TWI603839B - Flexible metal clad laminate - Google Patents
Flexible metal clad laminate Download PDFInfo
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- TWI603839B TWI603839B TW102114687A TW102114687A TWI603839B TW I603839 B TWI603839 B TW I603839B TW 102114687 A TW102114687 A TW 102114687A TW 102114687 A TW102114687 A TW 102114687A TW I603839 B TWI603839 B TW I603839B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
本發明係關於一種製造可撓式印刷電路板用的可撓式金屬包層層合物,其特徵在於不會產生產品的捲曲、具有金屬包層的黏著強度是有利的、在熱處理後的尺寸變化小、尤其在吸收水氣後對焊料具有優異的阻抗性。 BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a flexible metal clad laminate for use in the manufacture of flexible printed circuit boards, which is characterized in that it does not cause curling of the product, adhesion strength with a metal cladding is advantageous, and dimensions after heat treatment. The change is small, especially after absorbing moisture, it has excellent resistance to solder.
用以製造可撓式印刷電路板的可撓式金屬包層層合物是導電金屬包層與絕緣樹脂的層合物,其可受到精細的電路處理以及可在窄小空間中彎折,是以隨著電子設備的尺寸與重量持續減少,此種層合物的使用持續增加。可撓式金屬包層層合物被分成兩層式及三層式,使用黏著劑的三層式相較於兩層式具有下列問題:抗熱性及阻燃性較低且在熱處理製程時會有較大的尺寸變化。因此,製造可撓式印刷電路板的目前驅勢通常是使用兩層式而非三層式的可撓式金屬包層層合物。 The flexible metal clad laminate for manufacturing a flexible printed circuit board is a laminate of a conductive metal clad and an insulating resin, which can be subjected to fine circuit processing and can be bent in a narrow space, As the size and weight of electronic devices continue to decrease, the use of such laminates continues to increase. The flexible metal clad laminate is divided into two layers and three layers. The three layers using the adhesive have the following problems compared to the two layers: heat resistance and flame retardancy are low and will be used in the heat treatment process. There are large dimensional changes. Therefore, the current driving force in the manufacture of flexible printed circuit boards is generally to use a two-layer, rather than three-layer, flexible metal clad laminate.
根據電路之修長、重量、長度與尺寸皆下降的現行驅勢,雙側的金屬包層層合物的使用持續增加。雙側的金屬包層層合物大致上是藉由堆疊金屬箔及形成在絕緣層之最外層上的熱塑性聚醯亞胺所製造,但具有下列問題:由於熱塑性聚醯亞胺樹脂的存在,在絕緣層吸收水氣之後,對於焊料的阻抗變得較差。尤其,正常的焊接溫度係位於200℃的位準,但由於無鉛焊接製程變得普遍且其溫度為250℃或更高,所以在吸收水氣之後對焊料的阻抗變得愈來愈重要。 The use of double-sided metal clad laminates continues to increase, depending on the current drive for the slenderness, weight, length and size of the circuit. The double-sided metal clad laminate is substantially fabricated by stacking a metal foil and a thermoplastic polyimide which is formed on the outermost layer of the insulating layer, but has the following problems: due to the presence of the thermoplastic polyimide resin, After the insulating layer absorbs moisture, the impedance to the solder becomes poor. In particular, the normal soldering temperature is at a level of 200 ° C, but since the lead-free soldering process becomes common and its temperature is 250 ° C or higher, the resistance to solder after absorbing moisture becomes more and more important.
關於已知技術的專利文件1舉出下列實例:使用具有特殊結構的聚醯亞胺樹脂作為熱塑性聚醯亞胺樹脂層,在此實例中,吸收水氣後的耐熱溫度剛好是260℃,是以在300℃或更高溫度之嚴刻條件下對焊料的 阻抗會有問題。 Patent Document 1 on the known art cites the following example: using a polyimine resin having a special structure as a thermoplastic polyimide resin layer, in this example, the heat-resistant temperature after absorbing moisture is just 260 ° C, To the solder under severe conditions of 300 ° C or higher There is a problem with the impedance.
(專利文件1)日本專利申請案公開號2002-363284 (Patent Document 1) Japanese Patent Application Publication No. 2002-363284
本發明係關於一種用以製造印刷電路板的可撓式金屬包層層合物以及其製造方法,其具有藉由下列方式來解決先前技術中之問題的目標:提供一種可撓式金屬包層層合物,在吸收水氣後其於300℃或更高的溫度下對於焊料具有優異的阻抗性、其不會產生產品的捲曲、其與銅箔的鍵結強度高、其在熱處理後的尺寸變化小。 The present invention relates to a flexible metal clad laminate for manufacturing a printed circuit board and a method of manufacturing the same, which has the object of solving the problems of the prior art by providing a flexible metal cladding The laminate has excellent resistance to solder at 300 ° C or higher after absorbing moisture, it does not cause curling of the product, its bond strength with copper foil is high, and it is after heat treatment. The dimensional change is small.
下面為用以達成上述目標的本發明。 The following is the invention for achieving the above object.
在一通常態樣中,提供一種可撓式金屬包層層合物,其中金屬層係形成在複數聚醯亞胺系之樹脂層所構成之絕緣層的一表面或兩表面上,與該金屬層接觸之該複數聚醯亞胺系之樹脂層在300℃下具有1 X 108Pa或更高且在350℃下具有1 X 108Pa或更低的儲存模數。 In a general aspect, a flexible metal clad laminate is provided, wherein a metal layer is formed on one surface or both surfaces of an insulating layer composed of a plurality of polyimine-based resin layers, and the metal the plurality of polyimide-based resin layer into contact with the layer 1 X 10 8 Pa at 300 deg.] C or higher and having 1 X 10 8 Pa or lower storage modulus at 350 ℃.
本發明提供一種可撓式金屬包層層合物,其在吸收水氣後對於焊料具有優異的阻抗性、不會產生產品的捲曲、與銅箔的鍵結強度高、在熱處理後的尺寸變化小。 The present invention provides a flexible metal clad laminate which has excellent resistance to solder after absorbing moisture, does not cause curling of the product, has high bonding strength with copper foil, and has dimensional change after heat treatment. small.
本發明提供一種可撓式金屬包層層合物,其中金屬層係形成在複數聚醯亞胺系之樹脂層所構成之絕緣層的一表面或兩表面上,與該金屬層接觸的該聚醯亞胺系之樹脂層在300℃下具有1 X 108Pa或更高且在350℃下具有1 X 108Pa或更低的儲存模數。 The present invention provides a flexible metal clad laminate in which a metal layer is formed on one surface or both surfaces of an insulating layer composed of a plurality of polyimine-based resin layers, and the poly layer is in contact with the metal layer. the acyl imine resin layer having a 1 X 10 8 Pa or more and having 1 X 10 8 Pa or less at 350 deg.] C storage modulus at 300 ℃.
提供一種可撓式金屬包層層合物,其中該複數聚醯亞胺系之 樹脂層具有一熱塑性聚醯亞胺系之樹脂層、一熱固性聚醯亞胺系之樹脂層與一熱塑性聚醯亞胺系之樹脂層依序層合的形式。 Providing a flexible metal clad laminate, wherein the plurality of polyimide groups are The resin layer has a thermoplastic polyimide-based resin layer, a thermosetting polyimide-based resin layer, and a thermoplastic polyimide-based resin layer laminated in this order.
又,與該金屬層接觸的該聚醯亞胺系之樹脂層為玻璃轉換溫度等於或小於300℃的熱塑性聚醯亞胺系之樹脂層。 Further, the polyimine-based resin layer in contact with the metal layer is a thermoplastic polyimide-based resin layer having a glass transition temperature of 300 ° C or lower.
與該金屬層接觸的該聚醯亞胺系之樹脂層在100℃至200℃的溫度範圍下量測到50ppm/K或更低的線性熱膨脹係數。 The polyimine-based resin layer in contact with the metal layer measures a linear thermal expansion coefficient of 50 ppm/K or less at a temperature ranging from 100 ° C to 200 ° C.
又,在根據本發明藉由該聚醯亞胺系之樹脂層所製造之可撓式金屬包層層合物中,在40℃及90%相對濕度的條件下處理72小時後,其吸收水氣後對焊料的阻抗溫度為300℃或更高。 Further, in the flexible metal clad laminate produced by the polyimine-based resin layer according to the present invention, it is absorbed after being treated at 40 ° C and 90% relative humidity for 72 hours. The resistance temperature to the solder after the gas is 300 ° C or higher.
又,本發明提供該可撓式金屬包層層合物,其中與該金屬層接觸之該聚醯亞胺系之樹脂層包含50至100莫耳%之下列[化學通式1]所代表的結構單元。 Moreover, the present invention provides the flexible metal clad laminate, wherein the polyimine-based resin layer in contact with the metal layer contains 50 to 100 mol% of the following [Chemical Formula 1] Structural units.
[化學通式1]中所包含的-X-為芳香族二氨化合物,其包含選自下列結構的一或兩或更多者且可單獨使用或藉由共聚合來加以使用。 The -X- contained in [Chemical Formula 1] is an aromatic diamine compound containing one or two or more selected from the following structures and which can be used singly or by copolymerization.
-X1-係選自-O-、-CO-、-S-、-SO2-、-C(CH3)2-、-CONH-、-C(CF3)2-、-(CH2)-或其組合。 -X 1 - is selected from the group consisting of -O-, -CO-, -S-, -SO 2 -, -C(CH 3 ) 2 -, -CONH-, -C(CF 3 ) 2 -, -(CH 2 ) - or a combination thereof.
[化學通式1]中所包含的為二酐,其包含選自下列結構的一 或兩或更多者且可單獨使用或藉由共聚合來加以使用。 Included in [Chemical Formula 1] It is a dianhydride which contains one or two or more selected from the following structures and can be used singly or by copolymerization.
此後,將詳細說明本發明之構成。 Hereinafter, the constitution of the present invention will be described in detail.
本發明提供一種具有多層結構的可撓式金屬包層層合物,其中金屬包層係形成於絕緣層的一表面或兩表面上,該絕緣層係由複數聚醯亞胺系之樹脂所構成。 The present invention provides a flexible metal clad laminate having a multilayer structure in which a metal clad layer is formed on one surface or both surfaces of an insulating layer, which is composed of a plurality of polyimine-based resins. .
複數聚醯亞胺系之樹脂層具有一熱塑性聚醯亞胺系之樹脂層、一熱固性聚醯亞胺系之樹脂層與一熱塑性聚醯亞胺系之樹脂層依序層合的形式。 The polyimine-based resin layer has a thermoplastic polyimide-based resin layer, a thermosetting polyimide-based resin layer, and a thermoplastic polyimide-based resin layer laminated in this order.
該可撓式金屬包層層合物可藉著將單一聚醯亞胺系之樹脂層形成至金屬包層上所製造,但在此情況下會有下列問題。首先,在單獨使用熱固性聚醯亞胺系之樹脂層的情況下,與金屬箔的黏著強度很低,且由於不具有熱塑性聚醯亞胺系之樹脂層,所以無法進行製造雙側可撓式金屬包層的熱層合製程,又在蝕刻之前與之後會有產品發生捲曲的問題。相對地,在單獨使用熱塑性聚醯亞胺系之樹脂層的情況下,由於絕緣層的線性熱膨脹係數高,故在熱處理後的尺寸變化大,且在蝕刻之前與之後會有產品發生捲曲的問題。因此,構成本發明之可撓式金屬包層層合物的絕緣層具有多層結構,其係由熱塑性聚醯亞胺系之樹脂層、熱固性聚醯亞胺系之樹脂層與熱塑性聚醯亞胺系之樹脂層的複數聚醯亞胺系之樹脂層所構成。 The flexible metal clad laminate can be produced by forming a single polyimide-based resin layer onto a metal clad layer, but in this case, there are the following problems. First, when a thermosetting polyimine-based resin layer is used alone, the adhesion strength to the metal foil is low, and since the thermoplastic polyimide-based resin layer is not provided, it is impossible to manufacture a double-sided flexible type. The thermal lamination process of the metal cladding has the problem of curling of the product before and after etching. In contrast, in the case of using a thermoplastic polyimide-based resin layer alone, since the linear thermal expansion coefficient of the insulating layer is high, the dimensional change after heat treatment is large, and there is a problem that the product is curled before and after the etching. . Therefore, the insulating layer constituting the flexible metal clad laminate of the present invention has a multilayer structure composed of a thermoplastic polyimide-based resin layer, a thermosetting polyimide-based resin layer, and a thermoplastic polyimide. The resin layer of the resin layer is composed of a plurality of polyimine-based resin layers.
根據本發明之熱塑性聚醯亞胺系之樹脂層代表與金屬層接觸之聚醯亞胺系之樹脂層且具有在300℃下1 X 108Pa或更高及在350℃下1 X 108Pa或更低之儲存模數的特性。 The resin layer of the thermoplastic resin layer Juxi Juxi imine of the present invention and the metal layer in contact with representatives of the imine and having at 300 ℃ 1 X 10 8 Pa or more and X 10 8 at 1 at 350 ℃ The characteristics of Pa or lower storage modulus.
具體而言,較佳地在300℃下有1 X 108Pa或更高與1 X 1010Pa或更低的儲存模數及在350℃下有1 X 108Pa或更低與1 X 105Pa或更高的儲存模數。 Specifically, it is preferably 1 X 10 8 Pa or higher and 1 X 10 10 Pa or lower storage modulus at 300 ° C and 1 X 10 8 Pa or lower and 1 X at 350 ° C. 10 5 Pa or higher storage modulus.
在300℃下儲存模數低於1 X 108Pa的情況中,會有吸收水 氣後難以阻抗焊料的問題,在儲存模數大於1 X 1010Pa的情況中,會有材料脆度增加且彎曲特性減少的問題。又,在350℃下儲存模數大於1 X 108Pa的情況中會有熱塑性不足的問題,在儲存模數小於1 X 105Pa的情況中,由於樹脂熔融流動,所以會有難以進行熱層合製程的問題。 In the case where the storage modulus is lower than 1 X 10 8 Pa at 300 ° C, there is a problem that it is difficult to resist the solder after absorbing moisture, and the material brittleness increases in the case where the storage modulus is more than 1 X 10 10 Pa. And the problem of reduced bending characteristics. Further, in the case where the storage modulus is more than 1 × 10 8 Pa at 350 ° C, there is a problem of insufficient thermoplasticity. In the case where the storage modulus is less than 1 × 10 5 Pa, since the resin melts and flows, it is difficult to carry out heat. The problem of the lamination process.
又,根據本發明之熱塑性聚醯亞胺系之樹脂層可具有300℃或更低的玻璃轉換溫度。更具體而言,玻璃轉換溫度係介於200至300℃。 Further, the thermoplastic polyimide-based resin layer according to the present invention may have a glass transition temperature of 300 ° C or lower. More specifically, the glass transition temperature is between 200 and 300 °C.
在熱塑性聚醯亞胺系之樹脂層不滿足上述條件的情況下,例如若玻璃轉換溫度不高於300℃且在350℃下所量測到的儲存模數高於1 X 108Pa,則在吸收水氣後對於焊料的阻抗是有利的但在高溫下樹脂的流動性不足,是以會有無法進行熱層合製程且與另一基板如蓋層與預浸層(prepreg)之鍵結強度低的問題。考慮到前述之問題,構成本發明之熱塑性聚醯亞胺系之樹脂層具有300℃或更小的玻璃轉換溫度以及在350℃下1 X 108Pa或更小的儲存模數。 In the case where the thermoplastic polyimide-based resin layer does not satisfy the above conditions, for example, if the glass transition temperature is not higher than 300 ° C and the storage modulus measured at 350 ° C is higher than 1 X 10 8 Pa, then It is advantageous for the resistance of the solder after absorbing moisture, but the fluidity of the resin is insufficient at a high temperature, so that there is a possibility that the thermal lamination process cannot be performed and bonding with another substrate such as a cap layer and a prepreg. The problem of low strength. In view of the foregoing problems, the thermoplastic polyimine-based resin layer constituting the present invention has a glass transition temperature of 300 ° C or less and a storage modulus of 1 × 10 8 Pa or less at 350 ° C.
若將吸收水氣後之聚醯亞胺樹脂浸泡至高溫下的焊料浴中,被吸收的水氣會快速地揮發且在聚醯亞胺樹脂層之間或在聚醯亞胺樹脂層與金屬包層之間之介面處會發生缺陷如層分離以及在樹脂層中會發生缺陷如泡沫與膨脹。若將聚醯亞胺樹脂浸沒於高溫的焊料浴中,樹脂層中所吸收的水氣會快速地蒸發,這時似乎只有在聚醯亞胺樹脂具有能耐受水氣之水蒸氣壓力的儲存模數位準的情況下,才能避免浸沒至焊料浴時所出現的缺陷。本發明人基於此觀點已進行了研究,結論是,在300℃下所量測到的儲存模數應為108Pa或更大以在40℃及90%相對濕度的條件下吸收水氣72小時或更久後具有吸收水氣後對300℃之焊料的阻抗,且經由此特性,可製造在吸收水氣後對於焊料具有特別優異之阻抗的可撓式金屬包層層合物。 If the water-absorbing polyimine resin is immersed in a solder bath at a high temperature, the absorbed moisture will rapidly evaporate and between the polyimide layer or the polyimide layer and the metal. Defects such as layer separation and defects such as foaming and swelling occur in the resin layer at the interface between the cladding layers. If the polyimide resin is immersed in a high-temperature solder bath, the water vapor absorbed in the resin layer will evaporate rapidly. At this time, it seems that only the polyimide resin has a storage mold capable of withstanding the water vapor pressure of moisture. In the case of a digital level, defects that occur when immersed in the solder bath can be avoided. The present inventors have conducted research based on this point of view, and concluded that the storage modulus measured at 300 ° C should be 10 8 Pa or more to absorb moisture 72 at 40 ° C and 90% relative humidity. After an hour or more, there is an impedance to 300 ° C of solder after absorbing moisture, and via this characteristic, a flexible metal clad laminate having a particularly excellent resistance to solder after absorbing moisture can be manufactured.
又,與金屬層接觸的熱塑性聚醯亞胺系之樹脂層具有在100℃至200℃之間量測到50ppm/K或更小的線性熱膨脹係數。 Further, the thermoplastic polyimide-based resin layer in contact with the metal layer has a linear thermal expansion coefficient of 50 ppm/K or less measured between 100 ° C and 200 ° C.
更具體而言,線性熱膨脹係數較佳介於17至50ppm/K之間。 More specifically, the coefficient of linear thermal expansion is preferably between 17 and 50 ppm/K.
整個絕緣層的線性熱膨脹係數應低以避免可撓式金屬包層層合物在熱處理之後捲曲並增加尺寸穩定性。由於熱塑性聚醯亞胺系之樹脂層對熱固性聚醯亞胺系之樹脂層的線性熱膨脹係數高,因此很重要的是 控制熱塑性聚醯亞胺系之樹脂層的線性熱膨脹係數以控制整個絕緣層的線性熱膨脹係數。需要在較高溫度下具有高儲存模數之熱塑性聚醯亞胺系之樹脂以控制熱塑性聚醯亞胺系之樹脂層之線性熱膨脹係數。本發明之熱塑性聚醯亞胺系之樹脂層具有在300℃下量測到1 X 108Pa或更高之儲存模數,且由於儲存模數在高溫下高,因此在100至200℃之間所量測到的線性熱膨脹係數為50ppm/K或更小。 The linear thermal expansion coefficient of the entire insulating layer should be low to avoid curling of the flexible metal clad laminate after heat treatment and to increase dimensional stability. Since the thermoplastic polyimide-based resin layer has a high coefficient of linear thermal expansion to the thermosetting polyimide-based resin layer, it is important to control the linear thermal expansion coefficient of the thermoplastic polyimide-based resin layer to control the entire insulating layer. Linear thermal expansion coefficient. A thermoplastic polyimide-based resin having a high storage modulus at a relatively high temperature is required to control the linear thermal expansion coefficient of the thermoplastic polyimide-based resin layer. The thermoplastic polyimide-based resin layer of the present invention has a storage modulus of 1 × 10 8 Pa or higher measured at 300 ° C, and is 100 to 200 ° C because the storage modulus is high at a high temperature. The measured linear thermal expansion coefficient is 50 ppm/K or less.
接下來,將說明根據本發明之聚醯亞胺系之樹脂。 Next, a polyimide-based resin according to the present invention will be explained.
本發明中所用之聚醯亞胺系之樹脂的前驅物係藉著在有機 溶液中反應二胺及二酸酐所獲得。在惰性環境如氬氣或氮氣中,將二胺以漿料形式溶解至或擴散至有機溶液中,當將二胺以漿料形式溶解或擴散於有機溶劑中時或當二胺處於固態時,添加二酸酐。 The precursor of the polyimide-based resin used in the present invention is based on organic The solution is obtained by reacting a diamine and a dianhydride. Dissolving or diffusing the diamine as a slurry into the organic solution in an inert environment such as argon or nitrogen, when the diamine is dissolved or diffused in the organic solvent as a slurry or when the diamine is in a solid state, A dianhydride is added.
只要能溶解聚醯亞胺前驅物,並不特別限制合成聚醯亞胺前 驅物溶液時所用的溶劑。其實例可包含亞碸系溶劑如二甲基亞碸與二乙基亞碸、甲醯胺系溶劑如N,N-二甲基甲醯胺與N,N-二乙基甲醯胺、乙醯胺系溶劑如N,N-二甲基乙醯胺與N,N-二乙基乙醯胺、吡咯烷酮系溶劑如N-甲基-2-吡咯烷酮與N-乙烯基-2-吡咯烷酮、酚系溶劑如酚、鄰甲酚、間甲酚或對甲酚、二甲酚、鹵化酚與兒茶酚、醚系溶劑如二甘醇二甲醚、三甘醇二甲醚、四甘醇二甲醚、四氫呋喃與二羥酸、醇系溶劑如甲醇、乙醇與丁醇、溶纖劑如丁基溶纖劑、六甲基磷醯胺、γ-丁內酯等,此些實例可較佳地單獨使用或以混合物的方式使用,又,可使用芳香族碳氫化合物如二甲苯與甲苯。 As long as it can dissolve the polyimine precursor, it is not particularly limited before the synthesis of the polyimine The solvent used to drive the solution. Examples thereof may include an anthraquinone solvent such as dimethyl hydrazine and diethyl hydrazine, a formamide solvent such as N,N-dimethylformamide and N,N-diethylformamide, B. Amidoxime solvent such as N,N-dimethylacetamide and N,N-diethylacetamide, pyrrolidone solvent such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol a solvent such as phenol, o-cresol, m-cresol or p-cresol, xylenol, halogenated phenol and catechol, ether solvent such as diglyme, triglyme, tetraethylene glycol Methyl ether, tetrahydrofuran and dihydroxy acid, alcohol solvent such as methanol, ethanol and butanol, cellosolve such as butyl cellosolve, hexamethylphosphonium, γ-butyrolactone, etc., these examples may preferably be separate Use or use as a mixture, and in turn, aromatic hydrocarbons such as xylene and toluene may be used.
只要二酐是二酸酐,並不特別限定根據本發明之複數聚醯亞 胺系之樹脂層中所包含的二酐,其實例可包含脂肪族或環脂族四羧酸二酐如2,2'-六氟亞丙基二丁酸二酐、2,2-二(4-羥基苯基)二苯甲酸丙酯-3,3'4,4'-四羧酸二酐、丁烷四羧酸二酐、1,2,3,4-環丁烷四羧酸二酐、1,3-二甲基-1,2,3,4-環丁烷四羧酸、1,2,3,4-環戊烷四羧酸二酐、2,3,5-三羧基環戊基乙酸二酐、3,5,6-三羧基降冰片烷(3,5,6-tricarboxynorbornane)-2-乙酸二酐、2,3,4,5-四氫呋喃四羧酸二酐、5-(2,5-二氧四氫呋喃)-3-甲基-3-環己烯-1,2-二羧酸二酐與二環[2,2,2]-辛-7-酮-2,3,5,6-四羧酸二酐;及芳香族四羧酸二酐如均苯四甲酸二酐、3,3'4,4'-二苯酮四羧酸二酐、3,3'4,4'-二苯基碸四羧酸二酐、1,4,5,8-萘四 羧酸二酐、2,3,6,7-萘四羧酸二酐、3,3'4,4'-二苯基醚四羧酸二酐、3,3'4,4'-二甲基二苯基矽烷四羧酸二酐、3,3'4,4'-四苯基矽烷四羧酸二酐、1,2,3,4-呋喃四羧酸二酐、4,4'-二(3,4-二羧基苯氧基)二苯基硫化物二酐、4,4'-二(3,4-二羧基苯氧基)二苯基碸二酐、4,4'-雙酚A二酐、3,3'4,4'-全氟異亞丙基二酞酸二酐、3,3'4,4'-二苯基四羧酸二酐、二(酞酸)苯基膦氧化物二酐、對-亞苯基-二(三苯基酞酸)二酐、間-亞苯基-二(三苯基酞酸)二酐、二(三苯基酞酸)-4,4'-二苯基醚二酐、3,3',4,4'-二苯酮四羧酸二酐與二(三苯基酞酸)-4,4'二苯基甲烷二酸酐。 The polycondensate according to the present invention is not particularly limited as long as the dianhydride is a dianhydride. The dianhydride contained in the amine resin layer may, for example, be an aliphatic or cycloaliphatic tetracarboxylic dianhydride such as 2,2'-hexafluoropropylenedibutyric dianhydride, 2,2-di ( 4-hydroxyphenyl)dibenzoate propyl-3,3'4,4'-tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid Anhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxyl Cyclopentyl acetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 5 -(2,5-dioxotetrahydrofuran)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride and bicyclo[2,2,2]-oct-7-one-2, 3,5,6-tetracarboxylic dianhydride; and aromatic tetracarboxylic dianhydride such as pyromellitic dianhydride, 3,3'4,4'-benzophenonetetracarboxylic dianhydride, 3,3' 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 1,4,5,8-naphthalene Carboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3'4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3'4,4'-dimethyl Diphenyl decane tetracarboxylic dianhydride, 3,3'4,4'-tetraphenylnonane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'- Bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylphosphonium dianhydride, 4,4'-double Phenol A dianhydride, 3,3'4,4'-perfluoroisopropylidene dicarboxylic acid dianhydride, 3,3'4,4'-diphenyltetracarboxylic dianhydride, bis(decanoic acid) benzene Phosphine dianhydride, p-phenylene-bis(triphenylphosphonate) dianhydride, m-phenylene-bis(triphenylphosphonate) dianhydride, bis(triphenylphosphonic acid)- 4,4'-diphenylether dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride and bis(triphenylphosphonic acid)-4,4' diphenylmethane dianhydride .
根據本發明之複數聚醯亞胺系之樹脂層中所包含的二胺並 未受而大幅限制,其實例可包含芳香族二胺如對-苯二胺、間-苯二胺、4,4'-二氨基二苯基甲烷、4,4'-二氨基二苯基乙烷、4,4'-二氨基二苯基醚、4,4'-二氨基苯基硫化物、4,4'-二氨基苯基碸、1,5-二氨基萘、3,3-二甲基-4,4'-二氨基二苯基、3,5-二氨基-苯甲酸、5-氨基-1-(4'-氨基苯基)-1,3,3-三甲基茚、6-氨基-1-(4'-氨基苯基)-1,3,3-三甲基茚、4,4'-二氨基苯甲醯胺苯、3,5-二氨基-3'-三氟甲基苯甲醯胺苯、3,5-二氨基-4'-三氟甲基苯甲醯胺苯、3,4'-二氨基二苯基醚、2,7-二氨基芴、2,2-二(4-氨基苯基)六氟丙烷、4,4'-亞甲基-二(2-氯苯胺)、2,2'5,5'-四氯-4,4'-二氨基二苯基、2,2'-二氯-4,4'-二氨基-5,5'-二甲氧基二苯基、3,3'-二甲氧基-4,4'-二氨基苯基、4,4'-二氨基-2,2'-二(三氟甲基)二苯基、2,2-二[4-(4-氨基苯氧基)苯基]丙烷、2,2-二[4-(4-氨基苯氧基)苯基]六氟丙烷、1,4-二(4-氨基苯氧基)苯、4,4-二(4-氨基苯氧基)-二苯基、1,3-二(4-氨基苯氧基)苯、9,9-二(4-氨基苯基)芴、4,4'(對-亞苯基異亞丙基)二苯胺、4,4'(間-亞苯基異亞丙基)二苯胺、4,4'-二氨基二苯醚、2,2'-二[4-(4-氨基-2-三氟甲基苯氧基)苯基]六氟丙烷與4,4'-二[4-(4-氨基-2-三氟甲基)苯氧基]-八氟苯基;芳香族二胺如具有兩個氨基團鍵結至芳香環及一個非對應氨基團之氮原子的雜原子的二氨基四苯基噻吩;脂肪族二胺與環脂族二胺如1,1-間苯二甲胺、1,3-丙二胺、四亞甲二胺、五亞甲二胺、八亞甲二胺、九亞甲二胺、4,4-二氨基庚烷亞甲二胺、1,4-二氨基環己烷、異佛爾酮二胺、四氫二環戊二亞乙二胺、六氫-4,7-橋亞甲基亚茚满二亞甲基二胺與4,4'-亞甲基二(環己胺)等。 a diamine contained in a plurality of polyimine-based resin layers according to the present invention Unrestricted and greatly limited, examples thereof may include aromatic diamines such as p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl Alkane, 4,4'-diaminodiphenyl ether, 4,4'-diaminophenyl sulfide, 4,4'-diaminophenyl fluorene, 1,5-diaminonaphthalene, 3,3-di Methyl-4,4'-diaminodiphenyl, 3,5-diamino-benzoic acid, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylhydrazine, 6-Amino-1-(4'-aminophenyl)-1,3,3-trimethylhydrazine, 4,4'-diaminobenzamide, 3,5-diamino-3'-three Fluoromethylbenzamide, 3,5-diamino-4'-trifluoromethylbenzamide, 3,4'-diaminodiphenyl ether, 2,7-diaminopurine, 2 ,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-methylene-bis(2-chloroaniline), 2,2'5,5'-tetrachloro-4,4'-di Aminodiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxydiphenyl, 3,3'-dimethoxy-4,4'-di Aminophenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)diphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2 ,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene, 4,4-di(4- Aminophenoxy)-diphenyl, 1,3-bis(4-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)anthracene, 4,4' (p-phenylene) Propylene)diphenylamine, 4,4'(m-phenylene isopropylidene)diphenylamine, 4,4'-diaminodiphenyl ether, 2,2'-bis[4-(4-amino- 2-trifluoromethylphenoxy)phenyl]hexafluoropropane and 4,4'-bis[4-(4-amino-2-trifluoromethyl)phenoxy]-octafluorophenyl; aromatic a diamine such as diaminotetraphenylthiophene having two amino groups bonded to an aromatic ring and a hetero atom of a nitrogen atom other than the amino group; an aliphatic diamine and a cycloaliphatic diamine such as 1,1-m-phenylene Dimethylamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, octamethyldiamine, ninethylenediamine, 4,4-diaminoheptane methylenediamine, 1 , 4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadiethylenediamine, hexahydro-4,7-bridged methylene fluorene dimethylenediamine and 4, 4'-methylenebis(cyclohexylamine) and the like.
尤其,考慮到前述物理特性時,構成本發明之熱塑性聚醯亞 胺系之樹脂層應適當地包含50至100莫耳%由下面[化學通式1]所代表的結 構單元。 In particular, the thermoplastic polysiloxane constituting the present invention is considered in consideration of the aforementioned physical properties. The amine resin layer should suitably contain 50 to 100 mol% of the knot represented by the following [Chemical Formula 1] Construction unit.
[化學通式1]中所包含的-X-為芳香族二氨化合物,其包含選自下列結構的一或兩或更多者且可單獨使用或藉由共聚合來加以使用。 The -X- contained in [Chemical Formula 1] is an aromatic diamine compound containing one or two or more selected from the following structures and which can be used singly or by copolymerization.
