TW201540494A - Polyimide/metal composite laminate plate and its manufacturing method - Google Patents
Polyimide/metal composite laminate plate and its manufacturing method Download PDFInfo
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本發明係關於一種聚醯亞胺/金屬複合積層板及其製備方法，尤指一種可省去膠層的聚醯亞胺/金屬複合積層板及其製備方法。 The invention relates to a polyimine/metal composite laminate and a preparation method thereof, in particular to a polyamidene/metal composite laminate which can eliminate the adhesive layer and a preparation method thereof.
芳香族之聚醯亞胺因具有高耐溫、抗化學、優異之機械與電氣等特性，廣泛的被使用在筆記型電腦、消費性電子與通信用手持式的電子產品中的電子零組件之軟性印刷電路板(flexible printed circuit board，FPCB)。 Aromatic polyimine is widely used in electronic components of notebook computers, consumer electronics and communication handheld electronic products due to its high temperature resistance, chemical resistance, and excellent mechanical and electrical properties. Flexible printed circuit board (FPCB).
現有的軟性印刷電路板的製造方式，係以聚醯亞胺膜為基材，於聚醯亞胺膜之兩側面分別塗佈環氧樹脂或壓克力樹脂以成形一膠層，再令兩金屬銅箔分別透過兩膠層貼合於聚醯亞胺膜之兩側面上，得到該軟性印刷電路板。 The existing flexible printed circuit board is manufactured by using a polyimide film as a substrate, and coating epoxy resin or acrylic resin on both sides of the polyimide film to form a rubber layer, and then making two The metal copper foil is adhered to both sides of the polyimide film through the two adhesive layers to obtain the flexible printed circuit board.
然而，由環氧樹脂或壓克力樹脂製成的膠層會對於軟性印刷電路板之耐熱、耐燃、抗化與尺寸安定性產生不良之影響，且膠層係具有相當的厚度，係無法滿足軟性印刷電路板之薄型化趨勢。 However, the adhesive layer made of epoxy resin or acrylic resin may have adverse effects on the heat resistance, flame resistance, chemical resistance and dimensional stability of the flexible printed circuit board, and the rubber layer has a considerable thickness and cannot be satisfied. The trend of thinning of flexible printed circuit boards.
有鑒於上述現有技術之缺點，本發明之目的在於提供一種可省去膠層的聚醯亞胺/金屬複合積層板及其 製備方法。 In view of the above disadvantages of the prior art, the object of the present invention is to provide a polyimide/metal composite laminate which can eliminate the adhesive layer and Preparation.
為了可達到前述之發明目的，本發明所採取之技術手段係令該聚醯亞胺/金屬複合積層板，其中包含：一第一金屬膜；一第一熱塑性聚醯亞胺膜，係貼靠重疊於該第一金屬膜之一側面上；一第一熱固性聚醯亞胺膜，係貼靠重疊於該第一熱塑性聚醯亞胺膜遠離該第一金屬膜的一側面上，且該第一熱固性聚醯亞胺膜之水氣穿透率不低於170公克-微米/平方公尺-天(g-μm/m2-day)；以及，一第二熱塑性聚醯亞胺膜，係貼靠重疊於該第一熱固性聚醯亞胺膜遠離該第一熱塑性聚醯亞胺膜的一側面上，且該第二熱塑性聚醯亞胺膜之水氣穿透率不低於該第一熱固性聚醯亞胺膜之水氣穿透率。 In order to achieve the foregoing object, the technical means adopted by the present invention is to obtain the polyimine/metal composite laminate comprising: a first metal film; a first thermoplastic polyimide film, which is adhered to Superimposed on one side of the first metal film; a first thermosetting polyimide film adheres to a side of the first thermoplastic polyimide film away from the first metal film, and the first a thermosetting polyimide film having a water vapor permeability of not less than 170 g-micrometers per square meter-day (g-μm/m 2 -day); and, a second thermoplastic polyimide film, Adheringly overlapping the first thermosetting polyimide film on one side of the first thermoplastic polyimide film, and the water permeability of the second thermoplastic polyimide film is not lower than the first Water vapor transmission rate of thermosetting polyimide film.
所述聚醯亞胺/金屬複合積層板由於不具有膠層，係能滿足軟性印刷電路板之薄型化的趨勢且具有良好的耐焊性、尺寸安定性及剝離強度；同時，藉由具有不低於170g-μm/m2-day的水氣穿透率的第一熱固性聚醯亞胺膜及第二熱塑性聚醯亞胺膜，所述聚醯亞胺/金屬複合積層板係可避免脫層及白化現象的發生。 Since the polyimide/metal composite laminate has no adhesive layer, it can satisfy the trend of thinning of a flexible printed circuit board and has good solder resistance, dimensional stability and peel strength; a first thermosetting polyimide film and a second thermoplastic polyimide film having a water vapor permeability of less than 170 g-μm/m 2 -day, the polyamidene/metal composite laminated plate can be prevented from taking off The occurrence of layers and whitening.
於一實施態樣中，所述的聚醯亞胺/金屬複合積層板包含一貼靠重疊於該第二熱塑性聚醯亞胺膜遠離該第一熱固性聚醯亞胺膜的一側面上的第二金屬膜。 In one embodiment, the polyamidene/metal composite laminate comprises a layer that is attached to a side of the second thermoplastic polyimide film that is away from the first thermosetting polyimide film. Two metal film.
於另一實施態樣中，所述的聚醯亞胺/金屬複合積層板包含一第三熱塑性聚醯亞胺膜，該第二金屬膜透過 該第三熱塑性聚醯亞胺膜貼靠重疊於該第二熱塑性聚醯亞胺膜上。 In another embodiment, the polyamidene/metal composite laminate comprises a third thermoplastic polyimide film, and the second metal film is transparent. The third thermoplastic polyimide film is placed against the second thermoplastic polyimide film.
於又一實施態樣中，所述的聚醯亞胺/金屬複合積層板包含一第二熱固性聚醯亞胺膜，該第三熱塑性聚醯亞胺膜透過該第二熱固性聚醯亞胺膜貼靠重疊於該第二熱塑性聚醯亞胺膜上。 In still another embodiment, the polyamidene/metal composite laminate comprises a second thermosetting polyimide film, and the third thermoplastic polyimide film is passed through the second thermosetting polyimide film. Adhering to the second thermoplastic polyimide film.
於再一實施態樣中，所述的聚醯亞胺/金屬複合積層板包含一第四熱塑性聚醯亞胺膜，該第二熱固性聚醯亞胺膜透過該第四熱塑性聚醯亞胺膜貼靠重疊於該第二熱塑性聚醯亞胺膜相接。 In still another embodiment, the polyamidene/metal composite laminate comprises a fourth thermoplastic polyimide film, and the second thermosetting polyimide film is passed through the fourth thermoplastic polyimide film. The abutting overlaps the second thermoplastic polyimide film to meet.
較佳的是，該第二熱塑性聚醯亞胺膜之水氣穿透率不低於200g-μm/m2-day。 Preferably, the second thermoplastic polyimide film has a water vapor permeability of not less than 200 g-μm/m 2 -day.
較佳的是，該第一熱固性聚醯亞胺膜之水氣穿透率不低於200g-μm/m2-day。 Preferably, the first thermosetting polyimide film has a water vapor permeability of not less than 200 g-μm/m 2 -day.
較佳的是，該第一熱塑性聚醯亞胺膜、該第一熱固性聚醯亞胺膜及該第二熱塑性聚醯亞胺膜之總厚度係介於9微米(μm)至25微米(μm)之間。 Preferably, the first thermoplastic polyimide film, the first thermosetting polyimide film and the second thermoplastic polyimide film have a total thickness of from 9 micrometers (μm) to 25 micrometers (μm). )between.
較佳的是，該第一熱塑性聚醯亞胺膜、該第一熱固性聚醯亞胺膜及該第二熱塑性聚醯亞胺膜整體之水氣穿透率係不低於180g-μm/m2-day。 Preferably, the water permeability of the first thermoplastic polyimide film, the first thermosetting polyimide film, and the second thermoplastic polyimide film is not less than 180 g-μm/m. 2 -day.
為了可達到前述之發明目的，本發明所採取之技術手段係令該聚醯亞胺/金屬複合積層板之製備方法，其步驟包含：令第一二胺單體、第一反應性單體及第一二酸酐單體於第一溶劑中聚合，以得到一熱固性聚醯亞胺前驅物，該 第一反應性單體係選自下列構成之群組：2,2'-雙(4-氨基苯基)丙烷(2,2'-bis(4-aminophenyl)propane)、1,3-雙(3-氨基苯氧基)苯(1,3-bis(3-aminophenoxy)benzene)、4,4'-(1,3-二異丙烷基苯)二苯胺(4,4'-(1,3-phenylenediisopropylidene)bisaniline，Bisaniline-M)、9,9'-雙(4-氨基苯基)芴(9,9'-bis(4-aminophenyl)fluorene)、聚氧丙烯醚二胺(polyoxypropylenediamine)，且以該二胺單體及該反應性單體之總莫耳數為基準，該第一反應性單體之莫耳數係介於3.00至7.00莫耳百分比之間；令第二二胺單體、第二反應性單體及第二二酸酐單體於第二溶劑中聚合，以得到一熱塑性聚醯亞胺前驅物，該第二反應性單體係選自下列構成之群組：2,2'-雙(4-氨基苯基)丙烷、1,3-雙(3-氨基苯氧基)苯、4,4'-(1,3-二異丙烷基苯)二苯胺、9,9'-雙(4-氨基苯基)芴及聚氧丙烯醚二胺，且以該第二二胺單體及該第二反應性單體之總莫耳數為基準，該第二反應性單體之莫耳數係介於35.00至65.00莫耳百分比之間；塗佈該熱塑性聚醯亞胺前驅物於一第一銅箔之一側面上，以形成一第一熱塑性聚醯亞胺前驅物層；塗佈該熱固性聚醯亞胺前驅物於該第一熱塑性聚醯亞胺前驅物層遠離該第一銅箔之一側面上，以成型一第一熱固性聚醯亞胺前驅物層；塗佈該熱塑性聚醯亞胺前驅物於該第一熱固性聚醯亞胺前驅物層遠離該第一熱塑性聚醯亞胺前驅物層之一側面 上，以成型一第二熱塑性聚醯亞胺前驅物層；以及，令該第一熱塑性聚醯亞胺前驅物層、該第一熱固性聚醯亞胺前驅物層及該第二熱塑性聚醯亞胺前驅物層環化為一第一熱塑性聚醯亞胺膜、一第一熱固性聚醯亞胺膜及一第二熱塑性聚醯亞胺膜，得到該聚醯亞胺/金屬複合積層板。 In order to achieve the foregoing object, the technical means adopted by the present invention is a method for preparing the polyamidene/metal composite laminate, the steps comprising: first diamine monomer, first reactive monomer and The first dianhydride monomer is polymerized in the first solvent to obtain a thermosetting polyimine precursor, The first reactive single system is selected from the group consisting of 2,2'-bis(4-aminophenyl)propane (2,2'-bis(4-aminophenyl)propane), 1,3-double ( 3-aminophenoxy)benzene, 4,4'-(1,3-diisopropylalkylbenzene)diphenylamine (4,4'-(1,3) -phenylenediisopropylidene)bisaniline, Bisaniline-M), 9,9'-bis(4-aminophenyl)fluorene, polyoxypropylenediamine, and Based on the total number of moles of the diamine monomer and the reactive monomer, the molar number of the first reactive monomer is between 3.00 and 7.00 mole percent; the second diamine monomer The second reactive monomer and the second dianhydride monomer are polymerized in a second solvent to obtain a thermoplastic polyimine precursor, and the second reactive single system is selected from the group consisting of: 2'-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 4,4'-(1,3-diisopropylalkylbenzene)diphenylamine, 9,9 '-bis(4-aminophenyl)fluorene and polyoxypropylene ether diamine, and based on the total number of moles of the second diamine monomer and the second reactive monomer, the second The molar number of the monomer is between 35.00 and 65.00 mole percent; the thermoplastic polyimide precursor is coated on one side of a first copper foil to form a first thermoplastic polyimide. a precursor layer; coating the thermosetting polyimide precursor on the side of the first thermoplastic polyimide precursor layer away from the side of the first copper foil to form a first thermosetting polyimide precursor layer Coating the thermoplastic polyimide precursor to the side of the first thermosetting polyimide precursor layer away from the first thermoplastic polyimide precursor layer Forming a second thermoplastic polyimide precursor layer; and, the first thermoplastic polyimide precursor layer, the first thermosetting polyimide precursor layer, and the second thermoplastic polyimide The amine precursor layer is cyclized into a first thermoplastic polyimide film, a first thermosetting polyimide film, and a second thermoplastic polyimide film to obtain the polyimide/metal composite laminate.
