sum of low thermal coefficient of expansion thermoset polyimide resin layer 30 and high thermal expansion coefficient thermoset polyimide resin layer 40 is 2～6: 1 with the thickness ratio of thermoplastic polyimide resin layer 20, more preferably 4～5: 1, otherwise will produce warpage or curling phenomenon.Because the thermoset polyimide resin stratum proportion in these two layers of method double side flexible copper coated boards is bigger, therefore have high-fire resistance and high moisture-proof, can under severe rugged environments such as high temperature, high humidity, still have outstanding high-fire resistance and good dimensional stability, have excellent industrial application foreground.
As shown in Figure 5, be the preparation method flow chart of two layers of double side flexible copper coated board first embodiment of the present invention, this method comprises:
Step 6, be coated with on the above-mentioned surface high thermal expansion coefficient thermoset polyimide resin layer, low thermal coefficient of expansion thermoset polyimide resin layer, and the Copper Foil of thermoplastic polyimide resin layer in baking oven, adopts step by step temperature-raising method with temperature to 300～400 ℃, handled 5～30 minutes, and made single-side coated copper plate.Because the thickness proportion of above-mentioned three kinds of polyimide resin layers has a strong impact on the dimensional stability and the curling situation of base material after the copper-clad plate etching, therefore, among the present invention, the thickness sum of low thermal coefficient of expansion thermoset polyimide resin layer and high thermal expansion coefficient thermoset polyimide resin layer is 2～6: 1 with the thickness ratio of thermoplastic polyimide resin layer, more preferably 4～5: 1, otherwise will produce warpage or curling phenomenon.Because the thermoset polyimide resin stratum proportion in these two layers of method double side flexible copper coated boards is bigger, therefore have high-fire resistance and high moisture-proof, can under severe rugged environments such as high temperature, high humidity, still have outstanding high-fire resistance and good dimensional stability, have excellent industrial application foreground.
Step 7, get a Copper Foil in addition, this Copper Foil is overlying on the thermoplastic polyimide resin layer of single-side coated copper plate, this Copper Foil and single-side coated copper plate are carried out pressing, make double side flexible copper coated board.
Synthesizing of high thermal expansion coefficient thermoset polyimide resin:
Synthesis example 1: the p-PDA of weighing 10.2g, in the there-necked flask of 500ml, be dissolved among the NMP340g while stirring, and then the ODA of weighing 12.6g, be dissolved in the solution, this solution is cooled off in water-bath, flow down the BPDA that adds 45.7g at nitrogen, then solution is returned to room temperature, continue to stir 3 hours, carry out polymerisation, prepare the acid solution of the high thermal expansion coefficient thermoset polyimide resin of thickness.
Synthesizing of low thermal coefficient of expansion thermoset polyimide resin:
Synthesis example 2: the p-PDA of weighing 14.7g, in the there-necked flask of 500ml, be dissolved among the NMP340g while stirring, and then the ODA of weighing 6.8g, be dissolved in the solution, this solution is cooled off in water-bath, flow down the PMDA that adding successively adds 39.6BPDA and 7.3g at nitrogen, then solution is returned to room temperature, continue to stir 3 hours, carry out polymerisation, prepare the acid solution of the low thermal coefficient of expansion thermoset polyimide resin of thickness.
Synthesizing of thermoplastic polyimide resin:
Synthesis example 3: the ODA of weighing 11.3g, in the there-necked flask of 500ml, be dissolved among the DMAc340g while stirring, the APB-N of weighing 16.5g adds in the solution, then this solution is cooled off in water-bath, flow down the BPDA that adds 33.6g successively at nitrogen, then solution is returned to room temperature, continue to stir 3 hours, carry out polymerisation, the acid solution of the thermoplastic polyimide resin of the thickness of system.
The acid solution that uses the high thermal expansion coefficient thermoset polyimide resin of 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 5 μ m, heated-air drying 1～10 minute, form high thermal expansion coefficient thermoset polyimide resin layer, be coated with the acid solution of the low thermal coefficient of expansion thermoset polyimide resin of synthesis example 2 preparations thereon, making the thickness after this layer curing is 17 μ m, heated-air drying 1～10 minute, form low thermal coefficient of expansion thermoset polyimide resin layer, be coated with the acid solution of the thermoplastic polyimide resin of synthesis example 3 preparations thereon, making the thickness after this layer curing is 3 μ m, heated-air drying 1～10 minute forms thermoplastic polyimide resin.
