TWI661005B - Polyamic acid, polyimide, resin film and metal-clad laminated board - Google Patents

Polyamic acid, polyimide, resin film and metal-clad laminated board Download PDF

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TWI661005B
TWI661005B TW104131994A TW104131994A TWI661005B TW I661005 B TWI661005 B TW I661005B TW 104131994 A TW104131994 A TW 104131994A TW 104131994 A TW104131994 A TW 104131994A TW I661005 B TWI661005 B TW I661005B
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polyimide
diamine
mol
metal
layer
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TW201612243A (en
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安藤智典
柴崎拓也
安達康弘
須藤芳樹
森亮
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日商日鐵化學材料股份有限公司
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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
    • 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
    • B32B15/088—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 comprising polyamides
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Laminated Bodies (AREA)

Abstract

聚醯胺酸是使二胺成分、與包含四羧酸酐的酸酐成分反應而得。相對於全部二胺成分，二胺成分在10莫耳%～60莫耳%的範圍內包含通式（i）所示的二胺化合物，相對於全部酸酐成分，酸酐成分在50莫耳%～100莫耳%的範圍內包含選自由均苯四羧酸二酐（PMDA）及3,3'4,4'-聯苯四羧酸二酐（BPDA）所組成的組群中的一種以上的四羧酸酐； [化1][式中，R表示碳數1～8的烷基，p表示1～4的數；此處，在p為2以上時，R可獨立地取不同的碳數]。Polyamino acid is obtained by reacting a diamine component and an acid anhydride component containing a tetracarboxylic anhydride. The diamine component contains a diamine compound represented by the general formula (i) in a range of 10 mol% to 60 mol% with respect to all the diamine components, and the acid anhydride component is 50 mol% to all acid anhydride components The range of 100 mol% includes at least one selected from the group consisting of pyromellitic dianhydride (PMDA) and 3,3'4,4'-biphenyltetracarboxylic dianhydride (BPDA) Tetracarboxylic anhydride [In the formula, R represents an alkyl group having 1 to 8 carbon atoms, and p represents a number of 1 to 4; here, when p is 2 or more, R can independently take a different carbon number].

Description

聚醯胺酸、聚醯亞胺、樹脂膜及覆金屬積層板Polyamic acid, polyimide, resin film and metal-clad laminated board

本發明是有關於一種聚醯胺酸、聚醯亞胺、以及利用所述聚醯亞胺的樹脂膜及覆金屬積層板。 The present invention relates to a polyimide acid, a polyimide, and a resin film and a metal-clad laminated board using the polyimide.

近年來，隨著電子設備的小型化、輕量化、節省空間化的進展，而薄且輕量、具有可撓性、即便反覆彎曲亦具有優異的耐久性的可撓性印刷配線板(Flexible Printed Circuits，FPC)的需求在增大。FPC即便在有限的空間亦可實現立體且高密度的安裝，因此例如在硬碟驅動器(Hard Disk Drive，HDD)、數位影音光碟(Digital Video Disc，DVD)、行動電話等電子設備的可動部分的配線、或電纜(cable)、連接器(connector)等零件中其用途不斷擴大。 In recent years, with the progress of miniaturization, weight reduction, and space saving of electronic devices, flexible printed wiring boards that are thin and light, have flexibility, and have excellent durability even after repeated bending are provided. Demand for Circuits (FPC) is increasing. FPC can realize three-dimensional and high-density installation even in a limited space. Therefore, for example, the FPC can be used in the movable parts of electronic devices such as hard disk drives (HDD), digital video discs (DVD), and mobile phones. Wiring, cable, connector, and other parts are used for more and more applications.

除了所述的高密度化外，還進行了設備的高性能化，因此亦必須應對傳輸訊號的高頻化。在傳輸高頻訊號時，在訊號的傳輸路徑的傳輸損失大時，會產生電訊號的損失或訊號的延遲時間變長等異常情況。因此，重要的是減小FPC的傳輸損失。為了應對高頻化，而使用將以低介電常數、低介電正切為特徵的液晶聚合物作為介電體層的FPC。然而，液晶聚合物雖然介電特性優異，但在耐熱性或與金屬箔的黏接性方面有改善的餘地。 In addition to the above-mentioned high-density, high-performance equipment has also been implemented, so it is necessary to cope with high-frequency transmission signals. When transmitting a high-frequency signal, when the transmission loss of the transmission path of the signal is large, an abnormal situation such as a loss of the electric signal or a long delay time of the signal may occur. Therefore, it is important to reduce the transmission loss of the FPC. In order to cope with high frequency, FPC using a liquid crystal polymer characterized by a low dielectric constant and a low dielectric tangent as a dielectric layer is used. However, although the liquid crystal polymer has excellent dielectric properties, there is room for improvement in terms of heat resistance or adhesion to a metal foil.

為了改善耐熱性或黏接性，而提出了將聚醯亞胺設為絕 緣層的覆金屬積層板(專利文獻1)。根據專利文獻1可知，通常藉由使用單體為高分子材料的脂肪族系者而介電常數降低，由於使用脂肪族(鏈狀)四羧酸二酐而得的聚醯亞胺的耐熱性顯著低，因此無法供於焊接等加工，而實用上存在問題，但若使用脂肪族四羧酸二酐，則與鏈狀者相比，可獲得耐熱性提高的聚醯亞胺。然而，此種聚醯亞胺膜雖然10GHz時的介電常數為3.2以下，但介電正切超過0.01，介電特性仍不充分。再者，使用所述脂肪族單體的聚醯亞胺多數情況是熱膨脹係數大，在將所述聚醯亞胺設為絕緣層的覆金屬積層板中產生翹曲，因此難以作為電路基板的絕緣層。 In order to improve heat resistance or adhesion, it is proposed to make polyimide Edge-clad metal-clad laminate (Patent Document 1). According to Patent Document 1, it is known that the dielectric constant is lowered by using an aliphatic monomer whose monomer is a polymer material, and the heat resistance of polyimide obtained by using an aliphatic (chain) tetracarboxylic dianhydride Remarkably low, it cannot be used for processing such as welding, and there are practical problems. However, if an aliphatic tetracarboxylic dianhydride is used, a polyimide having improved heat resistance can be obtained compared with a chain-like one. However, although such a polyfluorene film has a dielectric constant of 3.2 or less at 10 GHz, the dielectric tangent exceeds 0.01, and the dielectric characteristics are still insufficient. In addition, polyimide using the aliphatic monomer often has a large thermal expansion coefficient, and warpage occurs in a metal-clad laminated board using the polyimide as an insulating layer, so it is difficult to use it as a circuit board. Insulation.

現有技術文獻 Prior art literature 專利文獻 Patent literature

專利文獻1：日本專利特開2004-358961號公報 Patent Document 1: Japanese Patent Laid-Open No. 2004-358961

本發明的目的在於提供一種一邊可應對伴隨著電子設備的小型化、高性能化的高頻化，一邊可抑制翹曲的產生的電路基板的絕緣層材料。 An object of the present invention is to provide an insulating layer material for a circuit board that can suppress the occurrence of warpage while responding to the increase in the size of an electronic device and the high-frequency increase in performance.

為了解決所述課題，本發明者等人發現，由具有特定的二胺結構的聚醯胺酸獲得的聚醯亞胺為低介電特性，且在形成樹脂膜時可將熱膨脹係數(Coefficient of Thermal Expansion，CTE) 抑制在低的水準，可獲得抑制翹曲的產生、並且傳輸特性亦良好的FPC等電路基板，從而完成了本發明。 In order to solve the problems, the inventors have found that polyimide obtained from a polyamidic acid having a specific diamine structure has low dielectric properties and that the coefficient of thermal expansion (Coefficient of Thermal Expansion (CTE) The present invention has been achieved by suppressing the circuit board at a low level to obtain a circuit board such as FPC that suppresses the occurrence of warpage and has good transmission characteristics.

本發明的聚醯胺酸是使二胺成分、與包含四羧酸酐的酸酐成分反應而得者。本發明的聚醯胺酸的特徵在於：相對於全部二胺成分，所述二胺成分在10莫耳%~60莫耳%的範圍內包含下述通式(i)所示的二胺化合物，且相對於全部酸酐成分，所述酸酐成分在50莫耳%~100莫耳%的範圍內包含選自由均苯四羧酸二酐(Pyromellitic Dianhydride，PMDA)及3,3'4,4'-聯苯四羧酸二酐(3,3'4,4'-Biphenyl Tetracarboxylic Dianhydride，BPDA)所組成的組群中的一種以上的四羧酸酐。 The polyamidic acid of the present invention is obtained by reacting a diamine component and an acid anhydride component containing a tetracarboxylic anhydride. The polyamidic acid of the present invention is characterized in that the diamine component includes a diamine compound represented by the following general formula (i) in a range of 10 mol% to 60 mol% with respect to all diamine components. And the acid anhydride component is selected from the group consisting of Pyromellitic Dianhydride (PMDA) and 3,3'4,4 'in a range of 50 mol% to 100 mol% relative to the entire acid anhydride component. -One or more tetracarboxylic anhydrides in a group consisting of biphenyltetracarboxylic dianhydride (3,3'4,4'-Biphenyl Tetracarboxylic Dianhydride, BPDA).

[式中，R表示碳數1~8的烷基，p表示1~4的數。此處，在p為2以上時，R可獨立地取不同的碳數。] [In the formula, R represents an alkyl group having 1 to 8 carbons, and p represents a number of 1 to 4. Here, when p is 2 or more, R may independently take a different number of carbons. ]

本發明的聚醯胺酸亦可為如下者：在所述通式(i)中，R表示碳數4~8的支鏈烷基，p表示1~2的數。 The polyamic acid of the present invention may be one in which R represents a branched alkyl group having 4 to 8 carbon atoms, and p represents a number of 1 to 2 in the general formula (i).

本發明的聚醯胺酸亦可為如下者：在所述通式(i)中， R表示碳數1~4的直鏈烷基，p表示1~4的數，並且相對於全部二胺成分，所述二胺成分在15莫耳%~45莫耳%的範圍內亦可包含所述通式(i)所示的二胺化合物。 The polyamidic acid of the present invention may also be as follows: In the general formula (i), R represents a linear alkyl group having 1 to 4 carbon atoms, and p represents a number of 1 to 4, and the diamine component may also be contained in a range of 15 mol% to 45 mol% with respect to all the diamine components. A diamine compound represented by the general formula (i).

本發明的聚醯胺酸在所述二胺成分中，相對於全部二胺成分，可在40莫耳%~90莫耳%的範圍內包含選自由2,2'-二甲基-4,4'-二胺基聯苯(m-TB)、2,2'-二乙基-4,4'-二胺基聯苯(m-EB)及2,2'-正丙基-4,4'-二胺基聯苯(m-NPB)所組成的組群中的一種以上的二胺化合物。 The polyamidic acid of the present invention may include, in the diamine component, selected from 2,2'-dimethyl-4 in a range of 40 mol% to 90 mol% relative to the total diamine component. 4'-diaminobiphenyl (m-TB), 2,2'-diethyl-4,4'-diaminobiphenyl (m-EB) and 2,2'-n-propyl-4, One or more diamine compounds in a group consisting of 4'-diaminobiphenyl (m-NPB).

本發明的聚醯亞胺是將所述聚醯胺酸進行醯亞胺化而得者。 The polyfluorene imine of the present invention is obtained by fluorimidinating the polyphosphonium acid.

本發明的樹脂膜是包含將所述聚醯胺酸進行醯亞胺化而得的聚醯亞胺者。 The resin film of this invention is a thing containing the polyfluorene imidation obtained by carrying out the fluorination of the said polyphosphomic acid.

本發明的樹脂膜中，熱膨脹係數可處於10×10-6(1/K)~30×10-6(1/K)的範圍內。 In the resin film of the present invention, the thermal expansion coefficient may be in a range of 10 × 10 -6 (1 / K) to 30 × 10 -6 (1 / K).

本發明的覆金屬積層板是具有包含所述聚醯亞胺的樹脂層者。 The metal-clad laminate according to the present invention is one having a resin layer containing the polyimide.

本發明的聚醯胺酸及聚醯亞胺藉由使用在側鏈導入了碳數1~8的烷基的通式(i)的二胺化合物，而為低介電特性，且在形成樹脂膜時可將熱膨脹係數(CTE)抑制在低的水準。因此，使用本發明的聚醯胺酸及聚醯亞胺的樹脂膜例如可較佳地用作覆金屬積層板的基礎膜層。另外，藉由使用本發明的聚醯胺酸及聚 醯亞胺作為絕緣層材料，而可提供抑制翹曲的產生、並且傳輸特性良好的FPC等電路基板。 The polyamidoacid and polyamidoimide of the present invention have low dielectric properties by using a diamine compound of the general formula (i) in which a 1 to 8 carbon alkyl group is introduced into a side chain, and a resin is formed. The film can suppress the coefficient of thermal expansion (CTE) to a low level. Therefore, the resin film using the polyamic acid and the polyimide of the present invention can be preferably used as a base film layer of a metal-clad laminated board, for example. In addition, by using the polyamic acid and the polyamine of the present invention As a material for the insulating layer, arsenimide can provide circuit boards such as FPC that suppress the occurrence of warpage and have good transmission characteristics.

以下，對本發明的實施形態進行說明。 Hereinafter, embodiments of the present invention will be described.

[聚醯胺酸及聚醯亞胺] [Polyamic acid and polyimide]

<聚醯胺酸> <Polyamic acid>

本實施形態的聚醯胺酸是本實施形態的聚醯亞胺的前驅物，使二胺成分、與包含四羧酸酐的酸酐成分反應而得。此處，相對於全部二胺成分，二胺成分在10莫耳%~60莫耳%的範圍內包含通式(i)所示的二胺化合物(以下有時記為「二胺化合物(i)」)。 The polyamidic acid of this embodiment is a precursor of the polyamidoimide of this embodiment, and is obtained by reacting a diamine component and an acid anhydride component containing a tetracarboxylic anhydride. Here, the diamine component includes a diamine compound represented by the general formula (i) (hereinafter sometimes referred to as "diamine compound (i ) ").

[式中，R表示碳數1~8的烷基，p表示1~4的數。此處，在p為2以上時，R可獨立地取不同的碳數。] [In the formula, R represents an alkyl group having 1 to 8 carbons, and p represents a number of 1 to 4. Here, when p is 2 or more, R may independently take a different number of carbons. ]

作為二胺化合物(i)的特徵，可列舉在側鏈具有碳數1~8的烷基。即，作為通式(i)中的基團R，例如可列舉：直鏈或支鏈的甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基。 藉由必須使用在側鏈具有碳數1~8的烷基的二胺化合物(i)作為二胺成分，而可降低醯亞胺基濃度，獲得低介電特性，並且抑制樹脂膜的CTE的大幅增加。就所述觀點而言，作為通式(i)中的基團R的較佳的例子，可列舉：直鏈的甲基、乙基、丙基或丁基、或支鏈的丁基、戊基、己基、庚基或辛基。另外，在二胺化合物(i)中，兩端的芳香環中的胺基的取代位置較佳為相對於醚鍵而分別為3位(間位)或4位(對位)。所述通式(i)中，R較佳為表示碳數4~8的支鏈烷基，p表示1~2的數，R更佳為表示碳數1~4的直鏈烷基，p表示1~4的數。 Examples of the characteristics of the diamine compound (i) include an alkyl group having 1 to 8 carbon atoms in a side chain. That is, examples of the group R in the general formula (i) include a linear or branched methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl group. By using a diamine compound (i) having an alkyl group having 1 to 8 carbon atoms as a diamine component in the side chain, it is possible to reduce the concentration of the fluorenimine group, obtain low dielectric characteristics, and suppress the CTE of the resin film. A substantial increase. From this viewpoint, as a preferable example of the group R in the general formula (i), straight-chain methyl, ethyl, propyl or butyl, or branched butyl, pentyl Base, hexyl, heptyl or octyl. Moreover, in the diamine compound (i), it is preferable that the substitution position of the amine group in the aromatic ring of both ends is a 3 position (meta position) or a 4 position (para position) with respect to an ether bond, respectively. In the general formula (i), R is preferably a branched alkyl group having 4 to 8 carbon atoms, p is a number of 1 to 2, R is more preferably a linear alkyl group having 1 to 4 carbon atoms, and p Represents a number from 1 to 4.

在本實施形態的聚醯胺酸中，相對於全部酸酐成分，酸酐成分在50莫耳%~100莫耳%的範圍內包含均苯四羧酸二酐(PMDA)及/或3,3'4,4'-聯苯四羧酸二酐(BPDA)。藉由以50莫耳%以上的調配量使用PMDA及/或BPDA，而具有控制聚醯亞胺中的分子的配向性，並抑制CTE的增加的作用，因此可實現使用本實施形態的聚醯胺酸而形成的樹脂膜的低CTE化。 In the polyamic acid according to this embodiment, the anhydride component contains pyromellitic dianhydride (PMDA) and / or 3,3 'in the range of 50 mol% to 100 mol% with respect to the entire acid anhydride component. 4,4'-biphenyltetracarboxylic dianhydride (BPDA). By using PMDA and / or BPDA at a compounding amount of 50 mol% or more, it has the effect of controlling the orientation of molecules in polyimide and suppressing the increase in CTE. Therefore, the polyfluorene using this embodiment can be realized. Reduction of CTE of resin film formed by uric acid.