所述之製備方法，係能製得一不具有膠層的聚醯亞胺/金屬複合積層板，且由於不具有膠層，該聚醯亞胺/金屬複合積層板能具有厚度低及良好的耐焊性、尺寸安定性及剝離強度；此外，藉由該第一反應性單體及該第二反應性單體之使用，所述之製備方法所製得的聚醯亞胺/金屬複合積層板，其第一熱固性聚醯亞胺膜及第二熱塑性聚醯亞胺膜係具有大於或等於170g-μm/m2-day的水氣穿透率，則能避免脫層及白化現象之發生。 The preparation method can produce a polyimide/metal composite laminate without a rubber layer, and since the rubber layer is not provided, the polyimide/metal composite laminate can have a low thickness and good Solder resistance, dimensional stability and peel strength; in addition, by the use of the first reactive monomer and the second reactive monomer, the polyimine/metal composite layer prepared by the preparation method The plate, the first thermosetting polyimide film and the second thermoplastic polyimide film having a water vapor permeability of greater than or equal to 170 g-μm/m 2 -day can avoid delamination and whitening .
較佳的是，令該第一熱塑性聚醯亞胺前驅物層、該第一熱固性聚醯亞胺前驅物層及該第二熱塑性聚醯亞胺前驅物層環化為該第一熱塑性聚醯亞胺膜、該第一熱固性聚醯亞胺膜及該第二熱塑性聚醯亞胺膜，得到該聚醯亞胺/金屬複合積層板之步驟包含：令該第一熱塑性聚醯亞胺前驅物層、該第一熱固性聚醯亞胺前驅物層及該第二熱塑性聚醯亞胺前驅物層環化為該第一熱塑性聚醯亞胺膜、該第一熱固性聚醯亞胺膜及該第二熱塑性聚醯亞胺膜之步驟；以及，壓合一第二銅箔於該第二熱塑性聚醯亞胺膜遠離該第一熱固性聚醯亞胺膜之一側面上，得到該聚醯亞胺/金屬複 合積層板之步驟。 Preferably, the first thermoplastic polyimide precursor layer, the first thermosetting polyimide precursor layer and the second thermoplastic polyimide precursor layer are cyclized into the first thermoplastic polymer The imide film, the first thermosetting polyimide film, and the second thermoplastic polyimide film, the step of obtaining the polyimide/metal composite laminate comprises: preparing the first thermoplastic polyimide precursor The layer, the first thermosetting polyimide precursor layer and the second thermoplastic polyimide precursor layer are cyclized into the first thermoplastic polyimide film, the first thermosetting polyimide film, and the first a second thermoplastic polyimide film step; and pressing a second copper foil on the side of the second thermoplastic polyimide film away from the first thermosetting polyimide film to obtain the polyimine /Metal complex The steps of stacking the layers.
較佳的是，令該第一熱塑性聚醯亞胺前驅物層、該第一熱固性聚醯亞胺前驅物層及該第二熱塑性聚醯亞胺前驅物層環化為該第一熱塑性聚醯亞胺膜、該第一熱固性聚醯亞胺膜及該第二熱塑性聚醯亞胺膜，得到該聚醯亞胺/金屬複合積層板之步驟包含：以80℃至150℃之除溶劑溫度下，除去該第一熱塑性聚醯亞胺前驅物層、該第一熱固性聚醯亞胺前驅物層及該第二熱塑性聚醯亞胺前驅物層所含有的溶劑，得到一經去除溶劑的第一熱塑性聚醯亞胺前驅物層、一經去除溶劑的第一熱固性聚醯亞胺前驅物層及一經去除溶劑的第二熱塑性聚醯亞胺前驅物層之步驟；以及令該經去除溶劑的第一熱塑性聚醯亞胺前驅物層、該經去除溶劑的第一熱固性聚醯亞胺前驅物層及該經去除溶劑的第二熱塑性聚醯亞胺前驅物層同時依序加熱至160℃至190℃之溫度、190℃至300℃之溫度及300℃至350℃之溫度以分別環化為該第一熱塑性聚醯亞胺膜、該第一熱固性聚醯亞胺膜及該第二熱塑性聚醯亞胺，得到該聚醯亞胺/金屬複合積層板之步驟。 Preferably, the first thermoplastic polyimide precursor layer, the first thermosetting polyimide precursor layer and the second thermoplastic polyimide precursor layer are cyclized into the first thermoplastic polymer The imine film, the first thermosetting polyimide film and the second thermoplastic polyimide film, the step of obtaining the polyimide/metal composite laminate comprises: removing the solvent at a temperature of 80 ° C to 150 ° C Removing the solvent of the first thermoplastic polyimide precursor layer, the first thermosetting polyimide precursor layer and the second thermoplastic polyimide precursor layer to obtain a solvent-removed first thermoplastic a step of a polyimide intermediate precursor layer, a solvent-removing first thermosetting polyimide precursor layer, and a solvent-removed second thermoplastic polyimide precursor layer; and a first thermoplastic that removes the solvent The polyimine precursor layer, the solvent-removed first thermosetting polyimide precursor layer and the solvent-removed second thermoplastic polyimide precursor layer are simultaneously heated to 160 ° C to 190 ° C Temperature, temperature from 190 ° C to 300 ° C Circulating the first thermoplastic polyimide film, the first thermosetting polyimide film, and the second thermoplastic polyimide, respectively, at a temperature of 300 ° C to 350 ° C to obtain the polyimide/metal composite The steps of laminating the board.
較佳的是，該第一二胺單體及該第二二胺單體可為3,4'-二氨基二苯基醚(3,4'-diaminodiphenyl ether)、4,4'-二氨基二苯基醚(4,4'-diaminodiphenyl ether)、對苯二胺(p-phenylenediamine)、間苯二胺(m-phenylenediamine)、3,5-二氨基苯甲酸(3,5-diaminobenzoic acid)、2,2'-雙(4-氨基苯基)丙烷(2,2'-bis(4-aminophenyl)propane)、4,4'-二氨基 二苯基甲烷(4,4'-diaminodiphenyl methane)、4,4'-二氨基二苯基碸(4,4'-diaminodiphenyl sulfone)、3,3'-二氨基二苯基碸(3,4'-diaminodiphenyl sulfone)、4,4'-二氨基二苯基硫醚(4,4'-diaminodiphenyl sulfide)、1,3-雙(4-氨基苯氧基)苯(1,3-bis(4-aminophenoxy)benzene)、1,3-雙(3-氨基苯氧基)苯(1,3-bis(3-aminophenoxy)benzene)、1,4-雙(4-氨基苯氧基)苯(1,4-bis(4-aminophenoxy)benzene)、4,4-雙(4-氨基苯氧基)-聯苯(4,4-bis(3-aminophenoxy)biphenyl)、2,2'-雙[4-(4-氨基苯氧基)苯基]丙烷(2,2'-bis[4-(4-aminophenoxy)phenyl]propane)、2,2'-雙[4-(3-氨基苯氧基苯)基]丙烷(2,2'-bis[4-(3-aminophenoxy)pheny]propane)、2,2'-二甲基-4,4'-二氨基聯苯(2,2'-dimethyl-4,4'-diaminobiphenyl)、3,3'-二甲基-4,4'-二氨基聯苯(3,3'-dimethyl-4,4'-diaminobiphenyl)、3,3'-二烴基-4,4'-二氨基聯苯(3,3’-dihydroxybiphenyl-4,4’-diamino)、9,9'-雙(4-氨基苯基)芴(9,9'-bis(4-aminophenyl)fluorene)、2,2'-雙(4-[3-氨基苯氧基]苯基)碸(2,2’-bis(4-(3-aminophenoxy)phenyl)sulfon)、2,6-二氨基嘧啶(2,6-diaminopyridine)、聚丙烯醚二胺(polyoxypropylenediamine)、4,4'-(1,3-二異丙烷基苯)二苯胺(4,4'-(1,3-phenylenediisopropylidene)bisaniline，Bisaniline-M)、4,4'-(1,4-二異丙烷基苯)二苯胺(4,4'-(1,4-phenylenediisopropylidene)bisaniline， Bisaniline-P)、冰片烷二胺(norbornane dimethylamine，NBDA)及其組合，但不以此為限。 Preferably, the first diamine monomer and the second diamine monomer may be 3,4'-diaminodiphenyl ether, 4,4'-diamino group. 4,4'-diaminodiphenyl ether, p-phenylenediamine, m-phenylenediamine, 3,5-diaminobenzoic acid 2,2'-bis(4-aminophenyl)propane (2,2'-bis(4-aminophenyl)propane), 4,4'-diamino 4,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfonium (3,4) '-diaminodiphenyl sulfone), 4,4'-diaminodiphenyl sulfide, 1,3-bis(4-aminophenoxy)benzene (1,3-bis (4) -aminophenoxy)benzene), 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene (1) , 4-bis(4-aminophenoxy)benzene), 4,4-bis(4-aminophenoxy)biphenyl, 2,2'-double [4 -(4-aminophenoxy)phenyl]propane (2,2'-bis[4-(4-aminophenoxy)phenyl]propane), 2,2'-bis[4-(3-aminophenoxybenzene) )]propane (2,2'-bis[4-(3-aminophenoxy)pheny]propane), 2,2'-dimethyl-4,4'-diaminobiphenyl (2,2'-dimethyl-) 4,4'-diaminobiphenyl), 3,3'-dimethyl-4,4'-diaminobiphenyl (3,3'-dimethyl-4,4'-diaminobiphenyl), 3,3'-dihydrocarbyl- 4,4'-diaminobiphenyl (3,3'-dihydroxybiphenyl-4,4'-diamino), 9,9'-bis(4-aminophenyl)indole (9,9'-bis(4-aminophenyl) )fluorene), 2,2'-bis(4-[3-aminophenoxy]phenyl)indole (2,2 '-bis(4-(3-aminophenoxy)phenyl)sulfon), 2,6-diaminopyridine, polyoxypropylenediamine, 4,4'-(1,3- Diisoalkylamine (4,4'-(1,3-phenylenediisopropylidene)bisaniline, Bisaniline-M), 4,4'-(1,4-diisopropylalkylbenzene)diphenylamine (4,4 '-(1,4-phenylenediisopropylidene)bisaniline, Bisaniline-P), norbornane dimethylamine (NBDA) and combinations thereof, but not limited thereto.
更佳的是，所述聚丙烯醚二胺購自下列構成之群組：Jeffamine® D230、Jeffamine® D400及Jeffamin® D2000。 More preferably, the polypropylene ether diamine is purchased from the group consisting of Jeffamine® D230, Jeffamine® D400 and Jeffamin® D2000.
較佳的是，該第一二酸酐單體及該第二二酸酐單體可為苯均四羧酸二酐(pyromellitic dianhydride)、3,3',4,4'-聯苯四羧酸二酐(3,3',4,4'-biphenyl tetracarboxylic dianhydride)、3,3',4,4'-二苯甲酮四羧酸二酐(3,3',4,4'-benzophenone tetracarboxylic dianhydride)、4,4'-氧二鄰苯二酸二酐(4,4'-oxydiphthalic dianhydride)、3,3',4,4'-二苯基碸四羧酸二酐(3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride)、2,2'-雙(3,4-二羧基苯基)六氟丙烷(2,2'-bis(4-carboxyphenyl)hexafluoropropane)、乙二醇-雙偏苯三酸酐(ethylene glycol-bis-trimellitate anhydride)、1,3-二氫-1,3-二氧-5-異苯并呋喃羧酸亞苯酯(1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid phenylene ester，)、1,2,3,4-丁烷四羧酸二酐(1,2,3,4-butanetetracarboxylic dianhydride)、1,2,3,4-環戊烷四羧酸二酐(1,2,3,4-cyclopentanetetracarboxylic dianhydride)及其組合，但不以此為限。 Preferably, the first dianhydride monomer and the second dianhydride monomer are pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride (3,3',4,4'-benzophenone tetracarboxylic dianhydride , 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride (3,3', 4,4'-diphenylsulfone tetracarboxylic dianhydride), 2,2'-bis(3,4-dicarboxyphenyl)hexafluoropropane, ethylene glycol-trimellitic anhydride (ethylene glycol-bis-trimellitate anhydride), 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylate (1,3-dihydro-1,3-dioxo-5- Isobenzofurancarboxylic acid phenylene ester,), 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid Anhydride (1,2,3,4-cyclopentanetetracarboxylic dianhydride) and combinations thereof, but not limited thereto.
較佳的是，該第一溶劑及該第二溶劑可為四氫呋喃(tetrahydrofuran，THF)、N,N-二甲基甲醯胺(N,N-dimethylformide，DMF)、N,N-二甲基乙醯胺 (N,N-dimethylacetamide，DMAC)、N-甲基-2-吡咯烷酮(N-methyl-2-pyrrolidone，NMP)、γ-丁內酯(γ-butyrolactone，GBL)及其組合，但不以此為限。 Preferably, the first solvent and the second solvent are tetrahydrofuran (THF), N,N-dimethylformide (DMF), N,N-dimethyl Acetamine (N, N-dimethylacetamide, DMAC), N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), and combinations thereof, but not Limited.
較佳的是，以該第一二胺單體及該第一反應性單體之總莫耳數為基準，該第一反應性單體之莫耳數係介於3.00至7.00莫耳百分比之間。 Preferably, the first reactive monomer has a molar number of from 3.00 to 7.00% by mole based on the total number of moles of the first diamine monomer and the first reactive monomer. between.
較佳的是，以該第二二胺單體及該第二反應性單體之總莫耳數為基準，該第二反應性單體之莫耳數係介於35.00至65.00莫耳百分比之間。 Preferably, the molar number of the second reactive monomer is from 35.00 to 65.00% by mole based on the total number of moles of the second diamine monomer and the second reactive monomer. between.
10‧‧‧第一銅箔 10‧‧‧First copper foil
20‧‧‧第一熱塑性聚醯亞胺膜 20‧‧‧First thermoplastic polyimide film
30‧‧‧第一熱固性聚醯亞胺膜 30‧‧‧First thermosetting polyimide film
40‧‧‧第二熱塑性聚醯亞胺膜 40‧‧‧Second thermoplastic polyimide film
50‧‧‧第二銅箔 50‧‧‧second copper foil
60‧‧‧第三熱塑性聚醯亞胺膜 60‧‧‧ Third thermoplastic polyimide film
70‧‧‧第二熱固性聚醯亞胺膜 70‧‧‧Second thermosetting polyimide film
80‧‧‧第四熱塑性聚醯亞胺膜 80‧‧‧Fourth thermoplastic polyimide film
10A、10B、10C‧‧‧銅箔 10A, 10B, 10C‧‧‧ copper foil
20B、40C‧‧‧熱塑性聚醯亞胺膜 20B, 40C‧‧‧ Thermoplastic polyimide film
30B、30C‧‧‧熱固性聚醯亞胺膜 30B, 30C‧‧‧ thermosetting polyimide film
圖1為本發明之實施例1至9及比較例1之聚醯亞胺/金屬複合積層板之側視剖面圖。 1 is a side cross-sectional view showing a polyimide/metal composite laminate of Examples 1 to 9 and Comparative Example 1 of the present invention.
圖2為本發明之實施例10之聚醯亞胺/金屬複合積層板之側視剖面圖。 Figure 2 is a side cross-sectional view showing a polyimide/metal composite laminate of Example 10 of the present invention.
圖3為本發明之實施例11之聚醯亞胺/金屬複合積層板之側視剖面圖。 Figure 3 is a side cross-sectional view showing a polyimide/metal composite laminate of Example 11 of the present invention.
圖4為本發明之實施例12之聚醯亞胺/金屬複合積層板之側視剖面圖。 Figure 4 is a side cross-sectional view showing a polyimide/metal composite laminate of Example 12 of the present invention.
圖5為本發明之實施例13之聚醯亞胺/金屬複合積層板之側視剖面圖。 Figure 5 is a side cross-sectional view showing a polyimide/metal composite laminate of Example 13 of the present invention.
圖6為本發明之比較例2至7之聚醯亞胺/金屬複合積層板之側視剖面圖。 Figure 6 is a side cross-sectional view showing a polyimide/metal composite laminate of Comparative Examples 2 to 7 of the present invention.
圖7為本發明之比較例8至13之聚醯亞胺/金屬複合積層板之側視剖面圖。 Figure 7 is a side cross-sectional view showing a polyimide/metal composite laminate of Comparative Examples 8 to 13 of the present invention.
製備例1 熱固性聚醯亞胺前驅物之製備Preparation Example 1 Preparation of Thermosetting Polyimine Precursor
在通入氮氣的1000毫升之四口反應器中，令19.877公克之對苯二胺及1.940公克之4,4'-二氨基二苯基醚於25±5℃之溫度下溶解於425公克之N-甲基-2-吡咯烷酮中，得到一二胺單體溶液；再將8.029公克之苯均四羧酸二酐加入該二胺單體溶液以進行初次聚合反應，待初次聚合反應充分後，得到一經初次聚合的溶液；之後，將45.60公克之3,3',4,4'-二苯基四羧酸二酐分三批次加入該經初次聚合的溶液中並持續攪拌4小時以進行二次聚合反應，於二次聚合反應結束後，得到本製備例之熱固性聚醯亞胺酸前驅物。本製備例之熱固性聚醯亞胺酸前驅物標示為PI-1。 19.877 g of p-phenylenediamine and 1.940 g of 4,4'-diaminodiphenyl ether were dissolved in 425 g at 25 ± 5 ° C in a 1000 ml four-neck reactor with nitrogen gas. In the N-methyl-2-pyrrolidone, a solution of the monoamine monomer is obtained; and 8.029 grams of the benzene tetracarboxylic dianhydride is added to the diamine monomer solution to carry out the primary polymerization reaction, after the initial polymerization reaction is sufficient, A first polymerization solution is obtained; after that, 45.60 g of 3,3',4,4'-diphenyltetracarboxylic dianhydride is added to the initially polymerized solution in three batches and stirring is continued for 4 hours. The secondary polymerization reaction is carried out, and after completion of the secondary polymerization reaction, the thermosetting polyimide precursor of the present preparation is obtained. The thermosetting polyimidazolium precursor of this preparation example is designated PI-1.
製備例2 熱固性聚醯亞胺前驅物之製備Preparation 2 Preparation of Thermosetting Polyimine Precursor
本製備例與製備例1概同，本製備例與製備例1之區別如下所述。 This preparation example is the same as Preparation Example 1, and the difference between this preparation example and Preparation Example 1 is as follows.
本製備例係令19.159公克之對苯二胺、1.870公克之4,4'-二氨基二苯基醚及一第一反應性單體溶解425公克之N-甲基-2-吡咯烷酮中，得到該二胺單體溶液，並令7.739公克之苯均四羧酸二酐加入至該二胺單體溶液以進行初次聚合反應並得到該經初次聚合的溶液。 The preparation example is obtained by dissolving 19.159 g of p-phenylenediamine, 1.870 g of 4,4'-diaminodiphenyl ether and a first reactive monomer in 425 g of N-methyl-2-pyrrolidone. The diamine monomer solution was prepared, and 7.739 g of benzene tetracarboxylic dianhydride was added to the diamine monomer solution to carry out primary polymerization and obtain the primary polymerization solution.
其中，本製備例之第一反應性單體為聚氧丙稀二胺單體(Jeffamine® D400)，其使用量為2.260公克，且以對苯二胺、4,4'-二氨基二苯基醚及該第一反應性單體之總莫耳數為基準，該第一反應性單體之含量為2.74莫耳百分比。 Wherein, the first reactive monomer in the preparation example is a polyoxypropylene diamine monomer (Jeffamine® D400), which is used in an amount of 2.260 grams, and is p-phenylenediamine, 4,4'-diaminodiphenyl. The content of the first reactive monomer is 2.74 mole percent based on the total moles of the ether and the first reactive monomer.
此外，本製備例之熱固性聚醯亞胺酸前驅物，標示為PI-2。 Further, the thermosetting polyimidazolium precursor of this preparation example is designated as PI-2.
製備例3 熱固性聚醯亞胺前驅物之製備Preparation 3 Preparation of Thermosetting Polyimine Precursor
本製備例與製備例1概同，本製備例與製備例1之區別如下所述。 This preparation example is the same as Preparation Example 1, and the difference between this preparation example and Preparation Example 1 is as follows.
本製備例係令18.708公克之對苯二胺、1.826公克之4,4'-二氨基二苯基醚及一第一反應性單體溶解於425公克之N-甲基-2-吡咯烷酮中，得到該二胺單體溶液；再令7.557公克之苯均四羧酸二酐加入至該二胺單體溶液，以進行初次聚合反應並得到該經初次聚合的溶液。 This preparation is prepared by dissolving 18.708 g of p-phenylenediamine, 1.826 g of 4,4'-diaminodiphenyl ether and a first reactive monomer in 425 g of N-methyl-2-pyrrolidone. The diamine monomer solution was obtained; and 7.557 g of benzene tetracarboxylic dianhydride was further added to the diamine monomer solution to carry out primary polymerization and obtain the primary polymerization solution.
其中，本製備例之第一反應性單體為聚氧丙稀二胺單體(Jeffamine® D400)，其使用量為3.772公克，且以對苯二胺、4,4'-二氨基二苯基醚及該第一反應性單體之總莫耳數為基準，該第一反應性單體之含量為為4.59莫耳百分比。 Wherein, the first reactive monomer in the preparation example is a polyoxypropylene diamine monomer (Jeffamine® D400), which is used in an amount of 3.772 g, and is p-phenylenediamine and 4,4′-diaminodiphenyl. The content of the first reactive monomer is 4.59 mole percent based on the total moles of the ether and the first reactive monomer.
此外，本製備例之熱固性聚醯亞胺酸前驅物係標示為PI-3。 Further, the thermosetting polyimidazolium precursor of the present preparation is designated as PI-3.
製備例4 熱固性聚醯亞胺前驅物之製備Preparation Example 4 Preparation of Thermosetting Polyimine Precursor
本製備例與製備例1概同，本製備例與製備例1之區別如下所述。 This preparation example is the same as Preparation Example 1, and the difference between this preparation example and Preparation Example 1 is as follows.
本製備例係令19.044公克之對苯二胺、1.858公克之4,4'-二氨基二苯基醚及一第一反應性單體溶解於425公克之N-甲基-2-吡咯烷酮中，得到該二胺單體溶液；再令7.692公克之苯均四羧酸二酐加入至該二胺單體溶液中，以進行初次聚合反應並得到該經初次聚合的溶液。 The preparation example is such that 19.044 g of p-phenylenediamine, 1.858 g of 4,4'-diaminodiphenyl ether and a first reactive monomer are dissolved in 425 g of N-methyl-2-pyrrolidone. The diamine monomer solution was obtained; and 7.692 g of benzene tetracarboxylic dianhydride was further added to the diamine monomer solution to carry out primary polymerization and obtain the primary polymerization solution.
其中，本製備例之第一反應性單體為9,9-雙(4-氨基苯基)芴，其使用量為2.263公克，且以對苯二胺、4,4'-二氨基二苯基醚及該第一反應性單體之總莫耳數為基準，該第一反應性單體之含量為3.39莫耳百分比。 Wherein, the first reactive monomer in the preparation example is 9,9-bis(4-aminophenyl)fluorene, which is used in an amount of 2.263 g, and is p-phenylenediamine, 4,4'-diaminodiphenyl. The content of the first reactive monomer is 3.39 mole percent based on the total moles of the ether and the first reactive monomer.
此外，本製備例之熱固性聚醯亞胺酸前驅物係標示為PI-4。 Further, the thermosetting polyimidazolium precursor of the present preparation is designated as PI-4.
製備例5 熱固性聚醯亞胺前驅物之製備Preparation Example 5 Preparation of Thermosetting Polyimine Precursor
本製備例與製備例1概同，本製備例與製備例1之區別如下所述。 This preparation example is the same as Preparation Example 1, and the difference between this preparation example and Preparation Example 1 is as follows.
本製備例係令18.490公克之對苯二胺、1.804公克之4,4'-二氨基二苯基醚及一第一反應性單體溶解於425公克之N-甲基-2-吡咯烷酮中，得到該二胺單體溶液；再令7.469公克之苯均四羧酸二酐加入至該二胺單體溶液中，以進行初次聚合反應並得到該經初次聚合的溶液。 The preparation example is such that 18.490 g of p-phenylenediamine, 1.804 g of 4,4'-diaminodiphenyl ether and a first reactive monomer are dissolved in 425 g of N-methyl-2-pyrrolidone. The diamine monomer solution was obtained; and 7.469 g of benzene tetracarboxylic dianhydride was further added to the diamine monomer solution to carry out primary polymerization and obtain the primary polymerization solution.
其中，本製備例之第一反應性單體為9,9-雙(4-氨基苯基)芴，其使用量為3.772公克，且以對苯二胺、4,4'-二氨基二苯基醚及該第一反應性單體之總莫耳數為基準，該第一反應性單體之含量為5.67莫耳百分比。 Wherein, the first reactive monomer in the preparation example is 9,9-bis(4-aminophenyl)fluorene, which is used in an amount of 3.772 g, and is p-phenylenediamine and 4,4'-diaminodiphenyl. The content of the first reactive monomer is 5.67 mole percent based on the total moles of the ether and the first reactive monomer.
此外，本製備例之熱固性聚醯亞胺酸前驅物係標示為PI-5。 Further, the thermosetting polyimidazolium precursor of this preparation example is designated as PI-5.
製備例6 熱固性聚醯亞胺前驅物之製備Preparation Example 6 Preparation of Thermosetting Polyimine Precursor
本製備例與製備例1概同，本製備例與製備例1之區別如下所述。 This preparation example is the same as Preparation Example 1, and the difference between this preparation example and Preparation Example 1 is as follows.
本製備例係令19.322公克之對苯二胺及一第一反應性單體溶解於425公克之N-甲基-2-吡咯烷酮中，得 到該二胺單體溶液；再令7.512公克之苯均四羧酸二酐加入至該二胺單體溶液中，以進行初次聚合反應並得到該經初次聚合的溶液。 The preparation example is prepared by dissolving 19.322 g of p-phenylenediamine and a first reactive monomer in 425 g of N-methyl-2-pyrrolidone. To the diamine monomer solution; 7.512 g of benzene tetracarboxylic dianhydride was further added to the diamine monomer solution to carry out primary polymerization and obtain the primary polymerization solution.
其中，本製備例之第一反應性單體包含聚氧丙烯醚二胺單體(Jeffamine® D400)及9,9-雙(4-氨基苯基)芴，聚氧丙烯醚二胺單體之使用量為2.057公克，9,9-雙(4-氨基苯基)芴之使用量為2.667公克，且以對苯二胺及該第一反應性單體之總莫耳數為基準，該第一反應性單體之含量為6.50莫耳百分比。 Wherein, the first reactive monomer of the preparation example comprises a polyoxypropylene ether diamine monomer (Jeffamine® D400) and 9,9-bis(4-aminophenyl)fluorene, and a polyoxypropylene ether diamine monomer The amount used is 2.057 grams, and the amount of 9,9-bis(4-aminophenyl)fluorene used is 2.667 grams, and based on the total number of moles of p-phenylenediamine and the first reactive monomer, The content of a reactive monomer is 6.50 mole percent.
此外，本製備例之熱固性聚醯亞胺前驅物係標示為PI-6。 Further, the thermosetting polyimine precursor precursor of this preparation example is designated as PI-6.
製備例7 熱塑性聚醯亞胺前驅物之製備Preparation Example 7 Preparation of Thermoplastic Polyimine Precursor
在通入氮氣的1000毫升之四口反應器中，令5.515公克之對苯二胺及一第二反應性單體於25±5℃之溫度下溶解於425公克之N-甲基-2-吡咯烷酮中，得到一二胺單體溶液；再將45.60公克之3,3',4,4'-二苯基四羧酸二酐分三批次加入該二胺單體溶液中並持續攪拌4小時以進行聚合反應，於聚合反應結束後，得到本製備例之熱塑性聚醯亞胺前驅物。本製備例之熱塑性聚醯亞胺前驅物標示為TPI-1。 In a 1000 ml four-neck reactor with nitrogen gas, 5.515 g of p-phenylenediamine and a second reactive monomer were dissolved in 425 g of N-methyl-2- at 25±5 ° C. In the pyrrolidone, a solution of the monoamine monomer is obtained; and 45.60 grams of 3,3',4,4'-diphenyltetracarboxylic dianhydride is added to the diamine monomer solution in three batches and stirring is continued. The polymerization reaction was carried out for an hour, and after the completion of the polymerization, the thermoplastic polyimide precursor of the present preparation was obtained. The thermoplastic polyimine precursor of this preparation example is designated as TPI-1.
其中，本製備例之第二反應性單體為1,3-雙(3-氨基苯氧基)苯，其使用量為27.693公克，且以對苯二胺及該第二反應性單體之總莫耳數為基準，該第二反應性單體之含量為65.00莫耳百分比。 Wherein, the second reactive monomer in the preparation example is 1,3-bis(3-aminophenoxy)benzene, which is used in an amount of 27.693 g, and is a p-phenylenediamine and the second reactive monomer. Based on the total number of moles, the content of the second reactive monomer is 65.00 mole percent.
製備例8 熱塑性聚醯亞胺前驅物之製備Preparation Example 8 Preparation of Thermoplastic Polyimine Precursor
本製備例與製備例7概同，本製備例與製備例7之區別如下所述。 This preparation example is the same as Preparation Example 7, and the difference between the present preparation example and Preparation Example 7 is as follows.
本製備例係令5.516公克之對苯二胺及該第二反應性單體於25±5℃之溫度下溶解於425公克之N-甲基-2-吡咯烷酮中，得到該二胺單體溶液。 The preparation example is such that 5.516 g of p-phenylenediamine and the second reactive monomer are dissolved in 425 g of N-methyl-2-pyrrolidone at a temperature of 25 ± 5 ° C to obtain the diamine monomer solution. .
其中，本製備例之第二反應性單體包含4,4'-(1,3-二異丙烷基苯)二苯胺及2,2'-雙(4-氨基苯基)丙烷，4,4'-(1,3-二異丙烷基苯)二苯胺之使用量為23.435公克，2,2'-雙(4-氨基苯基)丙烷之使用量為5.990公克，且以對苯二胺及該第二反應性單體之總莫耳數為基準，該第二反應性單體之含量為61.80莫耳百分比。 Wherein, the second reactive monomer of the preparation example comprises 4,4'-(1,3-diisopropylalkylbenzene)diphenylamine and 2,2'-bis(4-aminophenyl)propane, 4,4 '-(1,3-Diisopropylalkylbenzene)diphenylamine was used in an amount of 23.435 g, and 2,2'-bis(4-aminophenyl)propane was used in an amount of 5.990 g, and p-phenylenediamine and The total number of moles of the second reactive monomer is based on the amount of the second reactive monomer being 61.80 mole percent.
本製備例之熱塑性聚醯亞胺前驅物標示為TPI-2。 The thermoplastic polyimine precursor of this preparation example is designated as TPI-2.
製備例9 熱塑性聚醯亞胺前驅物之製備Preparation 9 Preparation of Thermoplastic Polyimine Precursor
本製備例與製備例7概同，本製備例與製備例7之區別如下所述。 This preparation example is the same as Preparation Example 7, and the difference between the present preparation example and Preparation Example 7 is as follows.
本製備例係令23.821公克之1,3-雙(4-氨基苯氧基)苯及該第二反應性單體於25±5℃之溫度下溶解於425公克之N-甲基-2-吡咯烷酮中，得到該二胺單體溶液，再將14.383公克之苯均四羧酸二酐加入該二胺單體溶液以進行初次聚合反應，待初次聚合反應充分後，得到一經初次聚合的溶液；之後，將20.00公克之3,3',4,4'-二苯基四羧酸二酐分二批次加入該經初次聚合的溶液中並持續攪拌4小時以進行二次聚合反應，於二次聚合反應結束後，得到本製備例之熱塑性聚醯亞胺酸前驅物 This preparation is such that 23.821 grams of 1,3-bis(4-aminophenoxy)benzene and the second reactive monomer are dissolved in 425 grams of N-methyl-2- at a temperature of 25 ± 5 ° C. In the pyrrolidone, the diamine monomer solution is obtained, and 14.383 grams of benzene tetracarboxylic dianhydride is added to the diamine monomer solution to carry out the primary polymerization reaction, and after the initial polymerization reaction is sufficient, a first polymerization solution is obtained; Thereafter, 20.00 g of 3,3',4,4'-diphenyltetracarboxylic dianhydride was added to the primary polymerization solution in two batches and stirring was continued for 4 hours to carry out secondary polymerization. After the completion of the sub-polymerization, the thermoplastic polyimine precursor of the present preparation is obtained.
其中，本製備例之第二反應性單體為4,4'-(1,3-二異丙烷基苯)二苯胺，其使用量為18.735公克，且以1,3-雙(4-氨基苯氧基)苯及該第二反應性單體之總莫耳數為基準，該第二反應性單體之含量為35.87莫耳百分比。 Wherein, the second reactive monomer in the preparation example is 4,4′-(1,3-diisopropylalkylbenzene)diphenylamine, which is used in an amount of 18.735 g and is 1,3-bis(4-amino group). The content of the second reactive monomer is 35.87 mole percent based on the total moles of phenoxy)benzene and the second reactive monomer.
此外，本製備例之熱塑性聚醯亞胺前驅物標示為TPI-3。 Further, the thermoplastic polyimine precursor of this preparation example is designated as TPI-3.
製備例10 熱塑性聚醯亞胺前驅物之製備Preparation Example 10 Preparation of Thermoplastic Polyimine Precursor
本製備例與製備例7概同，本製備例與製備例7之區別如下所述。 This preparation example is the same as Preparation Example 7, and the difference between the present preparation example and Preparation Example 7 is as follows.
本製備例係令18.196公克之1,3-雙(4-氨基苯氧基)苯及該第二反應性單體於25±5℃之溫度下溶解於425公克之N-甲基-2-吡咯烷酮中，得到該二胺單體溶液，再將10.466公克之苯均四羧酸二酐加入該二胺單體溶液以進行初次聚合反應，待初次聚合反應充分後，得到一經初次聚合的溶液；之後，將22.00公克之3,3',4,4'-二苯基四羧酸二酐分二批次加入該經初次聚合的溶液中並持續攪拌4小時以進行二次聚合反應，於二次聚合反應結束後，得到本製備例之熱塑性聚醯亞胺酸前驅物 The preparation example is such that 18.196 g of 1,3-bis(4-aminophenoxy)benzene and the second reactive monomer are dissolved in 425 g of N-methyl-2- at a temperature of 25±5 ° C. In the pyrrolidone, the diamine monomer solution is obtained, and 10.466 g of the benzene tetracarboxylic dianhydride is added to the diamine monomer solution to carry out the primary polymerization reaction. After the initial polymerization reaction is sufficient, a first polymerization solution is obtained; Thereafter, 22.00 grams of 3,3',4,4'-diphenyltetracarboxylic dianhydride was added to the initially polymerized solution in two batches and stirring was continued for 4 hours to carry out secondary polymerization. After the completion of the sub-polymerization, the thermoplastic polyimine precursor of the present preparation is obtained.
其中，本製備例之第二反應性單體為2',2-雙(4-氨基苯基)丙烷，其使用量為25.581公克，且以1,3-雙(4-氨基苯氧基)苯及該第二反應性單體之總莫耳數為基準，該第二反應性單體之含量為50.00莫耳百分比。 Wherein, the second reactive monomer in the preparation example is 2',2-bis(4-aminophenyl)propane, which is used in an amount of 25.581 g, and is 1,3-bis(4-aminophenoxy). The content of the second reactive monomer is 5% by mole based on the total moles of benzene and the second reactive monomer.
此外，本製備例之熱塑性聚醯亞胺前驅物標示為TPI-4。 Further, the thermoplastic polyimide precursor of this preparation example is designated as TPI-4.
實施例1 聚醯亞胺/金屬複合積層板及其製備Example 1 Polyimine/metal composite laminate and preparation thereof 方法method
如圖1所示，本實施例之聚醯亞胺/金屬複合積層板包含一第一銅箔10、一第一熱塑性聚醯亞胺膜20、一第一熱固性聚醯亞胺膜30、一第二熱塑性聚醯亞胺膜40及一第二銅箔50。該第一熱塑性聚醯亞胺膜20、該第一熱固性聚醯亞胺膜30及該第二熱塑性聚醯亞胺膜40依序貼靠重疊於該第一銅箔10及該第二銅箔50之間，該第一熱塑性聚醯亞胺膜20與該第一銅箔10相接，該第二熱塑性聚醯亞胺膜40與該第二銅箔50相接。其中，該第一熱塑性聚醯亞胺膜20及該第二熱塑性聚醯亞胺膜40之厚度為2微米，該第一熱固性聚醯亞胺膜30之厚度為15微米。 As shown in FIG. 1 , the polyimide/metal composite laminate of the present embodiment comprises a first copper foil 10 , a first thermoplastic polyimide film 20 , a first thermosetting polyimide film 30 , and a first thermosetting polyimide film 30 . The second thermoplastic polyimide film 40 and a second copper foil 50. The first thermoplastic polyimide film 20, the first thermosetting polyimide film 30 and the second thermoplastic polyimide film 40 are sequentially adhered to the first copper foil 10 and the second copper foil. Between 50, the first thermoplastic polyimide film 20 is in contact with the first copper foil 10, and the second thermoplastic polyimide film 40 is in contact with the second copper foil 50. The first thermoplastic polyimide film 20 and the second thermoplastic polyimide film 40 have a thickness of 2 μm, and the first thermosetting polyimide film 30 has a thickness of 15 μm.
如圖1所示，本實施例之聚醯亞胺/金屬複合積層板製備方法如下所述。 As shown in Fig. 1, the preparation method of the polyimide/metal composite laminate of the present embodiment is as follows.
先將TPI-1塗佈於該第一銅箔10之一側面上，形成一第一熱塑性聚醯亞胺前驅物層；再將PI-5塗佈於該第一熱塑性聚醯亞胺前驅物層遠離該第一銅箔10之一側面上，形成一第一熱固性聚醯亞胺前驅物層；又將TPI-1塗佈於該第一熱固性聚醯亞胺前驅物層遠離該第一熱塑性聚醯亞胺前驅物層之一側面上，形成一第二熱塑性聚醯亞胺前驅物層。 First, TPI-1 is coated on one side of the first copper foil 10 to form a first thermoplastic polyimide precursor layer; and PI-5 is coated on the first thermoplastic polyimide precursor. The layer is away from a side of the first copper foil 10 to form a first thermosetting polyimide precursor layer; and TPI-1 is coated on the first thermosetting polyimide precursor layer away from the first thermoplastic On the side of one of the polyimide precursor layers, a second thermoplastic polyimide precursor layer is formed.
然後，以80℃至150℃之除溶劑溫度除去該第一熱塑性聚醯亞胺前驅物層、該第一熱固性聚醯亞胺前驅物層及該第二熱塑性聚醯亞胺前驅物層中所含有的溶劑，即N-甲基-2-吡咯烷酮。 Then, removing the first thermoplastic polyimide film precursor layer, the first thermosetting polyimide phase precursor layer, and the second thermoplastic polyimide film precursor layer at a solvent removal temperature of 80 ° C to 150 ° C The solvent contained, that is, N-methyl-2-pyrrolidone.
之後，於含氮氣之環境下，令經去除溶劑的第 一熱塑性聚醯亞胺前驅物層、經去除溶劑的第一熱固性聚醯亞胺前驅物層及經去除溶劑的第二熱塑性聚醯亞胺前驅物層三者同時依序加熱至160℃至190℃之溫度、190℃至300℃之溫度及300℃至350℃之溫度以進行環化反應；於該環化反應結束後，該經去除溶劑的第一熱塑性聚醯亞胺前驅物層環化為該第一熱塑性聚醯亞胺膜20，該經去除溶劑的第一熱固性聚醯亞胺前驅物層環化為該第一熱固性聚醯亞胺膜30，該經去除溶劑的第二熱塑性聚醯亞胺前驅物層環化為該第二熱塑性聚醯亞胺膜40。 After that, in the environment containing nitrogen, the solvent is removed. A thermoplastic polyimide precursor layer, a solvent-removed first thermosetting polyimide precursor layer, and a solvent-removed second thermoplastic polyimide precursor layer are simultaneously heated to 160 ° C to 190 a temperature of °C, a temperature of 190 ° C to 300 ° C, and a temperature of 300 ° C to 350 ° C to carry out a cyclization reaction; after the end of the cyclization reaction, the solvent-removed first thermoplastic polyimine precursor layer is cyclized For the first thermoplastic polyimide film 20, the solvent-removed first thermosetting polyimide precursor layer is cyclized into the first thermosetting polyimide film 30, the solvent-free second thermoplastic polymer The quinone imine precursor layer is cyclized to the second thermoplastic polyimide film 40.
最後，將該第二銅箔50在320℃至380℃之壓合溫度、50至100公斤力/平方公分(KgF/cm2)之壓合壓力下壓合於該第二熱塑性聚醯亞胺膜40遠離該第一熱固性聚醯亞胺膜30之一側面上，得到該聚醯亞胺/金屬複合積層板。 Finally, the second copper foil 50 is pressed against the second thermoplastic polyimine at a pressing temperature of 320 ° C to 380 ° C and a pressing pressure of 50 to 100 kgf / cm 2 (KgF / cm 2 ) . The film 40 is separated from one side of the first thermosetting polyimide film 30 to obtain the polyimide/metal composite laminate.
實施例2 聚醯亞胺/金屬複合積層板及其製備方法Example 2 Polyimine/metal composite laminate and preparation method thereof
本實施例與實施例1概同，惟本實施例之第一熱固性聚醯亞胺膜之厚度為8微米。 This embodiment is the same as Embodiment 1, except that the thickness of the first thermosetting polyimide film of the present embodiment is 8 μm.
實施例3 聚醯亞胺/金屬複合積層板及其製備方法Example 3 Polyimine/metal composite laminate and preparation method thereof
本實施例與實施例1概同，惟本實施例之第一熱固性聚醯亞胺膜係由PI-6所製成。 This embodiment is the same as Example 1, except that the first thermosetting polyimide film of the present embodiment is made of PI-6.
實施例4 聚醯亞胺/金屬複合積層板及其製備方法Example 4 Polyimine/metal composite laminate and preparation method thereof
本實施例與實施例1概同，惟本實施例之第一 熱固性聚醯亞胺膜係由PI-6所製成，且其厚度為5微米。 This embodiment is the same as Embodiment 1, but the first embodiment The thermosetting polyimide film was made of PI-6 and had a thickness of 5 μm.
實施例5 聚醯亞胺/金屬複合積層板及其製備方法Example 5 Polyimine/metal composite laminate and preparation method thereof
本實施例與實施例1概同，惟本實施例之第一熱塑性聚醯亞胺膜及第二熱塑性聚醯亞胺膜係由TPI-2所製成，第一熱固性聚醯亞胺膜係由PI-6所製成，且第一熱固性聚醯亞胺膜之厚度為20微米。 This embodiment is the same as the first embodiment except that the first thermoplastic polyimide film and the second thermoplastic polyimide film of the present embodiment are made of TPI-2, and the first thermosetting polyimide film system is Made of PI-6, and the thickness of the first thermosetting polyimide film was 20 μm.
實施例6 聚醯亞胺/金屬複合積層板及其製備方法Example 6 Polyimine/metal composite laminate and preparation method thereof
本實施例與實施例1概同，惟本實施例之第一熱塑性聚醯亞胺膜及第二熱塑性聚醯亞胺膜係由TPI-2所製成，第一熱固性聚醯亞胺膜係由PI-6所製成，且第一熱固性聚醯亞胺膜之厚度為8微米。 This embodiment is the same as the first embodiment except that the first thermoplastic polyimide film and the second thermoplastic polyimide film of the present embodiment are made of TPI-2, and the first thermosetting polyimide film system is Made of PI-6, and the thickness of the first thermosetting polyimide film was 8 μm.
實施例7 聚醯亞胺/金屬複合積層板及其製備方法Example 7 Polyimine/metal composite laminate and preparation method thereof
本實施例與實施例1概同，惟本實施例之第一熱塑性聚醯亞胺膜及第二熱塑性聚醯亞胺膜係由TPI-3所製成，第一熱固性聚醯亞胺膜係由PI-6所製成，且第一熱固性聚醯亞胺膜之厚度為8微米。 This embodiment is the same as Embodiment 1, except that the first thermoplastic polyimide film and the second thermoplastic polyimide film of the present embodiment are made of TPI-3, the first thermosetting polyimide film system. Made of PI-6, and the thickness of the first thermosetting polyimide film was 8 μm.
實施例8 聚醯亞胺/金屬複合積層板及其製備方法Example 8 Polyimine/metal composite laminate and preparation method thereof
本實施例與實施例1概同，惟本實施例之第一熱塑性聚醯亞胺膜及第二熱塑性聚醯亞胺膜係由TPI-4所製成，第一熱固性聚醯亞胺膜係由PI-6所製成，且第一熱固性聚醯亞胺膜之厚度為8微米。 This embodiment is the same as the first embodiment except that the first thermoplastic polyimide film and the second thermoplastic polyimide film of the present embodiment are made of TPI-4, and the first thermosetting polyimide film system is Made of PI-6, and the thickness of the first thermosetting polyimide film was 8 μm.
實施例9 聚醯亞胺/金屬複合積層板及其製備方法Example 9 Polyimine/metal composite laminate and preparation method thereof
本實施例與實施例1概同，惟本實施例之第一熱固性聚醯亞胺膜係由PI-4所製成 This embodiment is the same as Embodiment 1, except that the first thermosetting polyimide film of the present embodiment is made of PI-4.
實施例10 聚醯亞胺/金屬複合積層板Example 10 Polyimine/Metal Composite Laminate
如圖2所示，本實施例之聚醯亞胺/金屬複合積層板包含一銅箔10A、一第一熱塑性聚醯亞胺膜20A、一第一熱固性聚醯亞胺膜30A及一第二熱塑性聚醯亞胺膜40A。該第一熱塑性聚醯亞胺膜20A、該第一熱固性聚醯亞胺膜30A及該第二熱塑性聚醯亞胺膜40A依序貼靠重疊於該銅箔10A上。 As shown in FIG. 2, the polyimide/metal composite laminate of the present embodiment comprises a copper foil 10A, a first thermoplastic polyimide film 20A, a first thermosetting polyimide film 30A and a second. Thermoplastic polyimide film 40A. The first thermoplastic polyimide film 20A, the first thermosetting polyimide film 30A, and the second thermoplastic polyimide film 40A are sequentially laminated on the copper foil 10A.
如圖1及2所示，本實施例之聚醯亞胺/金屬複合積層板之銅箔10A相當於實施例1之聚醯亞胺/金屬複合積層板之第一銅箔10。 As shown in Figs. 1 and 2, the copper foil 10A of the polyimide/metal composite laminate of the present embodiment corresponds to the first copper foil 10 of the polyimide/metal composite laminate of Example 1.
實施例11 聚醯亞胺/金屬複合積層板Example 11 Polyimine/Metal Composite Laminate
如圖1及3所示，本實施例與實施例1之聚醯亞胺/金屬複合積層板概同，本實施例與實施例1之區別在於：該第二銅箔50係透過一第三熱塑性聚醯亞胺膜60與該第二熱塑性聚醯亞胺膜40相接。 As shown in FIG. 1 and FIG. 3, the present embodiment is the same as the polyimine/metal composite laminate of the first embodiment. The difference between the embodiment and the embodiment 1 is that the second copper foil 50 is transmitted through a third. The thermoplastic polyimide film 60 is in contact with the second thermoplastic polyimide film 40.
實施例12 聚醯亞胺/金屬複合積層板Example 12 Polyimine/Metal Composite Laminate
如圖3及4所示，本實施例與實施例11之聚醯亞胺/金屬複合積層板概同，本實施例與實施例11之區別在於：該第三熱塑性聚醯亞胺膜60係透過一第二熱固性聚醯亞胺膜70與該第二熱塑性聚醯亞胺膜40相接。 As shown in FIGS. 3 and 4, the present embodiment is the same as the polyimine/metal composite laminate of the embodiment 11. The difference between this embodiment and the embodiment 11 is that the third thermoplastic polyimide film 60 is The second thermoplastic polyimide film 40 is joined to the second thermoplastic polyimide film 40 through a second thermosetting polyimide film 70.
實施例13 聚醯亞胺/金屬複合積層板Example 13 Polyimine/Metal Composite Laminate
如圖4及5所示，本實施例與實施例12之聚醯亞胺/金屬複合積層板概同，本實施例與實施例12之區別在於：該第二熱固性聚醯亞胺膜70係透過一第四熱塑性聚醯亞胺膜80與該第二熱塑性聚醯亞胺膜40相接。 As shown in FIGS. 4 and 5, the present embodiment is the same as the polyimide/metal composite laminate of the embodiment 12. The difference between this embodiment and the embodiment 12 is that the second thermosetting polyimide film 70 is The second thermoplastic polyimide film 40 is bonded to the second thermoplastic polyimide film 40 through a fourth thermoplastic polyimide film 80.
比較例1 聚醯亞胺/金屬複合積層板及其製備方法Comparative Example 1 Polyimine/metal composite laminate and preparation method thereof
本比較例與實施例1概同，惟本比較例之第一熱固性聚醯亞胺膜係由PI-6所製成，且第一熱固性聚醯亞胺膜之厚度為8微米。 This comparative example is the same as that of Example 1, except that the first thermosetting polyimide film of the comparative example was made of PI-6, and the thickness of the first thermosetting polyimide film was 8 μm.
比較例2 聚醯亞胺/金屬複合積層板及其製備方法Comparative Example 2 Polyimine/metal composite laminate and preparation method thereof
如圖6所示，本比較例之聚醯亞胺/金屬複合積層板包含一銅箔10B、一熱塑性聚醯亞胺膜20B及一熱固性聚醯亞胺膜30B。該熱塑性聚醯亞胺膜20B之兩側面分別與該銅箔10B及該熱固性聚醯亞胺膜30B相接。其中，該熱塑性聚醯亞胺膜20B之厚度為2至3微米，該熱固性聚醯亞胺膜30B之厚度為17至18微米。 As shown in FIG. 6, the polyimide/metal composite laminate of this comparative example comprises a copper foil 10B, a thermoplastic polyimide film 20B, and a thermosetting polyimide film 30B. Both sides of the thermoplastic polyimide film 20B are in contact with the copper foil 10B and the thermosetting polyimide film 30B, respectively. Wherein the thermoplastic polyimide film 20B has a thickness of 2 to 3 μm, and the thermosetting polyimide film 30B has a thickness of 17 to 18 μm.
如圖1及6所示，本比較例之聚醯亞胺/金屬複合積層板之銅箔10B、熱塑性聚醯亞胺膜20B及熱固性聚醯亞胺膜30B，係分別相當於實施例1之聚醯亞胺/金屬複合積層板之第一銅箔10、第一熱塑性聚醯亞胺膜20及第一熱固性聚醯亞胺膜30。 As shown in FIGS. 1 and 6, the copper foil 10B, the thermoplastic polyimide film 20B, and the thermosetting polyimide film 30B of the polyimide/metal composite laminate of the comparative example are respectively equivalent to those of the first embodiment. The first copper foil 10 of the polyimide/metal composite laminate, the first thermoplastic polyimide film 20, and the first thermosetting polyimide film 30.
如圖6所示，本比較例之聚醯亞胺/金屬複合積層板製備方法如下所述。 As shown in Fig. 6, the preparation method of the polyimine/metal composite laminate of the comparative example is as follows.
先將TPI-1塗佈於該銅箔10B之一側面上，形 成一熱塑性聚醯亞胺前驅物層；再將PI-1塗佈於該熱塑性聚醯亞胺前驅物層遠離該銅箔10B之一側面上，形成一熱固性聚醯亞胺前驅物層。 First, TPI-1 is coated on one side of the copper foil 10B. Forming a thermoplastic polyimide precursor layer; and applying PI-1 to the thermoplastic polyimide precursor layer away from one side of the copper foil 10B to form a thermosetting polyimide precursor layer.
接著，以80℃至150℃之除溶劑溫度除去該熱塑性聚醯亞胺前驅物層及該熱固性聚醯亞胺前驅物層中所含有的溶劑，即N-甲基-2-吡咯烷酮。 Next, the thermoplastic polyimideimide precursor layer and the solvent contained in the thermosetting polyimide phase precursor layer, that is, N-methyl-2-pyrrolidone, are removed at a solvent removal temperature of 80 ° C to 150 ° C .
其後，令經去除溶劑的熱塑性聚醯亞胺前驅物層及經去除溶劑的熱固性聚醯亞胺前驅物層同時依序加熱至160℃至190℃之溫度、190℃至300℃之溫度及300℃至350℃之溫度以進行環化反應；於該環化反應結束後，該經去除溶劑的熱塑性聚醯亞胺前驅物層環化為該熱塑性聚醯亞胺膜20B，該經去除溶劑的熱固性聚醯亞胺前驅物層環化為該熱固性聚醯亞胺膜30B，得到該聚醯亞胺/金屬複合積層板。 Thereafter, the solvent-removed thermoplastic polyimide precursor layer and the solvent-removed thermosetting polyimide precursor layer are simultaneously heated to a temperature of 160 ° C to 190 ° C, a temperature of 190 ° C to 300 ° C, and a temperature of 300 ° C to 350 ° C to carry out a cyclization reaction; after the end of the cyclization reaction, the solvent-removed thermoplastic polyimide precursor layer is cyclized to the thermoplastic polyimide film 20B, the solvent is removed The thermosetting polyimine precursor layer is cyclized to the thermosetting polyimide film 30B to obtain the polyimide/metal composite laminate.
比較例3 聚醯亞胺/金屬複合積層板及其製備方法Comparative Example 3 Polyimine/metal composite laminate and preparation method thereof
本比較例與比較例2概同，惟本比較例之熱固性聚醯亞胺膜為PI-2所製。 This comparative example is the same as Comparative Example 2 except that the thermosetting polyimide film of the comparative example was made of PI-2.
比較例4 聚醯亞胺/金屬複合積層板及其製備方法Comparative Example 4 Polyimine/metal composite laminate and preparation method thereof
本比較例與比較例2概同，惟本比較例之熱固性聚醯亞胺膜為PI-3所製。 This comparative example is the same as Comparative Example 2 except that the thermosetting polyimide film of the comparative example was made of PI-3.
比較例5 聚醯亞胺/金屬複合積層板及其製備方法Comparative Example 5 Polyimine/metal composite laminate and preparation method thereof
本比較例與比較例2概同，惟本比較例之熱固 性聚醯亞胺膜為PI-4所製。 This comparative example is the same as Comparative Example 2, but the thermosetting of this comparative example The polyimine film was made of PI-4.
比較例6 聚醯亞胺/金屬複合積層板及其製備方法Comparative Example 6 Polyimine/metal composite laminate and preparation method thereof
本比較例與比較例2概同，惟本比較例之熱固性聚醯亞胺膜為PI-5所製。 This comparative example is the same as Comparative Example 2 except that the thermosetting polyimide film of the comparative example was made of PI-5.
比較例7 聚醯亞胺/金屬複合積層板及其製備方法Comparative Example 7 Polyimine/metal composite laminate and preparation method thereof
本比較例與比較例2概同，惟本比較例之熱固性聚醯亞胺膜為PI-6所製。 This comparative example is the same as Comparative Example 2 except that the thermosetting polyimide film of the comparative example was made of PI-6.
比較例8 聚醯亞胺/金屬複合積層板及其製備方法Comparative Example 8 Polyimine/metal composite laminate and preparation method thereof
如圖7所示，本比較例之聚醯亞胺/金屬複合積層板包含一銅箔10C、一熱固性聚醯亞胺膜30C及一熱塑性聚醯亞胺膜40C。該熱固性聚醯亞胺膜30C之兩側面分別與該銅箔10C及該熱塑性聚醯亞胺膜40C相接。其中，該熱塑性聚醯亞胺膜40C之厚度為2至3微米，該第一熱固性聚醯亞胺膜30C之厚度為17至18微米。 As shown in FIG. 7, the polyimide/metal composite laminate of the comparative example comprises a copper foil 10C, a thermosetting polyimide film 30C, and a thermoplastic polyimide film 40C. Both sides of the thermosetting polyimide film 30C are in contact with the copper foil 10C and the thermoplastic polyimide film 40C, respectively. Wherein the thermoplastic polyimide film 40C has a thickness of 2 to 3 μm, and the first thermosetting polyimide film 30C has a thickness of 17 to 18 μm.
如圖1及7所示，本比較例之聚醯亞胺/金屬複合積層板之銅箔10C、熱固性聚醯亞胺膜30C及熱塑性聚醯亞胺膜40C，係分別相當於實施例1之聚醯亞胺/金屬複合積層板之第一銅箔10、第一熱固性聚醯亞胺膜30及第二熱塑性聚醯亞胺膜40。 As shown in FIGS. 1 and 7, the copper foil 10C, the thermosetting polyimide film 30C, and the thermoplastic polyimide film 40C of the polyimide/metal composite laminate of the comparative example are respectively equivalent to those of the first embodiment. The first copper foil 10 of the polyimide/metal composite laminate, the first thermosetting polyimide film 30 and the second thermoplastic polyimide film 40.
如圖7所示，本比較例之聚醯亞胺/金屬複合積層板製備方法如下所述。 As shown in Fig. 7, the preparation method of the polyimide/metal composite laminate of the comparative example is as follows.
先將PI-3塗佈於該銅箔10C之一側面上，形 成一熱固性聚醯亞胺前驅物層；再將TPI-1塗佈於該熱固性聚醯亞胺前驅物層遠離該銅箔10C之一側面上，形成一熱塑性聚醯亞胺前驅物層。 First, PI-3 is coated on one side of the copper foil 10C. Forming a thermosetting polyimine precursor layer; applying TPI-1 to the thermosetting polyimine precursor layer away from one side of the copper foil 10C to form a thermoplastic polyimide precursor layer.
然後，以80℃至150℃之除溶劑溫度除去該熱固性聚醯亞胺前驅物層及該熱塑性聚醯亞胺前驅物層中所含有的溶劑，即N-甲基-2-吡咯烷酮。 Then, the thermosetting polyimine precursor layer and the solvent contained in the thermoplastic polyimide precursor layer, that is, N-methyl-2-pyrrolidone, are removed at a solvent removal temperature of 80 ° C to 150 ° C .
之後，令經去除溶劑的熱固性聚醯亞胺前驅物層及經去除溶劑的熱塑性聚醯亞胺前驅物層同時依序加熱至160℃至190℃之溫度、190℃至300℃之溫度及300℃至350℃之溫度以進行環化反應；於該環化反應結束後，該經去除溶劑的熱固性聚醯亞胺前驅物層環化為該熱固性聚醯亞胺膜30C，該經去除溶劑的熱塑性聚醯亞胺前驅物層環化為該熱塑性聚醯亞胺膜40C，得到該聚醯亞胺/金屬複合積層板。 Thereafter, the solvent-removed thermosetting polyimine precursor layer and the solvent-removed thermoplastic polyimide precursor layer are simultaneously heated to a temperature of 160 ° C to 190 ° C, a temperature of 190 ° C to 300 ° C, and 300. a temperature of from ° C to 350 ° C to carry out a cyclization reaction; after the end of the cyclization reaction, the solvent-removed thermosetting polyimine precursor layer is cyclized to the thermosetting polyimide film 30C, the solvent-removed The thermoplastic polyimide film precursor layer is cyclized to the thermoplastic polyimide film 40C to obtain the polyimide/metal composite laminate.
比較例9 聚醯亞胺/金屬複合積層板及其製備方法Comparative Example 9 Polyimine/metal composite laminate and preparation method thereof
本比較例與比較例8概同，惟本比較例之熱固性聚醯亞胺膜為PI-4所製成。 This comparative example is the same as Comparative Example 8, except that the thermosetting polyimide film of the comparative example was made of PI-4.
比較例10 聚醯亞胺/金屬複合積層板及其製備方法Comparative Example 10 Polyimine/metal composite laminate and preparation method thereof
本比較例與比較例8概同，惟本比較例之熱固性聚醯亞胺膜為PI-5所製成。 This comparative example is the same as Comparative Example 8, except that the thermosetting polyimide film of the comparative example was made of PI-5.
比較例11 聚醯亞胺/金屬複合積層板及其製備方法Comparative Example 11 Polyimine/metal composite laminate and preparation method thereof
本比較例與比較例8概同，惟本比較例之熱固 性聚醯亞胺膜及熱塑性聚醯亞胺膜分別為PI-5及TPI-2所製成。 This comparative example is the same as Comparative Example 8, except that the thermosetting of this comparative example The polyimine film and the thermoplastic polyimide film are made of PI-5 and TPI-2, respectively.
比較例12 聚醯亞胺/金屬複合積層板及其製備方法Comparative Example 12 Polyimine/metal composite laminate and preparation method thereof
本比較例與比較例8概同，惟本比較例之熱固性聚醯亞胺膜及熱塑性聚醯亞胺膜分別為PI-6及TPI-3所製成。 This comparative example is the same as Comparative Example 8, except that the thermosetting polyimide film and the thermoplastic polyimide film of the comparative example were made of PI-6 and TPI-3, respectively.
比較例13 聚醯亞胺/金屬複合積層板及其製備方法Comparative Example 13 Polyimine/metal composite laminate and preparation method thereof
本比較例與比較例8概同，惟本比較例之熱固性聚醯亞胺膜及熱塑性聚醯亞胺膜分別為PI-6及TPI-4所製成。 This comparative example is the same as Comparative Example 8, except that the thermosetting polyimide film and the thermoplastic polyimide film of the comparative example were made of PI-6 and TPI-4, respectively.
分析結果與討論Analysis results and discussion
本分析結果與討論所涉及的分析方法如下所述。 The analysis methods involved in the analysis and discussion of this analysis are as follows.
玻璃轉換溫度(Tg)：以PerkinElmer公司之Pyris Diamond動態機械分析儀量測而得，溫度梯度為10℃/分鐘。 Glass transition temperature (Tg): measured by PerkinElmer's Pyris Diamond Dynamic Mechanical Analyzer with a temperature gradient of 10 ° C / min.
熱膨脹係數(coefficient of thermal expansion，CTE)：以PerkinElmer公司之Pyris Diamond熱機械分析儀量測而得，溫度梯度為10℃/分鐘。 Coefficient of thermal expansion (CTE): measured by PerkinElmer's Pyris Diamond thermomechanical analyzer with a temperature gradient of 10 ° C / min.
水氣穿透率(water vapor transmission rate，WVTR)：以水氣穿透率分析儀量測，該水氣穿透率分析儀為美國膜康公司(Mocon Inc.)之PERMATRAN-W Model 3/61，量測參數為40℃及90%RH。 Water vapor transmission rate (WVTR): measured by a water vapor permeability analyzer, PERMATRAN-W Model 3/ by Mocon Inc., USA. 61, the measurement parameters are 40 ° C and 90% RH.
剝離強度(peeling strength)：依據IPC-TM-650 2.4.9。 Peeling strength: according to IPC-TM-650 2.4.9.
尺寸安定性(dimensional stability)：依據IPC-TM-650 2.2.4之方法B及方法C。 Dimensional stability: Method B and Method C according to IPC-TM-650 2.2.4.
耐焊性(solder resistance)測試：依據IPC-TM-650 2.4.13，量測條件為300℃/30秒。 Solder resistance test: According to IPC-TM-650 2.4.13, the measurement conditions are 300 ° C / 30 seconds.
此外，本分析結果與討論亦涉及環化反應所造成的脫層及白化現象。 In addition, the results and discussion of this analysis also involve delamination and whitening caused by the cyclization reaction.
如表1、2及圖1所示，實施例1至9之第一熱固性聚醯亞胺膜30與第一熱塑性聚醯亞胺膜20之間；以及，第二熱塑性聚醯亞胺膜40與第一熱固性聚醯亞胺膜30之間未發生脫層及白化現象，顯示實施例1至9之第一熱固性聚醯亞胺膜30與第一熱塑性聚醯亞胺膜20之間；以及，第二熱塑性聚醯亞胺膜40與第一熱固性聚醯亞胺膜30之間的水氣得以排出。比較例1之聚醯亞胺/金屬複合積層板之第一熱固性聚醯亞胺膜30與第一熱塑性聚醯亞胺膜20之間；以及，第二熱塑性聚醯亞胺膜40與第一熱固性聚醯亞胺膜30之間發生脫層及白化現象，顯示比較例1之第一熱固性聚醯亞胺膜30與第一熱塑性聚醯亞胺膜20之間；以及，第二熱塑性聚醯亞胺膜40與第一熱固性聚醯亞胺膜30之間的水氣未能完全排出。 As shown in Tables 1, 2 and 1, the first thermosetting polyimide film 30 of Examples 1 to 9 is interposed between the first thermoplastic polyimide film 20; and the second thermoplastic polyimide film 40 No delamination and whitening occurred between the first thermosetting polyimide film 30, and between the first thermosetting polyimide film 30 of Examples 1 to 9 and the first thermoplastic polyimide film 20; The moisture between the second thermoplastic polyimide film 40 and the first thermosetting polyimide film 30 is discharged. The first thermosetting polyimide film 30 of the polyimide/metal composite laminate of Comparative Example 1 is interposed between the first thermoplastic polyimide film 20; and the second thermoplastic polyimide film 40 and the first Debonding and whitening occurred between the thermosetting polyimide film 30, showing the first thermosetting polyimide film 30 of Comparative Example 1 and the first thermoplastic polyimide film 20; and, the second thermoplastic polymer The moisture between the imine film 40 and the first thermosetting polyimide film 30 is not completely discharged.
表1比較例1、實施例1至4之聚醯亞胺/金屬複合積層板之特性與其第一熱塑性聚醯亞胺膜、第二熱塑性聚醯亞胺膜及第一熱固性聚醯亞胺膜的原料與厚度。
如表3及圖6所示，比較例2至4之聚醯亞胺/金屬複合積層板的熱塑性聚醯亞胺膜20B與熱固性聚醯亞胺膜30B之間發生脫層及白化現象，而比較例5至7之聚醯亞胺/金屬複合積層板則未發生脫層及白化現象；進一步配合參照表4及5可知，比較例2至4之熱固性聚醯亞胺膜30B之水氣穿透率小於170公克-微米/平方公尺-天(g-μm/m2-day)，而比較例5至7之熱固性聚醯亞胺膜30B之水氣穿透率大於或等於170g-μm/m2-day；顯示比較例5至7之聚醯亞胺/金屬複合積層板未發生脫層及白化現象係由於比較例5至7之熱固性聚醯亞胺膜30B之水氣穿透率大於或等於170g-μm/m2-day所致。 As shown in Table 3 and FIG. 6, the delamination and whitening occurred between the thermoplastic polyimide film 20B of the polyimide/metal composite laminate of Comparative Examples 2 to 4 and the thermosetting polyimide film 30B. The polydecimide/metal composite laminates of Comparative Examples 5 to 7 did not undergo delamination and whitening; further, with reference to Tables 4 and 5, the water vapor permeation of the thermosetting polyimide membranes 30B of Comparative Examples 2 to 4 was observed. The permeability is less than 170 gram-micrometers per square meter-day (g-μm/m 2 -day), and the moisture permeability of the thermosetting polyimide membrane 30B of Comparative Examples 5 to 7 is greater than or equal to 170 g-μm. /m 2 -day; shows that the polydecimide/metal composite laminate of Comparative Examples 5 to 7 did not undergo delamination and whitening due to the water vapor permeability of the thermosetting polyimide film 30B of Comparative Examples 5 to 7. Greater than or equal to 170g-μm/m 2 -day.
表4標示為TPI-1、TPI-2、TPI-3及TPI-4之熱塑性聚醯亞胺酸前驅物經由高溫環化後所得到之熱塑性聚醯亞胺膜的玻璃轉換溫度、熱膨脹係數、水氣穿透率。
再進一步比較比較例2至4及比較例5至7可知，比較例5至7之熱固性聚醯亞胺膜30B係分別由PI-4、PI-5及PI-6所製成，而比較例2至4之熱固性聚醯亞胺膜30B係分別由PI-1、PI-2及PI-3所製成；以第一反應性單體與二胺單體之總莫耳數為基準，PI-4、PI-5及PI-6所含有的第一反應性單體至少為2.7莫耳百分比，而PI-2及PI-3所含有的第一反應性單體係低於2.7莫耳百分比，PI-1則未含有第一反應性單體。 Further comparing Comparative Examples 2 to 4 and Comparative Examples 5 to 7, it was found that the thermosetting polyimide membranes 30B of Comparative Examples 5 to 7 were made of PI-4, PI-5 and PI-6, respectively, and Comparative Examples The thermosetting polyimine film 30B of 2 to 4 is made of PI-1, PI-2 and PI-3, respectively; based on the total number of moles of the first reactive monomer and the diamine monomer, PI -4, PI-5 and PI-6 contain at least 2.7 mole percent of the first reactive monomer, while PI-2 and PI-3 contain less than 2.7 mole percent of the first reactive monomer system PI-1 does not contain the first reactive monomer.
如表6及圖7所示，比較例8至13之聚醯亞胺/金屬複合積層板的熱塑性聚醯亞胺膜40C與熱固性聚 醯亞胺膜30C之間未發生脫層及白化現象，進一步配合參照表4及5可知，係由於比較例8至13之熱塑性聚醯亞胺膜40C之水氣穿透率係大於170g-μm/m2-day，使得比較例8至13之熱塑性聚醯亞胺膜40C與熱固性聚醯亞胺膜30C之間的水氣得以排出。 As shown in Table 6 and FIG. 7, the delamination and whitening did not occur between the thermoplastic polyimide film 40C of the polyimide/metal composite laminate of Comparative Examples 8 to 13 and the thermosetting polyimide film 30C. Further, with reference to Tables 4 and 5, since the water vapor permeability of the thermoplastic polyimide film 40C of Comparative Examples 8 to 13 was more than 170 g-μm/m 2 -day, the thermoplastic polymerization of Comparative Examples 8 to 13 was obtained. The moisture between the quinone imine film 40C and the thermosetting polyimide film 30C is discharged.
由上述可推知，實施例1至9之第一熱固性聚醯亞胺膜30與第一熱塑性聚醯亞胺膜20之間；以及，第二熱塑性聚醯亞胺膜40與第一熱固性聚醯亞胺膜30之間未發生脫層及白化現象，而比較例1之聚醯亞胺/金屬複合積層板之第一熱固性聚醯亞胺膜30與第一熱塑性聚醯亞胺膜20之間；以及，第二熱塑性聚醯亞胺膜40與第一熱固性聚醯亞胺膜30之間發生脫層及白化現象，乃由於實施例1至9之第一熱固性聚醯亞胺膜30及第二熱塑性聚醯亞胺膜40之水氣穿透率係大於或等於170g-μm/m2-day，且實施例1至9之及第二熱塑性聚醯亞胺膜40之水氣穿透率大於第一熱固性聚醯亞胺膜30之水氣穿透率所致。且上述可 推知藉由以二胺單體與反應性單體為基準，含有3.39莫耳百分比以上之第一反應性單體的PI-4、PI-5及PI-6，係可令實施例1至9之第一熱固性聚醯亞胺膜及第二熱塑性聚醯亞胺膜之水氣穿透率係大於或等於170g-μm/m2-day；而含有35.89莫耳百分比以上之第二反應性單體的TPI-1、TPI-2、TPI-3及TPI-4，係可令實施例1至9之第二熱塑性聚醯亞胺膜之水氣穿透率係大於或等於170g-μm/m2-day。 It can be inferred from the above that between the first thermosetting polyimide film 30 of Examples 1 to 9 and the first thermoplastic polyimide film 20; and, the second thermoplastic polyimide film 40 and the first thermosetting polycondensate No delamination and whitening occurred between the imine films 30, and between the first thermosetting polyimide film 30 of the polyimide/metal composite laminate of Comparative Example 1 and the first thermoplastic polyimide film 20 And delamination and whitening between the second thermoplastic polyimide film 40 and the first thermosetting polyimide film 30, because the first thermosetting polyimide film 30 and the first embodiment of Examples 1 to 9 The water vapor permeability of the second thermoplastic polyimide film 40 is greater than or equal to 170 g-μm/m 2 -day, and the water vapor permeability of the first thermoplastic polyimide film 40 of Examples 1 to 9 and It is larger than the water vapor permeability of the first thermosetting polyimide film 30. Further, it is possible to infer that PI-4, PI-5 and PI-6 containing a first reactive monomer of 3.39 mol% or more based on the diamine monomer and the reactive monomer are examples. The water vapor permeability of the first thermosetting polyimide film and the second thermoplastic polyimide film of 1 to 9 is greater than or equal to 170 g-μm/m 2 -day; and the second containing more than 35.89 mole percent The TPI-1, TPI-2, TPI-3 and TPI-4 of the reactive monomer are such that the water vapor permeability of the second thermoplastic polyimide film of Examples 1 to 9 is greater than or equal to 170 g- Mm/m 2 -day.
如表1及2所示，實施例1至9之聚醯亞胺膜/金屬複合積層板係能通過300℃/30秒的耐焊性測試，顯示實施例1至9之聚醯亞胺膜/金屬複合積層板具有良好的耐焊性。 As shown in Tables 1 and 2, the polyimine film/metal composite laminate sheets of Examples 1 to 9 were able to pass the 300 ° C / 30 second solder resistance test, showing the polyimide films of Examples 1 to 9. /Metal composite laminate has good solder resistance.
如表1及2所示，實施例1至9之聚醯亞胺膜/金屬複合積層板之尺寸安定性(B)之T.D.及M.D.趨近於0，且實施例1至9之聚醯亞胺膜/金屬複合積層板之尺寸安定性(C)之T.D.及M.D.趨近於0，顯示實施例1至9之聚醯亞胺膜/金屬複合積層板具有良好的尺寸安定性。 As shown in Tables 1 and 2, the TD and MD of the dimensional stability (B) of the polyimide film/metal composite laminate sheets of Examples 1 to 9 approached 0, and the polyimides of Examples 1 to 9 The dimensional stability (C) of the amine film/metal composite laminate was close to 0, indicating that the polyimide film/metal composite laminate of Examples 1 to 9 had good dimensional stability.
如表1及表2所示，實施例1至9之聚醯亞胺膜/金屬複合積層板之剝離強度係大於0.8Kg/cm，顯示實施例1至9之聚醯亞胺膜/金屬複合積層板具有良好剝離強度。 As shown in Tables 1 and 2, the peel strength of the polyimine film/metal composite laminate sheets of Examples 1 to 9 was more than 0.8 kg/cm, and the polyimine film/metal composite of Examples 1 to 9 was shown. The laminate has good peel strength.
綜上所述，藉由含有3.39莫耳百分比以上之第一反應性單體的PI-4、PI-5及PI-6與含有35.89莫耳百分比以上之第二反應性單體的TPI-1、TPI-2、TPI-3及TPI-4之使用，實施例1至9之第一熱固性聚醯亞胺膜及第二熱塑性聚醯亞胺膜係具有大於或等於170g-μm/m2-day的水氣 穿透率，因而避免脫層及白化現象之發生，且經由測試得知，實施例1至9之聚醯亞胺膜/金屬複合積層板係具有良好的耐焊性、尺寸安定性及剝離強度。 In summary, PI-4, PI-5 and PI-6 containing a first reactive monomer of 3.39 mole percent or more and TPI-1 containing a second reactive monomer of 35.89 mole percent or more , the use of TPI-2, TPI-3 and TPI-4, the first thermosetting polyimide film of Examples 1 to 9 and the second thermoplastic polyimide film having greater than or equal to 170 g-μm/m 2 - The water vapor transmission rate of day, thus avoiding the occurrence of delamination and whitening, and it is found through testing that the polyimide film/metal composite laminate of Examples 1 to 9 has good solder resistance and dimensional stability. Sex and peel strength.
10‧‧‧第一銅箔 10‧‧‧First copper foil
20‧‧‧第一熱塑性聚醯亞胺膜 20‧‧‧First thermoplastic polyimide film
30‧‧‧第一熱固性聚醯亞胺膜 30‧‧‧First thermosetting polyimide film
40‧‧‧第二熱塑性聚醯亞胺膜 40‧‧‧Second thermoplastic polyimide film
50‧‧‧第二銅箔 50‧‧‧second copper foil
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