Copper Foil-polyimide coating that coating is obtained adopts the substep temperature-raising method with temperature to 300～400 ℃ in high temperature oven, handled 5～30 minutes, finish the imidization process, making polyimide coating thickness is the single face metal foil laminates body of 25 μ m, i.e. single-side coated copper plate.With the Copper Foil etching, it is 240 ℃ that base material is carried out testing its glass transition temperature on DMA, and the thermal coefficient of expansion of testing on TMA (CTE) is 80ppm/ ℃.
Then, with thickness is that the electrolytic copper foil of 12 μ m overlaps on the resin aspect of single face metal foil laminates body, pressing 15MPa institute in table 1 to pressurize more than 300 ℃ with vacuum press with face carried out hot pressing in 20 minutes, and made the double side flexible copper coated board that base material thickness is 25 μ m.
As shown in Figure 6, be the preparation method flow chart of two layers of double side flexible copper coated board second embodiment of the present invention, this method comprises:
Step 1, preparation thermoplastic polyimide resin, thermal coefficient of expansion be 0～20ppm/ ℃ the low thermal coefficient of expansion thermoset polyimide resin, and thermal coefficient of expansion be the high thermal expansion coefficient thermoset polyimide resin of 20ppm/ ℃～40ppm/ ℃.Among the present invention, its synthon of thermoplastic polyimide resin can comprise: p-phenylenediamine (PPD) (p-PDA), diamino-diphenyl ether (ODA), pyromellitic acid anhydride (PMDA) or bibenzene tetracarboxylic dianhydride (BPDA).The synthon of preparation low thermal coefficient of expansion thermoset polyimide resin and high thermal expansion coefficient thermoset polyimide resin comprises: 1, and 3-pair-(3-amino-benzene oxygen) benzene (APB-N), diamino-diphenyl ether (ODA) or bibenzene tetracarboxylic dianhydride (BPDA).The thermal coefficient of expansion of prepared thermoplastic polyimide resin is greater than 40ppm/ ℃, and its CTE is preferably greater than 50ppm/ ℃, and its glass transition temperature has the fusion pressing between 200～260 ℃; The CTE of low thermal coefficient of expansion thermoset polyimide resin layer 30 is preferably less than 15ppm/ ℃, if thermal coefficient of expansion greater than 20ppm/ ℃, can't obtain good dimensional stability, its glass transition temperature is higher than 300 ℃; The CTE of high thermal expansion coefficient thermoset polyimide resin layer 40 is preferably less than 30ppm/ ℃, if thermal coefficient of expansion less than 20ppm/ ℃, will be difficult to guarantee and the peel strength of copper-clad plate that its glass transition temperature is higher than 300 ℃.
Step 6, be coated with on the above-mentioned surface high thermal expansion coefficient thermoset polyimide resin layer, low thermal coefficient of expansion thermoset polyimide resin layer, and the Copper Foil of thermoplastic polyimide resin layer in baking oven, adopts step by step temperature-raising method with temperature to 300～400 ℃, handled 5～30 minutes, and made single-side coated copper plate.Because the thickness proportion of above-mentioned three kinds of polyimide resin layers has a strong impact on the dimensional stability and the curling situation of base material after the copper-clad plate etching, therefore, among the present invention, the thickness sum of low thermal coefficient of expansion thermoset polyimide resin layer and high thermal expansion coefficient thermoset polyimide resin layer is 2～6: 1 with the thickness ratio of thermoplastic polyimide resin layer, more preferably 4～5: 1, otherwise will produce warpage or curling phenomenon.Because the thermoset polyimide resin stratum proportion in these two layers of method double side flexible copper coated boards is bigger, therefore have high-fire resistance and high moisture-proof, can under severe rugged environments such as high temperature, high humidity, still have outstanding high-fire resistance and good dimensional stability, have excellent industrial application foreground.
Step 7, get above-mentioned two single-side coated copper plates, the thermoset polyimide resin layer of two single-side coated copper plates is fitted mutually to be mirror image and to be symmetrical arranged, and this two single-side coated copper plate is carried out pressing make double side flexible copper coated board.
Preparation prepares thermoplastic polyimide resin, low thermal coefficient of expansion thermoset polyimide resin, reaches the synthesis example of high thermal expansion coefficient thermoset polyimide resin with embodiment 1.