另外，在本實施形態的聚醯胺酸中，較佳為相對於全部二胺成分，二胺成分在40莫耳%~90莫耳%的範圍內、較佳為以55莫耳%~85莫耳%的調配量，包含選自由2,2'-二甲基-4,4'-二胺基聯苯(m-TB)、2,2'-二乙基-4,4'-二胺基聯苯(m-EB)及2,2'-正丙基-4,4'-二胺基聯苯(m-NPB)所組成的組群中的一種以上的二胺化合物(以下，有時記為「聯苯系二胺化合物」)。藉由使用所述聯苯系二胺化合物作為原料，而有助於兼顧使用本實施形態的 聚醯胺酸而形成的樹脂膜的低介電化與低CTE化。 In addition, in the polyamic acid of this embodiment, the diamine component is preferably in a range of 40 mol% to 90 mol%, and more preferably 55 mol% to 85, with respect to all the diamine components. Molar% blending amount, selected from the group consisting of 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB), 2,2'-diethyl-4,4'-di One or more diamine compounds in the group consisting of aminobiphenyl (m-EB) and 2,2'-n-propyl-4,4'-diaminobiphenyl (m-NPB) (hereinafter, Sometimes referred to as "biphenyl-based diamine compound"). By using the biphenyl-based diamine compound as a raw material, it is possible to contribute to the use of this embodiment. Dielectric reduction and CTE reduction of a resin film formed by polyamic acid.

<聚醯亞胺> <Polyimide>

本實施形態的聚醯亞胺是將所述聚醯胺酸進行醯亞胺化而成者。本實施形態的聚醯亞胺較佳為具有下述通式(1)及通式(2)所示的結構單元。 The polyfluorene imine of this embodiment is obtained by fluorinating the polyphosphonium acid. The polyfluoreneimide of this embodiment preferably has a structural unit represented by the following general formula (1) and general formula (2).

[式中，Ar表示由包含PMDA及/或BPDA的芳香族四羧酸酐衍生的4價芳香族基，R1表示由二胺化合物(i)衍生的2價芳香族二胺殘基，R2表示由二胺化合物(i)以外的芳香族二胺衍生的2價芳香族二胺殘基，m、n表示各結構單元的存在莫耳比，m為0.1~0.6的範圍內，n為0.4~0.9的範圍內] [In the formula, Ar represents a tetravalent aromatic group derived from an aromatic tetracarboxylic anhydride containing PMDA and / or BPDA, R 1 represents a divalent aromatic diamine residue derived from a diamine compound (i), and R 2 Represents a divalent aromatic diamine residue derived from an aromatic diamine other than the diamine compound (i), m and n represent the mole ratio of each structural unit, m is in the range of 0.1 to 0.6, and n is 0.4 Within the range of ~ 0.9]

基團Ar例如可列舉：下述式(3)或式(4)所示者。 Examples of the group Ar include the following formula (3) or formula (4).

[化4] [Chemical 4]

[式中，W表示單鍵、選自碳數1~15的2價烴基、-O-、-S-、-CO-、-SO-、-SO2-、-NH-或-CONH-中的2價基團] [In the formula, W represents a single bond, a divalent hydrocarbon group selected from 1 to 15 carbon atoms, -O-, -S-, -CO-, -SO-, -SO 2- , -NH-, or -CONH- Divalent group]

特別是就減少聚醯亞胺的極性基，提高介電特性的觀點而言，作為基團Ar，較佳為式(3)、或式(4)中的W以單鍵、碳數1~15的2價烴基、-O-、-S-、-CO-表示者，更佳為式(3)、或式(4)中的W為單鍵、碳數1~15的2價烴基、-CO-者。 In particular, from the viewpoint of reducing the polar group of polyfluoreneimide and improving the dielectric properties, the group Ar is preferably W in Formula (3) or Formula (4) with a single bond and a carbon number of 1 to The bivalent hydrocarbon group represented by 15, or -O-, -S-, or -CO- is more preferably a divalent hydrocarbon group having 1 to 15 carbon atoms in formula (3) or formula (4), wherein W is a single bond, -CO-people.

再者，所述通式(1)及通式(2)所示的結構單元可存在於均聚物中，亦可作為共聚物的結構單元而存在。在為具有多個結構單元的共聚物時，可作為嵌段共聚物而存在，亦可作為無規共聚物而存在。 The structural units represented by the general formulae (1) and (2) may be present in a homopolymer or may be present as a structural unit of a copolymer. When it is a copolymer having a plurality of structural units, it may exist as a block copolymer or as a random copolymer.

聚醯亞胺通常使酸酐與二胺反應而製造，因此藉由對酸酐與二胺進行說明，而可理解本實施形態的聚醯亞胺的具體例。在所述通式(1)及通式(2)中，基團Ar可稱為酸酐的殘基，基團R1及基團R2可稱為二胺的殘基，因此藉由酸酐與二胺對較佳的聚醯亞胺進行說明。 Polyfluorene imine is generally produced by reacting an acid anhydride with a diamine. Therefore, a specific example of the polyfluorene imide in this embodiment can be understood by explaining the acid anhydride and the diamine. In the general formulae (1) and (2), the group Ar may be referred to as a residue of an acid anhydride, and the groups R 1 and R 2 may be referred to as residues of a diamine. Diamines describe preferred polyfluorene imines.

作為具有基團Ar作為殘基的酸酐，必須使用基團Ar以所述式(3)表示的PMDA及BPDA的至少一個。藉由使用PMDA及/或BPDA，而控制聚醯亞胺中的分子的配向性，藉此抑制CTE 的增加，並可實現使用本實施形態的聚醯亞胺的樹脂膜的低CTE化。另外，除了PMDA及BPDA以外具有基團Ar作為殘基的酸酐例如較佳為可例示：3,3'4,4'-二苯基碸四羧酸二酐、4,4'-氧基二鄰苯二甲酸酐。另外，作為酸酐，可列舉：2,2',3,3'-二苯甲酮四羧酸二酐、2,3,3',4'-二苯甲酮四羧酸二酐或3,3',4,4'-二苯甲酮四羧酸二酐、2,3',3,4'-聯苯四羧酸二酐、2,2',3,3'-聯苯四羧酸二酐、2,3',3,4'-二苯醚四羧酸二酐、雙(2,3-二羧基苯基)醚二酐、3,3",4,4"-對聯三苯四羧酸二酐、2,3,3",4"-對聯三苯四羧酸二酐或2,2",3,3"-對聯三苯四羧酸二酐、2,2-雙(2,3-二羧基苯基)-丙烷二酐、2,2-雙(3,4-二羧基苯基)-丙烷二酐、雙(2,3-二羧基苯基)甲烷二酐、雙(3,4-二羧基苯基)甲烷二酐、雙(2,3-二羧基苯基)碸二酐、雙(3,4-二羧基苯基)碸二酐、1,1-雙(2,3-二羧基苯基)乙烷二酐、1,1-雙(3,4-二羧基苯基)乙烷二酐、1,2,7,8-菲-四羧酸二酐、1,2,6,7-菲-四羧酸二酐或1,2,9,10-菲-四羧酸二酐、2,3,6,7-蒽四羧酸二酐、2,2-雙(3,4-二羧基苯基)四氟丙烷二酐、2,3,5,6-環己烷二酐、2,3,6,7-萘四羧酸二酐、1,2,5,6-萘四羧酸二酐、1,4,5,8-萘四羧酸二酐、4,8-二甲基-1,2,3,5,6,7-六氫萘-1,2,5,6-四羧酸二酐、2,6-二氯萘-1,4,5,8-四羧酸二酐或2,7-二氯萘-1,4,5,8-四羧酸二酐、2,3,6,7-(或1,4,5,8-)四氯萘-1,4,5,8-(或2,3,6,7-)四羧酸二酐、2,3,8,9-苝-四羧酸二酐、3,4,9,10-苝-四羧酸二酐、4,5,10,11-苝-四羧酸二酐或5,6,11,12-苝-四羧酸二酐、環戊烷-1,2,3,4-四羧酸二酐、吡嗪-2,3,5,6-四羧酸二酐、吡咯啶-2,3,4,5-四羧酸二酐、噻吩-2,3,4,5-四羧酸二酐、4,4'- 雙(2,3-二羧基苯氧基)二苯基甲烷二酐等。 As the acid anhydride having the group Ar as a residue, it is necessary to use at least one of PMDA and BPDA represented by the formula (3) in the group Ar. By using PMDA and / or BPDA to control the orientation of molecules in polyimide, thereby suppressing CTE The CTE of the resin film using the polyfluorene imide of this embodiment can be increased. In addition, acid anhydrides having a group Ar as a residue other than PMDA and BPDA are preferably exemplified by 3,3'4,4'-diphenylphosphonium tetracarboxylic dianhydride, and 4,4'-oxydiamine. Phthalic anhydride. Examples of the acid anhydride include 2,2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, or 3, 3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,3', 3,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic acid Acid dianhydride, 2,3 ', 3,4'-diphenyl ether tetracarboxylic dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, 3,3 ", 4,4" -coupling triple Pyromellitic dianhydride, 2,3,3 ", 4" -terephthalic dianhydride or 2,2 ", 3,3" -terephthalic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -propane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, Bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) fluorene dianhydride, bis (3,4-dicarboxyphenyl) fluorene dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,7,8-phenanthrene-tetracarboxylic dianhydride 1,2,6,7-phenanthrene-tetracarboxylic dianhydride or 1,2,9,10-phenanthrene-tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 2, 2-bis (3,4-dicarboxyphenyl) tetrafluoropropane dianhydride, 2,3,5,6-cyclohexane dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1, 2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 2,6 -Dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride or 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7- ( Or 1,4,5,8-) tetrachloronaphthalene-1,4,5,8- (or 2,3,6,7-) tetracarboxylic dianhydride, 2,3,8,9-fluorene-tetra Carboxylic dianhydride, 3,4,9,10-fluorene-tetracarboxylic dianhydride, 4,5,10,11-fluorene-tetracarboxylic dianhydride or 5,6,11,12-fluorene-tetracarboxylic acid Dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetra Carboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 4,4'- Bis (2,3-dicarboxyphenoxy) diphenylmethane dianhydride and the like.

基團R1為由二胺化合物(i)衍生的2價芳香族二胺殘基。藉由必須使用在側鏈具有碳數1~8的烷基的二胺化合物(i)作為二胺成分，而使醯亞胺基濃度降低，獲得低介電特性，並且可抑制樹脂膜的CTE的大幅增加。 The group R 1 is a divalent aromatic diamine residue derived from the diamine compound (i). By using a diamine compound (i) having an alkyl group having 1 to 8 carbons as a diamine component in the side chain, the concentration of the fluorene imino group can be reduced, low dielectric properties can be obtained, and CTE of the resin film can be suppressed A substantial increase.

相對於全部二胺成分，二胺化合物(i)的投入量為10莫耳%~60莫耳%的範圍內、較佳為15莫耳%~45莫耳%的範圍內、更佳為19莫耳%~44莫耳%的範圍內、最佳為20莫耳%~40莫耳%的範圍內。若二胺化合物(i)小於10莫耳%，則有聚醯亞胺的熱膨脹係數過度降低、且介電常數增加的傾向，若超過60莫耳%，則有聚醯亞胺的熱膨脹係數過度上升的傾向，因此產生所得的覆金屬積層板翹曲的課題。 The input amount of the diamine compound (i) is in the range of 10 mol% to 60 mol%, preferably in the range of 15 mol% to 45 mol%, and more preferably 19 with respect to all the diamine components. Molar% to 44 Molar%, preferably 20 Molar% to 40 Molar%. If the diamine compound (i) is less than 10 mole%, the thermal expansion coefficient of polyimide tends to be excessively reduced and the dielectric constant is increased. If it exceeds 60 mole%, the thermal expansion coefficient of polyimide is excessive. As a result, the problem of warping of the obtained metal-clad laminated board arises.

另外，基團R2例如可列舉下述式(5)~式(7)所示者。 Examples of the group R 2 include those represented by the following formulae (5) to (7).

[式(5)~式(7)中，R3獨立地表示碳數1~6的1價烴基 或烷氧基，Z表示單鍵、選自碳數1~15的2價烴基、-O-、-S-、-CO-、-SO-、-SO2-、-NH-或-CONH-中的2價基團，n1獨立地表示0~4的整數] [In formulae (5) to (7), R 3 independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 6 carbon atoms, Z represents a single bond, a divalent hydrocarbon group selected from 1 to 15 carbon atoms, -O A divalent group in-, -S-, -CO-, -SO-, -SO 2- , -NH- or -CONH-, n 1 independently represents an integer from 0 to 4]

特別是就減少聚醯亞胺的極性基、提高介電特性的觀點而言，作為基團R2，較佳為式(5)~式(7)中的Z為單鍵、碳數1~15的2價烴基，R3為碳數1~6的1價烴基，n1為0~4的整數。 Especially from the viewpoint of reducing the polar group of polyfluoreneimide and improving the dielectric properties, as the group R 2 , Z in the formulae (5) to (7) is preferably a single bond, and the number of carbon atoms is 1 to 15 is a divalent hydrocarbon group, R 3 is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and n 1 is an integer of 0 to 4.

作為具有基團R2作為殘基的二胺，例如可列舉：4,4'-二胺基二苯醚、2'-甲氧基-4,4'-二胺基苯甲醯苯胺、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、2,2'-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2'-二甲基-4,4'-二胺基聯苯(m-TB)、2,2'-二乙基-4,4'-二胺基聯苯(m-EB)、2,2'-正丙基-4,4'-二胺基聯苯(m-NPB)、3,3'-二羥基-4,4'-二胺基聯苯、4,4'-二胺基苯甲醯苯胺、2,2-雙-[4-(3-胺基苯氧基)苯基]丙烷、雙[4-(4-胺基苯氧基)苯基]碸、雙[4-(3-胺基苯氧基)苯基]碸、雙[4-(4-胺基苯氧基)]聯苯、雙[4-(3-胺基苯氧基)]聯苯、雙[1-(4-胺基苯氧基)]聯苯、雙[1-(3-胺基苯氧基)]聯苯、雙[4-(4-胺基苯氧基)苯基]甲烷、雙[4-(3-胺基苯氧基)苯基]甲烷、雙[4-(4-胺基苯氧基)苯基]醚、雙[4-(3-胺基苯氧基)苯基]醚、雙[4-(4-胺基苯氧基)]二苯甲酮、雙[4-(3-胺基苯氧基)]二苯甲酮、雙[4,4'-(4-胺基苯氧基)]苯甲醯苯胺、雙[4,4'-(3-胺基苯氧基)]苯甲醯苯胺、9,9-雙[4-(4-胺基苯氧基)苯基]茀、9,9-雙[4-(3-胺基苯氧基)苯基]茀、2,2-雙-[4-(4-胺基苯氧基)苯基]六氟丙烷、2,2-雙-[4-(3-胺基苯 氧基)苯基]六氟丙烷、4,4'-亞甲基二-鄰甲苯胺、4,4'-亞甲基二-2,6-二甲苯胺、4,4'-亞甲基-2,6-二乙基苯胺、4,4'-二胺基二苯基丙烷、3,3'-二胺基二苯基丙烷、4,4'-二胺基二苯基乙烷、3,3'-二胺基二苯基乙烷、4,4'-二胺基二苯基甲烷、3,3'-二胺基二苯基甲烷、4,4'-二胺基二苯基硫醚、3,3'-二胺基二苯基硫醚、4,4'-二胺基二苯基碸、3,3'-二胺基二苯基碸、4,4'-二胺基二苯醚、3,3-二胺基二苯醚、3,4'-二胺基二苯醚、聯苯胺、3,3'-二胺基聯苯、3,3'-二甲基-4,4'-二胺基聯苯、3,3'-二甲氧基聯苯胺、4,4"-二胺基-對聯三苯、3,3"-二胺基-對聯三苯、間苯二胺、對苯二胺、2,6-二胺基吡啶、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、4,4'-[1,4-苯雙(1-甲基亞乙基)]雙苯胺、4,4'-[1,3-苯雙(1-甲基亞乙基)]雙苯胺、雙(對胺基環己基)甲烷、雙(對β-胺基-第三丁基苯基)醚、雙(對β-甲基-δ-胺基戊基)苯、對雙(2-甲基-4-胺基戊基)苯、對雙(1,1-二甲基-5-胺基戊基)苯、1,5-二胺基萘、2,6-二胺基萘、2,4-雙(β-胺基-第三丁基)甲苯、2,4-二胺基甲苯、間二甲苯-2,5-二胺、對二甲苯-2,5-二胺、間二甲苯二胺、對二甲苯二胺、2,6-二胺基吡啶、2,5-二胺基吡啶、2,5-二胺基-1,3,4-噁二唑、哌嗪等。 Examples of the diamine having a group R 2 as a residue include 4,4'-diaminodiphenyl ether, 2'-methoxy-4,4'-diaminobenzidineaniline, 1 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2'-bis [4- (4-aminophenoxy) benzene Group) propane, 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB), 2,2'-diethyl-4,4'-diaminobiphenyl (m -EB), 2,2'-n-propyl-4,4'-diaminobiphenyl (m-NPB), 3,3'-dihydroxy-4,4'-diaminobiphenyl, 4, 4'-Diaminobenzidine aniline, 2,2-bis- [4- (3-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] Hydrazone, bis [4- (3-aminophenoxy) phenyl] fluorene, bis [4- (4-aminophenoxy)] biphenyl, bis [4- (3-aminophenoxy) ] Biphenyl, bis [1- (4-aminophenoxy)] biphenyl, bis [1- (3-aminophenoxy)] biphenyl, bis [4- (4-aminophenoxy) ) Phenyl] methane, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-amine Phenylphenoxy) phenyl] ether, bis [4- (4-aminophenoxy)] benzophenone, bis [4- (3-aminophenoxy)] benzophenone, bis [ 4,4 '-(4-aminophenoxy)] benzidine, aniline, bis [ 4,4 '-(3-Aminophenoxy)] benzidineaniline, 9,9-bis [4- (4-aminophenoxy) phenyl] fluorene, 9,9-bis [4- (3-Aminophenoxy) phenyl] fluorene, 2,2-bis- [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis- [4- (3 -Aminophenoxy) phenyl] hexafluoropropane, 4,4'-methylenebis-o-toluidine, 4,4'-methylenebis-2,6-xylyleneamine, 4,4 ' -Methylene-2,6-diethylaniline, 4,4'-diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4,4'-diaminodiphenyl Ethane, 3,3'-diaminodiphenylethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-di Aminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfonium, 3,3'-diaminodiphenylsulfonium, 4, 4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, benzidine, 3,3'-diaminodiphenyl, 3,3 '-Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxybenzidine, 4,4 "-diamino-p-terphenyl, 3,3" -diamine -P-terphenyl, m-phenylenediamine, p-phenylenediamine, 2,6-diaminopyridine, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-amine Phenoxy ) Benzene, 4,4 '-[1,4-phenylbis (1-methylethylene)] bisaniline, 4,4'-[1,3-benzenebis (1-methylethylene)] Dianiline, bis (p-aminocyclohexyl) methane, bis (p-β-amino-third butylphenyl) ether, bis (p-β-methyl-δ-aminopentyl) benzene, p-bis ( 2-methyl-4-aminopentyl) benzene, p-bis (1,1-dimethyl-5-aminopentyl) benzene, 1,5-diaminonaphthalene, 2,6-diamino Naphthalene, 2,4-bis (β-amino-third butyl) toluene, 2,4-diaminotoluene, m-xylene-2,5-diamine, p-xylene-2,5-diamine , M-xylylenediamine, p-xylylenediamine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-diamino-1,3,4-oxadiazole, piperazine Hydrazine, etc.