-X1-係選自-O-、-CO-、-S-、-SO2-、-C(CH3)2-、-CONH-、-C(CF3)2-、-(CH2)-或其組合。 -X 1 - is selected from the group consisting of -O-, -CO-, -S-, -SO 2 -, -C(CH 3 ) 2 -, -CONH-, -C(CF 3 ) 2 -, -(CH 2 ) - or a combination thereof.
[化學通式1]中所包含的為二酐,其包含選自下列結構的一 或兩或更多者且可單獨使用或藉由共聚合來加以使用。 Included in [Chemical Formula 1] It is a dianhydride which contains one or two or more selected from the following structures and can be used singly or by copolymerization.
更具體而言,提供一種可撓式金屬包層層合物,其中-X1- 為包含-O-的芳香二氨化合物且為包含選自下列結構之一或兩者 的二酐。 More specifically, a flexible metal clad laminate is provided wherein -X 1 - is an aromatic diamine compound comprising -O- and is included A dianhydride selected from one or both of the following structures.
根據本發明之熱塑性聚醯亞胺系之樹脂層應適當地包含50至100莫耳%由[化學通式1]所代表的結構單元。在含量小於50莫耳%的情況中,350℃下的儲存模數大於1 X 108Pa,故熱塑性聚醯亞胺樹脂層在高溫下的流動性不足,是以會有無法進行熱層合製程的問題。 The thermoplastic polyimide-based resin layer according to the present invention should suitably contain 50 to 100 mol% of the structural unit represented by [Chemical Formula 1]. In the case where the content is less than 50 mol%, the storage modulus at 350 ° C is more than 1 X 10 8 Pa, so that the flowability of the thermoplastic polyimide film at a high temperature is insufficient, so that thermal lamination cannot be performed. Process problems.
本發明中所提及之聚醯亞胺系之樹脂包含具有醯亞胺環如下列[化學通式2]的所有樹脂,其實例可包含聚醯亞胺、聚醯胺醯亞胺、聚酯醯亞胺、矽氧烷-改質之聚醯亞胺等。又,除了聚醯亞胺系樹脂的單一物質之外,亦包含上述聚醯亞胺系樹脂與其他聚合物樹脂彼此混合所形成的混合物質。又,亦包含聚醯亞胺系之樹脂與其他添加物的混合物,此些添加物例如是固化加速劑如吡啶與喹啉、耦合劑如矽烷、附著度提供劑如環氧化物、使塗佈製程容易進行的消泡劑與平整劑。 The polyimine-based resin mentioned in the present invention contains all resins having a quinone ring such as the following [Chemical Formula 2], and examples thereof may include polyimine, polyamidimide, polyester Yttrium imine, decane-modified polyimine, and the like. Further, in addition to the single substance of the polyimine-based resin, a mixture of the above-mentioned polyimine-based resin and another polymer resin is mixed. Further, it also contains a mixture of a polyimine-based resin and other additives such as a curing accelerator such as pyridine and quinoline, a coupling agent such as decane, an adhesion providing agent such as an epoxide, and coating. Defoamer and leveling agent that are easy to process.
本發明之可撓式金屬包層層合物的製造方法包含壓鑄法及層合法。 The method for producing a flexible metal clad laminate of the present invention comprises a die casting method and a lamination method.
藉由壓鑄法所製成的可撓式金屬包層層合物係由下列方式製造:將聚醯胺酸系樹脂(聚醯亞胺系之樹脂的前驅物)施加至金屬層上,並經由熱或化學固化製程來形成聚醯亞胺系之樹脂層。又,雙側之可撓式金屬包層層合物係由下列方式製造:將藉由壓鑄法所製得之單側可撓式金屬包層層合物與金屬層熱層合,此種方式也被包含於壓鑄法中。 The flexible metal clad laminate produced by the die casting method is produced by applying a polyaminic acid resin (precursor of a polyimine resin) to the metal layer and via A thermal or chemical curing process is used to form a polyimine-based resin layer. Further, the double-sided flexible metal clad laminate is manufactured by thermally laminating a single-sided flexible metal clad laminate obtained by a die casting method with a metal layer. Also included in the die casting process.
藉由層合法所製成的可撓式金屬包層層合物係由下列方式製造:預先製造具有熱塑性聚醯亞胺系之樹脂層、熱固性聚醯亞胺系之樹 脂層與熱塑性聚醯亞胺系之樹脂層之多層結構的聚醯亞胺系膜層,然後以熱層合將金屬層層合於其一表面上或兩表面上以完成製造。 A flexible metal clad laminate produced by lamination is produced by pre-manufacturing a resin layer having a thermoplastic polyimine system, a thermosetting polyimide tree The polyimine film layer of the multilayer structure of the resin layer of the resin layer and the thermoplastic polyimide layer is then laminated to one surface or both surfaces by thermal lamination to complete the manufacture.
在本文中,熱塑性聚醯亞胺樹脂層包含了50至100莫耳%由[化學通式1]所代表的結構單元,且例如作為二酸酐的苯均四酸二酐與作為二胺的1,3-二(4-氨基苯氧基)苯可以反應,使得以用來形成醯胺酸的整體聚醯亞胺為基準,結構單元的含量係介於50至100莫耳%之間,且可施加醯胺酸並加熱之以進行亞胺化反應,是以製造熱塑性聚醯亞胺樹脂層。 Herein, the thermoplastic polyimide resin layer contains 50 to 100 mol% of a structural unit represented by [Chemical Formula 1], and, for example, pyromellitic dianhydride as a dianhydride and 1 as a diamine , 3-bis(4-aminophenoxy)benzene can be reacted such that the content of the structural unit is between 50 and 100 mol% based on the overall polyimine used to form the valine acid, and The imidization may be applied and heated to carry out the imidization reaction to produce a thermoplastic polyimide resin layer.
熱固性聚醯亞胺樹脂層並未受到大幅限制,但根據本發明之實例,作為二胺之對-苯二胺與4,4'-二氨基二苯醚及作為二酸酐之3,3’,4,4’-二苯基四羧酸二酐可以反應使得以用來形成醯胺酸的整體聚醯亞胺為基準其含量係介於50至100莫耳%之間,且可施加醯胺酸並加熱之以進行亞胺化反應,是以製造熱固性聚醯亞胺樹脂層。 The thermosetting polyimine resin layer is not greatly limited, but according to an example of the present invention, p-phenylenediamine as a diamine and 4,4'-diaminodiphenyl ether and 3,3' as a dianhydride, 4,4'-diphenyltetracarboxylic dianhydride can be reacted so that the content is between 50 and 100 mol% based on the overall polyimine used to form the valine acid, and the guanamine can be applied. The acid is heated and heated to carry out the imidization reaction to produce a thermosetting polyimide resin layer.
在下方式中,藉著脫水縮合反應來進行亞胺化,反應溫度較佳地介於100至400℃而所需的反應時間介於10分鐘至24小時,但毋需對其大幅限制。 In the next embodiment, the imidization is carried out by a dehydration condensation reaction, and the reaction temperature is preferably from 100 to 400 ° C and the reaction time required is from 10 minutes to 24 hours, but it is not required to be greatly limited.
只要能溶解作為聚醯亞胺前驅物的聚醯胺酸,並不大幅地限制合成時所用的溶劑,可使用亞碸系溶劑如二甲基亞碸與二乙基亞碸、甲醯胺系溶劑如N,N-二甲基甲醯胺與N,N-二乙基甲醯胺、乙醯胺系溶劑如N,N-二甲基乙醯胺與N,N-二乙基乙醯胺、吡咯烷酮系溶劑如N-甲基-2-吡咯烷酮與N-乙烯基-2-吡咯烷酮、酚系溶劑如酚、鄰甲酚、間甲酚或對甲酚、二甲酚、鹵化酚與兒茶酚、醚系溶劑如二甘醇二甲醚、三甘醇二甲醚、四甘醇二甲醚、四氫呋喃與二羥酸、醇系溶劑如甲醇、乙醇與丁醇、溶纖劑如丁基溶纖劑、六甲基磷醯胺、γ-丁內酯等,此些實例可較佳地單獨使用或以混合物的方式使用,又,可使用芳香族碳氫化合物如二甲苯與甲苯。 As long as it can dissolve the polyamic acid as the precursor of the polyimine, the solvent used in the synthesis is not greatly limited, and an anthraquinone solvent such as dimethyl hydrazine and diethyl hydrazine or formamide can be used. Solvents such as N,N-dimethylformamide and N,N-diethylformamide, acetaminophen solvents such as N,N-dimethylacetamide and N,N-diethylacetamidine Amine, pyrrolidone solvent such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenolic solvent such as phenol, o-cresol, m-cresol or p-cresol, xylenol, halogenated phenol and children A tea phenol, an ether solvent such as diglyme, triglyme, tetraglyme, tetrahydrofuran and dihydroxy acid, an alcohol solvent such as methanol, ethanol and butanol, a cellosolve such as butyl A granule, hexamethylphosphoniumamine, γ-butyrolactone or the like, and these examples may preferably be used singly or in the form of a mixture, and an aromatic hydrocarbon such as xylene and toluene may be used.
構成可撓式金屬包層層合物的金屬層表示導電金屬如銅、鋁、銀、鈀、鎳、鉻、鉬及鎢及包含其合金或其混合物。一般而言,銅被廣泛地使用,但金屬層並不限於此。又,在本發明之金屬層中包含一物質,在此物質中金屬的表面會受到物理或化學表面處理以增加金屬包層與樹脂層之間的鍵結強度。 The metal layer constituting the flexible metal clad laminate represents a conductive metal such as copper, aluminum, silver, palladium, nickel, chromium, molybdenum, and tungsten, and alloys thereof or mixtures thereof. In general, copper is widely used, but the metal layer is not limited thereto. Further, a metal layer of the present invention contains a substance in which the surface of the metal is subjected to physical or chemical surface treatment to increase the bonding strength between the metal clad layer and the resin layer.
可被應用至本發明之塗佈方法的實例包含刮塗、輥塗、模具 式塗佈、淋幕塗佈等,且只要能滿足本發明所追求的目標,該方法不限。前先已半固化或全固化的聚醯亞胺溶液以及聚醯亞胺前驅物溶液可被用來作為塗佈溶液。 Examples of the coating method that can be applied to the present invention include blade coating, roll coating, and mold Coating, curtain coating, etc., and the method is not limited as long as it satisfies the object pursued by the present invention. The previously semi-cured or fully cured polyimine solution and the polyimine precursor solution can be used as a coating solution.
在塗佈後可選擇性地進行該絕緣層的乾燥及固化處理,可進行各種已知的方法如熱風固化法、IR固化法、批次式固化法、連續式固化法及化學固化法。 The drying and curing treatment of the insulating layer can be selectively performed after coating, and various known methods such as hot air curing, IR curing, batch curing, continuous curing, and chemical curing can be carried out.
之後,將藉由實驗實例詳細地說明本發明。然而,本發明並不限於此些實例。 Hereinafter, the present invention will be described in detail by way of experimental examples. However, the invention is not limited to such examples.
在實例使用如下之縮寫。 The following abbreviations are used in the examples.
DMAc:N,N-二甲基乙醯胺 DMAc: N,N-dimethylacetamide
TPE-R:1,3-二(4-氨基苯氧基)苯 TPE-R: 1,3-bis(4-aminophenoxy)benzene
p-PDA:p-苯二胺 p-PDA: p-phenylenediamine
ODA:4,4’-二氨基二苯醚 ODA: 4,4'-diaminodiphenyl ether
BAPP:2,2-二(4-氨基苯氧基)苯丙烷 BAPP: 2,2-bis(4-aminophenoxy)phenylpropane
DABA:3,5-二氨基-苯甲酸 DABA: 3,5-diamino-benzoic acid
BPDA:3,3’,4,4’-二苯基四羧酸二酐 BPDA: 3,3',4,4'-diphenyltetracarboxylic dianhydride
PMDA:均苯四酸二酐 PMDA: pyromellitic dianhydride
BPADA:4,4'-雙酚A二酐 BPADA: 4,4'-bisphenol A dianhydride
BTDA:3,3',4,4'-二苯甲酮四羧酸二酐 BTDA: 3,3',4,4'-benzophenone tetracarboxylic dianhydride
TMEG:乙二醇二(偏苯三酸二酐) TMEG: ethylene glycol di(trimellitic dianhydride)
在本發明中所提及的物理特性係根據下列方法所量測。 The physical properties mentioned in the present invention were measured according to the following methods.
線性熱膨脹係數係於下列條件下量測:在氮氣環境下以5℃/min的升溫速率從30℃升溫至400℃、其間利用Mettler-Toledo GmbH所製造的TMA/SDTA 861e施加0.03N之張力。線性熱膨脹係數的平均值係於100℃至200℃之間以25℃作為間隔量測,量測到的值被認定為100℃至200℃之間的線性熱膨脹係數。 The linear thermal expansion coefficient was measured under the following conditions: a temperature rise from 30 ° C to 400 ° C at a heating rate of 5 ° C / min under a nitrogen atmosphere, during which a tension of 0.03 N was applied using TMA/SDTA 861e manufactured by Mettler-Toledo GmbH. The average value of the linear thermal expansion coefficient is measured between 25 ° C and 200 ° C at 25 ° C as an interval, and the measured value is regarded as a linear thermal expansion coefficient between 100 ° C and 200 ° C.
在下列條件下量測儲存模數:氮氣環境下以5℃/min的升溫速率從30℃升溫至400℃、其間利用Mettler-Toledo GmbH所製造的 DMA/SDTA 861e施加0.1N之張力、10Hz之頻率、30um之位移。 The storage modulus was measured under the following conditions: from 30 ° C to 400 ° C at a heating rate of 5 ° C / min under a nitrogen atmosphere, during which Mettler-Toledo GmbH was used. The DMA/SDTA 861e applies a tension of 0.1 N, a frequency of 10 Hz, and a displacement of 30 um.
在與量測儲存模數相同的條件下使用DMA,此時所獲得之Tan δ的最大值被認定為玻璃轉換溫度。 The DMA was used under the same conditions as the measured storage modulus, and the maximum value of Tan δ obtained at this time was regarded as the glass transition temperature.
在本發明所提及之熱塑性聚醯亞胺系之樹脂中,350℃下儲存模數為1 X 108Pa或更低的聚醯亞胺系之樹脂被認為是熱塑性聚醯亞胺系之樹脂,而在350℃下儲存模數為1 X 108Pa或更高的聚醯亞胺系之樹脂被認為是熱固性聚醯亞胺系樹脂。儲存模數的量測係基於上述方法。 In the thermoplastic polyimide-based resin mentioned in the present invention, a polyimide-based resin having a storage modulus of 1×10 8 Pa or less at 350 ° C is considered to be a thermoplastic polyimide-based resin. The resin, and a polyimine-based resin having a storage modulus of 1 X 10 8 Pa or higher at 350 ° C is considered to be a thermosetting polyimide-based resin. The measurement of the stored modulus is based on the above method.
在恆溫恆濕器40℃及90%相對濕度的設定下預處理大小為5cm X 5cm的樣本72小時或更久,然後將樣本浸沒至300℃下的焊料浴。將未產生外觀缺陷如膨脹與層分離的情況認定為通過,將外觀產生缺陷的情況認定為不通過。在單側之銅包層層合物的類型中,毋需去除銅箔而對具有銅箔與絕緣層的樣本進行評估。在雙側之銅包層層合物的類型中,在去除一側上之銅箔後進行評估並分別對每一側進行評估。 The sample having a size of 5 cm X 5 cm was pretreated at a setting of 40 ° C and 90% relative humidity for 72 hours or more, and then the sample was immersed in a solder bath at 300 ° C. The case where no appearance defects such as swelling and layer separation were caused was confirmed as passing, and the case where the appearance was defective was judged as not passing. In a single-sided copper clad laminate type, samples with copper foil and insulating layers were evaluated without the need to remove copper foil. In the type of the double-sided copper clad laminate, the copper foil on one side was removed and evaluated and each side was evaluated separately.
量測係基於JIS-C6471進行。 The measurement was performed based on JIS-C6471.
於常溫下當莫耳%比為90:10之p-PDA與ODA完全溶解於DMAc中之後,將100.9莫耳%的BPDA逐漸地加入溶液中。在常溫下使混合物反應24小時。在此情況中,整個溶液的固體含量被設定成13重量%。 After the p-PDA and ODA at a molar ratio of 90:10 at room temperature were completely dissolved in DMAc, 100.9 mol% of BPDA was gradually added to the solution. The mixture was allowed to react at room temperature for 24 hours. In this case, the solid content of the entire solution was set to 13% by weight.
利用與合成實例1相同的製造條件根據[表1]中所顯示的成分與含量來進行製造。 The production was carried out according to the components and contents shown in [Table 1] using the same production conditions as in Synthesis Example 1.
將經由[合成實例2]所製造之聚醯胺酸溶液施加至厚度12um的電解銅箔(由Furukawa circuit foil所製造的F2WS銅箔,粗糙度Rz=2.0um),接著在140℃下乾燥以形成第一聚醯亞胺前驅物層。將經由[合成實例1]所製造之聚醯胺酸溶液施加至第一聚醯亞胺前驅物層的一表面上,接著在140℃下乾燥以形成第二聚醯亞胺前驅物層。之後,將經由[合成實例2]所製造之聚醯胺酸溶液施加至第二聚醯亞胺前驅物層的一表面上,接著在140℃下乾燥以形成第三聚醯亞胺前驅物層。在氮氣的環境下將製造所得的層合物從150℃加熱至385℃9分鐘。在固化後,第一聚醯亞胺前驅物層、第二聚醯亞胺前驅物層及第三聚醯亞胺前驅物層中每一層的厚度分別達到2.5um、14um與3um。評估層合物的特性並將其結果顯示於[表2]中。 The polyamine acid solution produced by [Synthesis Example 2] was applied to an electrolytic copper foil (F2WS copper foil manufactured by Furukawa circuit foil, roughness Rz = 2.0 μm) having a thickness of 12 μm, followed by drying at 140 ° C. A first polyimine precursor layer is formed. The polyamic acid solution produced through [Synthesis Example 1] was applied to one surface of the first polyimideimine precursor layer, followed by drying at 140 °C to form a second polyimideimide precursor layer. Thereafter, a polyamic acid solution produced through [Synthesis Example 2] was applied to one surface of the second polyimideimide precursor layer, followed by drying at 140 ° C to form a third polyimideimide precursor layer. . The resulting laminate was heated from 150 ° C to 385 ° C for 9 minutes under a nitrogen atmosphere. After curing, each of the first polyimideimine precursor layer, the second polyimideimine precursor layer, and the third polyimideimine precursor layer has a thickness of 2.5 um, 14 um, and 3 um, respectively. The characteristics of the laminate were evaluated and the results are shown in [Table 2].
藉著與實例1相同的方法根據[表2]的膜層構成來製造可撓 式金屬包層層合物。 By the same method as in Example 1, the flexible layer was fabricated according to the film layer composition of [Table 2]. Metal clad laminate.
藉著與實例1相同的方法根據[表2]的膜層構成來製造可撓式金屬包層層合物。 A flexible metal clad laminate was produced according to the film layer constitution of [Table 2] by the same method as in Example 1.
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