The acid solution that uses the high thermal expansion coefficient thermoset polyimide resin of 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 2 μ m, heated-air drying 1～10 minute forms high thermal expansion coefficient thermoset polyimide resin layer; Be coated with the acid solution of the low thermal coefficient of expansion thermoset polyimide resin of synthesis example 2 preparation thereon, making the thickness after this layer curing is 8 μ m, and heated-air drying 1～10 minute forms low thermal coefficient of expansion thermoset polyimide resin layer; Be coated with the acid solution of the thermoplastic polyimide resin of synthesis example 3 preparation thereon, making the thickness after this layer curing is 3 μ m, forms the thermoplastic polyimide resin layer.
Copper Foil-polyimide coating that coating is obtained adopts the substep temperature-raising method with temperature to 300～400 ℃ in high temperature oven, handled 5～30 minutes, finish the imidization process, making polyimide coating thickness is the single face metal foil laminates body of 12 μ m, i.e. single-side coated copper plate.
Then, press 15MPa in 300 ℃ or more pressurization 20 minute to carry out hot pressing with face to sheet in vacuum press two single face metal foil laminates body sheets, making base material thickness is 25 μ m double side flexible copper coated boards.The pressing program is with embodiment 1.
The performance of two layers of method double side flexible copper coated board that embodiment 1 and embodiment 2 obtain sees Table 1.
Table 1
---represent no unit;
In the table 1, test condition " after the thermal stress " all refers to the state behind the processing 10s in 340 ℃ of tin stoves; Test condition " C-96/35/90 " refers under 35 ℃, the constant-temperature constant-humidity environment of 90% relative humidity and placed 96 hours.
The method of testing of various characteristics parameter is as follows among the present invention:
1), peel strength (PS):, test the peel strength of 90 ° of metal levels according to IPC-TM-650 2.4.9 method.Record data are that less value of peel strength in two faces of dual platen in the table.
2), crimpness: flexibility coat copper plate is tiled on the horizontal table top, tests the depth of camber at four angles of P, four average height are angularity.
3), dimensional stability: press IPC-TM-650 method 2.2.4 test.
4), the test of glass transition temperature: dynamics thermal analyzer (DMA2980, U.S. TA company); Give the vibration frequency of 1Hz, rise to 400 ℃ from room temperature, obtain the glass transition temperature of sample at the maximum place of dielectric loss angle tangent (Tan δ) with the heating rate of 10 ℃/min.
5), the test of thermal coefficient of expansion (CTE): use Thermomechanical Analyzer (TMA), be warmed up to 250 ℃, after this temperature keeps 10 minutes,, obtain the mean thermal expansion coefficients between 240 ℃ to 100 ℃ with 5 ℃/minute speed cooling.
In sum, two layers of method double side flexible copper coated board provided by the invention, it has higher hear resistance and high moisture-proof, can still have outstanding high-fire resistance and good dimensional stability and high-peeling strength under severe rugged environments such as high temperature, high humidity, has excellent industrial application foreground.The double side flexible copper coated board that utilizes the inventive method to make, its dimensional stability under the big condition of humidity has obtained substantial raising, this double side flexible copper coated board and made printed circuit applications thereof have more excellent hear resistance, high temperature reliability and moisture-proof stability when environment such as high temperature, high humidity.
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. two layers of method double side flexible copper coated board, it is characterized in that, comprising: up and down two Copper Foils, successively be located between this two Copper Foil thermal coefficient of expansion greater than 40ppm/ ℃ thermoplastic polyimide resin layer, low thermal coefficient of expansion thermoset polyimide resin layer that thermal coefficient of expansion is 0～20ppm/ ℃, and thermal coefficient of expansion be the high thermal expansion coefficient thermoset polyimide resin layer of 20ppm/ ℃～40ppm/ ℃.
2. two layers of method double side flexible copper coated board as claimed in claim 1 is characterized in that the thermal coefficient of expansion of the thermoplastic polyimide resin of described thermoplastic polyimide resin layer is greater than 40ppm/ ℃.
3. two layers of method double side flexible copper coated board as claimed in claim 1, it is characterized in that the thickness sum of described low thermal coefficient of expansion thermoset polyimide resin layer and high thermal expansion coefficient thermoset polyimide resin layer is 2～6: 1 with the thickness ratio of thermoplastic polyimide resin layer.
4. two layers of method double side flexible copper coated board, it is characterized in that, comprise: symmetrically arranged two single-side coated copper plates of mirror image, this single-side coated copper plate comprises Copper Foil, is coated on high thermal expansion coefficient thermoset polyimide resin layer on this Copper Foil, low thermal coefficient of expansion thermoset polyimide resin layer, and thermoplastic polyimide resin layer successively, and this two single-side coated copper plate is fitted mutually along this thermoplastic polyimide resin layer and is mirror image and is symmetrical arranged.