根據聚醯亞胺的介電特性，作為用於製備本實施形態的聚醯亞胺的前驅物的芳香族四羧酸酐，必須使用50莫耳%以上的PMDA及/或BPDA。藉由使用50莫耳%以上的PMDA及/或BPDA，而可實現使用本實施形態的聚醯亞胺的樹脂膜的低CTE化。另外，作為PMDA及BPDA以外的芳香族四羧酸酐，例如可 列舉：3,3',4,4'-二苯甲酮四羧酸二酐(BTDA)、3,3',4,4'-二苯基碸四羧酸二酐(DSDA)等。其中，作為特佳的酸酐，可列舉：3,3',4,4'-二苯甲酮四羧酸二酐(BTDA)等。所述芳香族四羧酸酐亦可組合兩種以上而調配。 According to the dielectric properties of polyfluorene imide, as the aromatic tetracarboxylic anhydride used to prepare the polyfluorene imide precursor of this embodiment, PMDA and / or BPDA must be used in an amount of 50 mol% or more. By using PMDA and / or BPDA in an amount of 50 mol% or more, it is possible to reduce the CTE of the resin film using the polyimide of the present embodiment. In addition, as the aromatic tetracarboxylic anhydride other than PMDA and BPDA, for example, Examples: 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 3,3', 4,4'-diphenylphosphonium tetracarboxylic dianhydride (DSDA), and the like. Among them, particularly preferred acid anhydrides include 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA) and the like. The aromatic tetracarboxylic anhydride may be prepared by combining two or more kinds.

另外，根據聚醯亞胺的介電特性，作為較佳為用於製備本實施形態的聚醯亞胺的前驅物的芳香族二胺，將二胺化合物(i)作為必需成分，此外例如可列舉：2,2-雙(4-胺基苯氧基苯基)丙烷(BAPP)、2,2'-二乙烯基-4,4'-二胺基聯苯(VAB)、2,2'-二甲基-4,4'-二胺基聯苯(m-TB)、2,2'-二乙基-4,4'-二胺基聯苯(m-EB)、2,2'-正丙基-4,4'-二胺基聯苯(m-NPB)、2,2',6,6'-四甲基-4,4'-二胺基聯苯、2,2'-二苯基-4,4'-二胺基聯苯、9,9-雙(4-胺基苯基)茀等。所述芳香族二胺亦可組合兩種以上而調配。其中，作為有助於使用本實施形態的聚醯亞胺的樹脂膜的低CTE化的二胺成分，特佳為2,2-雙(4-胺基苯氧基苯基)丙烷(BAPP)、2,2'-二乙烯基-4,4'-二胺基聯苯(VAB)、2,2'-二甲基-4,4'-二胺基聯苯(m-TB)、2,2'-二乙基-4,4'-二胺基聯苯(m-EB)、2,2'-正丙基-4,4'-二胺基聯苯(m-NPB)等。 In addition, according to the dielectric properties of polyfluorene imine, as the aromatic diamine which is preferably used as a precursor for preparing the polyfluorene imide of the present embodiment, the diamine compound (i) is an essential component. Examples: 2,2-bis (4-aminophenoxyphenyl) propane (BAPP), 2,2'-divinyl-4,4'-diaminobiphenyl (VAB), 2,2 ' -Dimethyl-4,4'-diaminobiphenyl (m-TB), 2,2'-diethyl-4,4'-diaminobiphenyl (m-EB), 2,2 ' -N-propyl-4,4'-diaminobiphenyl (m-NPB), 2,2 ', 6,6'-tetramethyl-4,4'-diaminobiphenyl, 2,2' -Diphenyl-4,4'-diaminobiphenyl, 9,9-bis (4-aminophenyl) fluorene and the like. The aromatic diamine may be prepared by combining two or more kinds. Among them, as the diamine component contributing to the reduction in CTE of the resin film using the polyfluorene imide of the present embodiment, 2,2-bis (4-aminophenoxyphenyl) propane (BAPP) is particularly preferred. , 2,2'-divinyl-4,4'-diaminobiphenyl (VAB), 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB), 2 , 2'-diethyl-4,4'-diaminobiphenyl (m-EB), 2,2'-n-propyl-4,4'-diaminobiphenyl (m-NPB) and the like.

另外，作為本實施形態中所用的二胺化合物(i)的較佳的具體例，可列舉以下的式(ia)~式(if)所示者。 Moreover, as a preferable specific example of the diamine compound (i) used by this embodiment, the following formula (ia)-formula (if) are mentioned.

[化6] [Chemical 6]

式(ia)為1,4雙(4-胺基苯氧基)-2,5-二-第三丁基苯(DTBAB)。另外，式(ib)為1,4雙(4-胺基苯氧基)-2,3-二-第三丁基苯。此處，在通式(i)所示的二胺化合物為式(ia)及/或式(ib)所示的化合物，且使用m-TB作為其他二胺成分時，酸酐成分、與所述式(ia)及/或式(ib)所示的化合物的調配量較佳為滿足下述數式A所示的關係。此時，以使用50莫耳%以上的PMDA及/或BPDA作為酸酐成分為前提，較佳為僅使用PMDA及/或BPDA作為酸酐成分。 Formula (ia) is 1,4-bis (4-aminophenoxy) -2,5-di-third-butylbenzene (DTBAB). In addition, formula (ib) is 1,4 bis (4-aminophenoxy) -2,3-di-tert-butylbenzene. Here, when the diamine compound represented by the general formula (i) is a compound represented by the formula (ia) and / or the formula (ib), and m-TB is used as another diamine component, the acid anhydride component and the It is preferable that the compounding quantity of the compound represented by Formula (ia) and / or Formula (ib) satisfies the relationship shown by following formula A. In this case, it is premised that PMDA and / or BPDA are used as the acid anhydride component, and it is preferable to use only PMDA and / or BPDA as the acid anhydride component.

y=0.2996x-8.4193......(數式A) y = 0.2996x-8.4193 ... (Equation A)

[式中，x表示將式(ia)及/或式(ib)所示的化合物的總調 配量(莫耳%)乘以係數2.1而得的值、與酸酐成分中的BPDA的調配量(莫耳%)的和，y表示10以上、30以下的範圍內的數] [In the formula, x represents the total adjustment of the compound represented by formula (ia) and / or formula (ib) The value obtained by multiplying the compounding amount (mol%) by a factor of 2.1 and the blending amount (mol%) of BPDA in the anhydride component, y represents a number in a range of 10 or more and 30 or less]

在所述數式A中，y相當於將使用所述各單體而得的聚醯胺酸進行醯亞胺化而加工成膜狀時的熱膨脹係數[×10-6(1/K)]。因此，藉由以滿足所述數式A的方式調配各單體，而可形成熱膨脹係數為10×10-6(1/K)~30×10-6(1/K)的範圍內的聚醯亞胺膜。 In the formula A, y corresponds to a thermal expansion coefficient [x10 -6 (1 / K)] when polyimide acid obtained by using each of the monomers is amidated and imidized. . Therefore, by formulating each monomer in such a manner as to satisfy the formula A, a polymer having a thermal expansion coefficient in a range of 10 × 10 -6 (1 / K) to 30 × 10 -6 (1 / K) can be formed.醯 imine film.

另外，在通式(i)所示的二胺化合物為式(ia)及/或式(ib)所示的化合物、且使用2,2'-二乙基-4,4'-二胺基聯苯(m-EB)作為其他二胺成分時，較佳為酸酐成分、與所述式(ia)及/或式(ib)所示的化合物的調配量滿足下述數式B所示的關係。此時，以使用50莫耳%以上的PMDA及/或BPDA作為酸酐成分為前提，較佳為僅使用PMDA及/或BPDA作為酸酐成分。 The diamine compound represented by the general formula (i) is a compound represented by the formula (ia) and / or the formula (ib), and a 2,2'-diethyl-4,4'-diamine group is used. When biphenyl (m-EB) is used as another diamine component, an acid anhydride component is preferably used, and the compounded amount with the compound represented by the formula (ia) and / or formula (ib) satisfies the following formula B relationship. In this case, it is premised that PMDA and / or BPDA are used as the acid anhydride component, and it is preferable to use only PMDA and / or BPDA as the acid anhydride component.

y=0.3013x-3.3320......(數式B) y = 0.3013x-3.3320 ... (Equation B)

[式中，x表示將式(ia)及/或式(ib)所示的化合物的總調配量(莫耳%)乘以係數1.9而得的值、與酸酐成分中的BPDA的調配量(莫耳%)的和，y表示10以上、30以下的範圍內的數] [Wherein, x represents a value obtained by multiplying a total compounding amount (mole%) of a compound represented by formula (ia) and / or formula (ib) by a factor of 1.9, and a compounding amount with BPDA in an acid anhydride component ( Mol%), y represents a number in the range of 10 or more and 30 or less]

在所述數式B中，y相當於將使用所述各單體而得的聚醯胺酸進行醯亞胺化而加工成膜狀時的熱膨脹係數[×10-6(1/K)]。因此，藉由以滿足所述數式B的方式調配各單體，而可形成熱膨脹係數為10×10-6(1/K)~30×10-6(1/K)的範圍內的 聚醯亞胺膜。 In the formula B, y corresponds to the coefficient of thermal expansion when the polyamidoacid obtained by using each of the monomers is subjected to amidimidation to form a film [× 10 -6 (1 / K)] . Therefore, by formulating each monomer in such a manner as to satisfy the formula B, a polymer having a thermal expansion coefficient in a range of 10 × 10 -6 (1 / K) to 30 × 10 -6 (1 / K) can be formed.醯 imine film.

另外，在通式(i)所示的二胺化合物為式(ia)及/或式(ib)所示的化合物、且使用2,2'-正丙基-4,4'-二胺基聯苯(m-NPB)作為其他二胺成分時，較佳為酸酐成分、與所述式(ia)及/或式(ib)所示的化合物的調配量滿足下述數式C所示的關係。此時，以使用50莫耳%以上的PMDA及/或BPDA作為酸酐成分為前提，較佳為僅使用PMDA及/或BPDA作為酸酐成分。 The diamine compound represented by the general formula (i) is a compound represented by the formula (ia) and / or the formula (ib), and a 2,2'-n-propyl-4,4'-diamine group is used. When biphenyl (m-NPB) is used as the other diamine component, it is preferred that the amount of the acid anhydride component and the compound represented by the formula (ia) and / or the formula (ib) satisfy the formula C relationship. In this case, it is premised that PMDA and / or BPDA are used as the acid anhydride component, and it is preferable to use only PMDA and / or BPDA as the acid anhydride component.

y=0.3005x+15.0500......(數式C) y = 0.3005x + 15.0500 ... (Equation C)

[式中，x表示將式(ia)及/或式(ib)所示的化合物的總調配量(莫耳%)乘以係數1.3而得的值、與酸酐成分中的BPDA的調配量(莫耳%)的和，y表示10以上、30以下的範圍內的數] [In the formula, x represents a value obtained by multiplying the total compounding amount (mol%) of the compound represented by the formula (ia) and / or the formula (ib) by a factor of 1.3, and the compounding amount of BPDA in the acid anhydride component ( Mol%), y represents a number in the range of 10 or more and 30 or less]

在所述數式C中，y相當於將使用所述各單體而得的聚醯胺酸進行醯亞胺化而加工成膜狀時的熱膨脹係數[×10-6(1/K)]。因此，藉由以滿足所述數式C的方式調配各單體，而可形成熱膨脹係數為10×10-6(1/K)~30×10-6(1/K)的範圍內的聚醯亞胺膜。 In the formula C, y corresponds to a thermal expansion coefficient [x10 -6 (1 / K)] when polyimide obtained by using each of the monomers is subjected to amidimidation and processed into a film. . Therefore, by formulating each monomer in such a manner as to satisfy the formula C, a polymer having a thermal expansion coefficient in a range of 10 × 10 -6 (1 / K) to 30 × 10 -6 (1 / K) can be formed.醯 imine film.

[化8] [Chemical 8]

式(ic)為1,4雙(4-胺基苯氧基)-2,5-二(1-甲基丙基)苯。此處，在通式(i)所示的二胺化合物為式(ic)所示的化合物、且使用m-TB作為其他二胺成分時，較佳為酸酐成分、與式(ic)所示的化合物的調配量滿足下述數式D所示的關係。此時，以使用50莫耳%以上的PMDA及/或BPDA作為酸酐成分為前提，較佳為僅使用PMDA及/或BPDA作為酸酐成分。 Formula (ic) is 1,4-bis (4-aminophenoxy) -2,5-bis (1-methylpropyl) benzene. Here, when the diamine compound represented by the general formula (i) is a compound represented by the formula (ic) and m-TB is used as another diamine component, an acid anhydride component and the compound represented by the formula (ic) are preferred. The compounding amount of the compound satisfies the relationship shown by the following formula D. In this case, it is premised that PMDA and / or BPDA are used as the acid anhydride component, and it is preferable to use only PMDA and / or BPDA as the acid anhydride component.

y=0.2986x-8.3977......(數式D) y = 0.2986x-8.3977 ... (Equation D)

[式中，x表示將式(ic)所示的化合物的調配量(莫耳%)乘以係數4.3而得的值、與酸酐成分中的BPDA的調配量(莫耳%)的和，y表示10以上、30以下的範圍內的數] [Wherein, x represents the value obtained by multiplying the compounded amount (mol%) of the compound represented by formula (ic) by a factor of 4.3 and the sum of the compounded amount (mol%) of BPDA in the acid anhydride component, y Represents a number in the range of 10 or more and 30 or less]

在所述數式D中，y相當於將使用所述各單體而得的聚醯胺酸進行醯亞胺化而加工成膜狀時的熱膨脹係數[×10-6(1/K)]。因此，藉由以滿足所述數式D的方式調配各單體，而可形成熱膨脹係數為10×10-6(1/K)~30×10-6(1/K)的範圍內的聚醯亞胺膜。 In the formula D, y corresponds to the coefficient of thermal expansion when the polyamidoacid obtained by using each of the monomers is subjected to amidimidation and processed into a film shape [× 10 -6 (1 / K)] . Therefore, by formulating each monomer in such a manner as to satisfy the formula D, a polymer having a thermal expansion coefficient in a range of 10 × 10 -6 (1 / K) to 30 × 10 -6 (1 / K) can be formed.醯 imine film.

另外，在通式(i)所示的二胺化合物為式(ic)所示的 化合物、且使用2,2'-二乙基-4,4'-二胺基聯苯(m-EB)作為其他二胺成分時，較佳為酸酐成分、與所述式(ic)所示的化合物的調配量滿足下述數式E所示的關係。此時，以使用50莫耳%以上的PMDA及/或BPDA作為酸酐成分為前提，較佳為僅使用PMDA及/或BPDA作為酸酐成分。 The diamine compound represented by the general formula (i) is represented by the formula (ic). When using a compound and using 2,2'-diethyl-4,4'-diaminobiphenyl (m-EB) as another diamine component, it is preferably an acid anhydride component and the formula (ic) The compounding amount of the compound satisfies the relationship shown by the following formula E. In this case, it is premised that PMDA and / or BPDA are used as the acid anhydride component, and it is preferable to use only PMDA and / or BPDA as the acid anhydride component.

y=0.3003x-3.4028......(數式E) y = 0.3003x-3.4028 ... (Equation E)

[式中，x表示將式(ic)所示的化合物的調配量(莫耳%)乘以係數4.1而得的值、與酸酐成分中的BPDA的調配量(莫耳%)的和，y表示10以上、30以下的範圍內的數] [Wherein, x represents the value obtained by multiplying the compounded amount (mol%) of the compound represented by formula (ic) by a factor of 4.1 and the sum of the compounded amount (mol%) of BPDA in the anhydride component, Represents a number in the range of 10 or more and 30 or less]

在所述數式E中，y相當於將使用所述各單體而得的聚醯胺酸進行醯亞胺化而加工成膜狀時的熱膨脹係數[×10-6(1/K)]。因此，藉由以滿足所述數式E的方式調配各單體，而可形成熱膨脹係數為10×10-6(1/K)~30×10-6(1/K)的範圍內的聚醯亞胺膜。 In the formula E, y corresponds to a thermal expansion coefficient [× 10 -6 (1 / K)] when polyimide acid obtained by using each of the monomers is subjected to amidimidation to form a film. . Therefore, by formulating each monomer in such a manner as to satisfy the formula E, a polymer having a thermal expansion coefficient in a range of 10 × 10 -6 (1 / K) to 30 × 10 -6 (1 / K) can be formed.醯 imine film.

式(id)為1,4雙(4-胺基苯氧基)-2,6-二-第三丁基苯。此處，在通式(i)所示的二胺化合物為式(id)所示的化合物、且使用m-TB作為其他二胺成分時，較佳為酸酐成分、與式(id)所示的化合物的調配量滿足下述數式F所示的關係。此時，以使用50莫耳%以上的PMDA及/或BPDA作為酸酐成分為前提，較佳為僅使用PMDA及/或BPDA作為酸酐成分。 Formula (id) is 1,4 bis (4-aminophenoxy) -2,6-di-tert-butylbenzene. Here, when the diamine compound represented by the general formula (i) is a compound represented by the formula (id), and m-TB is used as another diamine component, the acid anhydride component and the compound represented by the formula (id) are preferred. The compounding amount of the compound satisfies the relationship shown by the following formula F. In this case, it is premised that PMDA and / or BPDA are used as the acid anhydride component, and it is preferable to use only PMDA and / or BPDA as the acid anhydride component.

y=0.2971x-8.3862......(數式F) y = 0.2971x-8.3862 ... (Equation F)

[式中，x表示將式(id)所示的化合物的調配量(莫耳%)乘以係數4.5而得的值、與酸酐成分中的BPDA的調配量(莫耳%)的和，y表示10以上、30以下的範圍內的數] [Wherein, x represents the value obtained by multiplying the compounded amount (mol%) of the compound represented by formula (id) by a factor of 4.5 and the sum of the compounded amount (mol%) of BPDA in the anhydride component, y Represents a number in the range of 10 or more and 30 or less]

在所述數式F中，y相當於將使用所述各單體而得的聚醯胺酸進行醯亞胺化而加工成膜狀時的熱膨脹係數[×10-6(1/K)]。因此，藉由以滿足所述數式F的方式調配各單體，而可形成熱膨脹係數為10×10-6(1/K)~30×10-6(1/K)的範圍內的聚醯亞胺膜。 In the formula F, y corresponds to the coefficient of thermal expansion when the polyamidoacid obtained by using each of the monomers is subjected to amidimidation to form a film [× 10 -6 (1 / K)] . Therefore, by formulating each monomer in such a manner as to satisfy the formula F, a polymer having a thermal expansion coefficient in a range of 10 × 10 -6 (1 / K) to 30 × 10 -6 (1 / K) can be formed.醯 imine film.

另外，在通式(i)所示的二胺化合物為式(id)所示的化合物、且使用2,2'-二乙基-4,4'-二胺基聯苯(m-EB)作為其他二胺成分時，較佳為酸酐成分、與式(id)所示的化合物的調配量滿足下述數式G所示的關係。此時，以使用50莫耳%以上的PMDA及/或BPDA作為酸酐成分為前提，較佳為僅使用PMDA及/或BPDA作為酸酐成分。 The diamine compound represented by the general formula (i) is a compound represented by the formula (id), and 2,2'-diethyl-4,4'-diaminobiphenyl (m-EB) is used. In the case of other diamine components, it is preferable that the amount of the acid anhydride component and the compound represented by the formula (id) satisfy the relationship represented by the following formula G. In this case, it is premised that PMDA and / or BPDA are used as the acid anhydride component, and it is preferable to use only PMDA and / or BPDA as the acid anhydride component.

y=0.2986x-3.3977......(數式G) y = 0.2986x-3.3977 ... (Equation G)

[式中，x表示將式(id)所示的化合物的調配量(莫耳%)乘以係數4.3而得的值、與所述酸酐成分中的BPDA的調配量(莫耳%)的和，y表示10以上、30以下的範圍內的數] [Wherein, x represents the value obtained by multiplying the compounded amount (mol%) of the compound represented by formula (id) by a factor of 4.3 and the sum of the compounded amount (mol%) of BPDA in the acid anhydride component , Y represents a number in the range of 10 or more and 30 or less]

在所述數式G中，y相當於將使用所述各單體而得的聚醯胺酸進行醯亞胺化而加工成膜狀時的熱膨脹係數[×10-6(1/K)]。因此，藉由以滿足所述數式G的方式調配各單體，而可形成熱膨脹係數為10×10-6(1/K)~30×10-6(1/K)的範圍內的聚醯亞胺膜。 In the formula G, y corresponds to a thermal expansion coefficient [x10 -6 (1 / K)] when polyimide acid obtained by using each of the monomers is subjected to amidimidation to form a film. . Therefore, by formulating each monomer in such a manner as to satisfy the formula G, it is possible to form a polymer having a thermal expansion coefficient in a range of 10 × 10 -6 (1 / K) to 30 × 10 -6 (1 / K).醯 imine film.

式(ie)為1,4雙(4-胺基苯氧基)-2,5-二(2-甲基丙基)苯。此處，在通式(i)所示的二胺化合物為式(ie)所示的化合物、且使用m-TB作為其他二胺成分時，較佳為酸酐成分、與式(ie)所示的化合物的調配量滿足下述數式H所示的關係。此時，以使用50莫耳%以上的PMDA及/或BPDA作為酸酐成分為前提，較 佳為僅使用PMDA及/或BPDA作為酸酐成分。 Formula (ie) is 1,4-bis (4-aminophenoxy) -2,5-bis (2-methylpropyl) benzene. Here, when the diamine compound represented by the general formula (i) is a compound represented by the formula (ie) and m-TB is used as the other diamine component, an acid anhydride component and the compound represented by the formula (ie) are preferred. The compounding amount of the compound satisfies the relationship shown by the following formula H. At this time, it is premised that PMDA and / or BPDA of 50 mol% or more is used as the acid anhydride component. Preferably, only PMDA and / or BPDA are used as the anhydride component.

y=0.3011x-8.6596......(數式H) y = 0.3011x-8.6596 ... (Equation H)

[式中，x表示將式(ie)所示的化合物的調配量(莫耳%)乘以係數6.1而得的值、與酸酐成分中的BPDA的調配量(莫耳%)的和，y表示10以上、30以下的範圍內的數] [Wherein, x represents the value obtained by multiplying the compounded amount (mol%) of the compound represented by formula (ie) by a factor of 6.1 and the sum of the compounded amount (mol%) of BPDA in the acid anhydride component, y Represents a number in the range of 10 or more and 30 or less]

在所述數式H中，y相當於將使用所述各單體而得的聚醯胺酸進行醯亞胺化而加工成膜狀時的熱膨脹係數[×10-6(1/K)]。因此，藉由以滿足所述數式H的方式調配各單體，而可形成熱膨脹係數為10×10-6(1/K)~30×10-6(1/K)的範圍內的聚醯亞胺膜。 In the formula H, y corresponds to a thermal expansion coefficient [x10 -6 (1 / K)] when polyimide acid obtained by using each of the monomers is amidated and imidized. . Therefore, by formulating each monomer in such a manner as to satisfy the formula H, a polymer having a thermal expansion coefficient in a range of 10 × 10 -6 (1 / K) to 30 × 10 -6 (1 / K) can be formed.醯 imine film.

另外，在通式(i)所示的二胺化合物為式(ie)所示的化合物、且使用2,2'-二乙基-4,4'-二胺基聯苯(m-EB)作為其他二胺成分時，較佳為酸酐成分、與式(ie)所示的化合物的調配量滿足下述數式I所示的關係。此時，以使用50莫耳%以上的PMDA及/或BPDA作為酸酐成分為前提，較佳為僅使用PMDA及/或BPDA作為酸酐成分。 The diamine compound represented by the general formula (i) is a compound represented by the formula (ie), and 2,2'-diethyl-4,4'-diaminobiphenyl (m-EB) is used. In the case of other diamine components, the acid anhydride component and the compounded amount of the compound represented by the formula (ie) preferably satisfy the relationship represented by the following formula I. In this case, it is premised that PMDA and / or BPDA are used as the acid anhydride component, and it is preferable to use only PMDA and / or BPDA as the acid anhydride component.

y=0.2984x-3.6137......(數式I) y = 0.2984x-3.6137 ... (Equation I)

[式中，x表示將式(id)所示的化合物的調配量(莫耳%)乘以係數6.0而得的值、與所述酸酐成分中的BPDA的調配量(莫耳%)的和，y表示10以上、30以下的範圍內的數] [Wherein, x represents a value obtained by multiplying the compounded amount (mol%) of the compound represented by formula (id) by a factor of 6.0 and the sum of the compounded amount (mol%) of BPDA in the acid anhydride component , Y represents a number in the range of 10 or more and 30 or less]

在所述數式I中，y相當於將使用所述各單體而得的聚醯胺酸進行醯亞胺化而加工成膜狀時的熱膨脹係數[×10-6(1/K)]。因此，藉由以滿足所述數式I的方式調配各單體，而可形成熱膨脹係數為10×10-6(1/K)~30×10-6(1/K)的範圍內的聚醯亞胺膜。 In the formula I, y corresponds to a thermal expansion coefficient [× 10 -6 (1 / K)] when polyimide acid obtained by using each of the monomers is amidated and imidized. . Therefore, by formulating the monomers so as to satisfy the formula I, it is possible to form a polymer having a thermal expansion coefficient in a range of 10 × 10 -6 (1 / K) to 30 × 10 -6 (1 / K).醯 imine film.

式(if)為1,4雙(4-胺基苯氧基)-2,5-二(1-甲基庚基)苯。 Formula (if) is 1,4-bis (4-aminophenoxy) -2,5-bis (1-methylheptyl) benzene.

所述酸酐及二胺分別可僅使用其一種，亦可併用兩種以上而使用。另外，亦可與所述酸酐或二胺一起使用所述通式(1)及通式(2)所不含的其他二胺及酸酐，此時，其他酸酐或二胺的使用比例較佳為設為10莫耳%以下，更佳為設為5莫耳%以下。藉由選定酸酐及二胺的種類、或使用兩種以上的酸酐或二胺時的各莫耳比，而可控制熱膨脹性、黏接性、玻璃轉移溫度等。 The acid anhydride and the diamine may be used alone, or two or more of them may be used in combination. In addition, other diamines and acid anhydrides not included in the general formula (1) and the general formula (2) may be used together with the acid anhydride or diamine. In this case, the use ratio of the other acid anhydride or diamine is preferably It is set to 10 mol% or less, and more preferably 5 mol% or less. By selecting the type of acid anhydride and diamine, or the molar ratios when two or more kinds of acid anhydrides or diamines are used, thermal expansion properties, adhesion properties, glass transition temperature, and the like can be controlled.

具有通式(1)及通式(2)所示的結構單元的聚醯亞胺可藉由以下方式製造：使包含所述PMDA及/或BPDA的芳香族四 羧酸酐、二胺化合物(i)及其他芳香族二胺在溶劑中反應，生成前驅物樹脂後進行加熱閉環。例如使酸酐成分與二胺成分以大致等莫耳溶解於有機溶劑中，在0℃~100℃的範圍內的溫度下攪拌30分鐘~24小時進行聚合反應，藉此獲得作為聚醯亞胺的前驅物的聚醯胺酸。在反應時，以所生成的前驅物在有機溶劑中成為5重量%~30重量%的範圍內、較佳為10重量%~20重量%的範圍內的方式溶解反應成分。作為聚合反應所用的有機溶劑，例如可列舉：N,N-二甲基甲醯胺、N,N-二甲基乙醯胺(DMAc)、N-甲基-2-吡咯啶酮、2-丁酮、二甲基亞碸、硫酸二甲酯、環己酮、二噁烷、四氫呋喃、二乙二醇二甲醚、三乙二醇二甲醚等。亦可將所述溶劑併用兩種以上而使用，而且還可併用如二甲苯、甲苯般的芳香族烴。另外，作為此種有機溶劑的使用量，並無特別限制，較佳為調整為如藉由聚合反應而得的聚醯胺酸溶液(聚醯亞胺前驅物溶液)的濃度成為5重量%~30重量%左右的使用量而使用。 The polyfluorene imide having a structural unit represented by the general formula (1) and the general formula (2) can be produced by making the aromatic tetramer containing the PMDA and / or BPDA The carboxylic acid anhydride, the diamine compound (i), and other aromatic diamines are reacted in a solvent to generate a precursor resin and then heat-close the ring. For example, an acid anhydride component and a diamine component are dissolved in an organic solvent at approximately equal moles, and the polymerization reaction is performed by stirring at a temperature in a range of 0 ° C to 100 ° C for 30 minutes to 24 hours, thereby obtaining polyimide. Precursor Polyamic Acid. During the reaction, the produced precursor is dissolved in an organic solvent in a range of 5% to 30% by weight, preferably in a range of 10% to 20% by weight. Examples of the organic solvent used in the polymerization include N, N-dimethylformamide, N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone, 2- Methyl ethyl ketone, dimethyl sulfene, dimethyl sulfate, cyclohexanone, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and the like. These solvents may be used in combination of two or more kinds, and aromatic hydrocarbons such as xylene and toluene may also be used in combination. In addition, the use amount of such an organic solvent is not particularly limited, but it is preferably adjusted such that the concentration of the polyamidic acid solution (polyimide precursor solution) obtained by the polymerization reaction becomes 5% by weight ~ Use at about 30% by weight.

所合成的前驅物通常有利的是用作反應溶劑溶液，根據需要可進行濃縮、稀釋或置換成其他有機溶劑。另外，前驅物通常溶劑可溶性優異，因此可有利地使用。使前驅物進行醯亞胺化的方法並無特別限制，例如可較佳地採用在所述溶劑中、在80℃~400℃的範圍內的溫度條件下歷時1小時~24小時進行加熱的熱處理。 The synthesized precursors are generally advantageously used as a reaction solvent solution, and can be concentrated, diluted or replaced with other organic solvents as needed. In addition, the precursor is generally excellent in solvent solubility, and thus can be favorably used. The method for subjecting the precursor to sulfonimidization is not particularly limited. For example, heat treatment in the solvent at a temperature in the range of 80 ° C. to 400 ° C. for 1 hour to 24 hours can be preferably used. .

[樹脂膜] [Resin film]

本實施形態的樹脂膜若為包含由本實施形態的聚醯亞胺形成 的聚醯亞胺層的絕緣樹脂的膜，則並無特別限定，可為包含絕緣樹脂的膜(片)，亦可為積層在銅箔、玻璃板、聚醯亞胺系膜、聚醯胺系膜、聚酯系膜等樹脂片等基材上的狀態的絕緣樹脂的膜。另外，本實施形態的樹脂膜的厚度較佳為處於3μm~100μm的範圍內，更佳為處於3μm~75μm的範圍。 If the resin film of this embodiment is formed of polyimide containing this embodiment, The insulating resin film of the polyimide layer is not particularly limited, and may be a film (sheet) containing an insulating resin, or may be laminated on a copper foil, a glass plate, a polyimide-based film, or polyimide. A film of an insulating resin in a state on a substrate such as a resin film such as a base film and a polyester film. The thickness of the resin film in this embodiment is preferably in a range of 3 μm to 100 μm, and more preferably in a range of 3 μm to 75 μm.

本實施形態的聚醯亞胺較佳為用作基礎膜層(絕緣樹脂層的主層)。具體而言，若將熱膨脹係數處於10×10-6(1/K)~30×10-6(1/K)的範圍內、較佳為處於10×10-6(1/K)~25×10-6(1/K)的範圍內、更佳為處於15×10-6(1/K)~25×10-6(1/K)的範圍內的低熱膨脹性的聚醯亞胺層應用於基礎膜層，則可獲得大的效果。在低熱膨脹性的聚醯亞胺中，可較佳地利用的聚醯亞胺為非熱塑性聚醯亞胺。使用本實施形態的聚醯亞胺形成低熱膨脹性的基礎膜層時的厚度較佳為5μm~50μm的範圍內，更佳為10μm~35μm的範圍。 The polyimide of this embodiment is preferably used as a base film layer (main layer of an insulating resin layer). Specifically, if the thermal expansion coefficient is in the range of 10 × 10 -6 (1 / K) to 30 × 10 -6 (1 / K), it is preferably in the range of 10 × 10 -6 (1 / K) to 25 × 10 -6 (1 / K), more preferably low thermal expansion polyimide in the range of 15 × 10 -6 (1 / K) to 25 × 10 -6 (1 / K) When the layer is applied to the base film layer, a large effect can be obtained. Among the polyfluorene imines having a low thermal expansion property, the polyfluorene which can be preferably used is a non-thermoplastic polyimide. When the polyimide of this embodiment is used to form a base film layer with low thermal expansion, the thickness is preferably in the range of 5 μm to 50 μm, and more preferably in the range of 10 μm to 35 μm.

另一方面，超過所述熱膨脹係數的聚醯亞胺層例如亦較佳為用作與金屬層或其他樹脂層等基材的黏接層。作為可較佳地用作此種黏接性聚醯亞胺層的聚醯亞胺，其玻璃轉移溫度例如較佳為360℃以下者，更佳為處於200℃~320℃的範圍內者。 On the other hand, a polyimide layer exceeding the thermal expansion coefficient is also preferably used as an adhesive layer with a substrate such as a metal layer or another resin layer. As a polyimide which can be suitably used as such an adhesive polyamidine layer, the glass transition temperature is preferably 360 ° C. or lower, for example, and more preferably within a range of 200 ° C. to 320 ° C.

在黏接性聚醯亞胺中，可較佳地利用的聚醯亞胺為熱塑性聚醯亞胺。作為可較佳地用於形成熱塑性聚醯亞胺的酸酐，例如可列舉：均苯四羧酸二酐、3,3',4,4'-聯苯四羧酸二酐、3,3',4,4'-二苯基碸四羧酸二酐、4,4'-氧基二鄰苯二甲酸酐等。此外，可列 舉所述聚醯亞胺的說明中所列舉的酸酐。其中，作為特佳的酸酐，可列舉：選自均苯四羧酸二酐(PMDA)、3,3',4,4'-聯苯四羧酸二酐(BPDA)、3,3',4,4'-二苯甲酮四羧酸二酐(BTDA)、3,3',4,4'-二苯基碸四羧酸二酐(DSDA)中的一種以上的酸酐。 Among the adhesive polyimides, the polyimide that can be preferably used is a thermoplastic polyimide. Examples of the acid anhydride that can be preferably used to form a thermoplastic polyfluorene imine include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, and 3,3' , 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride and the like. In addition, can be listed The acid anhydrides listed in the description of polyimide are mentioned. Among them, particularly preferred anhydrides include: selected from pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), 3,3', One or more types of anhydrides of 4,4'-benzophenonetetracarboxylic dianhydride (BTDA) and 3,3 ', 4,4'-diphenylfluorenetetracarboxylic dianhydride (DSDA).

作為可較佳地用於形成熱塑性聚醯亞胺的芳香族二胺，就耐熱性及黏接性的觀點而言，較佳為在分子內具有伸苯基或伸聯苯基者、或者在分子內具有包含氧元素或硫元素的2價連結基者，例如可列舉：1,4雙(4-胺基苯氧基)-2,5-二-第三丁基苯(DTBAB)、4,4'-二胺基二苯醚、2'-甲氧基-4,4'-二胺基苯甲醯苯胺、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2'-二甲基-4,4'-二胺基聯苯、3,3'-二羥基-4,4'-二胺基聯苯、4,4'-二胺基苯甲醯苯胺等。此外，可列舉在所述聚醯亞胺的說明中所列舉的二胺。其中，作為特佳的二胺成分，可列舉：選自1,3-雙(4-胺基苯氧基)-2,2-二甲基丙烷(DANPG)、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷(BAPP)、1,3-雙(3-胺基苯氧基)苯(APB)、對苯二胺(p-PDA)、3,4'-二胺基二苯醚(DAPE34)、4,4'-二胺基二苯醚(DAPE44)中的一種以上的二胺。 As the aromatic diamine which can be preferably used to form a thermoplastic polyfluorene imide, from the viewpoints of heat resistance and adhesiveness, those having an phenylene group or a phenylene group in the molecule, or Those having a divalent linking group containing an oxygen element or a sulfur element in the molecule include, for example, 1,4bis (4-aminophenoxy) -2,5-di-third-butylbenzene (DTBAB), 4 , 4'-diaminodiphenyl ether, 2'-methoxy-4,4'-diaminobenzidine aniline, 1,4-bis (4-aminophenoxy) benzene, 1,3 -Bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2'-dimethyl-4,4'-di Aminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 4,4'-diaminobenzidine aniline and the like. In addition, the diamines mentioned in the description of the polyfluorene imine can be mentioned. Among them, particularly preferred diamine components include: selected from 1,3-bis (4-aminophenoxy) -2,2-dimethylpropane (DANPG), 2,2-bis [4- (4-Aminophenoxy) phenyl] propane (BAPP), 1,3-bis (3-aminophenoxy) benzene (APB), p-phenylenediamine (p-PDA), 3,4 ' -One or more diamines of diaminodiphenyl ether (DAPE34) and 4,4'-diaminodiphenyl ether (DAPE44).

作為本實施形態的樹脂膜的聚醯亞胺膜的形成方法，並無特別限定，例如可列舉如下的方法：將聚醯亞胺溶液(或聚醯胺酸溶液)塗佈於任意的基材上後實施熱處理(乾燥、硬化)，而在基材上形成聚醯亞胺層(或聚醯胺酸層)，然後進行剝離而形成聚醯亞胺膜。作為將聚醯亞胺溶液(或聚醯胺酸溶液)塗佈於基 材上的方法，並無特別限制，例如可藉由缺角輪(comma)、模具、刀、模唇等的塗佈機進行塗佈。在形成多層的聚醯亞胺層時，較佳為重複進行將聚醯亞胺溶液(或聚醯胺酸溶液)塗佈於基材上並乾燥的操作的方法。 The method for forming the polyimide film as the resin film of this embodiment is not particularly limited, and examples thereof include a method in which a polyimide solution (or a polyamic acid solution) is applied to an arbitrary substrate After heat treatment (drying and hardening), a polyimide layer (or a polyamic acid layer) is formed on the substrate, and then the polyimide film is formed by peeling. The polyimide solution (or polyamidic acid solution) is applied as a base The method for applying the material is not particularly limited, and for example, coating can be performed by a coater such as a comma, a mold, a knife, and a die lip. When forming a multi-layer polyimide layer, it is preferable to repeat the operation of applying a polyimide solution (or a polyamic acid solution) to a substrate and drying it.

本實施形態的樹脂膜可包含單層或多層的聚醯亞胺層。此時，聚醯亞胺層的至少一層(較佳為基礎膜層)只要使用本實施形態的非熱塑性聚醯亞胺而形成即可。例如若將非熱塑性聚醯亞胺層設為P1、將熱塑性聚醯亞胺層設為P2，則在將樹脂膜設為2層時，較佳為以P2/P1的組合進行積層，在將樹脂膜設為3層時，較佳為按照P2/P1/P2的順序、或P2/P1/P1的順序進行積層。此處，P1成為使用本實施形態的非熱塑性聚醯亞胺而形成的基礎膜層。再者，P2亦可包含本實施形態的聚醯亞胺以外的聚醯亞胺。 The resin film of this embodiment may include a single-layer or multiple-layer polyimide layer. In this case, at least one layer (preferably a base film layer) of the polyfluorene imide layer may be formed by using the non-thermoplastic polyimide of this embodiment. For example, if the non-thermoplastic polyimide layer is set to P1 and the thermoplastic polyimide layer is set to P2, when the resin film is set to two layers, it is preferable to laminate in a combination of P2 / P1. When the resin film is provided in three layers, it is preferable to laminate in the order of P2 / P1 / P2 or the order of P2 / P1 / P1. Here, P1 is a base film layer formed using the non-thermoplastic polyimide of this embodiment. In addition, P2 may contain polyimide other than the polyimide of this embodiment.

本實施形態的樹脂膜根據需要可在聚醯亞胺層中含有無機填料。具體而言，例如可列舉：二氧化矽、氧化鋁、氧化鎂、氧化鈹、氮化硼、氮化鋁、氮化矽、氟化鋁、氟化鈣等。所述可使用一種或混合兩種以上而使用。 The resin film of this embodiment may contain an inorganic filler in a polyimide layer as needed. Specific examples include silicon dioxide, aluminum oxide, magnesium oxide, beryllium oxide, boron nitride, aluminum nitride, silicon nitride, aluminum fluoride, and calcium fluoride. These can be used singly or in combination of two or more kinds.

應用本實施形態的樹脂膜作為低熱膨脹性的聚醯亞胺膜者例如可用作覆蓋膜中的覆蓋用膜材。本實施形態的樹脂膜上可積層任意的黏接劑層而形成覆蓋膜。覆蓋用膜材層的厚度並無特別限定，例如較佳為5μm以上、100μm以下。另外，黏接劑層的厚度並無特別限定，例如較佳為25μm以上、50μm以下。 A person applying the resin film of this embodiment as a polyimide film having low thermal expansion can be used as a covering film material in a covering film, for example. An arbitrary adhesive layer can be laminated on the resin film of this embodiment to form a cover film. The thickness of the coating film layer is not particularly limited, and is preferably 5 μm or more and 100 μm or less, for example. The thickness of the adhesive layer is not particularly limited, and is preferably 25 μm or more and 50 μm or less, for example.

應用本實施形態的樹脂膜作為黏接性聚醯亞胺膜者例 如亦可用作多層FPC的接合片。在用作接合片時，可在任意的基材膜上將本實施形態的樹脂膜直接用作接合片，亦可在將所述樹脂膜與任意的基材膜積層的狀態下使用。 Example of application of the resin film of this embodiment as an adhesive polyfluorene film It can also be used as a bonding sheet for multilayer FPC. When used as a bonding sheet, the resin film of this embodiment may be used as a bonding sheet directly on an arbitrary base film, or may be used in a state where the resin film and any base film are laminated.

[覆金屬積層板] [Metal clad board]

本實施形態的覆金屬積層板具有：絕緣樹脂層、以及積層於所述絕緣樹脂層的至少單側的面的金屬層。作為覆金屬積層板的較佳的具體例，例如可列舉：覆銅積層板(Copper Clad Laminate，CCL)等。 The metal-clad laminated board according to this embodiment includes an insulating resin layer and a metal layer laminated on at least one side of the insulating resin layer. Preferred specific examples of the metal-clad laminated board include, for example, Copper Clad Laminate (CCL).

<絕緣樹脂層> <Insulating resin layer>

在本實施形態的覆金屬積層板中，絕緣樹脂層具有單層或多層的聚醯亞胺層。此時，為了對覆金屬積層板賦予優異的高頻特性，而聚醯亞胺層的至少一層(較佳為基礎膜層)只要使用本實施形態的非熱塑性聚醯亞胺而形成即可。另外，為了提高絕緣樹脂層與金屬層的黏接性，而絕緣樹脂層的與金屬層接觸的層較佳為熱塑性聚醯亞胺層。例如在將絕緣樹脂層設為2層時，若將非熱塑性聚醯亞胺層設為P1、將熱塑性聚醯亞胺層設為P2、將金屬層設為M1，則較佳為按照P1/P2/M1的順序進行積層。此處，P1成為使用本實施形態的非熱塑性聚醯亞胺而形成的基礎膜層。再者，P2可包含本實施形態的聚醯亞胺以外的聚醯亞胺。 In the metal-clad laminate according to this embodiment, the insulating resin layer includes a single or multiple polyimide layers. At this time, in order to impart excellent high-frequency characteristics to the metal-clad laminate, at least one layer (preferably, a base film layer) of the polyimide layer may be formed by using the non-thermoplastic polyimide of this embodiment. In addition, in order to improve the adhesion between the insulating resin layer and the metal layer, the layer in contact with the metal layer of the insulating resin layer is preferably a thermoplastic polyimide layer. For example, when two insulating resin layers are used, if the non-thermoplastic polyimide layer is P1, the thermoplastic polyimide layer is P2, and the metal layer is M1, it is preferably P1 / P2 / M1 is laminated in order. Here, P1 is a base film layer formed using the non-thermoplastic polyimide of this embodiment. In addition, P2 may contain polyimide other than the polyimide of this embodiment.

<金屬層> <Metal layer>

作為本實施形態的覆金屬積層板中的金屬層的材質，並無特別限制，例如可列舉：銅、不鏽鋼、鐵、鎳、鈹、鋁、鋅、銦、 銀、金、錫、鋯、鉭、鈦、鉛、鎂、錳及所述的合金等。其中，特佳為銅或銅合金。再者，後述的本實施形態的電路基板中的配線層的材質亦與金屬層相同。 The material of the metal layer in the metal-clad laminate according to this embodiment is not particularly limited, and examples thereof include copper, stainless steel, iron, nickel, beryllium, aluminum, zinc, indium, Silver, gold, tin, zirconium, tantalum, titanium, lead, magnesium, manganese, and alloys thereof. Among them, particularly preferred is copper or a copper alloy. The material of the wiring layer in the circuit board of the present embodiment described later is also the same as that of the metal layer.

在對訊號配線供給高頻訊號的狀態下，存在如下問題(表皮效應)：電流僅在所述訊號配線的表面流動，電流所流動的有效剖面積變少而直流電阻變大，從而訊號衰減。藉由降低金屬層的與絕緣樹脂層接觸的面的表面粗度，而可抑制因所述表皮效應引起的訊號配線的電阻增大。但是，若為了滿足電性能要求基準而降低表面粗度，則銅箔與介電體基板的黏接力(剝離強度)變弱。因此，就可滿足電性能要求、確保與絕緣樹脂層的黏接性且提高覆金屬積層板的視覺辨認性的觀點而言，金屬層的與絕緣樹脂層接觸的面的表面粗度較佳為十點平均粗糙度Rz為1.5μm以下，且算術平均粗糙度Ra為0.2μm以下。 In a state where a high-frequency signal is supplied to a signal wiring, there is a problem (skin effect): a current flows only on the surface of the signal wiring, an effective cross-sectional area through which the current flows is reduced, and a DC resistance is increased, so that the signal is attenuated. By reducing the surface roughness of the surface of the metal layer in contact with the insulating resin layer, it is possible to suppress an increase in the resistance of the signal wiring due to the skin effect. However, if the surface roughness is reduced in order to meet the standard of electrical performance requirements, the adhesive force (peel strength) between the copper foil and the dielectric substrate becomes weak. Therefore, from the viewpoint of satisfying the electrical performance requirements, ensuring the adhesion with the insulating resin layer, and improving the visibility of the metal-clad laminate, the surface roughness of the surface of the metal layer in contact with the insulating resin layer is preferably The ten-point average roughness Rz is 1.5 μm or less, and the arithmetic average roughness Ra is 0.2 μm or less.

覆金屬積層板例如可藉由以下方式製備：準備包含本實施形態的聚醯亞胺而構成的樹脂膜，對其濺鍍金屬而形成籽晶層後，藉由例如鍍敷而形成金屬層。 The metal-clad laminated board can be prepared, for example, by preparing a resin film composed of the polyfluorene imide of the present embodiment, sputtering the metal to form a seed layer, and then forming a metal layer by, for example, plating.

另外，覆金屬積層板亦可藉由以下方式製備：準備包含本實施形態的聚醯亞胺而構成的樹脂膜，藉由熱壓接等方法在其上積層金屬箔。 In addition, the metal-clad laminated board may be prepared by preparing a resin film including polyimide of the present embodiment, and laminating a metal foil thereon by a method such as thermocompression bonding.

而且，覆金屬積層板還可藉由以下方式製備：在金屬箔上澆鑄含有作為本實施形態的聚醯亞胺的前驅物的聚醯胺酸的塗佈液，進行乾燥而形成塗佈膜後，進行熱處理而醯亞胺化，從而 形成聚醯亞胺層。 In addition, the metal-clad laminated board can also be prepared by casting a coating solution containing a polyamic acid as a precursor of the polyimide of the present embodiment on a metal foil, and drying to form a coating film. , And then heat-treated and then imidized, so that A polyimide layer is formed.

[電路基板] [Circuit Board]

本實施形態的電路基板具有：絕緣樹脂層、以及形成於絕緣樹脂層上的配線層。在本實施形態的電路基板中，絕緣樹脂層可具有單層或多層的聚醯亞胺層。此時，為了對電路基板賦予優異的高頻特性，而聚醯亞胺層的至少一層(較佳為基礎膜層)只要使用本實施形態的非熱塑性聚醯亞胺而形成即可。另外，為了提高絕緣樹脂層與配線層的黏接性，較佳為絕緣樹脂層的與配線層接觸的層為使用本實施形態的聚醯亞胺而形成的熱塑性聚醯亞胺層。例如在將絕緣樹脂層設為2層時，若將非熱塑性聚醯亞胺層設為P1、將熱塑性聚醯亞胺層設為P2、將配線層設為M2，則較佳為按照P1/P2/M2的順序進行積層。此處，P1成為使用本實施形態的非熱塑性聚醯亞胺而形成的基礎膜層。再者，P2可包含本實施形態的聚醯亞胺以外的聚醯亞胺。 The circuit board of this embodiment includes an insulating resin layer and a wiring layer formed on the insulating resin layer. In the circuit board of this embodiment, the insulating resin layer may have a single or multiple polyimide layers. In this case, in order to impart excellent high-frequency characteristics to the circuit board, at least one layer (preferably, a base film layer) of the polyimide layer may be formed by using the non-thermoplastic polyimide of this embodiment. In addition, in order to improve the adhesion between the insulating resin layer and the wiring layer, it is preferable that the layer in contact with the wiring layer of the insulating resin layer is a thermoplastic polyimide layer formed using the polyimide of this embodiment. For example, when two insulating resin layers are used, if the non-thermoplastic polyimide layer is P1, the thermoplastic polyimide layer is P2, and the wiring layer is M2, it is preferably P1 / P2 / M2 are laminated in order. Here, P1 is a base film layer formed using the non-thermoplastic polyimide of this embodiment. In addition, P2 may contain polyimide other than the polyimide of this embodiment.

除了使用本實施形態的聚醯亞胺以外，製作電路基板的方法並無問題。例如亦可為減成法：準備包含含有本實施形態的聚醯亞胺的絕緣樹脂層與金屬層的覆金屬積層板，對金屬層進行蝕刻而形成配線。另外還可為半加成法：在本實施形態的聚醯亞胺層上形成籽晶層後，將抗蝕劑形成圖案，繼而將金屬進行圖案鍍敷，藉此形成配線。 Other than using the polyfluorene imide of this embodiment, there is no problem in the method for producing a circuit board. For example, it may be a subtractive method: a metal-clad laminate including an insulating resin layer containing a polyfluorene imide of the present embodiment and a metal layer is prepared, and the metal layer is etched to form wiring. In addition, a semi-additive method may be used. After forming a seed layer on the polyfluorene imide layer of this embodiment, a resist is patterned, and then metal is patterned to form wiring.

以下，列舉代表性的澆鑄法與減成法的組合的情形為例，對本實施形態的電路基板的製造方法進行具體地說明。 Hereinafter, a case where a representative combination of a casting method and a subtractive method is used as an example will be described in detail, and a method for manufacturing a circuit board according to this embodiment will be specifically described.

首先，本實施形態的覆金屬積層板的製造方法可包括以下步驟(1)~步驟(3)。 First, the method for manufacturing a metal-clad laminate according to this embodiment may include the following steps (1) to (3).

步驟(1)：步驟(1)是獲得作為本實施形態的聚醯亞胺的前驅物的聚醯胺酸的樹脂溶液的步驟。所述步驟如上所述般，可藉由使包含原料的二胺化合物(i)及其他芳香族二胺的二胺成分與酸酐成分在適當的溶劑中反應而進行。 Step (1): Step (1) is a step of obtaining a polyamic acid resin solution which is a precursor of the polyfluorene imine of the present embodiment. As described above, the step can be carried out by reacting a diamine component (i) containing a raw material and other aromatic diamines with a diamine component and an acid anhydride component in a suitable solvent.

步驟(2)：步驟(2)是在成為金屬層的金屬箔上塗佈聚醯胺酸的樹脂溶液而形成塗佈膜的步驟。金屬箔能以切片狀、捲狀、或環帶狀等形狀使用。為了獲得生產性，有效率的是設為捲狀或環帶狀的形態，並設為可連續生產的形式。而且，就表現出更大的電路基板的配線圖案精度的改善效果的觀點而言，銅箔較佳為呈長條形成的捲狀者。 Step (2): Step (2) is a step of applying a resin solution of polyamic acid on a metal foil that becomes a metal layer to form a coating film. The metal foil can be used in the shape of a slice, a roll, or an endless belt. In order to obtain productivity, it is effective to make it into a roll shape or an endless belt shape, and to make it a continuous production form. Furthermore, from the viewpoint of exhibiting a greater effect of improving the accuracy of the wiring pattern of the circuit board, the copper foil is preferably a roll-shaped one.

形成塗佈膜的方法可藉由以下方式形成：將聚醯胺酸的樹脂溶液直接塗佈在金屬箔上、或塗佈在由金屬箔支撐的聚醯亞胺層上後進行乾燥。進行塗佈的方法並無特別限制，例如可藉由缺角輪、模具、刀、模唇等的塗佈機進行塗佈。 The method for forming a coating film can be formed by directly coating a resin solution of polyamic acid on a metal foil, or coating the polyimide layer supported by the metal foil and then drying. The method of coating is not particularly limited, and for example, coating can be performed by a coating machine such as a notch wheel, a mold, a knife, a die lip, and the like.

聚醯亞胺層可為單層，亦可為包含多層者。在將聚醯亞胺層設為多層時，可在包含不同的構成成分的前驅物的層上依序塗佈其他前驅物而形成。在前驅物的層包含3層以上時，可使用2次以上相同構成的前驅物。層結構簡單的2層或單層在工業上可 有利地獲得，因此較佳。另外，前驅物的層的厚度(乾燥後)例如處於3μm~100μm的範圍內、較佳為處於3μm~75μm的範圍內。 The polyimide layer may be a single layer or a layer including multiple layers. When a polyimide layer is formed in multiple layers, it can be formed by sequentially coating other precursors on a layer containing precursors having different constituent components. When the precursor layer includes three or more layers, precursors having the same configuration twice or more can be used. Simple 2-layer or single-layer structure is industrially possible Obtained with advantage and therefore better. The thickness of the precursor layer (after drying) is, for example, in a range of 3 μm to 100 μm, and preferably in a range of 3 μm to 75 μm.

在將聚醯亞胺層設為多層時，基礎膜層為包含本實施形態的聚醯亞胺的非熱塑性聚醯亞胺層，較佳為以與金屬層接觸的聚醯亞胺層成為熱塑性聚醯亞胺層的方式形成前驅物的層。藉由使用熱塑性聚醯亞胺，而可提高與金屬層的密接性。此種熱塑性聚醯亞胺的玻璃轉移溫度(Tg)較佳為360℃以下，更佳為200℃~320℃。 When the polyimide layer is a plurality of layers, the base film layer is a non-thermoplastic polyimide layer containing the polyimide of this embodiment, and it is preferable that the polyimide layer in contact with the metal layer becomes thermoplastic. The polyimide layer forms a precursor layer. By using thermoplastic polyfluorene imide, the adhesion to the metal layer can be improved. The glass transition temperature (Tg) of such a thermoplastic polyfluorene imine is preferably 360 ° C or lower, and more preferably 200 ° C to 320 ° C.

另外，亦可將單層或多層的前驅物的層暫時醯亞胺化而形成單層或多層的聚醯亞胺層後，繼而在其上形成前驅物的層。 In addition, a single-layer or multiple-layer precursor layer may be temporarily imidized to form a single-layer or multiple-layer polyimide layer, and then a precursor layer may be formed thereon.

步驟(3)：步驟(3)是對塗佈膜進行熱處理而醯亞胺化，並形成絕緣樹脂層的步驟。醯亞胺化的方法並無特別限制，例如較佳為採用在80℃~400℃的範圍內的溫度條件下加熱1分鐘~60分鐘的範圍內的時間的熱處理。為了抑制金屬層的氧化，較佳為低氧氣環境下的熱處理，具體而言，較佳為在氮氣或稀有氣體等惰性氣體環境下、氫氣等還原氣體環境下、或真空中進行。藉由熱處理，而塗佈膜中的聚醯胺酸進行醯亞胺化，而形成聚醯亞胺。 Step (3): Step (3) is a step in which the coating film is heat-treated to be imidized to form an insulating resin layer. The method of hydrazone imidization is not particularly limited. For example, heat treatment is preferably performed by heating under a temperature range of 80 ° C to 400 ° C for a time in a range of 1 minute to 60 minutes. In order to suppress the oxidation of the metal layer, heat treatment in a low oxygen environment is preferred, and specifically, it is preferably performed in an inert gas environment such as nitrogen or a rare gas, a reducing gas environment such as hydrogen, or in a vacuum. The polyimide in the coating film is amidated by heat treatment to form a polyimide.

以如上所述方式，可製造具有聚醯亞胺層(單層或多層)與金屬層的覆金屬積層板。 In the manner described above, a metal-clad laminate having a polyimide layer (single or multiple layers) and a metal layer can be manufactured.

另外，本實施形態的電路基板的製造方法除了所述(1) ~(3)的步驟外，還可進一步包括以下步驟(4)。 In addition, the method for manufacturing a circuit board according to this embodiment is in addition to the above (1) In addition to steps (3), the following step (4) may be further included.

步驟(4)：步驟(4)是將覆金屬積層板的金屬箔進行圖案化而形成配線層的步驟。在本步驟中，藉由將金屬層蝕刻成特定形狀而形成圖案，藉由加工成配線層，而獲得電路基板。蝕刻例如可藉由利用光微影(photolithography)技術等的任意的方法進行。 Step (4): Step (4) is a step of patterning the metal foil of the metal-clad laminate to form a wiring layer. In this step, a pattern is formed by etching a metal layer into a specific shape, and a circuit substrate is obtained by processing into a wiring layer. Etching can be performed by, for example, an arbitrary method such as photolithography.

再者，在以上的說明中，僅對電路基板的製造方法的特徵性步驟進行了說明。即，在製造電路基板時，通常所進行的所述以外的步驟、例如前步驟中的通孔加工、或後步驟的端子鍍敷、外形加工等步驟可根據常法進行。 In the above description, only the characteristic steps of the method for manufacturing a circuit board have been described. That is, when manufacturing a circuit board, steps other than the above, such as through-hole processing in the previous step, or terminal plating and external shape processing in the later step, can be performed according to a conventional method.

如以上所述般，藉由使用本實施形態的聚醯亞胺，而可形成將傳輸損失抑制在小的水準的覆金屬積層板。 As described above, by using the polyimide of this embodiment, it is possible to form a metal-clad laminate that suppresses transmission loss to a small level.

實施例 Examples

以下表示實施例，對本發明的特徵進行更具體地說明。但本發明的範圍並不限定於實施例。再者，在以下的實施例中，只要無特別說明，則各種測定、評價根據以下所述。 Examples are given below to describe the features of the present invention more specifically. However, the scope of the present invention is not limited to the examples. In the following examples, unless otherwise specified, various measurements and evaluations are based on the following.

[熱膨脹係數(CTE)的測定] [Measurement of thermal expansion coefficient (CTE)]

熱膨脹係數是使用熱機械分析儀(布魯克(Bruker)公司製造、商品名；4000SA)，一邊對3mm×20mm的尺寸的聚醯亞胺膜施加5.0g的負荷，一邊以固定的升溫速度自30℃升溫至265℃，繼而在所述溫度下保持10分鐘後，以5℃/min的速度進行冷卻，求出自250℃至100℃為止的平均熱膨脹係數(線熱膨脹係數)。 The thermal expansion coefficient is a thermomechanical analyzer (manufactured by Bruker, trade name; 4000SA), while applying a load of 5.0 g to a polyimide film having a size of 3 mm × 20 mm, while maintaining a constant temperature increase rate from 30 ° C The temperature was raised to 265 ° C, and the temperature was maintained at the above temperature for 10 minutes, followed by cooling at a rate of 5 ° C / min, and the average thermal expansion coefficient (linear thermal expansion coefficient) from 250 ° C to 100 ° C was determined.

[介電常數及介電正切的測定] [Determination of dielectric constant and dielectric tangent]

介電常數及介電正切藉由以下方法求出。 The dielectric constant and the dielectric tangent are obtained by the following methods.

使用共振腔攝動法介電常數評價裝置(安捷倫(Agilent)公司製造、商品名；向量網路分析儀E8363B)，測定3GHz的頻率下的樹脂片(硬化後的樹脂片)的介電常數及介電正切。再者，測定所使用的樹脂片是在溫度：24℃~26℃、濕度：45%~55%的條件下放置24小時者。 The dielectric constant of a resin sheet (hardened resin sheet) at a frequency of 3 GHz and the dielectric constant of the resin sheet (cured resin sheet) at a frequency of 3 GHz were measured using a resonant cavity perturbation dielectric constant evaluation device (manufactured by Agilent, trade name; vector network analyzer E8363B) Dielectric tangent. The resin sheet used for the measurement was left to stand for 24 hours under the conditions of temperature: 24 ° C to 26 ° C and humidity: 45% to 55%.

實施例及比較例中所用的縮寫符號表示以下化合物。 The abbreviations used in the examples and comparative examples indicate the following compounds.

二胺A(DTBAB)：1,4雙(4-胺基苯氧基)-2,5-二-第三丁基苯(化學摘要服務社(Chemical Abstracts Service，CAS)編號189344-59-0) Diamine A (DTBAB): 1,4-bis (4-aminophenoxy) -2,5-di-third-butylbenzene (Chemical Abstracts Service (CAS) No. 189344-59-0 )

二胺B：1,4雙(4-胺基苯氧基)-2,3-二-第三丁基苯 Diamine B: 1,4 bis (4-aminophenoxy) -2,3-di-tert-butylbenzene

二胺C：1,4雙(4-胺基苯氧基)-2,5-二(1-甲基丙基)苯 Diamine C: 1,4bis (4-aminophenoxy) -2,5-bis (1-methylpropyl) benzene

二胺D：1,4雙(4-胺基苯氧基)-2,6-二-第三丁基苯 Diamine D: 1,4-bis (4-aminophenoxy) -2,6-di-third-butylbenzene

二胺E：1,4雙(4-胺基苯氧基)-2,5-二(2-甲基丙基)苯 Diamine E: 1,4bis (4-aminophenoxy) -2,5-bis (2-methylpropyl) benzene

二胺F：1,4雙(4-胺基苯氧基)-2,5-二(1-甲基庚基)苯 Diamine F: 1,4bis (4-aminophenoxy) -2,5-bis (1-methylheptyl) benzene

二胺G：1,4雙(4-胺基苯氧基)-2,5-二丙基苯 Diamine G: 1,4-bis (4-aminophenoxy) -2,5-dipropylbenzene

二胺H：1,4雙(4-胺基苯氧基)-2,5-二甲基苯 Diamine H: 1,4 bis (4-aminophenoxy) -2,5-dimethylbenzene

二胺I：1,4雙(4-胺基苯氧基)-2,5-二丁基苯 Diamine I: 1,4 bis (4-aminophenoxy) -2,5-dibutylbenzene

二胺J：1,4雙(4-胺基苯氧基)-2,3,5,6-四甲基苯 Diamine J: 1,4 bis (4-aminophenoxy) -2,3,5,6-tetramethylbenzene

二胺K：1,4雙(3-胺基苯氧基)-2,5-二丙基苯 Diamine K: 1,4bis (3-aminophenoxy) -2,5-dipropylbenzene

m-TB：2,2'-二甲基-4,4'-二胺基聯苯 m-TB: 2,2'-dimethyl-4,4'-diaminobiphenyl

m-EB：2,2'-二乙基-4,4'-二胺基聯苯 m-EB: 2,2'-diethyl-4,4'-diaminobiphenyl

m-NPB：2,2'-正丙基-4,4'-二胺基聯苯 m-NPB: 2,2'-n-propyl-4,4'-diaminobiphenyl

BAPP：2,2-雙(4-胺基苯氧基苯基)丙烷 BAPP: 2,2-bis (4-aminophenoxyphenyl) propane

PMDA：均苯四羧酸二酐 PMDA: pyromellitic dianhydride

BPDA：3,3',4,4'-聯苯四羧酸二酐 BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride

DMAc：N,N-二甲基乙醯胺 DMAc: N, N-dimethylacetamide

DMF：N,N-二甲基甲醯胺 DMF: N, N-dimethylformamide

[合成例1] [Synthesis example 1]

在氮氣流下在300ml的可分離式燒瓶中投入1.050g的DTBAB(0.0026莫耳)、4.957g的m-TB(0.0234莫耳)及68.0g的DMAc，在室溫下攪拌使其溶解。繼而，添加1.511g的BPDA(0.0051莫耳)及4.482g的PMDA(0.0206莫耳)後，在室溫下繼續攪拌3小時進行聚合反應，而獲得聚醯胺酸溶液A-a。聚醯胺酸溶液A-a的溶液黏度為7,025cps。 Under a nitrogen flow, 1.050 g of DTBAB (0.0026 mol), 4.957 g of m-TB (0.0234 mol), and 68.0 g of DMAc were put into a 300 ml separable flask, and the solution was stirred and dissolved at room temperature. Then, after adding 1.511 g of BPDA (0.0051 mol) and 4.482 g of PMDA (0.0206 mol), stirring was continued at room temperature for 3 hours to perform a polymerization reaction to obtain a polyamic acid solution A-a. The solution viscosity of the polyamic acid solution A-a was 7,025 cps.

[合成例2~合成例8] [Synthesis example 2 to synthesis example 8]

除了設為表1及表2所示的原料組成外，以與合成例1相同的方式，製備聚醯胺酸溶液A-b~聚醯胺酸溶液A-h。 A polyamic acid solution A-b to a polyamino acid solution A-h were prepared in the same manner as in Synthesis Example 1 except that the raw material compositions shown in Tables 1 and 2 were used.

[實施例1] [Example 1]

在厚度為18μm的電解銅箔的單面(表面粗糙度Rz；2.1μm)，以硬化後的厚度成為約25μm的方式均勻地塗佈合成例1中所製備的聚醯胺酸溶液A-a後，在120℃下進行加熱乾燥而除去溶劑。繼而，自120℃起進行階段性的熱處理至360℃為止，並完成醯亞胺化。對所得的覆金屬積層板，使用氯化鐵水溶液蝕刻除去銅箔，而獲得樹脂膜。再者，構成所得的樹脂膜的聚醯亞胺為非熱塑性。 On one side (surface roughness Rz; 2.1 μm) of the electrolytic copper foil having a thickness of 18 μm, the polyamic acid solution Aa prepared in Synthesis Example 1 was uniformly applied so that the thickness after curing became about 25 μm. The solvent was removed by heating and drying at 120 ° C. Then, stepwise heat treatment was performed from 120 ° C. to 360 ° C., and fluorene imidization was completed. The obtained metal-clad laminate was subjected to etching to remove copper foil using an aqueous solution of ferric chloride to obtain a resin film. The polyimide constituting the obtained resin film is non-thermoplastic.

求出所得的樹脂膜的熱膨脹係數、玻璃轉移溫度、介電常數及介電正切。將各測定結果表示於表3。 The thermal expansion coefficient, glass transition temperature, dielectric constant, and dielectric tangent of the obtained resin film were determined. Each measurement result is shown in Table 3.

[實施例2~實施例4、參考例1~參考例3] [Example 2 to Example 4, Reference Example 1 to Reference Example 3]

除了使用表3所示的聚醯胺酸溶液以外，以與實施例1相同的方式，獲得實施例2~實施例4及參考例1~參考例3的樹脂膜。求出所得的樹脂膜的熱膨脹係數、玻璃轉移溫度、介電常數及介電正切。將各測定結果表示於表3。 The resin films of Examples 2 to 4 and Reference Examples 1 to 3 were obtained in the same manner as in Example 1 except that the polyamic acid solution shown in Table 3 was used. The thermal expansion coefficient, glass transition temperature, dielectric constant, and dielectric tangent of the obtained resin film were determined. Each measurement result is shown in Table 3.

[表3] [table 3]

[實施例5] [Example 5]

在厚度為12μm的電解銅箔的單面(表面粗糙度Rz；1.39μm)，以硬化後的厚度成為約2μm~3μm的方式均勻地塗佈聚醯胺酸溶液A-h後，在120℃下進行加熱乾燥而除去溶劑。繼而，在其上以硬化後的厚度成為約25μm的方式均勻地塗佈聚醯胺酸溶液A-a，在120℃下進行加熱乾燥而除去溶劑。繼而，在其上以硬化後的厚度成為約2μm~3μm的方式均勻地塗佈聚醯胺酸溶液A-h後，在120℃下進行加熱乾燥而除去溶劑。如此，形成3層的聚醯胺酸層後，自120℃起進行階段性的熱處理至360℃為止，並完成醯亞胺化，而獲得覆金屬積層板。 A polyamic acid solution Ah was uniformly coated on one side (surface roughness Rz; 1.39 μm) of the electrolytic copper foil having a thickness of 12 μm so that the thickness after curing became about 2 μm to 3 μm, and then performed at 120 ° C. The solvent was removed by heating and drying. Then, the polyamic acid solution A-a was uniformly applied so that the thickness after hardening became about 25 micrometers, and it heat-dried at 120 degreeC, and the solvent was removed. Then, the polyamic acid solution A-h was uniformly applied so that the thickness after curing became about 2 μm to 3 μm, and the solvent was removed by heating and drying at 120 ° C. In this way, after forming three polyamic acid layers, stepwise heat treatment was performed from 120 ° C. to 360 ° C., and the imidization was completed to obtain a metal-clad laminate.

[實施例6] [Example 6]

代替實施例5中的聚醯胺酸溶液A-a，而使用聚醯胺酸溶液A-b，除此以外，以與實施例5相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 5 except that the polyamic acid solution A-b was used instead of the polyamino acid solution A-b in Example 5.

[實施例7] [Example 7]

代替實施例5中的聚醯胺酸溶液A-a，而使用聚醯胺酸溶液A-c，除此以外，以與實施例5相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 5 except that the polyamine solution A-c was used instead of the polyamino acid solution A-c in Example 5.

[實施例8] [Example 8]

代替實施例5中的聚醯胺酸溶液A-a，而使用聚醯胺酸溶液A-d，除此以外，以與實施例5相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 5 except that the polyamic acid solution A-d was used instead of the polyamino acid solution A-d in Example 5.

根據以上結果確認到，藉由使用在二胺成分中含有特定比率的DTBAB的聚醯胺酸及聚醯亞胺而形成樹脂膜，而可將CTE抑制在低的水準。因此揭示，藉由使用本發明的聚醯胺酸及聚醯亞胺作為絕緣層材料，而可提供抑制翹曲的產生、並且傳輸特性良好的FPC等電路基板。 From the above results, it was confirmed that CTE can be suppressed to a low level by forming a resin film by using a polyamic acid and a polyimide containing DTBAB in a specific ratio in the diamine component. Therefore, it was revealed that by using the polyamic acid and polyimide of the present invention as the material of the insulating layer, it is possible to provide a circuit board such as an FPC that suppresses the occurrence of warpage and has good transmission characteristics.

[合成例A-1] [Synthesis example A-1]

在氮氣環境下，在加入攪拌子的三口燒瓶中，添加15g的2,5-雙(1,1-二甲基乙基)對苯二酚(67.5mmol)而溶解於202.5ml的DMF中，在所得的溶液中添加20.5g的碳酸鉀(148.4mmol)及23.4g的4-氟硝基苯(148.4mmol)，並在100℃下進行6小時反應。在特定時間後停止反應並冷卻後，注入至純化水中藉由氯仿萃取後，自有機層除去溶劑。藉由利用氯仿/己烷的再結晶進行純化，而獲得化合物A。 Under a nitrogen atmosphere, in a three-necked flask equipped with a stirrer, 15 g of 2,5-bis (1,1-dimethylethyl) hydroquinone (67.5 mmol) was added and dissolved in 202.5 ml of DMF. To the obtained solution, 20.5 g of potassium carbonate (148.4 mmol) and 23.4 g of 4-fluoronitrobenzene (148.4 mmol) were added, and the reaction was performed at 100 ° C for 6 hours. The reaction was stopped and cooled after a specific time, and then poured into purified water and extracted with chloroform, and then the solvent was removed from the organic layer. The compound A was obtained by purification by recrystallization with chloroform / hexane.

[合成例A-2] [Synthesis example A-2]

在氮氣環境下，在加入攪拌子的三口燒瓶中，量取9.01g的鐵粉(161.5mmol)，添加53.8ml的飽和氯化銨水溶液。在將三口燒瓶加熱至110℃後，藉由滴液漏斗在三口燒瓶中滴加溶解於140ml的DMF中的25g的化合物A(53.8mmol)，然後在120℃下反應3小時。在反應剛結束後，藉由矽藻土過濾除去鐵粉，藉 由沸騰的DMF將過濾殘渣充分清洗。將濾液冷卻至0℃，藉由大量的純化水清洗析出物後，進行乾燥而獲得二胺A。 In a three-necked flask equipped with a stirrer under a nitrogen environment, 9.01 g of iron powder (161.5 mmol) was weighed out, and 53.8 ml of a saturated ammonium chloride aqueous solution was added. After the three-necked flask was heated to 110 ° C., 25 g of Compound A (53.8 mmol) dissolved in 140 ml of DMF was added dropwise to the three-necked flask through a dropping funnel, and then reacted at 120 ° C. for 3 hours. Immediately after the reaction, iron powder was removed by filtration through diatomaceous earth. The filtering residue was thoroughly washed with boiling DMF. The filtrate was cooled to 0 ° C, the precipitate was washed with a large amount of purified water, and then dried to obtain diamine A.

[合成例B-1、合成例B-2] [Synthesis Example B-1, Synthesis Example B-2]

代替2,5-雙(1,1-二甲基乙基)對苯二酚，而使用2,3-雙(1,1-二甲基乙基)對苯二酚，除此以外，以與合成例A-1、合成例A-2相同的方式，獲得二胺B。 Instead of 2,5-bis (1,1-dimethylethyl) hydroquinone and 2,3-bis (1,1-dimethylethyl) hydroquinone, in addition, In the same manner as in Synthesis Example A-1 and Synthesis Example A-2, diamine B was obtained.

[合成例C-1、合成例C-2] [Synthesis Example C-1, Synthesis Example C-2]

代替2,5-雙(1,1-二甲基乙基)對苯二酚，而使用2,5-雙(1-甲基丙基)對苯二酚，除此以外，以與合成例A-1、合成例A-2相同的方式，獲得二胺C。 Instead of 2,5-bis (1,1-dimethylethyl) hydroquinone, 2,5-bis (1-methylpropyl) hydroquinone was used. In the same manner as in A-1 and Synthesis Example A-2, diamine C was obtained.

[合成例D-1、合成例D-2] [Synthesis Example D-1, Synthesis Example D-2]

代替2,5-雙(1,1-二甲基乙基)對苯二酚，而使用2,6-雙(1,1-二甲基乙基)對苯二酚，除此以外，以與合成例A-1、合成例A-2相同的方式，獲得二胺D。 Instead of 2,5-bis (1,1-dimethylethyl) hydroquinone and 2,6-bis (1,1-dimethylethyl) hydroquinone, in addition, In the same manner as in Synthesis Example A-1 and Synthesis Example A-2, diamine D was obtained.

[合成例E-1、合成例E-2] [Synthesis Example E-1, Synthesis Example E-2]

代替2,5-雙(1,1-二甲基乙基)對苯二酚，而使用2,2-雙(2,2-二甲基乙基)對苯二酚，除此以外，以與合成例A-1、合成例A-2相同的方式，獲得二胺E。 Instead of 2,5-bis (1,1-dimethylethyl) hydroquinone and 2,2-bis (2,2-dimethylethyl) hydroquinone, in addition, In the same manner as in Synthesis Example A-1 and Synthesis Example A-2, diamine E was obtained.

[合成例F-1、合成例F-2] [Synthesis Example F-1, Synthesis Example F-2]

代替2,5-雙(1,1-二甲基乙基)對苯二酚，而使用2,5-雙(1-甲基庚基)對苯二酚，除此以外，以與合成例A-1、合成例A-2相同的方式，獲得二胺F。 Instead of 2,5-bis (1,1-dimethylethyl) hydroquinone, 2,5-bis (1-methylheptyl) hydroquinone was used in addition to the synthesis example In the same manner as in A-1 and Synthesis Example A-2, diamine F was obtained.

[合成例9] [Synthesis example 9]

在氮氣流下，在300ml的可分離式燒瓶中，投入3.567g的二胺A(0.0043莫耳)、8.045g的m-TB(0.0387莫耳)及127.5g的DMAc，在室溫下攪拌使其溶解。繼而，添加2.746g的BPDA(0.0426莫耳)後，在室溫下繼續攪拌3小時進行聚合反應，而獲得聚醯胺酸溶液B-a。聚醯胺酸溶液B-a的重量平均分子量為141,000。 Under a nitrogen stream, put 3.567 g of diamine A (0.0043 mol), 8.045 g of m-TB (0.0387 mol), and 127.5 g of DMAc into a separable flask of 300 ml. Stir at room temperature Dissolve. Next, after adding 2.746 g of BPDA (0.0426 mol), stirring was continued at room temperature for 3 hours to perform a polymerization reaction, thereby obtaining a polyamic acid solution B-a. The weight average molecular weight of the polyamic acid solution B-a was 141,000.

[合成例10~合成例48] [Synthesis example 10 to synthesis example 48]

除了設為表4~表11所示的原料組成外，以與合成例9相同的方式，製備聚醯胺酸溶液B-b~聚醯胺酸溶液B-i、聚醯胺酸溶液C-a~聚醯胺酸溶液C-i、聚醯胺酸溶液D-a~聚醯胺酸溶液D-f、聚醯胺酸溶液E-a~聚醯胺酸溶液E-f、聚醯胺酸溶液F-a~聚醯胺酸溶液F-f、聚醯胺酸溶液G-a~聚醯胺酸溶液G-c、聚醯胺酸溶液H-a。 A polyamic acid solution Bb to a polyamic acid solution Bi and a polyamino acid solution Ca to a polyamino acid were prepared in the same manner as in Synthesis Example 9 except that the raw material compositions shown in Tables 4 to 11 were used. Solution Ci, polyamic acid solution Da ~ polyamic acid solution Df, polyamic acid solution Ea ~ polyamic acid solution Ef, polyamino acid solution Fa ~ polyamic acid solution Ff, polyamino acid solution Ga ~ polyacid solution Gc, polyacid solution Ha.

[實施例9] [Example 9]

在厚度為12μm的電解銅箔的單面(表面粗糙度Rz；1.06μm)，以硬化後的厚度成為約25μm的方式均勻地塗佈合成例9中所製備的聚醯胺酸溶液B-a後，在120℃下進行加熱乾燥而除去溶劑。繼而，自120℃起進行熱處理至360℃為止，而完成醯亞胺化。對所得的覆金屬積層板，使用氯化鐵水溶液蝕刻除去銅箔，而獲得樹脂膜。 On one side (surface roughness Rz; 1.06 μm) of the electrolytic copper foil having a thickness of 12 μm, the polyamic acid solution Ba prepared in Synthesis Example 9 was uniformly applied so that the thickness after curing became about 25 μm. The solvent was removed by heating and drying at 120 ° C. Then, heat treatment was performed from 120 ° C to 360 ° C to complete the imidization. The obtained metal-clad laminate was subjected to etching to remove copper foil using an aqueous solution of ferric chloride to obtain a resin film.

求出所得的樹脂膜的熱膨脹係數(CTE)、介電常數。將各測定結果表示於表12。 The thermal expansion coefficient (CTE) and the dielectric constant of the obtained resin film were determined. Table 12 shows the measurement results.

[實施例10~實施例47] [Example 10 to Example 47]

除了使用表12~表18所示的聚醯胺酸溶液以外，以與實施例9相同的方式，獲得實施例10~實施例47的樹脂膜。求出所得的樹脂膜的熱膨脹係數(CTE)、介電常數。將各測定結果表示於表12~表18。 The resin films of Examples 10 to 47 were obtained in the same manner as in Example 9 except that the polyamidic acid solutions shown in Tables 12 to 18 were used. The thermal expansion coefficient (CTE) and the dielectric constant of the obtained resin film were determined. The measurement results are shown in Tables 12 to 18.

[實施例48] [Example 48]

在厚度為12μm的電解銅箔的單面(表面粗糙度Rz；1.39μm)，以硬化後的厚度成為約2μm~3μm的方式均勻地塗佈聚醯胺酸溶液H-a後，在120℃下進行加熱乾燥而除去溶劑。繼而，在其上以硬化後的厚度成為約25μm的方式均勻地塗佈聚醯胺酸溶液B-a，在120℃下進行加熱乾燥而除去溶劑。繼而，在其上以硬化後的厚度成為約2μm~3μm的方式均勻地塗佈聚醯胺酸溶液H-a後，在120℃下進行加熱乾燥而除去溶劑。如此，形成3層的聚醯胺酸層後，自120℃起進行階段性的熱處理至360℃為止，並完成醯亞胺化，而獲得覆金屬積層板。 A polyamic acid solution Ha was uniformly coated on one side (surface roughness Rz; 1.39 μm) of the electrolytic copper foil having a thickness of 12 μm so that the thickness after curing became about 2 μm to 3 μm, and then performed at 120 ° C. The solvent was removed by heating and drying. Then, the polyamic acid solution B-a was uniformly applied so that the thickness after hardening became about 25 micrometers, and it heat-dried at 120 degreeC, and the solvent was removed. Then, the polyamic acid solution H-a was uniformly applied so that the thickness after curing became about 2 μm to 3 μm, and then the solvent was removed by heating and drying at 120 ° C. In this way, after forming three polyamic acid layers, stepwise heat treatment was performed from 120 ° C. to 360 ° C., and the imidization was completed to obtain a metal-clad laminate.

[實施例49] [Example 49]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液B-b，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48, except that the polyamine solution B-b was used instead of the polyamino acid solution B-a in Example 48.

[實施例50] [Example 50]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液B-c，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution B-c was used instead of the polyamino acid solution B-c in Example 48.

[實施例51] [Example 51]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液B-d，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamine solution B-d was used instead of the polyamino acid solution B-a in Example 48.

[實施例52] [Example 52]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液B-e，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution B-a was used instead of the polyamino acid solution B-e in Example 48.

[實施例53] [Example 53]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液B-f，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamine solution B-f was used instead of the polyamino acid solution B-a in Example 48.

[實施例54] [Example 54]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液B-g，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamine solution B-g was used instead of the polyamino acid solution B-g in Example 48.

[實施例55] [Example 55]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液B-h，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamine solution B-h was used instead of the polyamino acid solution B-h in Example 48.

[實施例56] [Example 56]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液B-i，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution B-i was used instead of the polyamino acid solution B-i in Example 48.

[實施例57] [Example 57]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液C-a，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamine solution C-a was used instead of the polyamino acid solution B-a in Example 48.

[實施例58] [Example 58]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液C-b，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamine solution C-b was used instead of the polyamino acid solution B-a in Example 48.

[實施例59] [Example 59]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液C-c，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamine solution C-c was used instead of the polyamino acid solution B-a in Example 48.

[實施例60] [Example 60]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液C-d，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamine solution C-d was used instead of the polyamino acid solution B-a in Example 48.

[實施例61] [Example 61]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液C-e，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamine solution C-e was used instead of the polyamino acid solution B-a in Example 48.

[實施例62] [Example 62]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液C-f，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamine solution C-f was used instead of the polyamino acid solution B-a in Example 48.

[實施例63] [Example 63]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液C-g，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamine solution C-g was used instead of the polyamino acid solution B-a in Example 48.

[實施例64] [Example 64]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液C-h，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamine solution C-h was used instead of the polyamino acid solution B-a in Example 48.

[實施例65] [Example 65]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液 C-i，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 Instead of the polyamine solution B-a in Example 48, a polyamino acid solution was used Except for C-i, in the same manner as in Example 48, a metal-clad laminate was obtained.

[實施例66] [Example 66]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液D-a，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48, except that the polyamic acid solution D-a was used instead of the polyamic acid solution B-a in Example 48.

[實施例67] [Example 67]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液D-b，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution D-b was used instead of the polyamino acid solution B-a in Example 48.

[實施例68] [Example 68]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液D-c，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution D-c was used instead of the polyamic acid solution B-a in Example 48.

[實施例69] [Example 69]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液D-d，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution D-d was used instead of the polyamino acid solution B-a in Example 48.

[實施例70] [Example 70]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液D-e，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamine solution D-e was used instead of the polyamino acid solution B-a in Example 48.

[實施例71] [Example 71]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液D-f，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution D-f was used instead of the polyamino acid solution B-a in Example 48.

[實施例72] [Example 72]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液E-a，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48, except that the polyamic acid solution E-a was used instead of the polyamino acid solution B-a in Example 48.

[實施例73] [Example 73]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液E-b，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamine solution E-b was used instead of the polyamino acid solution B-a in Example 48.

[實施例74] [Example 74]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液E-c，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamine solution E-c was used instead of the polyamino acid solution B-a in Example 48.

[實施例75] [Example 75]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液E-d，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamine solution E-d was used instead of the polyamino acid solution B-a in Example 48.

[實施例76] [Example 76]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液E-e，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamine solution E-e was used instead of the polyamino acid solution B-a in Example 48.

[實施例77] [Example 77]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液E-f，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamine solution E-f was used instead of the polyamino acid solution B-a in Example 48.

[實施例78] [Example 78]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液F-a，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamine solution F-a was used instead of the polyamino acid solution B-a in Example 48.

[實施例79] [Example 79]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液F-b，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamine solution F-b was used instead of the polyamino acid solution B-a in Example 48.

[實施例80] [Example 80]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液F-c，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamine solution F-c was used instead of the polyamino acid solution B-a in Example 48.

[實施例81] [Example 81]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液F-d，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamine solution F-d was used instead of the polyamino acid solution B-a in Example 48.

[實施例82] [Example 82]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液F-e，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamine solution F-e was used instead of the polyamino acid solution B-a in Example 48.

[實施例83] [Example 83]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液F-f，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamine solution F-f was used instead of the polyamino acid solution B-a in Example 48.

[實施例84] [Example 84]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液G-a，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamine solution G-a was used instead of the polyamino acid solution B-a in Example 48.

[實施例85] [Example 85]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液G-b，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution G-b was used instead of the polyamic acid solution B-a in Example 48.

[實施例86] [Example 86]

代替實施例48中的聚醯胺酸溶液B-a，而使用聚醯胺酸溶液G-c，除此以外，以與實施例48相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamine solution G-c was used instead of the polyamino acid solution B-a in Example 48.

[合成例G-1] [Synthesis example G-1]

在氮氣環境下，在加入攪拌子的三口燒瓶中，添加19.43g 的2,5-二丙基苯-1,4-二醇(0.10莫耳)而溶解於300ml的DMF中，在所得的溶液中添加30.40g的碳酸鉀(0.22莫耳)及34.66g的1-氯-4-硝基苯(0.22莫耳)在100℃下進行6小時反應。在特定時間後停止反應並冷卻後，注入至純化水中藉由氯仿萃取後，自有機層除去溶劑。藉由利用氯仿/己烷的再結晶進行純化，而獲得化合物G。 Under a nitrogen atmosphere, add 19.43 g to a three-necked flask with a stirrer. 2,5-dipropylbenzene-1,4-diol (0.10 mole) was dissolved in 300 ml of DMF, and 30.40 g of potassium carbonate (0.22 mole) and 34.66 g of 1 were added to the obtained solution. -Chloro-4-nitrobenzene (0.22 moles) was reacted at 100 ° C for 6 hours. The reaction was stopped and cooled after a specific time, and then poured into purified water and extracted with chloroform, and then the solvent was removed from the organic layer. The compound G was obtained by purification by recrystallization with chloroform / hexane.

[合成例G-2] [Synthesis example G-2]

在氮氣環境下，在加入攪拌子的三口燒瓶中，量取11.73g的鐵粉(0.21莫耳)，添加70ml的飽和氯化銨水溶液。將三口燒瓶加熱至110℃後，藉由滴液漏斗在三口燒瓶中滴加溶解於140ml的DMF中的30.55g的化合物A(0.07莫耳)，然後在120℃下反應3小時。在反應剛結束後，藉由矽藻土過濾除去鐵粉，藉由沸騰的DMF將過濾殘渣充分清洗。將濾液冷卻至0℃，藉由大量的純化水清洗析出物後，進行乾燥而獲得二胺G。 Under a nitrogen environment, 11.73 g of iron powder (0.21 mol) was weighed into a three-necked flask equipped with a stirrer, and 70 ml of a saturated ammonium chloride aqueous solution was added. After the three-necked flask was heated to 110 ° C., 30.55 g of Compound A (0.07 mol) dissolved in 140 ml of DMF was added dropwise to the three-necked flask through a dropping funnel, and then reacted at 120 ° C. for 3 hours. Immediately after the reaction, the iron powder was removed by filtration through diatomaceous earth, and the filtration residue was sufficiently washed with boiling DMF. The filtrate was cooled to 0 ° C, and the precipitate was washed with a large amount of purified water, and then dried to obtain diamine G.

[合成例H-1、合成例H-2] [Synthesis Example H-1, Synthesis Example H-2]

代替2,5-二丙基苯-1,4-二醇，而使用2,5-二甲基苯-1,4-二醇，除此以外，以與合成例G-1、合成例G-2相同的方式，獲得化合物H、二胺H。 Instead of 2,5-dipropylbenzene-1,4-diol, 2,5-dimethylbenzene-1,4-diol was used, and in addition to Synthesis Example G-1 and Synthesis Example G, -2 In the same manner, compound H and diamine H were obtained.

[合成例I-1、合成例I-2] [Synthesis Example I-1, Synthesis Example I-2]

代替2,5-二丙基苯-1,4-二醇，而使用2,5-二丁基苯-1,4-二醇，除此以外，以與合成例G-1、合成例G-2相同的方式，獲得化合物I、二胺I。 Instead of 2,5-dipropylbenzene-1,4-diol, 2,5-dibutylbenzene-1,4-diol was used, and it was the same as in Synthesis Example G-1 and Synthesis Example G -2 In the same manner, Compound I and Diamine I were obtained.

[合成例J-1、合成例J-2] [Synthesis Example J-1, Synthesis Example J-2]

代替2,5-二丙基苯-1,4-二醇，而使用四甲基對苯二酚，除此以外，以與合成例G-1、合成例G-2相同的方式，獲得化合物J、二胺J。 A compound was obtained in the same manner as in Synthesis Example G-1 and Synthesis Example G-2 except that tetramethylhydroquinone was used instead of 2,5-dipropylbenzene-1,4-diol. J 、 Diamine J.

[合成例K-1、合成例K-2] [Synthesis Example K-1, Synthesis Example K-2]

代替1-氯-4-硝基苯，而使用1-氯-3-硝基苯，除此以外，以與合成例G-1、合成例G-2相同的方式，獲得化合物K、二胺K。 Compound K and diamine were obtained in the same manner as in Synthesis Example G-1 and Synthesis Example G-2, except that 1-chloro-3-nitrobenzene was used instead of 1-chloro-4-nitrobenzene. K.

[合成例49] [Synthesis Example 49]

在氮氣流下，在300ml的可分離式燒瓶中，投入3.567g的二胺G(0.0095莫耳)、8.045g的m-TB(0.0379莫耳)及127.5g的DMAc，在室溫下攪拌使其溶解。繼而，添加2.746g的BPDA(0.0093莫耳)及8.142g的PMDA(0.0373莫耳)後，在室溫下繼續攪拌3小時進行聚合反應，而獲得聚醯胺酸溶液I-a。聚醯胺酸溶液I-a的重量平均分子量為141,000。 Under a nitrogen stream, put 3.567 g of diamine G (0.0095 mol), 8.045 g of m-TB (0.0379 mol), and 127.5 g of DMAc into a separable flask of 300 ml, and stir at room temperature. Dissolve. Then, 2.746 g of BPDA (0.0093 mol) and 8.142 g of PMDA (0.0373 mol) were added, and then stirring was continued at room temperature for 3 hours to perform a polymerization reaction to obtain a polyamic acid solution I-a. The weight average molecular weight of the polyamic acid solution I-a was 141,000.

[合成例50~合成例56] [Synthesis example 50 to synthesis example 56]

除了設為表19及表20所示的原料組成以外，以與合成例49相同的方式，製備聚醯胺酸溶液I-b、聚醯胺酸溶液I-c、聚醯胺酸溶液J-a、聚醯胺酸溶液K-a、聚醯胺酸溶液L-a、聚醯胺酸溶液M-a、聚醯胺酸溶液N-a。 A polyamic acid solution Ib, a polyamic acid solution Ic, a polyamino acid solution Ja, and a polyamino acid were prepared in the same manner as in Synthesis Example 49 except that the raw material compositions shown in Tables 19 and 20 were used. Solution Ka, polyamic acid solution La, polyamino acid solution Ma, polyamino acid solution Na.

[實施例87] [Example 87]

在厚度為12μm的電解銅箔的單面(表面粗糙度Rz；106μm)，以硬化後的厚度成為約25μm的方式均勻地塗佈合成例49中所製備的聚醯胺酸溶液I-a後，在120℃下進行加熱乾燥而除去溶劑。繼而，自120℃起進行熱處理至360℃為止，而完成醯亞胺 化。對所得的覆金屬積層板，使用氯化鐵水溶液蝕刻除去銅箔，而獲得樹脂膜。 A polyamic acid solution Ia prepared in Synthesis Example 49 was uniformly coated on one side (surface roughness Rz; 106 μm) of the electrolytic copper foil having a thickness of 12 μm so that the thickness after curing became about 25 μm. The solvent was removed by heating and drying at 120 ° C. Then, heat treatment was performed from 120 ° C to 360 ° C to complete the imine. Into. The obtained metal-clad laminate was subjected to etching to remove copper foil using an aqueous solution of ferric chloride to obtain a resin film.

求出所得的樹脂膜的熱膨脹係數(CTE)、介電常數及介電正切。將各測定結果表示於表21。 The thermal expansion coefficient (CTE), dielectric constant, and dielectric tangent of the obtained resin film were determined. Each measurement result is shown in Table 21.

[實施例88~實施例93] [Example 88 to Example 93]

除了使用表21所示的聚醯胺酸溶液以外，以與實施例87相同的方式，獲得實施例88~實施例93的樹脂膜。求出所得的樹脂膜的熱膨脹係數(CTE)、介電常數及介電正切。將各測定結果表示於表21。 The resin films of Examples 88 to 93 were obtained in the same manner as in Example 87 except that the polyamic acid solution shown in Table 21 was used. The thermal expansion coefficient (CTE), dielectric constant, and dielectric tangent of the obtained resin film were determined. Each measurement result is shown in Table 21.

根據以上結果確認到，藉由使用在二胺成分中含有特定比率的二胺化合物(i)的聚醯胺酸及聚醯亞胺而形成樹脂膜，而可將CTE抑制在低的水準，並謀求低介電常數化。因此揭示，藉由使用本發明的聚醯胺酸及聚醯亞胺作為絕緣層材料，而可提供抑制翹曲的產生、並且傳輸特性良好的FPC等電路基板。 Based on the above results, it was confirmed that CTE can be suppressed to a low level by forming a resin film by using polyamidoacid and polyamidoimide containing a diamine compound (i) in a specific ratio in the diamine component, and To reduce the dielectric constant. Therefore, it was revealed that by using the polyamic acid and polyimide of the present invention as the material of the insulating layer, it is possible to provide a circuit board such as an FPC that suppresses the occurrence of warpage and has good transmission characteristics.

[實施例94] [Example 94]

在厚度為12μm的電解銅箔的單面(表面粗糙度Rz；1.39μm)，以硬化後的厚度成為約2μm~3μm的方式均勻地塗佈聚醯胺酸溶液N-a後，在120℃下進行加熱乾燥而除去溶劑。繼而，在其上以硬化後的厚度成為約25μm的方式均勻地塗佈聚醯胺酸溶液I-a，在120℃下進行加熱乾燥而除去溶劑。繼而，在其上以硬化後的厚度成為約2μm~3μm的方式均勻地塗佈聚醯胺酸溶液N-a後，在120℃下進行加熱乾燥而除去溶劑。如此，在形成3層的聚醯胺酸層後，自120℃起進行階段性的熱處理至360℃為止，並完成醯亞胺化，而獲得覆金屬積層板。 A polyamic acid solution Na was uniformly coated on one side (surface roughness Rz; 1.39 μm) of the electrolytic copper foil having a thickness of 12 μm so that the thickness after curing became about 2 μm to 3 μm, and then performed at 120 ° C. The solvent was removed by heating and drying. Then, the polyamic acid solution I-a was uniformly applied so that the thickness after hardening became about 25 micrometers, and it heat-dried at 120 degreeC, and the solvent was removed. Then, the polyamic acid solution N-a was uniformly applied so that the thickness after curing became about 2 μm to 3 μm, followed by heating and drying at 120 ° C. to remove the solvent. In this way, after forming three polyamidic acid layers, stepwise heat treatment was performed from 120 ° C. to 360 ° C., and the imidization was completed to obtain a metal-clad laminate.

[實施例95] [Example 95]

代替實施例94中的聚醯胺酸溶液I-a，而使用聚醯胺酸溶液I-b，除此以外，以與實施例94相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 94 except that the polyamic acid solution I-a was used instead of the polyamino acid solution I-b in Example 94.

[實施例96] [Example 96]

代替實施例94中的聚醯胺酸溶液I-a，而使用聚醯胺酸溶液I-c，除此以外，以與實施例94相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 94 except that the polyamine solution I-c was used instead of the polyamino acid solution I-c in Example 94.

[實施例97] [Example 97]

代替實施例94中的聚醯胺酸溶液I-a，而使用聚醯胺酸溶液J-a，除此以外，以與實施例94相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 94 except that the polyamine solution I-a in Example 94 was used instead of the polyamino acid solution J-a.

[實施例98] [Example 98]

代替實施例94中的聚醯胺酸溶液I-a，而使用聚醯胺酸溶液K-a，除此以外，以與實施例94相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 94 except that the polyamic acid solution K-a was used instead of the polyamino acid solution I-a in Example 94.

[實施例99] [Example 99]

代替實施例94中的聚醯胺酸溶液I-a，而使用聚醯胺酸溶液L-a，除此以外，以與實施例94相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 94 except that the polyamine solution L-a was used instead of the polyamino acid solution I-a in Example 94.

[實施例100] [Example 100]

代替實施例94中的聚醯胺酸溶液I-a，而使用聚醯胺酸溶液M-a，除此以外，以與實施例94相同的方式，獲得覆金屬積層板。 A metal-clad laminate was obtained in the same manner as in Example 94 except that the polyamine solution M-a was used instead of the polyamino acid solution I-a in Example 94.

以上，出於例示的目的詳細地說明了本發明的實施形態，但本發明並不受所述實施形態的制約，可進行各種變形。 As mentioned above, although the embodiment of this invention was described in detail for the purpose of illustration, this invention is not limited to the said embodiment, and various deformation | transformation are possible.

本國際申請案主張基於2014年9月30日提出申請的日本專利申請案2014-202470號的優先權，並將所述申請案的全部 內容引用至本文中。 This international application claims priority based on Japanese Patent Application No. 2014-202470 filed on September 30, 2014, and claims all of the applications The content is incorporated herein.

Claims (7)

一種聚醯胺酸，其使二胺成分、與包含四羧酸酐的酸酐成分反應而得，且其特徵在於：相對於全部二胺成分，所述二胺成分在10莫耳%~60莫耳%的範圍內包含下述通式(i)；[式中，R表示碳數1~8的烷基，p表示1~4的數；此處，在p為2以上時，R可獨立地取不同的碳數]所示的二胺化合物，且相對於全部二胺成分，所述二胺成分在40莫耳%~90莫耳%的範圍內包含選自由2,2'-二甲基-4,4'-二胺基聯苯(m-TB)、2,2'-二乙基-4,4'-二胺基聯苯(m-EB)及2,2'-正丙基-4,4'-二胺基聯苯(m-NPB)所組成的組群中的一種以上的二胺化合物；相對於全部酸酐成分，所述酸酐成分在50莫耳%~100莫耳%的範圍內包含選自由均苯四羧酸二酐(PMDA)及3,3',4,4'-聯苯四羧酸二酐(BPDA)所組成的組群中的一種以上的四羧酸酐。A polyamidic acid, which is obtained by reacting a diamine component with an acid anhydride component containing a tetracarboxylic anhydride, and is characterized in that the diamine component is 10 mol% to 60 mol relative to all the diamine components. The range of% includes the following general formula (i); [Wherein R represents an alkyl group having 1 to 8 carbon atoms, and p represents a number of 1 to 4; here, when p is 2 or more, R can independently take a different carbon number] In addition, the diamine component is selected from the group consisting of 2,2'-dimethyl-4,4'-diaminobiphenyl (m -TB), 2,2'-diethyl-4,4'-diaminobiphenyl (m-EB) and 2,2'-n-propyl-4,4'-diaminobiphenyl (m -NPB), one or more diamine compounds; the acid anhydride component is included in a range of 50 mol% to 100 mol% with respect to all acid anhydride components, and is selected from the group consisting of pyromellitic dianhydride (PMDA) and one or more tetracarboxylic anhydrides in a group consisting of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA). 如申請專利範圍第1項所述的聚醯胺酸，其中所述通式(i)中，R表示碳數4~8的支鏈烷基，p表示1~2的數。The polyamidic acid according to item 1 of the scope of the patent application, wherein in the general formula (i), R represents a branched alkyl group having 4 to 8 carbon atoms, and p represents a number of 1 to 2. 如申請專利範圍第1項所述的聚醯胺酸，其中所述通式(i)中，R表示碳數1~4的直鏈烷基，p表示1~4的數；並且相對於全部二胺成分，所述二胺成分在15莫耳%~45莫耳%的範圍內包含所述通式(i)所示的二胺化合物。The polyamidic acid according to item 1 of the scope of the patent application, wherein in the general formula (i), R represents a linear alkyl group having 1 to 4 carbon atoms, and p represents a number of 1 to 4; A diamine component containing the diamine compound represented by the general formula (i) in a range of 15 mol% to 45 mol%. 一種聚醯亞胺，其將如申請專利範圍第1項至第3項中任一項所述的聚醯胺酸進行醯亞胺化而得。A polyimide is obtained by subjecting a polyimide acid according to any one of the scope of claims 1 to 3 of the patent application to imidization. 一種樹脂膜，其包含將如申請專利範圍第1項至第3項中任一項所述的聚醯胺酸進行醯亞胺化而得的聚醯亞胺。A resin film comprising a polyimide obtained by subjecting a polyimide to a polyimide according to any one of the scope of claims 1 to 3 of the patent application. 如申請專利範圍第5項所述的樹脂膜，其中熱膨脹係數處於10×10-6(1/K)~30×10-6(1/K)的範圍內。The resin film according to item 5 of the patent application range, wherein the thermal expansion coefficient is in a range of 10 × 10 -6 (1 / K) to 30 × 10 -6 (1 / K). 一種覆金屬積層板，其具有包含如申請專利範圍第4項所述的聚醯亞胺的樹脂層。A metal-clad laminated board having a resin layer comprising polyimide as described in item 4 of the scope of patent application.
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