Abstract:
A polyimide metal laminated plate has a first metallic film, a first thermoplastic polyimide film laminated on a surface of the first metallic film, a first thermosetting polyimide film laminated on a surface of the first thermoplastic polyimide film distal from the first metallic film, and a second thermoplastic polyimide film laminated on a surface of the first thermosetting polyimide film distal from the first thermoplastic polyimide film. The polyimide metal laminated plate has no adhesive layer, so the polyimide metal laminated plate not only has good heat resistance, flame resistance, anti-chemical properties, and dimensional stability, but also meets the thinning tendency of FPCB. In addition, by the first thermosetting polyimide film and the second thermoplastic polyimide film having a water vapor transmission rate equal to or more than 170 g-μm/m 2 -day, the delamination and whitening of the polyimide metal laminated plate is prevented.

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to a polyimide metal laminated plate and a method of making the same; particularly relates to a polyimide metal laminated plate without an adhesive layer and a method of making the same 
     2. Description of the Prior Art(s) 
     Polyimide of aromatic group has excellent heat-resistant, anti-chemical, mechanical, and electrical properties, such that polyimide is widely applied to flexible printed circuit boards (FPCB) for electronic appliances, for example, notebook computers, consumer electronics, and communications handheld electronic products. 
     Conventionally, to fabricate a FPCB, a polyimide film is taken as a substrate. Each of two opposite surfaces of the polyimide film is coated with epoxy resin or acrylate resin to form an adhesive layer. Each of two copper foils is laminated on one of the two opposite surfaces of the polyimide film by the corresponding adhesive layer and the FPCB is fabricated. 
     However, the adhesive layer made by epoxy resin or acrylate resin deteriorates the heat resistance, flame resistance, anti-chemical properties, and dimensional stability of the FPCB. In addition, the adhesive layer is thick and unable to meet the thinning tendency of FPCB. 
     To overcome the shortcomings, the present invention provides a polyimide metal laminated plate without an adhesive layer and a method of making the same to mitigate or obviate the aforementioned problems. 
     SUMMARY OF THE INVENTION 
     The main objective of the present invention is to provide a polyimide metal laminated plate without an adhesive layer and a method of making the same. 
     The polyimide metal laminated plate in accordance with the present invention has
         a first metallic film;   a first thermoplastic polyimide film laminated on a surface of the first metallic film;   a first thermosetting polyimide film laminated on a surface of the first thermoplastic polyimide distal from the first metallic film, wherein the first thermosetting polyimide film has a water vapor transmission rate equal to or more than 170 g-μm/m 2 -day; and   a second thermoplastic polyimide film laminated on a surface of the first thermosetting polyimide film distal from the first thermoplastic polyimide film, wherein the second thermoplastic polyimide film has a water vapor transmission rate equal to or more than the water vapor transmission rate of the first thermosetting polyimide film.       

     The polyimide metal laminated plate in accordance with the present invention has no adhesive layer, so the polyimide metal laminated plate not only has good heat resistance, flame resistance, anti-chemical properties, and dimensional stability, but also meets the thinning tendency of FPCB. In addition, by the first thermosetting polyimide film and the second thermoplastic polyimide film having a water vapor transmission rate equal to or more than 170 g-μm/m 2 -day, the delamination and whitening of the polyimide metal laminated plate is prevented. 
     In an embodiment, the polyimide metal laminated plate has a second metallic film laminated on a surface of the second thermoplastic polyimide film distal from the first thermosetting polyimide film. 
     In an embodiment, the polyimide metal laminated plate has a third thermoplastic polyimide film laminated between the second metallic film and the second thermoplastic polyimide film. 
     In an embodiment, the polyimide metal laminated plate has a second thermosetting polyimide film laminated between the third thermoplastic polyimide film and the second thermoplastic polyimide film. 
     In an embodiment, the polyimide metal laminated plate has a fourth thermoplastic polyimide film laminated between the second thermosetting polyimide film and the second thermoplastic polyimide film. 
     Preferably, the second thermoplastic polyimide film has the water vapor transmission rate equal to or more than 200 g-μm/m 2 -day. 
     Preferably, the first thermosetting polyimide film has the water vapor transmission rate equal to or more than 200 g-μm/m 2 -day. 
     Preferably, a total thickness of the first thermoplastic polyimide film, the first thermosetting polyimide film, and the second thermoplastic polyimide film ranges from 9 μm to 25 μm. 
     Preferably, an overall water vapor transmission rate of the first thermoplastic polyimide film, the first thermosetting polyimide film, and the second thermoplastic polyimide film is equal to or more than 180 g-μm/m 2 -day. The method of making the polyimide metal laminated plate in accordance with the present invention comprises the steps of:
         polymerizing a first diamine, a first reactive monomer and a first dianhydride in a first solvent to obtain a thermosetting polyimide precursor, wherein the first reactive monomer is selected from a group consisted of: 2,2′-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 4,4′-(1,3-phenylenediisopropylidene)bisaniline, 9,9′-bis(4-aminophenyl)fluorene, and polyoxypropylenediamine, and the first reactive monomer has a concentration ranging from 3.00 mol. % to 7.00 mol. % based on the total molar amount of the first diamine and the first reactive monomer;   polymerizing a second diamine, a second reactive monomer and a second dianhydride in a second solvent to obtain a thermoplastic polyimide precursor, wherein the second reactive monomer is selected from a group consisted of: 2,2′-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 4,4′-(1,3-phenylenediisopropylidene)bisaniline, 9,9′-bis(4-aminophenyl)fluorene, and polyoxypropylenediamine, and the second reactive monomer has a concentration ranging from 35.00 mol. % to 65.00 mol. % based on the total molar amount of the second diamine and the second reactive monomer;   coating the thermoplastic polyimide precursor on a surface of a first metallic film to form a first thermoplastic polyimide precursor layer;   coating the thermosetting polyimide precursor on a surface of the first thermoplastic polyimide precursor layer distal from the first metallic film to form a first thermosetting polyimide precursor layer;   coating the thermoplastic polyimide precursor on a surface of the first thermosetting polyimide precursor layer distal from the first thermoplastic polyimide precursor layer to form a second thermoplastic polyimide precursor layer; and   imidizing the first thermoplastic polyimide precursor layer, the first thermosetting polyimide precursor layer, and the second thermoplastic polyimide precursor layer to a first thermoplastic polyimide film, a first thermosetting polyimide film, and a second thermoplastic polyimide film to obtain the polyimide metal laminated plate.       

     By the method in accordance with the present invention, a polyimide metal laminated plate having no adhesive layer is produced. Since the polyimide metal laminated plate has no adhesive layer, the polyimide metal laminated plate not only has good heat resistance, flame resistance, anti-chemical properties, and dimensional stability, but also meets the thinning tendency of FPCB. In addition, as the first thermosetting polyimide film and the second thermoplastic polyimide film of the polyimide metal laminated plate respectively have a water vapor transmission rate equal to or more than 170 g-μm/m 2 -day, the delamination and whitening of the polyimide metal laminated plate is prevented. 
     Preferably, the step of imidizing the first thermoplastic polyimide precursor layer, the first thermosetting polyimide precursor layer, and the second thermoplastic polyimide precursor layer to a first thermoplastic polyimide film, a first thermosetting polyimide film, and a second thermoplastic polyimide film to obtain the polyimide metal laminated plate comprises the steps of:
         imidizing the first thermoplastic polyimide precursor layer, the first thermosetting polyimide precursor layer, and the second thermoplastic polyimide precursor layer to a first thermoplastic polyimide film, a first thermosetting polyimide film, and a second thermoplastic polyimide film; and   laminating a second metallic film on a surface of the second thermoplastic polyimide film distal from the first thermosetting polyimide film to obtain the polyimide metal laminated plate.       

     Preferably, the step of imidizing the first thermoplastic polyimide precursor layer, the first thermosetting polyimide precursor layer, and the second thermoplastic polyimide precursor layer to a first thermoplastic polyimide film, a first thermosetting polyimide film, and a second thermoplastic polyimide film to obtain the polyimide metal laminated plate comprises the steps of:
         desolventizing the first thermoplastic polyimide precursor layer, the first thermosetting polyimide precursor layer, and the second thermoplastic polyimide precursor layer under a desolventizing temperature ranging from 80° C. to 150° C. to obtain a desolventized first thermoplastic polyimide precursor layer, a desolventized first thermosetting polyimide precursor layer, and a desolventized second thermoplastic polyimide precursor layer; and   heating the desolventized first thermoplastic polyimide precursor layer, the desolventized first thermosetting polyimide precursor layer, and the desolventized second thermoplastic polyimide precursor layer simultaneously to a imidization temperature of 160° C. to 190° C., a imidization temperature of 190° C. to 300° C., and a imidization temperature of 300° C. to 350° C. in sequence to obtain the first thermoplastic polyimide film, the first thermosetting polyimide film, and the second thermoplastic polyimide film.       

     Preferably, the first diamine and the second diamine are selected from a group consisted of 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, p-phenylenediamine, m-phenylenediamine, 3,5-diaminobenzoic acid, 2,2′-bis(4-aminophenyl)propane, 4,4′-diaminodiphenyl methane, 4,4′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide, 1,3-bis(4-aminophenoxy)benzene), 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4-bis(3-aminophenoxy)biphenyl, 2,2′-bis[4-(4-aminophenoxy)phenyl]propane, 2,2′-bis[4-(3-aminophenoxy)pheny]propane, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dihydroxybiphenyl-4,4′-diamino, 9,9′-bis(4-aminophenyl)fluorene), 2,2′-bis(4-(3-aminophenoxyl)phenyl)sulfon, 2,6-diaminopyridine, polyoxypropylenediamine, 4,4′-(1,3-phenylenediisopropylidene)bisaniline, 4,4′-(1,4-phenylenediisopropylidene)bisaniline, norbornane dimethylamine and a combination thereof. 
     More preferably, polyoxypropylenediamine is selected form a group consisted of Jeffamine® D230, Jeffamine® D400 and Jeffamin® D2000. 
     Preferably, the first dianhydride and the second dianhydride are selected from a group consisted of pyromellitic dianhydride, 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 3,3′,4,4′-benzophenone tetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride, 2,2′-bis(4-carboxyphenyl)hexafluoropropane, ethylene glycol-bis-trimellitate anhydride, 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid phenylene ester, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, and a combination thereof. 
     Preferably, the first solvent and the second solvent are selected from a group consisted of tetrahydrofuran, N,N-dimethylformide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone and a combination thereof. 
     Preferably, the concentration of the first reactive monomer ranges from 3.00 molar percent (mol. %) to 7.00 molar percent (mol. %) based on the total amount of the first diamine and the first reactive monomer. 
     Preferably, the concentration of the second reactive monomer ranges from 35.00 mol. % to 65.00 mol. % based on the total amount of the second diamine and the second reactive monomer. 
     Other objectives, advantages and novel features of the invention will become more apparent from the following detailed description when taken in conjunction with the accompanying drawings. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  is an enlarged side view in cross section of each polyimide metal laminated plate of Experiments 1 to 9 and Comparison 1 in accordance with the present invention; 
         FIG. 2  is an enlarged side view in cross section of a polyimide metal laminated plate of Experiment 10 in accordance with the present invention; 
         FIG. 3  is an enlarged side view in cross section of a polyimide metal laminated plate of Experiment 11 in accordance with the present invention; 
         FIG. 4  is an enlarged side view in cross section of a polyimide metal laminated plate of Experiment 12 in accordance with the present invention; 
         FIG. 5  is an enlarged side view in cross section of a polyimide metal laminated plate of Experiment 13 in accordance with the present invention; 
         FIG. 6  is an enlarged side view in cross section of each polyimide metal laminated plate of Comparisons 2 to 7 in accordance with the present invention; and 
         FIG. 7  is an enlarged side view in cross section of each polyimide metal laminated plate of Comparisons 8 to 13 in accordance with the present invention. 
     
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     Preparation 1 Fabrication of a Thermosetting Polyimide Precursor 
     In a 1 liter four-neck reaction flask, 19.877 grams of p-phenylenediamine and 1.940 grams of 4,4′-diaminodiphenyl ether were dissolved in 425 grams of N-methyl-2-pyrrolidone under a temperature of 25±5° C. and a nitrogen atmosphere to obtain a diamine solution. 8.029 grams of pyromellitic dianhydride was added into the diamine solution to process a first polymerization and a first polymerized solution was obtained. 45.60 grams of 3,3′,4,4′-biphenyl tetracarboxylic dianhydride was divided into three batches. The three batches of 3,3′,4,4′-biphenyl tetracarboxylic dianhydride were added into the first polymerized solution in sequence and stirred for 4 hours to process a secondary polymerization. The thermosetting polyimide precursor was obtained after the secondary polymerization. In the present preparation, the thermosetting polyimide precursor was marked as PI-1. 
     Preparation 2 Fabrication of a Thermosetting Polyimide Precursor 
     The present preparation was similar to Preparation 1. The differences between the present preparation and Preparation 1 were as follows. 
     19.159 grams of p-phenylenediamine, 1.870 grams of 4,4′-diaminodiphenyl ether, and a first reactive monomer were dissolved in 425 grams of N-methyl-2-pyrrolidone to obtain the diamine solution. 7.739 grams of pyromellitic dianhydride was added into the diamine solution to process the first polymerization and obtain the first polymerized solution. 
     The first reactive monomer was polyoxypropylenediamine (Jeffamine® D400). The usage amount of the first reactive monomer was 2.260 grams. The concentration of the first reactive monomer was 2.74 mol. % based on the total amount of p-phenylenediamine, 4,4′-diaminodiphenyl ether, and the first reactive monomer. 
     In the present preparation, the thermosetting polyimide precursor was marked as PI-2. 
     Preparation 3 Fabrication of a Thermosetting Polyimide Precursor 
     The present preparation was similar to Preparation 1. The differences between the present preparation and Preparation 1 were as follows. 
     18.708 grams of p-phenylenediamine, 1.826 grams of 4,4′-diaminodiphenyl ether, and a first reactive monomer were dissolved in 425 grams of N-methyl-2-pyrrolidone to obtain the diamine solution. 7.557 grams of pyromellitic dianhydride was added into the diamine solution to process the first polymerization and obtain the first polymerized solution. 
     The first reactive monomer was polyoxypropylenediamine (Jeffamine® D400). The usage amount of the first reactive monomer was 3.772 grams. The concentration of the first reactive monomer was 4.59 mol. % based on the total amount of p-phenylenediamine, 4,4′-diaminodiphenyl ether, and the first reactive monomer. 
     In the present preparation, the thermosetting polyimide precursor was marked as PI-3. 
     Preparation 4 Fabrication of a Thermosetting Polyimide Precursor 
     The present preparation was similar to Preparation 1. The differences between the present preparation and Preparation 1 were as follows. 
     19.044 grams of p-phenylenediamine, 1.858 grams of 4,4′-diaminodiphenyl ether, and a first reactive monomer were dissolved in 425 grams of N-methyl-2-pyrrolidone to obtain the diamine solution. 7.692 grams of pyromellitic dianhydride was added into the diamine solution to process the first polymerization and obtain the first polymerized solution. 
     The first reactive monomer was 9,9′-bis(4-aminophenyl)fluorene. The usage amount of the first reactive monomer was 2.263 grams. The concentration of the first reactive monomer was 3.39 mol. % based on the total amount of p-phenylenediamine, 4,4′-diaminodiphenyl ether, and the first reactive monomer. 
     In the present preparation, the thermosetting polyimide precursor was marked as PI-4. 
     Preparation 5 Fabrication of a Thermosetting Polyimide Precursor 
     The present preparation was similar to Preparation 1. The differences between the present preparation and Preparation 1 were as follows. 18.490 grams of p-phenylenediamine, 1.804 grams of 4,4′-diaminodiphenyl ether, and a first reactive monomer were dissolved in 425 grams of N-methyl-2-pyrrolidone to obtain the diamine solution. 7.469 grams of pyromellitic dianhydride was added into the diamine solution to process the first polymerization and obtain the first polymerized solution. 
     The first reactive monomer was 9,9′-bis(4-aminophenyl)fluorene. The usage amount of the first reactive monomer was 3.772 grams. The concentration of the first reactive monomer was 5.67 mol. % based on the total amount of p-phenylenediamine, 4,4′-diaminodiphenyl ether, and the first reactive monomer. 
     In the present preparation, the thermosetting polyimide precursor was marked as PI-5. 
     Preparation 6 Fabrication of a Thermosetting Polyimide Precursor 
     The present preparation was similar to Preparation 1. The differences between the present preparation and Preparation 1 were as follows. 
     19.332 grams of p-phenylenediamine and a first reactive monomer were dissolved in 425 grams of N-methyl-2-pyrrolidone to obtain the diamine solution. 7.512 grams of pyromellitic dianhydride was added into the diamine solution to process the first polymerization and obtain the first polymerized solution. 
     The first reactive monomer comprised polyoxypropylenediamine (Jeffamine® D400) and 9,9′-bis(4-aminophenyl)fluorene. The usage amount of polyoxypropylenediamine was 2.057 grams. The usage amount of 9,9′-bis(4-aminophenyl)fluorene was 2.667 grams. The concentration of the first reactive monomer was 6.50 mol. % based on the total amount of p-phenylenediamine and the first reactive monomer. 
     In the present preparation, the thermosetting polyimide precursor was marked as PI-6. 
     Preparation 7 Fabrication of a Thermoplastic Polyimide Precursor 
     In a 1 liter four-neck reaction flask, 5.515 grams of p-phenylenediamine and a second reactive monomer were dissolved in 425 grams of N-methyl-2-pyrrolidone under a temperature of 25±5° C. and a nitrogen atmosphere to obtain a diamine solution. 45.60 grams of 3,3′,4,4′-biphenyl tetracarboxylic dianhydride was divided into three batches. The three batches of 3,3′,4,4′-biphenyl tetracarboxylic dianhydride were added into the diamine solution in sequence and stirred for 4 hours to process a polymerization. The thermoplastic polyimide precursor was obtained after the polymerization. In the present preparation, the thermoplastic polyimide precursor was marked as TPI-1. 
     Preparation 8 Fabrication of a Thermoplastic Polyimide Precursor 
     The present preparation was similar to Preparation 7. The differences between the present preparation and Preparation 7 were as follows. 
     5.516 grams of p-phenylenediamine and the second reactive monomer were dissolved in 425 grams of N-methyl-2-pyrrolidone to obtain the diamine solution. 
     The second reactive monomer comprised 4,4′-(1,3-phenylenediisopropylidene) bisaniline and 2,2′-bis(4-aminophenyl)propane. The usage amount of 4,4′-(1,3-phenylenediisopropylidene)bisaniline was 23.435 grams. The usage amount of 2,2′-bis(4-aminophenyl)propane was 5.990 grams. The concentration of the second reactive monomer was 61.80 mol. % based on the total amount of p-phenylenediamine and the second reactive monomer. 
     In the present preparation, the thermoplastic polyimide precursor was marked as TPI-2. 
     Preparation 9 Fabrication of a Thermoplastic Polyimide Precursor 
     The present preparation was similar to Preparation 7. The differences between the present preparation and Preparation 7 were as follows. 
     23.821 grams of 1,3-bis(4-aminophenoxy)benzene and the second reactive monomer were dissolved in 425 grams of N-methyl-2-pyrrolidone to obtain the diamine solution. 14.383 grams of pyromellitic dianhydride was added into the diamine solution to process a first polymerization and a first polymerized solution was obtained. 20.00 grams of 3,3′,4,4′-biphenyl tetracarboxylic dianhydride was divided into two batches. The two batches of 3,3′,4,4′-biphenyl tetracarboxylic dianhydride were added into the first polymerized solution in sequence and stirred for 4 hours to process a secondary polymerization. The thermoplastic polyimide precursor was obtained after the secondary polymerization 
     The second reactive monomer was 4,4′-(1,3-phenylenediisopropylidene) bisaniline. The usage amount of 4,4′-(1,3-phenylenediisopropylidene)bisaniline was 18.735 grams. The concentration of the second reactive monomer was 35.87 mol. % based on the total amount of 1,3-bis(4-aminophenoxy)benzene and the second reactive monomer. 
     In the present preparation, the thermoplastic polyimide precursor was marked as TPI-3. 
     Preparation 10 Fabrication of a Thermoplastic Polyimide Precursor 
     The present preparation was similar to Preparation 7. The differences between the present preparation and Preparation 7 were as follows. 
     18.196 grams of 1,3-bis(4-aminophenoxy)benzene and the second reactive monomer were dissolved in 425 grams of N-methyl-2-pyrrolidone to obtain the diamine solution. 10.466 grams of pyromellitic dianhydride was added into the diamine solution to process a first polymerization and a first polymerized solution was obtained. 22.00 grams of 3,3′,4,4′-biphenyl tetracarboxylic dianhydride was divided into two batches. The two batches of 3,3′,4,4′-biphenyl tetracarboxylic dianhydride were added into the first polymerized solution in sequence and stirred for 4 hours to process a secondary polymerization. The thermoplastic polyimide precursor was obtained after the secondary polymerization. 
     The second reactive monomer was 2,2′-bis(4-aminophenyl)propane. The usage amount of 2,2′-bis(4-aminophenyl)propane was 25.581 grams. The concentration of the second reactive monomer was 50.00 mol. % based on the total amount of 1,3-bis(4-aminophenoxy)benzene and the second reactive monomer. 
     In the present preparation, the thermoplastic polyimide precursor was marked as TPI-4. 
     Experiment 1 Polyimide Metal Laminated Plate and Method of Making the Same 
     With reference to  FIG. 1 , a polyimide metal laminated plate comprised a first copper film  10 , a first thermoplastic polyimide film  20 , a first thermosetting polyimide film  30 , a second thermoplastic polyimide film  40 , and a second copper film  50 . The first thermoplastic polyimide film  20  was laminated on a surface of the first copper film  10 . The first thermosetting polyimide film  30  was laminated on a surface of the first thermoplastic polyimide film  20  distal from the first copper film  10 . The second thermoplastic polyimide film  40  was laminated on a surface of the first thermosetting polyimide film  30  distal from the first thermoplastic polyimide film  20 . The second copper film  50  was laminated on a surface of the second thermoplastic polyimide film  40  distal from the first thermosetting polyimide film  30 . Each of the first thermoplastic polyimide film  20  and the second thermoplastic polyimide film  40  had a thickness of 2 μm. The first thermosetting polyimide film  30  had a thickness of 15 μm. 
     The method of making the polyimide metal laminated plate was described in detail as follows. 
     TPI-1 was coated on a surface of the first copper film  10  to form a first thermoplastic polyimide precursor layer. And then, PI-5 was coated on a surface of the first thermoplastic polyimide precursor layer distal from the first copper film  10  to form a first thermosetting polyimide precursor layer. Then, TPI-1 was coated on a surface of the first thermosetting polyimide precursor layer distal from the first thermoplastic polyimide precursor layer to form a second thermoplastic polyimide precursor layer. 
     Afterwards, the solvent, which was N-methyl-2-pyrrolidone, was removed from the first thermoplastic polyimide precursor layer, the first thermosetting polyimide precursor layer, and the second thermoplastic polyimide precursor layer under a desolventizing temperature ranging from 80° C. to 150° C., and a desolventized first thermoplastic polyimide precursor layer, a desolventized first thermosetting polyimide precursor layer, and a desolventized second thermoplastic polyimide precursor layer were obtained. 
     Next, the desolventized first thermoplastic polyimide precursor layer, the desolventized first thermosetting polyimide precursor layer, and the desolventized second thermoplastic polyimide precursor layer were heated simultaneously to a imidization temperature of 160° C. to 190° C., a imidization temperature of 190° C. to 300, and a imidization temperature of 300° C. to 350° C. in sequence under a nitrogen atmosphere. After heating, the desolventized first thermoplastic polyimide precursor layer, the desolventized first thermosetting polyimide precursor layer, and the desolventized second thermoplastic polyimide precursor layer were respectively imidized to the first thermoplastic polyimide film  20 , the first thermosetting polyimide film  30 , and the second thermoplastic polyimide film  40 . 
     After the copper film  50  was laminated on a surface of the second thermoplastic polyimide film  40  distal from the first thermosetting polyimide film  30  under a lamination temperature ranging from 320° C. to 380° C. and a lamination pressure ranging from 50 KgF/cm 2  to 100 KgF/cm 2 , the polyimide metal laminated plate was obtained. 
     Experiment 2 Polyimide Metal Laminated Plate and Method of Making the Same 
     The present experiment was similar to Experiment 1. The difference between the present experiment and Experiment 1 was that the first thermosetting polyimide film had a thickness of 8 μm. 
     Experiment 3 Polyimide Metal Laminated Plate and Method of Making the Same 
     The present experiment was similar to Experiment 1. The difference between the present experiment and Experiment 1 was that the first thermosetting polyimide film was made from PI-6. 
     Experiment 4 Polyimide Metal Laminated Plate and Method of Making the Same 
     The present experiment was similar to Experiment 1. The differences between the present experiment and Experiment 1 were that the first thermosetting polyimide film was made from PI-6 and the first thermosetting polyimide had a thickness of 5 μm. 
     Experiment 5 Polyimide Metal Laminated Plate and Method of Making the Same 
     The present experiment was similar to Experiment 1. The differences between the present experiment and Experiment 1 were as follows. 
     The first and the second thermoplastic polyimide films were made from TPI-2. The first thermosetting polyimide film was made from PI-6 and the first thermosetting polyimide film had a thickness of 20 μm. 
     Experiment 6 Polyimide Metal Laminated Plate and Method of Making the Same 
     The present experiment was similar to Experiment 1. The differences between the present experiment and Experiment 1 were as follows. 
     The first and the second thermoplastic polyimide films were made from TPI-2. The first thermosetting polyimide film was made from PI-6 and the first thermosetting polyimide had a thickness of 8 μm. 
     Experiment 7 Polyimide Metal Laminated Plate and Method of Making the Same 
     The present experiment was similar to Experiment 1. The differences between the present experiment and Experiment 1 were as follows. 
     The first and the second thermoplastic polyimide films were made from TPI-3. The first thermosetting polyimide film was made from PI-6 and had a thickness of 8 μm. 
     Experiment 8 Polyimide Metal Laminated Plate and Method of Making the Same 
     The present experiment was similar to Experiment 1. The differences between the present experiment and Experiment 1 were as follows. 
     The first and the second thermoplastic polyimide films were made from TPI-4. The first thermosetting polyimide film was made from PI-6 and had a thickness of 8 μm. 
     Experiment 9 Polyimide Metal Laminated Plate and Method of Making the Same 
     The present experiment was similar to Experiment 1. The difference between the present experiment and Experiment 1 was that the first thermosetting polyimide film was made from PI-4. 
     Experiment 10 Polyimide Metal Laminated Plate 
     With reference to  FIG. 2 , a polyimide metal laminated plate comprised a copper film  10 A, a first thermoplastic polyimide film  20 A, a first thermosetting polyimide film  30 A, and a second thermoplastic polyimide film  40 A. The first thermoplastic polyimide film  20 A was laminated on a surface of the copper film  10 A. The first thermosetting polyimide film  30 A was laminated on a surface of the first thermoplastic polyimide film  20 A distal from the copper film  10 A. The second thermoplastic polyimide film  40 A was laminated on a surface of the first thermosetting polyimide film  30 A distal from the first thermoplastic polyimide film  20 A. 
     With reference to  FIGS. 1 and 2 , the copper film  10 A, the first thermoplastic polyimide film  20 A, the first thermosetting polyimide film  30 A, and the second thermoplastic polyimide film  40 A of the present experiment were respectively equivalent to the first copper film  10 , the first thermoplastic polyimide film  20 , the first thermosetting polyimide film  30 , and the second thermoplastic polyimide film  40  of Experiment 1. 
     Experiment 11 Polyimide Metal Laminated Plate 
     With reference to  FIGS. 1 and 3 , the present experiment was similar to Experiment 1. The difference between the present experiment and Experiment 1 was that the polyimide metal laminated plate had a third thermoplastic polyimide film  60  laminated between the second copper film  50  and the second thermoplastic polyimide film  40 . 
     Experiment 12 Polyimide Metal Laminated Plate 
     With reference to  FIGS. 3 and 4 , the present experiment was similar to Experiment 11. The difference between the present experiment and Experiment 11 was that the polyimide metal laminated plate had a second thermosetting polyimide film  70  laminated between the third thermoplastic polyimide film  60  and the second thermoplastic polyimide film  40 . 
     Experiment 13 Polyimide Metal Laminated Plate 
     With reference to  FIGS. 4 and 5 , the present experiment was similar to Experiment 12. The difference between the present experiment and Experiment 12 was that the polyimide metal laminated plate had a fourth thermoplastic polyimide film  80  laminated between the second thermosetting polyimide film  70  and the second thermoplastic polyimide film  40 . 
     Comparison 1 Polyimide Metal Laminated Plate and Method of Making the Same 
     The present comparison was similar to Experiment 1. The differences between the present comparison and Experiment 1 were as follows. 
     The first thermosetting polyimide film was made from PI-3 and had a thickness of 8 μm. 
     Comparison 2 Polyimide Metal Laminated Plate and Method of Making the Same 
     With reference to  FIG. 6 , a polyimide metal laminated plate comprised a copper film  10 B, a thermoplastic polyimide film  20 B and a thermosetting polyimide film  30 B. The thermoplastic polyimide film  20 B was laminated on a surface of the copper film  10 B. The thermosetting polyimide film  30 B was laminated on a surface of the thermoplastic polyimide film  20 B distal from the copper film  10 B. The thermoplastic polyimide film  20 B had a thickness ranging from 2 μm to 3 μm. The thermosetting polyimide film  30 B had a thickness ranging from 17 μm to 18 μm. 
     With reference to  FIGS. 1 and 6 , the copper film  10 B, the thermoplastic polyimide film  20 B, and the thermosetting polyimide film  30 B of the present comparison were respectively equivalent to the first copper film  10 , the first thermoplastic polyimide film  20 , and the first thermosetting polyimide film  30  of Experiment 1. 
     The method of making the polyimide metal laminated plate of the present comparison was described in detail as follows. 
     TPI-1 was coated on a surface of the copper film  10 B to form a thermoplastic polyimide precursor layer. Then, PI-1 was coated on a surface of the thermoplastic polyimide precursor layer distal from the copper film  10 B to form a thermosetting polyimide precursor layer. 
     Afterwards, the solvent, which was N-methyl-2-pyrrolidone, was removed from the thermoplastic polyimide precursor layer and the thermosetting polyimide precursor layer under a desolventizing temperature ranging from 80° C. to 150° C., and a desolventized thermoplastic polyimide precursor layer and a desolventized thermosetting polyimide precursor layer were obtained. 
     Next, the desolventized thermoplastic polyimide precursor layer and the desolventized thermosetting polyimide precursor layer were heated simultaneously to a imidization temperature of 160° C. to 190° C., a imidization temperature of 190° C. to 300° C., and a imidization temperature of 300° C. to 350° C. in sequence under a nitrogen atmosphere. After heating, the desolventized thermoplastic polyimide precursor layer and the desolventized thermosetting polyimide precursor layer were respectively imidized to the thermoplastic polyimide film  20 B and the thermosetting polyimide film  30 B; the polyimide metal laminated plate was obtained. 
     Comparison 3 Polyimide Metal Laminated Plate and Method of Making the Same 
     The present comparison was similar to Comparison 2. The difference between the present comparison and Comparison 2 was that the thermosetting polyimide film was made from PI-2. 
     Comparison 4 Polyimide Metal Laminated Plate and Method of Making the Same 
     The present comparison was similar to Comparison 2. The difference between the present comparison and Comparison 2 was that the thermosetting polyimide film was made from PI-3. 
     Comparison 5 Polyimide Metal Laminated Plate and Method of Making the Same 
     The present comparison was similar to Comparison 2. The difference between the present comparison and Comparison 2 was that the thermosetting polyimide film was made from PI-4. 
     Comparison 6 Polyimide Metal Laminated Plate and Method of Making the Same 
     The present comparison was similar to Comparison 2. The difference between the present comparison and Comparison 2 was that the thermosetting polyimide film was made from PI-5. 
     Comparison 7 Polyimide Metal Laminated Plate and Method of Making the Same 
     The present comparison was similar to Comparison 2. The difference between the present comparison and Comparison 2 was that the thermosetting polyimide film was made from PI-6. 
     Comparison 8 Polyimide Metal Laminated Plate and Method of Making the Same 
     With reference to  FIG. 7 , a polyimide metal laminated plate comprised a copper film  10 C, a thermosetting polyimide film  30 C and a thermoplastic polyimide film  40 C. The thermosetting polyimide film  30 C was laminated on a surface of the copper film  10 C. The thermoplastic polyimide film  40 C was laminated on a surface of the thermosetting polyimide film  30 C distal from the copper film  10 C. The thermosetting polyimide film  30 C had a thickness ranging from 17 μm to 18 μm. The thermoplastic polyimide film  40 C had a thickness ranging from 2 μm to 3 μm. 
     With reference to  FIGS. 1 and 7 , the copper film  10 C, the thermosetting polyimide film  30 C, and the thermoplastic polyimide film  40 C of the present comparison were respectively equivalent to the first copper film  10 , the first thermosetting polyimide film  30 , and the second thermoplastic polyimide film  40  of Experiment 1. 
     The method of making the polyimide metal laminated plate of the present comparison was described in detail as follows. 
     PI-3 was coated on a surface of the copper film  10 C to form a thermosetting plastic polyimide precursor layer. Then, TPI-1 was coated on a surface of the thermosetting polyimide precursor layer distal from the copper film  10 C to form a thermoplastic polyimide precursor layer. 
     Afterwards, the solvent, which was N-methyl-2-pyrrolidone, was removed from the thermosetting polyimide precursor layer and the thermoplastic polyimide precursor layer under a desolventizing temperature ranging from 80° C. to 150° C., and a desolventized thermosetting polyimide precursor layer and a desolventized thermoplastic polyimide precursor layer were obtained. 
     Next, the desolventized thermosetting polyimide precursor layer and the desolventized thermoplastic polyimide precursor layer were heated simultaneously to a imidization temperature of 160° C. to 190° C., a imidization temperature of 190° C. to 300° C., and a imidization temperature of 300° C. to 350° C. in sequence under a nitrogen atmosphere. After heating, the desolventized thermosetting polyimide precursor layer and the desolventized thermoplastic polyimide precursor layer were respectively imidized to the thermosetting polyimide film  30 C and the thermoplastic polyimide film  40 C; the polyimide metal laminated plate was obtained. 
     Comparison 9 Polyimide Metal Laminated Plate and Method of Making the Same 
     The present comparison was similar to Comparison 8. The difference between the present comparison and Comparison 8 was that the thermosetting polyimide film was made from PI-4. 
     Comparison 10 Polyimide Metal Laminated Plate and Method of Making the Same 
     The present comparison was similar to Comparison 8. The difference between the present comparison and Comparison 8 was that the thermosetting polyimide film was made from PI-5. 
     Comparison 11 Polyimide Metal Laminated Plate and Method of Making the Same 
     The present comparison was similar to Comparison 8. The differences between the present comparison and Comparison 8 were that the thermosetting polyimide film and the thermoplastic polyimide film were respectively made from PI-5 and TPI-2. 
     Comparison 12 Polyimide Metal Laminated Plate and Method of Making the Same 
     The present comparison was similar to Comparison 8. The differences between the present comparison and Comparison 8 were that the thermosetting polyimide film and the thermoplastic polyimide film were respectively made from PI-6 and TPI-3. 
     Comparison 13 Polyimide Metal Laminated Plate and Method of Making the Same 
     The present comparison was similar to Comparison 8. The differences between the present comparison and Comparison 8 were that the thermosetting polyimide film and the thermoplastic polyimide film were respectively made from PI-6 and TPI-4. 
     Results and Discussion 
     The results and discussion were related to the properties of glass transition temperature (T g ), coefficient of thermal expansion (C.T.E.), water vapor transmission rate (W.V.T.R.), peeling strength, dimensional stability and solder resistance. 
     T g  was measured by the Pyris Diamond dynamics mechanical analyzer of PerkinElmer Co. under a temperature gradient of 10° C./min. 
     C.T.E. was measured by the Pyris Diamond thermal mechanical analyzer of PerkinElmer Co. under a temperature gradient of 10° C./min. 
     W.V.T.R. was measured by PERMATRAN-W Model 3/61 water vapor transmission rate analyzer of Mocon Inc. under 40° C. and 90% RH. 
     According to IPC-TM-650 2.4.9, peeling strength was measured. 
     According to the method B and method C of IPC-TM-650 2.2.4, dimensional stability was measured. 
     According to IPC-TM-650 2.4.13, a solder resistance test was measured under a condition of 300° C./30 sec to evaluate the solder resistance. 
     In addition, the results and discussion were related to the delamination and whitening caused by a cyclization reaction. 
     
       
         
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Properties of each polyimide metal laminated plate of Experiments 1 to 4 and 
               
               
                 Comparison 1, and thickness and raw material of the films of the same. 
               
             
          
           
               
                   
                 Comparison 1 
                 Experiment 1 
                 Experiment 2 
                 Experiment 3 
                 Experiment 4 
               
               
                   
                   
               
             
          
           
               
                 Second 
                 Raw 
                 TPI-1 
                 TPI-1 
                 TPI-1 
                 TPI-1 
                 TPI-1 
               
               
                 thermoplastic 
                 material 
               
               
                 polyimide film 
                 Thickness 
                 2 
                 2 
                 2 
                 2 
                 2 
               
               
                   
                 (unit: μm) 
               
               
                 First 
                 Raw 
                 PI-3 
                 PI-5 
                 PI-5 
                 PI-6 
                 PI-6 
               
               
                 thermosetting 
                 material 
               
               
                 polyimide film 
                 Thickness 
                 8 
                 15 
                 8 
                 15 
                 5 
               
               
                   
                 (unit: μm) 
               
               
                 First 
                 Raw 
                 TPI-1 
                 TPI-1 
                 TPI-1 
                 TPI-1 
                 TPI-1 
               
               
                 thermoplastic 
                 material 
               
               
                 polyimide film 
                 Thickness 
                 2 
                 2 
                 2 
                 2 
                 2 
               
               
                   
                 (unit: μm) 
               
             
          
           
               
                 Peeling strength 
                 n/a 
                 1.28 
                 1.03 
                 1.66 
                 1.08 
               
               
                 (unit: kgf/cm) 
               
             
          
           
               
                 Dimensional 
                 M.D. 
                 n/a 
                 0.021% 
                 −0.025% 
                 0.040% 
                 0.026% 
               
               
                 Stability 
                 T.D. 
                 n/a 
                 −0.028% 
                 −0.062% 
                 −0.013% 
                 −0.023% 
               
               
                 (method B) 
               
               
                 Dimensional 
                 M.D. 
                 n/a 
                 0.016% 
                 −0.029% 
                 0.028% 
                 0.005% 
               
               
                 Stability 
                 T.D. 
                 n/a 
                 −0.039% 
                 −0.073% 
                 −0.019% 
                 −0.046% 
               
               
                 (method C) 
               
             
          
           
               
                 Solder resistance test 
                 n/a 
                 Passed 
                 Passed 
                 Passed 
                 Passed 
               
               
                 W.V.T.R. 
                 171  
                 232 
                 229 
                 183 
                 187 
               
               
                 (unit: g-μm/m 2 -day) 
               
               
                 Delamination and whitening 
                 Yes 
                 No 
                 No 
                 No 
                 No 
               
               
                 (Yes/No) 
               
               
                   
               
             
          
         
       
     
     With reference to Table 1, Table 2, and  FIG. 1 , there was no delamination and whitening observed between the first thermosetting polyimide film  30  and the first thermoplastic polyimide film  20  of each polyimide metal laminated plate of Experiments 1 to 9 and there was no delamination and whitening observed between the first thermosetting polyimide film  30  and the second thermoplastic polyimide film  40  of Experiments 1 to 9. A conclusion was made that not only the water vapor between the first thermosetting polyimide film  30  and the first thermoplastic polyimide film  20  of each polyimide metal laminated plate of Experiments 1 to 9 were exhausted, but also the water vapor between the first thermosetting polyimide film  30  and the second thermoplastic polyimide film  40  of each polyimide metal laminated plate of Experiments 1 to 9 were exhausted. 
     
       
         
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Properties of each polyimide metal laminated plate of Experiments 
               
               
                 5 to 9, and thickness and raw material of the films of the same. 
               
             
          
           
               
                   
                 Experiment 5 
                 Experiment 6 
                 Experiment 7 
                 Experiment 8 
                 Experiment 9 
               
               
                   
                   
               
             
          
           
               
                 Second 
                 Raw 
                 TPI-2 
                 TPI-2 
                 TPI-3 
                 TPI-4 
                 TPI-1 
               
               
                 thermoplastic 
                 material 
               
               
                 polyimide film 
                 Thickness 
                 2 
                 2 
                 2 
                 2 
                 2 
               
               
                   
                 (unit: μm) 
               
               
                 First 
                 Raw 
                 PI-6 
                 PI-6 
                 PI-6 
                 PI-6 
                 PI-4 
               
               
                 thermosetting 
                 material 
               
               
                 polyimide film 
                 Thickness 
                 20 
                 8 
                 8 
                 8 
                 15 
               
               
                   
                 (unit: μm) 
               
               
                 First 
                 Raw 
                 TPI-2 
                 TPI-2 
                 TPI-3 
                 TPI-4 
                 TPI-1 
               
               
                 thermoplastic 
                 material 
               
               
                 polyimide film 
                 Thickness 
                 2 
                 2 
                 2 
                 2 
                 2 
               
               
                   
                 (unit: μm) 
               
             
          
           
               
                 Peeling strength 
                 1.60 
                 1.59 
                 1.21 
                 1.17 
                 1.04 
               
               
                 (unit: kgf/cm) 
               
             
          
           
               
                 Dimensional 
                 M.D. 
                 0.027% 
                 0.037% 
                 −0.011% 
                 0.043% 
                 0.013% 
               
               
                 Stability 
                 T.D. 
                 −0.031% 
                 −0.005% 
                 −0.042% 
                 0.002% 
                 −0.012% 
               
               
                 (method B) 
               
               
                 Dimensional 
                 M.D. 
                 0.018% 
                 0.017% 
                 −0.021% 
                 0.029% 
                 −0.006% 
               
               
                 Stability 
                 T.D. 
                 −0.033% 
                 −0.012% 
                 −0.046% 
                 −0.013% 
                 −0.038% 
               
               
                 (method C) 
               
             
          
           
               
                 Solder resistance test 
                 Passed 
                 Passed 
                 Passed 
                 Passed 
                 Passed 
               
               
                 W.V.T.R. 
                 217 
                 190 
                 226 
                 245 
                 191 
               
               
                 (unit: g-μm/m 2 -day) 
               
               
                 Delamination and whitening 
                 No 
                 No 
                 No 
                 No 
                 No 
               
               
                 (Yes/No) 
               
               
                   
               
             
          
         
       
     
     On the contrary, there was delamination and whitening observed between the first thermosetting polyimide film  30  and the first thermoplastic polyimide film  20  of the polyimide metal laminated plate of Comparison 1, and there was delamination and whitening observed between the first thermosetting polyimide film  30  and the second thermoplastic polyimide film  40  of Comparison 1. A conclusion was made that both the water vapor between the first thermosetting polyimide film  30  and the first thermoplastic polyimide film 20 of the polyimide metal laminated plate of Comparison 1 and the water vapor between the first thermosetting polyimide film  30  and the second thermoplastic polyimide film  40  of Comparison 1 were not exhausted. 
     With reference to Table 3 and  FIG. 6 , there was delamination and whitening observed between the thermoplastic polyimide film  20 B and the thermosetting polyimide film  30 B of each polyimide metal laminated plate of Comparisons 2 to 4 whereas there was no delamination and whitening observed from each polyimide metal laminated plate of Comparisons 5 to 7. Further with reference to Tables 4 and 5, the thermosetting polyimide film  30 B of each polyimide metal laminated plate of Comparisons 2 to 4 had a W.V.T.R. less than 170 g μm/m 2 -day whereas the thermosetting polyimide film  30 B of each polyimide metal laminated plate of Comparisons 5 to 7 had a W.V.T.R. equal to or more than 170 g-μm/m 2 -day. Accordingly, a rationale conclusion was made that no delamination and whitening was observed from each of the polyimide metal laminated plate of Comparisons 5 to 7 because the thermosetting polyimide film  30 B of each polyimide metal laminated plate of Comparisons 5 to 7 had a W.V.T.R. equal to or more than 170 g-μm/m 2 -day. 
     
       
         
               
             
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 3 
               
             
             
               
                   
               
               
                 Glass transition temperature(T g ), coefficient of 
               
               
                 thermal expansion(C.T.E.), water vapor transmission 
               
               
                 rate(W.V.T.R.), and thickness of each thermosetting 
               
               
                 polyimide film obtained after thermally imidizing 
               
               
                 PI-1, PI-2, PI-3, PI-4, PI-5, and PI-6. 
               
             
          
           
               
                   
                 Raw material of thermosetting polyimide film 
               
             
          
           
               
                   
                 PI-1 
                 PI-2 
                 PI-3 
                 PI-4 
                 PI-5 
                 PI-6 
               
               
                   
                   
               
             
          
           
               
                 T g  (unit: ° C.) 
                 335 
                 323 
                 316 
                 349 
                 356 
                 342 
               
               
                 C.T.E. 
                 18 
                 18 
                 20 
                 17 
                 16 
                 18 
               
               
                 (unit: 10 −6 / 
               
               
                 ° C.) 
               
               
                 W.V.T.R. 
                 2.95 
                 6.41 
                 7.47 
                 9.44 
                 13.59 
                 11.20 
               
               
                 (unit: g/ 
               
               
                 m 2 -day) 
               
               
                 Thickness 
                 17 
                 17 
                 17 
                 18 
                 17 
                 20 
               
               
                 (unit: μm) 
               
               
                 W.V.T.R. 
                 50 
                 109 
                 127 
                 170 
                 231 
                 224 
               
               
                 (unit: g-μm/ 
               
               
                 m 2 -day) 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                 TABLE 4 
               
             
             
               
                   
               
               
                 Glass transition temperature(T g ), coefficient of thermal expansion 
               
               
                 (C.T.E.), water vapor transmission rate(W.V.T.R.), and thickness 
               
               
                 of each of thermoplastic polyimide films obtained after thermally 
               
               
                 imidizing TPI-1, TPI-2, TPI-3, and TPI-4. 
               
             
          
           
               
                   
                 Raw material of thermoplastic 
               
               
                   
                 polyimide film 
               
             
          
           
               
                   
                 TPI-1 
                 TPI-2 
                 TPI-3 
                 TPI-4 
               
               
                   
                   
               
             
          
           
               
                 T g  (unit: ° C.) 
                 234 
                 236 
                 265 
                 266 
               
               
                 C.T.E. (unit: 10 −6 /° C.) 
                 60 
                 55 
                 58 
                 55 
               
               
                 W.V.T.R. (unit: g/m 2 -day) 
                 26.76 
                 13.60 
                 38.40 
                 64.53 
               
               
                 Thickness (unit: μm) 
                 21 
                 15 
                 15 
                 15 
               
               
                 W.V.T.R. (unit: g-μm/m 2 -day) 
                 562 
                 204 
                 576 
                 968 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 5 
               
             
             
               
                   
               
               
                 Delamination and whitening of each polyimide metal laminated plate of Comparisons 
               
               
                 2 to 7, and thickness and raw material of the films of the same. 
               
             
          
           
               
                 Comparison No. 
                 2 
                 3 
                 4 
                 5 
                 6 
                 7 
               
               
                   
               
             
          
           
               
                 Thermosetting 
                 Raw 
                 PI-1 
                 PI-2 
                 PI-3 
                 PI-4 
                 PI-5 
                 PI-6 
               
               
                 polyimide film 
                 material 
               
               
                   
                 Thickness 
                 17~18 
                 17~18 
                 17~18 
                 17~18 
                 17~18 
                 17~18 
               
               
                   
                 (unit: μm) 
               
               
                 Thermoplastic 
                 Raw 
                 TPI-1 
                 TPI-1 
                 TPI-1 
                 TPI-1 
                 TPI-1 
                 TPI-1 
               
               
                 polyimide film 
                 material 
               
               
                   
                 Thickness 
                 2~3 
                 2~3 
                 2~3 
                 2~3 
                 2~3 
                 2~3 
               
               
                   
                 (unit: μm) 
               
             
          
           
               
                 Delamination and whitening 
                 Yes 
                 Yes 
                 Yes 
                 No 
                 No 
                 No 
               
               
                 (Yes/No) 
               
               
                   
               
             
          
         
       
     
     In addition, the thermosetting polyimide films  30 B of Comparisons 5 to 7 were respectively made from PI-4, PI-5, and PI-6. The thermosetting polyimide films  30 B of Comparisons 2 to 4 were respectively made from PI-1, PI-2, and PI-3. To fabricate PI-4, PI-5, and PI-6, the concentration of the first reactive monomer was 2.7 mol. % at least based on the total amount of the first reactive monomer and the diamine. To fabricate PI-2 and PI-3, the concentration of the first reactive monomer was less than 2.7 mol. % based on the total amount of the first reactive monomer and the diamine. There was no first reactive monomer used to fabricate PI-1. 
     With reference to Table 6 and  FIG. 7 , there was no delamination and whitening observed between the thermoplastic polyimide film  40 C and the thermosetting polyimide film  30 C of each polyimide metal laminated plate of Comparisons 8 to 13. Further with reference to Tables 4 and 5, the thermoplastic polyimide film  40 C of each polyimide metal laminated plate of Comparisons 8 to 13 had a W.V.T.R. more than 170 g-μm/m 2 -day. Accordingly, a conclusion was made that no delamination and whitening was observed from the polyimide metal laminated plate of Comparisons 8 to 13 because the thermoplastic polyimide film  40 C of each polyimide metal laminated plate of Comparisons 8 to 13 had a W.V.T.R. more than 170 g-μm/m 2 -day. 
     
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 6 
               
             
             
               
                   
               
               
                 Delamination and whitening of each polyimide metal laminated plate of Comparisons 
               
               
                 8 to 13, and thickness and raw material of the films of the same. 
               
             
          
           
               
                 Comparison No. 
                 8 
                 9 
                 10 
                 11 
                 12 
                 13 
               
               
                   
               
             
          
           
               
                 Thermoplastic 
                 Raw 
                 TPI-1 
                 TPI-1 
                 TPI-1 
                 TPI-2 
                 TPI-3 
                 TPI-4 
               
               
                 polyimide film 
                 material 
               
               
                   
                 Thickness 
                 2~3 
                 2~3 
                 2~3 
                 2~3 
                 2~3 
                 2~3 
               
               
                   
                 (unit: μm) 
               
               
                 Thermosetting 
                 Raw 
                 PI-3 
                 PI-4 
                 PI-5 
                 PI-5 
                 PI-6 
                 PI-6 
               
               
                 polyimide film 
                 material 
               
               
                   
                 Thickness 
                 17~18 
                 17~18 
                 17~18 
                 17~18 
                 17~18 
                 17~18 
               
               
                   
                 (unit: μm) 
               
             
          
           
               
                 Delamination and whitening 
                 No 
                 No 
                 No 
                 No 
                 No 
                 No 
               
               
                 (Yes/No) 
               
               
                   
               
             
          
         
       
     
     Based on the above, since both the first thermosetting polyimide film  30  and the second thermoplastic polyimide film  40  of each polyimide metal laminated plate of Experiments 1 to 9 had a W.V.T.R. more than 170 g-μm/m 2 -day, and the W.V.T.R. of the second thermoplastic polyimide film  40  was more than the W.V.T.R. of the first thermosetting polyimide film  30 , there was no delamination and whitening observed between the first thermosetting polyimide film  30  and the first thermoplastic polyimide film  20 , and between the first thermosetting polyimide film  30  and the second thermoplastic polyimide film  40  of each polyimide metal laminated plate of Experiments 1 to 9. In addition, by PI-4, PI-5, and PI-6 that were fabricated by using the first reactive monomer in an amount more than 3.39 mol. % based on the total amount of the first reactive monomer and the diamine, both the first thermosetting polyimide film  30  and the second thermoplastic polyimide film  40  of each polyimide metal laminated plate of Experiments 1 to 9 had a W. V. T. R. more than 170 g-μm/m 2 -day. By TPI-1, TPI-2, TPI-3, and TPI-4 that were fabricated by using the second reactive monomer in an amount more than 35.89 mol. % based on the total amount of the first reactive monomer and the diamine, the second thermoplastic polyimide film  40  of each polyimide metal laminated plate of Experiments 1 to 9 had a W.V.T.R. more than 170 g-μm/m 2 -day. 
     With reference to Tables 1 and 2, since each of the polyimide metal laminated plate of Experiments 1 to 9 passed the solder resistance measurement based on IPC-TM-650 2.4.13 under a condition of 300° C./30 sec, each polyimide metal laminated plate of Experiments 1 to 9 had a good solder resistance. 
     With reference to Tables 1 and 2, since the T.D. and M.D. measured according to the method B of IPC-TM-650 2.2.4 of each polyimide metal laminated plate of Experiments 1 to 9 was close to zero, and the T.D. and M.D. measured according to the method C of IPC-TM-650 2.2.4 of each polyimide metal laminated plate of Experiments 1 to 9 was close to zero, each polyimide metal laminated plate of Experiments 1 to 9 had a good dimensional stability. 
     With reference to Tables 1 and 2, each polyimide metal laminated plate of Experiments 1 to 9 had a peeling strength more than 0.8 kgf/cm, which demonstrates that each polyimide metal laminated plate of Experiments 1 to 9 had a good peeling strength. 
     To sum up, by PI-4, PI-5, and PI-6 that were fabricated by using the first reactive monomer in an amount more than 3.39 mol. % based on the total amount of the first reactive monomer and the diamine and TPI-1, TPI-2, TPI-3, and TPI-4 that were fabricated by using the second reactive monomer in an amount more than 35.89 mol. %, both the first thermosetting polyimide film  30  and the second thermoplastic polyimide film  40  of each polyimide metal laminated plate of Experiments 1 to 9 had W.V.T.R. more than 170 g-μm/m 2 -day. Therefore, there was no delamination and whitening observed from each polyimide metal laminated plate of Experiments 1 to 9. In addition, each polyimide metal laminated plate of Experiments 1 to 9 had good solder resistance, dimensional stability, and peeling strength. 
     Even though numerous characteristics and advantages of the present invention have been set forth in the foregoing description, together with details of the structure and features of the invention, the disclosure is illustrative only. Changes may be made in the details, especially in matters of shape, size, and arrangement of parts within the principles of the invention to the full extent indicated by the broad general meaning of the terms in which the appended claims are expressed.