5. two layers of method double side flexible copper coated board as claimed in claim 4, it is characterized in that, the thermal coefficient of expansion of the thermoplastic polyimide resin of described thermoplastic polyimide resin layer is greater than 40ppm/ ℃, the thermal coefficient of expansion of high thermal expansion coefficient thermoset polyimide resin layer is 20ppm/ ℃～40ppm/ ℃, and the thermal coefficient of expansion of low thermal coefficient of expansion thermoset polyimide resin layer is 0～20ppm/ ℃.
6. two layers of method double side flexible copper coated board as claimed in claim 4, it is characterized in that the thickness sum of described low thermal coefficient of expansion thermoset polyimide resin layer and high thermal expansion coefficient thermoset polyimide resin layer is 2～6: 1 with the thickness ratio of thermoplastic polyimide resin layer.
7. a preparation method of making two layers of method double side flexible copper coated board as claimed in claim 1 is characterized in that, comprises the steps:
Step 1, preparation thermoplastic polyimide resin, thermal coefficient of expansion be 0～20ppm/ ℃ the low thermal coefficient of expansion thermoset polyimide resin, and thermal coefficient of expansion be the high thermal expansion coefficient thermoset polyimide resin of 20ppm/ ℃～40ppm/ ℃;
Step 2, provide Copper Foil;
Step 3, get a Copper Foil, the above-mentioned high thermal expansion coefficient thermoset polyimide resin of coating on this Copper Foil one surface dry 1～10 minute, forms high thermal expansion coefficient thermoset polyimide resin layer;
Step 4, on high thermal expansion coefficient thermoset polyimide resin layer coating low thermal coefficient of expansion thermoset polyimide resin, dry 1～10 minute, form low thermal coefficient of expansion thermoset polyimide resin layer;
Step 5, on this low thermal coefficient of expansion thermoset polyimide resin layer the coating thermoplastic polyimide resin, dry 1～10 minute, form the thermoplastic polyimide resin layer;
Step 6, be coated with on the above-mentioned surface high thermal expansion coefficient thermoset polyimide resin layer, low thermal coefficient of expansion thermoset polyimide resin layer, and the Copper Foil of thermoplastic polyimide resin layer in baking oven, adopts step by step temperature-raising method with temperature to 300～400 ℃, handled 5～30 minutes, and made single-side coated copper plate;
Step 7, get a Copper Foil in addition, this Copper Foil is overlying on the thermoplastic polyimide resin layer of single-side coated copper plate, this Copper Foil and single-side coated copper plate are carried out pressing, make double side flexible copper coated board.
8. the preparation method of two layers of method double side flexible copper coated board as claimed in claim 7 is characterized in that, the thermal coefficient of expansion of described thermoplastic polyimide resin is greater than 40ppm/ ℃; The thickness of Copper Foil is 9-70 μ m, the thickness of thermoplastic polyimide resin layer is 5～30 μ m, the thickness of low thermal coefficient of expansion thermoset polyimide resin layer is 10～100 μ m, the thickness of high thermal expansion coefficient thermoset polyimide resin layer is 10～35 μ m, and the thickness sum of this low thermal coefficient of expansion thermoset polyimide resin layer and high thermal expansion coefficient thermoset polyimide resin layer is 2～6: 1 with the thickness ratio of thermoplastic polyimide resin layer.
9. a preparation method of making two layers of method double side flexible copper coated board as claimed in claim 4 is characterized in that, comprises the steps:
The low thermal coefficient of expansion thermoset polyimide resin that step 1, preparation are thermoplastic polyimide resin, thermal coefficient of expansion 0～20ppm/ ℃, and thermal coefficient of expansion be the high thermal expansion coefficient thermoset polyimide resin of 20ppm/ ℃～40ppm/ ℃;
Step 2, provide Copper Foil;
Step 3, get a Copper Foil, the above-mentioned high thermal expansion coefficient thermoset polyimide resin of coating on this Copper Foil one surface dry 1～10 minute, forms high thermal expansion coefficient thermoset polyimide resin layer;
Step 4, on high thermal expansion coefficient thermoset polyimide resin layer coating low thermal coefficient of expansion thermoset polyimide resin, dry 1-10 minute, form low thermal coefficient of expansion thermoset polyimide resin layer;
Step 5, on this low thermal coefficient of expansion thermoset polyimide resin layer the coating thermoplastic polyimide resin, dry 1～10 minute, form the thermoplastic polyimide resin layer;
Step 6, be coated with on the above-mentioned surface high thermal expansion coefficient thermoset polyimide resin layer, low thermal coefficient of expansion thermoset polyimide resin layer, and the Copper Foil of thermoplastic polyimide resin layer in baking oven with adopting the substep temperature-raising method with temperature to 300～400 ℃, handled 5～30 minutes, and made single-side coated copper plate;
Step 7, get above-mentioned two single-side coated copper plates, the thermoset polyimide resin layer of two single-side coated copper plates is fitted mutually to be mirror image and to be symmetrical arranged, and this two single-side coated copper plate is carried out pressing make double side flexible copper coated board.
10. the preparation method of two layers of method double side flexible copper coated board as claimed in claim 9 is characterized in that, the thermal coefficient of expansion of described thermoplastic polyimide resin is greater than 40ppm/ ℃; The thickness of Copper Foil is 9～70 μ m, the thickness of thermoplastic polyimide resin layer is 5～30 μ m, the thickness of low thermal coefficient of expansion thermoset polyimide resin layer is 10～100 μ m, the thickness of high thermal expansion coefficient thermoset polyimide resin layer is 10～35 μ m, and the thickness sum of this low thermal coefficient of expansion thermoset polyimide resin layer and high thermal expansion coefficient thermoset polyimide resin layer is 2～6.1 with the thickness ratio of thermoplastic polyimide resin layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910189365A CN101786354B (en) | 2009-12-24 | 2009-12-24 | Two-layer-process double-sided flexible copper-clad laminate (CCL) and manufacture method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910189365A CN101786354B (en) | 2009-12-24 | 2009-12-24 | Two-layer-process double-sided flexible copper-clad laminate (CCL) and manufacture method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101786354A true CN101786354A (en) | 2010-07-28 |
| CN101786354B CN101786354B (en) | 2012-10-10 |
Family
ID=42529797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910189365A Active CN101786354B (en) | 2009-12-24 | 2009-12-24 | Two-layer-process double-sided flexible copper-clad laminate (CCL) and manufacture method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101786354B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102166853A (en) * | 2010-12-18 | 2011-08-31 | 广东生益科技股份有限公司 | Manufacturing method of two-layer single-sided flexible copper clad laminate |
| 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 |
| CN102529223A (en) * | 2010-12-30 | 2012-07-04 | 比亚迪股份有限公司 | Polyimide metal overprinting body and preparation method thereof, and dual-sided metal overprinting body |
| 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 |
| CN102848642A (en) * | 2012-09-11 | 2013-01-02 | 广东生益科技股份有限公司 | Two-layer-method single-sided flexible copper clad laminate and manufacturing method thereof |
| CN103180138A (en) * | 2010-10-25 | 2013-06-26 | 大金工业株式会社 | Metal-clad laminate, method for producing same, and flexible printed board |
| 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 |
| TWI576370B (en) * | 2016-04-29 | 2017-04-01 | 長興材料工業股份有限公司 | Polyimide resin and metal-clad laminate comprising the same |
| US10995179B2 (en) | 2015-06-17 | 2021-05-04 | Eternal Materials Co., Ltd | Polyimide resin and metal-clad laminate comprising the same |
| CN114474895A (en) * | 2020-10-27 | 2022-05-13 | 昆山雅森电子材料科技有限公司 | Flexible copper foil base material with multilayer composite structure and preparation method thereof |
| CN116766712A (en) * | 2023-06-20 | 2023-09-19 | 江苏耀鸿电子有限公司 | IC packaging substrate based on epoxy resin and processing technology thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100668948B1 (en) * | 2004-09-21 | 2007-01-12 | 주식회사 엘지화학 | Metallic Laminate and Method for Preparing Thereof |
| WO2007097585A1 (en) * | 2006-02-24 | 2007-08-30 | Kolon Industries, Inc. | Double side conductor laminates and its manufacture |
| KR101467179B1 (en) * | 2007-12-20 | 2014-12-01 | 에스케이이노베이션 주식회사 | Metal-clad laminate |
-
2009
- 2009-12-24 CN CN200910189365A patent/CN101786354B/en active Active
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103180138B (en) * | 2010-10-25 | 2016-03-16 | 大金工业株式会社 | Metal-clad laminate and manufacture method thereof and flexible printed board |
| CN103180138A (en) * | 2010-10-25 | 2013-06-26 | 大金工业株式会社 | Metal-clad laminate, method for producing same, and flexible printed board |
| CN102166853A (en) * | 2010-12-18 | 2011-08-31 | 广东生益科技股份有限公司 | Manufacturing method of two-layer single-sided flexible copper clad laminate |
| CN102166853B (en) * | 2010-12-18 | 2013-09-18 | 广东生益科技股份有限公司 | Manufacturing method of two-layer single-sided flexible copper clad laminate |
| CN102529223A (en) * | 2010-12-30 | 2012-07-04 | 比亚迪股份有限公司 | Polyimide metal overprinting body and preparation method thereof, and dual-sided metal overprinting body |
| CN102529223B (en) * | 2010-12-30 | 2014-12-10 | 比亚迪股份有限公司 | Polyimide metal overprinting body and preparation method thereof, and dual-sided metal overprinting body |
| 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 |
| CN102514353B (en) * | 2011-12-13 | 2014-11-26 | 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 |
| CN102585222B (en) * | 2012-02-25 | 2014-05-07 | 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 |
| CN102848642A (en) * | 2012-09-11 | 2013-01-02 | 广东生益科技股份有限公司 | Two-layer-method single-sided flexible copper clad laminate and manufacturing method thereof |
| 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 |
| US10995179B2 (en) | 2015-06-17 | 2021-05-04 | Eternal Materials Co., Ltd | Polyimide resin and metal-clad laminate comprising the same |
| TWI576370B (en) * | 2016-04-29 | 2017-04-01 | 長興材料工業股份有限公司 | Polyimide resin and metal-clad laminate comprising the same |
| CN114474895A (en) * | 2020-10-27 | 2022-05-13 | 昆山雅森电子材料科技有限公司 | Flexible copper foil base material with multilayer composite structure and preparation method thereof |
| CN116766712A (en) * | 2023-06-20 | 2023-09-19 | 江苏耀鸿电子有限公司 | IC packaging substrate based on epoxy resin and processing technology thereof |
| CN116766712B (en) * | 2023-06-20 | 2024-01-02 | 江苏耀鸿电子有限公司 | IC packaging substrate based on epoxy resin and processing technology thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101786354B (en) | 2012-10-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101786354B (en) | Two-layer-process double-sided flexible copper-clad laminate (CCL) and manufacture method thereof | |
| KR102319574B1 (en) | Method of manufacturing flexible copper-clad laminate | |
| CN101420820B (en) | Double side flexible copper coated board and manufacturing method thereof | |
| JP5524475B2 (en) | Two-layer double-sided flexible metal laminate and its manufacturing method | |
| KR101844924B1 (en) | Polyimide resin and metal-clad laminate comprising the same | |
| CN101903169B (en) | Metal-clad laminate | |
| CN101494953B (en) | Preparation method of double-layer method flexibility two-side coated copper plate for multilayer flexibility printed circuit | |
| KR20000035259A (en) | Polyimide film and electric/electronic equipment bases with the use thereof | |
| CN102009515B (en) | Two-layer-method double-sided flexible CCL (Copper-Clad Laminate) and manufacture method thereof | |
| CN103180135B (en) | Thick layer polyimide metal clad laminate | |
| CN101787126B (en) | Polyamide acid composition, method for manufacturing two-layer process flexible copper-clad plates by use of same, and obtained two-layer process flexible copper-clad plate | |
| WO2009110387A1 (en) | Laminate for flexible board and heat conductive polyimide film | |
| WO2001028767A1 (en) | Laminate and process for producing the same | |
| KR20100048474A (en) | Flexible metal-clad laminate and a method of manufacturing the same | |
| JP6317399B2 (en) | Polyimide precursor composition and use thereof and polyimide made therefrom. | |
| EP1566263B1 (en) | Process for producing heat-resistant flexible laminate and heat-resistant flexible laminate produced thereby | |
| CN102009506A (en) | Double-surface flexible copper-clad plate and manufacturing method thereof | |
| CN102166853B (en) | Manufacturing method of two-layer single-sided flexible copper clad laminate | |
| CN105538827A (en) | Two-layer-process double-faced flexible copper-clad plate and production method thereof | |
| JP7428646B2 (en) | Metal-clad laminates and circuit boards | |
| TWI660649B (en) | Flexible circuit board and electronic equipment | |
| CN102848642B (en) | Two layers of method double side flexible copper coated board and preparation method thereof | |
| KR20050090139A (en) | Bonding sheet and one-side metal-clad laminate | |
| CN201307967Y (en) | Double-sided flexible copper-clad plate | |
| KR102335085B1 (en) | Polyimide flexible metal-clad laminate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |