TW202138435A - Resin composition, manufacturing method thereof, resin film, and metal-clad laminate wherein the resin composition includes a polyimide and a filler containing a liquid crystal polymer - Google Patents
Resin composition, manufacturing method thereof, resin film, and metal-clad laminate wherein the resin composition includes a polyimide and a filler containing a liquid crystal polymer Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- 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
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/036—Multilayers with layers of different types
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- 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
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
Abstract
Description
本發明是有關於一種例如作為電路基板材料有用的樹脂膜及覆金屬積層板、用於其的樹脂組成物及其製造方法。The present invention relates to, for example, a resin film useful as a material for a circuit board, a metal-clad laminate, a resin composition used therefor, and a manufacturing method thereof.
柔性電路基板（柔性印刷電路板（Flexible Printed Circuit Board，FPC））即便在有限的空間內也能夠進行立體且高密度的安裝，因此，其用途擴大到電子設備的可動部分的布線、或電纜、連接器等零件，並被搭載於很多領域的設備上。伴隨於此，使用FPC的環境的多樣化進展，所要求的性能也提高。Flexible printed circuit boards (Flexible Printed Circuit Boards (FPC)) can be mounted in a three-dimensional and high-density manner even in a limited space. Therefore, their use has expanded to wiring or cables for moving parts of electronic equipment. , Connectors and other parts, and are mounted on equipment in many fields. Along with this, the diversification of the environment in which FPC is used has progressed, and the required performance has also improved.
例如，在資訊處理或資訊通信中，為了傳輸和/或處理大容量資訊，而採取提高傳輸頻率的措施，並要求通過改善電路基板的絕緣樹脂層的介質特性來降低傳輸損失。作為改善電路基板的絕緣樹脂層的介電特性的技術，提出有在熱塑性樹脂或熱硬化性樹脂中調配液晶性聚合物粒子（專利文獻1）。其中，專利文獻1中，沒有作為熱硬化性樹脂的環氧樹脂以外的實施例，未對熱塑性樹脂進行詳細的研究。For example, in information processing or information communication, in order to transmit and/or process large-capacity information, measures are taken to increase the transmission frequency, and it is required to reduce the transmission loss by improving the dielectric properties of the insulating resin layer of the circuit substrate. As a technique for improving the dielectric properties of the insulating resin layer of the circuit board, it has been proposed to mix liquid crystal polymer particles in a thermoplastic resin or a thermosetting resin (Patent Document 1). Among them, in Patent Document 1, there are no examples other than epoxy resins as thermosetting resins, and no detailed studies have been made on thermoplastic resins.
另外，因伴隨高密度安裝的微細化的進展，而對電路基板的絕緣樹脂層也要求高的尺寸穩定性。作為用於改善電路基板的絕緣樹脂層的尺寸穩定性的技術，提出有調配有機填料或無機填料（專利文獻2～專利文獻4）。 [現有技術文獻] [專利文獻]In addition, due to the progress of miniaturization accompanying high-density mounting, the insulating resin layer of the circuit board is also required to have high dimensional stability. As a technique for improving the dimensional stability of the insulating resin layer of the circuit board, blending organic fillers or inorganic fillers has been proposed (Patent Document 2 to Patent Document 4). [Prior Art Literature] [Patent Literature]
[專利文獻1]日本專利第6295013號公報 [專利文獻2]日本專利特開平11-273456號公報 [專利文獻3]日本專利特開平10-338809號公報 [專利文獻4]日本專利特開2006-321853號公報[Patent Document 1] Japanese Patent No. 6295013 [Patent Document 2] Japanese Patent Laid-Open No. 11-273456 [Patent Document 3] Japanese Patent Laid-Open No. 10-338809 [Patent Document 4] Japanese Patent Laid-Open No. 2006-321853
[發明所要解決的問題] 聚醯亞胺是具有耐熱性、耐化學品性等優異的性質的樹脂，被通用作電路基板的絕緣樹脂層的材料。另一方面，液晶聚合物也被用作電路基板材料，介電特性優異。根據此情況，可考慮通過在聚醯亞胺中調配液晶聚合物作為填料，來改善聚醯亞胺膜的介電特性。然而，液晶聚合物的熱膨脹係數（Coefficient of Thermal Expansion，CTE）大，有可能會損毀絕緣樹脂層的尺寸穩定性。[The problem to be solved by the invention] Polyimide is a resin having excellent properties such as heat resistance and chemical resistance, and is commonly used as a material for insulating resin layers of circuit boards. On the other hand, liquid crystal polymers are also used as circuit board materials and have excellent dielectric properties. According to this situation, it can be considered to improve the dielectric properties of the polyimide film by blending a liquid crystal polymer in the polyimide as a filler. However, the liquid crystal polymer has a large coefficient of thermal expansion (CTE), which may damage the dimensional stability of the insulating resin layer.
因此，本發明的目的為提供一種在聚醯亞胺中分散有液晶聚合物的填料、兼顧了優異的介電特性與尺寸穩定性的樹脂膜。 [解決問題的技術手段]Therefore, the object of the present invention is to provide a resin film in which a filler in which a liquid crystal polymer is dispersed in polyimide, and which has both excellent dielectric properties and dimensional stability. [Technical means to solve the problem]
本發明的樹脂組成物含有：下述成分（A）及成分（B）， （A）使四羧酸酐成分與二胺成分反應而成的聚醯胺酸、以及 （B）包含液晶聚合物且具有形狀各向異性的填料。The resin composition of the present invention contains the following component (A) and component (B), (A) Polyamide acid formed by reacting a tetracarboxylic anhydride component and a diamine component, and (B) A filler containing a liquid crystal polymer and having shape anisotropy.
本發明的樹脂組成物中，作為所述（B）成分的填料的平均長軸徑（L）與平均短軸徑（D）的比（L/D）可為3～200的範圍內。In the resin composition of the present invention, the ratio (L/D) of the average major axis diameter (L) to the average minor axis diameter (D) of the filler as the component (B) may be in the range of 3 to 200.
本發明的樹脂組成物中，作為所述（B）成分的填料的平均長軸徑（L）可為50 μm～3000 μm的範圍內，平均短軸徑（D）可為1 μm～50 μm的範圍內。In the resin composition of the present invention, the filler as the component (B) may have an average major axis diameter (L) in the range of 50 μm to 3000 μm, and an average minor axis diameter (D) of 1 μm to 50 μm. In the range.
本發明的樹脂組成物中，作為所述（B）成分的填料的含量相對於所述（A）成分及所述（B）成分的合計量而可為1體積%～70體積%的範圍內。In the resin composition of the present invention, the content of the filler as the (B) component may be in the range of 1% by volume to 70% by volume relative to the total amount of the (A) component and the (B) component .
本發明的樹脂組成物中，所述液晶聚合物的熔點可為280℃以上。In the resin composition of the present invention, the melting point of the liquid crystal polymer may be 280°C or higher.
本發明的樹脂組成物中，所述液晶聚合物可具有聚酯結構。In the resin composition of the present invention, the liquid crystal polymer may have a polyester structure.
本發明的樹脂組成物中，作為所述（B）成分的填料的長軸方向上的拉伸彈性模量可為20 GPa以上。In the resin composition of the present invention, the filler as the component (B) may have a tensile elastic modulus in the major axis direction of 20 GPa or more.
本發明的樹脂組成物中，作為所述（B）成分的填料的長軸方向上的拉伸彈性模量相對於使作為所述（A）成分的聚醯胺酸硬化而獲得的聚醯亞胺的拉伸彈性模量的比可為1以上。In the resin composition of the present invention, the tensile modulus in the major axis direction of the filler as the (B) component is relative to the polyamide obtained by curing the polyamide as the (A) component The ratio of the tensile modulus of amine may be 1 or more.
本發明的樹脂組成物中，作為所述（B）成分的填料的真比重相對於使作為所述（A）成分的聚醯胺酸硬化而獲得的聚醯亞胺的真比重的比可為0.5～2.0的範圍內。In the resin composition of the present invention, the true specific gravity of the filler as the component (B) relative to the true specific gravity of the polyimide obtained by curing the polyimide as the component (A) may be Within the range of 0.5 to 2.0.
本發明的樹脂組成物中，所述（B）成分的液晶聚合物的1 GHz下的相對介電常數可為2.0～3.5的範圍內，且介電損耗正切可小於0.003。In the resin composition of the present invention, the relative dielectric constant at 1 GHz of the liquid crystal polymer of the component (B) may be in the range of 2.0 to 3.5, and the dielectric loss tangent may be less than 0.003.
本發明的樹脂組成物的製造方法是製造所述任一樹脂組成物，所述製造方法的特徵在於： 在使所述四羧酸酐成分與所述二胺成分反應來合成所述聚醯胺酸的反應完成之前，添加作為所述（B）成分的包含液晶聚合物且具有形狀各向異性的填料。The manufacturing method of the resin composition of the present invention is to manufacture any one of the above-mentioned resin compositions, and the manufacturing method is characterized in that: Before the reaction of the tetracarboxylic anhydride component and the diamine component to synthesize the polyamide acid is completed, a filler containing a liquid crystal polymer and having shape anisotropy as the component (B) is added.
本發明的樹脂組成物的製造方法中，也可在所述四羧酸酐成分與所述二胺成分的反應液的黏度達到1500 cps之前，添加並混合作為所述（B）成分的包含液晶聚合物且具有形狀各向異性的填料。In the manufacturing method of the resin composition of the present invention, the liquid crystal polymer containing liquid crystal polymer as the component (B) may be added and mixed before the viscosity of the reaction liquid of the tetracarboxylic anhydride component and the diamine component reaches 1500 cps. It is a filler with shape anisotropy.
本發明的樹脂膜包含聚醯亞胺層，所述樹脂膜的特徵在於： 所述聚醯亞胺層含有聚醯亞胺、以及分散於所述聚醯亞胺中的包含液晶聚合物且具有形狀各向異性的填料。The resin film of the present invention comprises a polyimide layer, and the resin film is characterized in: The polyimide layer contains polyimide, and a filler containing a liquid crystal polymer and having shape anisotropy dispersed in the polyimide.
本發明的樹脂膜中，所述聚醯亞胺層的熱膨脹係數可為30 ppm/K以下。In the resin film of the present invention, the thermal expansion coefficient of the polyimide layer may be 30 ppm/K or less.
本發明的樹脂膜中，所述聚醯亞胺層的10 GHz下的相對介電常數可為2.0～3.8的範圍內，且介電損耗正切可為0.004以下。In the resin film of the present invention, the relative dielectric constant of the polyimide layer at 10 GHz may be in the range of 2.0 to 3.8, and the dielectric loss tangent may be 0.004 or less.
本發明的樹脂膜中，相對於所述聚醯亞胺層中的樹脂成分的合計量的、包含液晶聚合物且具有形狀各向異性的填料的含量可為1體積%～70體積%的範圍內。In the resin film of the present invention, the content of the filler containing a liquid crystal polymer and having shape anisotropy relative to the total amount of the resin components in the polyimide layer may be in the range of 1% by volume to 70% by volume Inside.
本發明的樹脂膜中，在所述聚醯亞胺層中，所述液晶聚合物的長邊方向可進行配向。In the resin film of the present invention, in the polyimide layer, the longitudinal direction of the liquid crystal polymer may be aligned.
本發明的覆金屬積層板包括：絕緣樹脂層、以及積層於所述絕緣樹脂層的至少一面上的金屬層，所述覆金屬積層板的特徵在於： 所述絕緣樹脂層的至少一層為所述任一樹脂膜。 [發明的效果]The metal-clad laminate of the present invention includes an insulating resin layer and a metal layer laminated on at least one surface of the insulating resin layer, and the metal-clad laminate is characterized by: At least one layer of the insulating resin layer is any one of the resin films. [Effects of the invention]
根據本發明，可提供一種在聚醯亞胺中分散有液晶聚合物的填料、兼顧了優異的介電特性與尺寸穩定性的樹脂膜。本發明的樹脂膜由於可減低高頻訊號傳輸中的損失，還可維持尺寸穩定性，因此可適宜地用作各種電子設備中的FPC等的電路基板材料。According to the present invention, it is possible to provide a resin film in which a filler in which a liquid crystal polymer is dispersed in a polyimide, and which has both excellent dielectric properties and dimensional stability. Since the resin film of the present invention can reduce the loss in high-frequency signal transmission and can maintain dimensional stability, it can be suitably used as a circuit board material such as FPC in various electronic devices.
以下，對本發明的實施形態進行說明。Hereinafter, an embodiment of the present invention will be described.
[樹脂組成物] 本實施形態的樹脂組成物含有：下述成分（A）及成分（B）， （A）使四羧酸酐成分與二胺成分反應而成的聚醯胺酸、以及 （B）包含液晶聚合物且具有形狀各向異性的填料（以下，有時記述為「LCP填料」）。[Resin composition] The resin composition of this embodiment contains the following component (A) and component (B), (A) Polyamide acid formed by reacting a tetracarboxylic anhydride component and a diamine component, and (B) A filler containing a liquid crystal polymer and having shape anisotropy (hereinafter, sometimes referred to as "LCP filler").
[成分A：聚醯胺酸] 成分A的聚醯胺酸為聚醯亞胺的前體，是使四羧酸酐成分與二胺成分反應而獲得。聚醯亞胺是下述通式（1）所表示的具有醯亞胺基的聚合物。進而，在具有醯胺基或醚鍵的情況下，有時也稱為聚醯胺醯亞胺或聚醚醯亞胺，在本說明書中，將這些總記載為聚醯亞胺。聚醯亞胺可通過如下公知的方法來製造：使用實質上等莫耳的二胺成分與酸二酐成分，在有機極性溶媒中使其聚合。在此情況下，為了將黏度設為所期望的範圍，也可調整酸二酐成分相對於二胺成分的莫耳比，其範圍例如優選為設為0.98～1.03的莫耳比的範圍內。[Component A: Polyamide acid] The polyamide acid of component A is a precursor of polyimine, and is obtained by reacting a tetracarboxylic anhydride component and a diamine component. Polyimide is a polymer having an imine group represented by the following general formula (1). Furthermore, when it has an amide group or an ether bond, it may also be called polyamide imide or polyether imine, and in this specification, these are collectively described as polyimide. Polyimide can be produced by a well-known method in which a diamine component and an acid dianhydride component of substantially equal moles are used and polymerized in an organic polar solvent. In this case, in order to set the viscosity to a desired range, the molar ratio of the acid dianhydride component to the diamine component may be adjusted, and the range thereof is preferably within the range of 0.98 to 1.03 molar ratio, for example.
[化1]
通式（1）中，Ar1 表示由包含四羧酸二酐殘基的酸酐衍生的四價基，R2 表示由二胺衍生的二價二胺殘基，n為1以上的整數。In the general formula (1), Ar 1 represents a tetravalent group derived from an acid anhydride containing a tetracarboxylic dianhydride residue, R 2 represents a divalent diamine residue derived from a diamine, and n is an integer of 1 or more.
作為酸二酐，例如優選為由O(OC)2 -Ar1 -(CO)2 O表示的芳香族四羧酸二酐，可例示提供下述芳香族酸酐殘基作為Ar1 的酸二酐。As the acid dianhydride, for example, an aromatic tetracarboxylic dianhydride represented by O(OC) 2 -Ar 1 -(CO) 2 O is preferable, and the following aromatic acid anhydride residues can be exemplified as the acid dianhydride of Ar 1 .
[化2]
酸二酐可單獨使用或混合使用兩種以上。這些中，優選為使用選自均苯四甲酸二酐（pyromellitic dianhydride，PMDA）、3,3',4,4'-聯苯基四羧酸二酐（3,3',4,4'-biphenyl tetracarboxylic dianhydride，BPDA）、3,3',4,4'-二苯甲酮四羧酸二酐（3,3',4,4'-benzophenone tetracarboxylic dianhydride，BTDA）、3,3',4,4'-二苯基碸四羧酸二酐（3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride，DSDA）、及4,4'-氧基二鄰苯二甲酸二酐（4,4'-oxydiphthalic dianhydride，ODPA）中的酸二酐。The acid dianhydride can be used alone or in combination of two or more. Among these, it is preferable to use pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (3,3',4,4'- biphenyl tetracarboxylic dianhydride, BPDA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (3,3',4,4'-benzophenone tetracarboxylic dianhydride, BTDA), 3,3',4 ,4'-Diphenylsulfone tetracarboxylic dianhydride (3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, DSDA), and 4,4'-oxydiphthalic dianhydride (4,4 '-oxydiphthalic dianhydride, ODPA) in the acid dianhydride.
作為二胺，例如優選為由H2 N-R2 -NH2 表示的二胺，可例示提供下述二胺殘基作為R2 的二胺。As the diamine, for example, a diamine represented by H 2 NR 2 -NH 2 is preferable, and a diamine that provides the following diamine residue as R 2 can be exemplified.
[化3]
這些二胺中，可例示二胺基二苯基醚（diamino diphenyl ether，DAPE）、2,2'-二甲基-4,4'-二胺基聯苯（2,2'-dimethyl-4,4'-diamino biphenyl，m-TB）、對苯二胺（paraphenylenediamine，p-PDA）、1,3-雙(4-胺基苯氧基)苯（1,3-bis(4-aminophenoxy)benzene，TPE-R）、1,3-雙(3-胺基苯氧基)苯（1,3-bis(3-aminophenoxy)benzene，APB）、1,4-雙(4-胺基苯氧基)苯（1,4-bis(4-aminophenoxy)benzene，TPE-Q）、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷（2,2-bis[4-(4-aminophenoxy)phenyl]propane，BAPP）、及2,2-雙(三氟甲基)聯苯胺（2,2-bis(trifluoromethyl)benzidine，TFMB）作為適宜的二胺。Among these diamines, diamino diphenyl ether (DAPE), 2,2'-dimethyl-4,4'-diamino biphenyl (2,2'-dimethyl-4 ,4'-diamino biphenyl, m-TB), p-phenylenediamine (paraphenylenediamine, p-PDA), 1,3-bis(4-aminophenoxy) benzene (1,3-bis(4-aminophenoxy) benzene, TPE-R), 1,3-bis(3-aminophenoxy)benzene (1,3-bis(3-aminophenoxy)benzene, APB), 1,4-bis(4-aminophenoxy) Benzene (1,4-bis(4-aminophenoxy)benzene, TPE-Q), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (2,2-bis[4 -(4-aminophenoxy)phenyl]propane, BAPP), and 2,2-bis(trifluoromethyl)benzidine (TFMB) are suitable diamines.
關於所合成的聚醯胺酸，通常有利的是作為反應溶媒溶液來使用，視需要可進行濃縮、稀釋或置換為其他有機溶媒來形成樹脂組成物。使聚醯胺酸醯亞胺化的方法並無特別限制，例如可適宜地採用在所述溶媒中、在80℃～400℃的範圍內的溫度條件下歷時1小時～24小時進行加熱等熱處理。Regarding the synthesized polyamide acid, it is generally advantageous to use it as a reaction solvent solution, and it can be concentrated, diluted, or replaced with another organic solvent as necessary to form a resin composition. The method for imidizing the polyamide is not particularly limited. For example, heat treatment such as heating in the solvent under the temperature conditions in the range of 80°C to 400°C for 1 hour to 24 hours can be suitably used. .
[成分（B）：LCP填料] LCP填料包含液晶聚合物。液晶聚合物幾乎沒有介電特性的頻率依存性，具有非常優異的介電特性，並且也有助於提高阻燃性，因此通過將其作為填料來調配，可改善樹脂膜的介電特性與阻燃性。在出於改善樹脂膜的介電特性的目的來進行調配的情況下，LCP填料可以單質的形式使用1 GHz下的相對介電常數優選為2.0～3.5的範圍內、更優選為2.7～3.2的範圍內、且介電損耗正切優選為小於0.003、更優選為0.002以下的填料。[Component (B): LCP filler] The LCP filler contains a liquid crystal polymer. Liquid crystal polymer has almost no frequency dependence of the dielectric properties, has very excellent dielectric properties, and also contributes to the improvement of flame retardancy. Therefore, by blending it as a filler, the dielectric properties and flame retardancy of the resin film can be improved sex. In the case of blending for the purpose of improving the dielectric properties of the resin film, the LCP filler can be used in the form of a simple substance. The relative dielectric constant at 1 GHz is preferably in the range of 2.0 to 3.5, more preferably 2.7 to 3.2. The filler is within the range and the dielectric loss tangent is preferably less than 0.003, more preferably 0.002 or less.
液晶聚合物的熔點有時被稱為液晶相變溫度或液晶化溫度，優選為280℃以上。更優選為295℃以上，進而優選為310℃以上。若熔點低於280℃，則在電子設備等的製造過程中有可能會熔解而引起特性的變化。The melting point of the liquid crystal polymer is sometimes referred to as the liquid crystal phase transition temperature or the liquid crystal transition temperature, and is preferably 280°C or higher. It is more preferably 295°C or higher, and still more preferably 310°C or higher. If the melting point is lower than 280°C, it may melt during the manufacturing process of electronic devices and the like, which may cause changes in characteristics.
液晶聚合物並無特別限定，例如優選為由分類為以下的（1）～（4）的化合物及其衍生物導出的公知的熱致（thermotropic）液晶聚酯及聚酯醯胺等具有聚酯結構的液晶聚合物。 （1）芳香族二羥基化合物或脂肪族二羥基化合物 （2）芳香族二羧酸或脂肪族二羧酸 （3）芳香族羥基羧酸 （4）芳香族二胺、芳香族羥基胺或芳香族胺基羧酸The liquid crystal polymer is not particularly limited. For example, it is preferably a known thermotropic liquid crystal polyester derived from the compounds classified into the following (1) to (4) and their derivatives, and polyester amides. Structured liquid crystal polymer. (1) Aromatic dihydroxy compound or aliphatic dihydroxy compound (2) Aromatic dicarboxylic acid or aliphatic dicarboxylic acid (3) Aromatic hydroxy carboxylic acid (4) Aromatic diamine, aromatic hydroxylamine or aromatic amino carboxylic acid
作為由這些原料化合物獲得的液晶聚合物的代表例，優選為是具有選自下述式（a）～式（j）所表示的結構單元中的兩個以上的組合的共聚物、且包含式（a）所表示的結構單元或式（e）所表示的結構單元的任一者的共聚物，尤其更優選為包含式（a）所表示的結構單元與式（e）所表示的結構單元的共聚物。另外，液晶聚合物中的芳香環越多，越可期待提高介電特性與阻燃性的效果，因此，優選為包含芳香族二羥基化合物作為所述（1）、且包含芳香族二羧酸作為所述（2）的液晶聚合物。As a representative example of a liquid crystal polymer obtained from these raw material compounds, it is preferable to be a copolymer having a combination of two or more structural units selected from the following formulas (a) to (j), and including the formula (A) A copolymer of any one of the structural unit represented by the formula (e) or the structural unit represented by the formula (e), and particularly preferably contains the structural unit represented by the formula (a) and the structural unit represented by the formula (e)的copolymer. In addition, the more aromatic rings in the liquid crystal polymer, the more the effect of improving the dielectric properties and flame retardancy can be expected. Therefore, it is preferable to include an aromatic dihydroxy compound as the above (1) and an aromatic dicarboxylic acid As the liquid crystal polymer of (2).
[化4]
LCP填料具有形狀各向異性。所謂形狀各向異性，是指LCP填料的平均長軸徑（L）與平均短軸徑（D）的比（L/D）為3以上，優選為3～200的範圍內。此處，在設想為呈直線狀延伸的狀態下的LCP填料所外接的假想長方體時，將所述長方體的彼此垂直的3邊的長度中的最短的邊的長度設為短軸徑，將最長的邊的長度設為長軸徑。LCP filler has shape anisotropy. The term "shape anisotropy" means that the ratio (L/D) of the average major axis diameter (L) to the average minor axis diameter (D) of the LCP filler is 3 or more, preferably in the range of 3 to 200. Here, when assuming a imaginary cuboid circumscribed by the LCP filler in a linearly extending state, the length of the shortest side among the lengths of the three sides perpendicular to each other of the cuboid is set as the minor axis diameter, and the longest The length of the side of is set as the major axis diameter.
LCP填料的平均長軸徑（L）例如優選為50 μm～3000 μm的範圍內，更優選為100 μm～1000 μm的範圍內。另外，LCP填料的平均短軸徑（D）例如優選為1 μm～50 μm的範圍內，更優選為3 μm～30 μm的範圍內。若平均長軸徑（L）及平均短軸徑（D）為所述範圍內，則不會使由樹脂組成物形成樹脂膜時的表面平滑性惡化，可獲得外觀良好的樹脂膜。The average major axis diameter (L) of the LCP filler is, for example, preferably in the range of 50 μm to 3000 μm, and more preferably in the range of 100 μm to 1000 μm. In addition, the average minor axis diameter (D) of the LCP filler is, for example, preferably in the range of 1 μm to 50 μm, and more preferably in the range of 3 μm to 30 μm. If the average major axis diameter (L) and the average minor axis diameter (D) are within the above ranges, the surface smoothness when the resin film is formed from the resin composition is not deteriorated, and a resin film with good appearance can be obtained.
作為LCP填料的具體形狀，例如可列舉纖維狀（包含針狀）、板狀等。作為纖維狀，例如可為磨碎纖維（milled fiber）、短切纖維（chopped fiber）、切斷纖維（cut fiber）等。作為板狀，可例示圓盤狀、扁平狀、平板狀、薄片狀、鱗片狀、長條狀等。另外，LCP填料的剖面形狀並不限於圓形，也可為星型或花型、十字型、中空型。通過改變LCP填料的剖面形狀，可調整LCP填料的表面積而控制與聚醯亞胺的黏接性、或可控制樹脂溶液的黏度。就樹脂膜的CTE控制的容易性的觀點而言，特別優選為短纖維狀的LCP填料。As the specific shape of the LCP filler, for example, a fibrous shape (including a needle shape), a plate shape, and the like can be cited. As the fiber shape, for example, milled fiber, chopped fiber, cut fiber, or the like can be used. As the plate shape, a disk shape, a flat shape, a flat shape, a flake shape, a scaly shape, an elongated shape, etc. can be exemplified. In addition, the cross-sectional shape of the LCP filler is not limited to a circular shape, and may also be a star shape, a flower shape, a cross shape, or a hollow shape. By changing the cross-sectional shape of the LCP filler, the surface area of the LCP filler can be adjusted to control the adhesion with the polyimide, or the viscosity of the resin solution can be controlled. From the viewpoint of the ease of CTE control of the resin film, a short-fibrous LCP filler is particularly preferable.
LCP填料優選為以其長軸方向與液晶聚合物分子的長邊方向大致一致的方式進行配向。為了使液晶聚合物分子配向，重要的是經過利用熔融步驟與擠出步驟進行的成形，尤其是，可將由下式求出的擠出時的最大剪切速度u設為優選為103 sec-1 以上、更優選為104 sec-1 以上。 u=4Q/{π×（d/2）3 } [其中，Q表示單位時間內通過擠出噴出口剖面的聚合物噴出量（cm3 /sec），d表示擠出噴出口剖面的最短的徑的長度（cm），例如在管狀噴嘴或細孔等圓形的擠出噴出口的情況下，設為其直徑（cm）] 若為此種最大剪切速度，則液晶分子的配向變得充分，容易獲得用作LCP填料時的CTE的控制性。The LCP filler is preferably aligned so that the long axis direction thereof substantially coincides with the long side direction of the liquid crystal polymer molecules. In order to align the molecules of the liquid crystal polymer, it is important to undergo molding by a melting step and an extrusion step. In particular, the maximum shear rate u during extrusion calculated from the following formula can be set to preferably 10 3 sec − 1 or more, more preferably 10 4 sec -1 or more. u=4Q/{π×(d/2) 3 } [Among them, Q represents the amount of polymer ejected through the extrusion nozzle section per unit time (cm 3 /sec), and d represents the shortest extrusion nozzle section The length (cm) of the diameter, for example, in the case of a circular extrusion nozzle such as a tubular nozzle or a pore, set the diameter (cm)] At such a maximum shear rate, the alignment of the liquid crystal molecules becomes Sufficient, easy to obtain CTE controllability when used as LCP filler.
另外，在LCP填料的配向不充分的情況下，可通過在流延或擠出步驟後進行延伸來控制配向。再者，通過自細孔噴出樹脂，可省略延伸步驟，為此，優選為將紡絲模口的孔徑（直徑）設為例如1.0 mm以下，更優選為設為0.5 mm以下。In addition, in the case where the alignment of the LCP filler is insufficient, the alignment can be controlled by performing extension after the casting or extrusion step. Furthermore, by ejecting the resin from the pores, the stretching step can be omitted. For this reason, the hole diameter (diameter) of the spinning die is preferably 1.0 mm or less, and more preferably 0.5 mm or less.
LCP填料可通過如下方式來製造：將利用所述方法製造的長纖維捆扎並切斷為規定的長度、或加以粉碎。另外，也可不製成纖維狀，而是對提高了液晶聚合物分子的配向度的成型物進行粉碎，由此也可製造LCP填料。The LCP filler can be produced by bundling and cutting the long fibers produced by the above method into a predetermined length, or by pulverizing. In addition, instead of making it into a fibrous shape, it is also possible to pulverize a molded product with an increased degree of alignment of the liquid crystal polymer molecules, thereby making it possible to produce an LCP filler.
另外，為了減低樹脂膜的CTE，LCP填料的長軸方向上的拉伸彈性模量例如優選為20 GPa以上，更優選為40 GPa～200 GPa的範圍內。特別優選為LCP填料的長軸方向上的拉伸彈性模量EL 相對於使作為（A）成分的聚醯胺酸硬化而獲得的聚醯亞胺的拉伸彈性模量EP 的比（EL /EP ）為1以上。在樹脂膜中的作為基質的聚醯亞胺的拉伸彈性模量EP 與LCP填料的拉伸彈性模量EL 的關係為EL ≧EP 的情況下，減低CTE的效果變大。In addition, in order to reduce the CTE of the resin film, the tensile elastic modulus in the major axis direction of the LCP filler is preferably 20 GPa or more, and more preferably in the range of 40 GPa to 200 GPa. Particularly preferred E P ratio of tensile modulus of elasticity is polyimide tensile modulus E L in the longitudinal direction with respect to the filler LCP polyamide acid-hardening serving as component (A) is obtained ( E L /E P ) is 1 or more. When the relationship between the resin film as a substrate of polyimide tensile modulus E P LCP and filler tensile modulus is E L E L ≧ E P, reducing the effect of CTE becomes large.
另外，LCP填料的真比重SL 相對於使作為（A）成分的聚醯胺酸硬化而獲得的聚醯亞胺的真比重SP 的比（SL /SP ）例如優選為0.5～2.0的範圍內。通過樹脂膜中的作為基質的聚醯亞胺的真比重SP 與LCP填料的真比重SL 的關係為所述範圍內，LCP填料的分散性變良好，並且可實現樹脂膜整體的輕量化。Further, polyimide true specific gravity than S L LCP phase filler for making polyamide acid-hardening as component (A) obtained by the true specific gravity of S P (S L / S P) is preferably 0.5 to 2.0 e.g. In the range. The resin film as the relationship between L polyimide matrix and a true specific gravity of LCP S P S true specific gravity of the filler is within the above range, the dispersibility of the filler LCP becomes good, and the overall weight of the resin film can be achieved .
出於提高分散性及與聚醯亞胺的密合性的目的，LCP填料也可實施表面改質處理。作為表面改質處理，例如可列舉等離子體處理、塗布處理等。另外，LCP填料也可為芯鞘型結構。作為芯鞘型結構，例如優選為芯部分為液晶聚合物、鞘部分為與聚醯亞胺的黏接性高的樹脂的結構。作為與聚醯亞胺的黏接性高的樹脂，例如適宜的是聚醯亞胺、聚醯胺、全氟烷氧基氟樹脂（perfluoroalkoxy fluororesin，PFA）、聚烯烴等熱塑性樹脂。For the purpose of improving dispersibility and adhesion to polyimide, LCP fillers can also be surface-modified. Examples of the surface modification treatment include plasma treatment and coating treatment. In addition, the LCP filler can also have a core-sheath structure. As the core-sheath structure, for example, a structure in which the core part is a liquid crystal polymer and the sheath part is a resin with high adhesion to polyimide is preferable. As a resin with high adhesion to polyimide, for example, thermoplastic resins such as polyimide, polyamide, perfluoroalkoxy fluororesin (PFA), and polyolefin are suitable.
LCP填料可適宜地選定使用市售品。例如，作為纖維狀的填料，可優選地使用可樂麗（Kuraray）公司製造的維克特倫（Vectran）（商品名）、可樂麗（Kuraray）公司製造的貝克利（Vecry）（商品名）、東麗公司製的西韋拉斯（Siveras）（商品名）、KB索倫（KB SEIREN）公司製造的澤克西翁（Zxion）（商品名）等。再者，作為LCP填料，也可並用兩種以上的不同的填料。Commercially available LCP fillers can be appropriately selected and used. For example, as the fibrous filler, Vectran (trade name) manufactured by Kuraray, Vecry (trade name) manufactured by Kuraray, Siveras (trade name) manufactured by Toray, Zxion (trade name) manufactured by KB SEIREN, etc. Furthermore, as the LCP filler, two or more different fillers may be used in combination.
[溶劑] 樹脂組成物優選為進而含有溶劑。作為溶劑，例如可列舉：N,N-二甲基甲醯胺（N,N-dimethyl formamide，DMF）、N,N-二甲基乙醯胺（N,N-dimethyl acetamide，DMAc）、N,N-二乙基乙醯胺、N-甲基-2-吡咯烷酮（N-methyl-2-pyrrolidone，NMP）、2-丁酮、二甲基亞碸（dimethyl sulfoxide，DMSO）、六甲基磷醯胺、N-甲基己內醯胺、硫酸二甲酯、環己酮、二噁烷、四氫呋喃、二乙二醇二甲醚（diglyme）、三乙二醇二甲醚（triglyme）、甲酚、丙酮、甲基異丁基酮等有機溶媒。也可將這些溶劑並用兩種以上，也可進而並用二甲苯、甲苯那樣的芳香族烴。溶劑的含量並無特別限制，優選為調整為樹脂組成物中的固體成分濃度成為5重量%～50重量%左右那樣的使用量來使用。[Solvent] The resin composition preferably further contains a solvent. As the solvent, for example, N,N-dimethyl formamide (N,N-dimethyl formamide, DMF), N,N-dimethyl acetamide (N,N-dimethyl acetamide, DMAc), N , N-Diethylacetamide, N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone, NMP), 2-butanone, dimethyl sulfoxide (DMSO), hexamethyl Phosphatiamine, N-methylcaprolactam, dimethyl sulfate, cyclohexanone, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), Organic solvents such as cresol, acetone, and methyl isobutyl ketone. Two or more of these solvents may be used in combination, and aromatic hydrocarbons such as xylene and toluene may be used in combination. The content of the solvent is not particularly limited, but it is preferably adjusted to a usage amount such that the solid content concentration in the resin composition becomes about 5 to 50% by weight.
[任意成分] 在樹脂組成物中，視需要，可適宜調配聚醯胺酸以外的樹脂成分、阻燃劑、交聯劑、硬化促進劑、化學催化劑、LCP填料以外的有機填料、無機填料、塑化劑、偶合劑、顏料等作為任意成分。[Arbitrary Ingredients] In the resin composition, if necessary, resin components other than polyamide acid, flame retardants, crosslinking agents, hardening accelerators, chemical catalysts, organic fillers other than LCP fillers, inorganic fillers, plasticizers, Coupling agents, pigments, etc. are used as optional components.
[組成] 樹脂組成物中的作為（B）成分的LCP填料的含量可根據樹脂膜的使用目的來適宜設定，例如，相對於（A）成分及（B）成分的合計量而優選為1體積%～70體積%的範圍內，更優選為5體積%～65體積%的範圍內。若LCP填料的調配量小於下限值，則有時無法充分獲得介電特性的改善效果及CTE減低效果，若超過上限值，則有時會因樹脂溶液的增黏而導致處理性降低或樹脂膜變脆弱。 再者，溶劑優選為以溶解作為（A）成分的聚醯胺酸且可製成溶液狀態的量進行調配。[composition] The content of the LCP filler as the component (B) in the resin composition can be appropriately set according to the purpose of use of the resin film. For example, it is preferably 1% by volume to 70% relative to the total amount of the component (A) and the component (B). It is in the range of vol%, and more preferably in the range of 5% to 65% by volume. If the blending amount of the LCP filler is less than the lower limit, the improvement effect of the dielectric properties and the CTE reduction effect may not be sufficiently obtained. If it exceeds the upper limit, the handling property may be reduced due to the viscosity increase of the resin solution. The resin film becomes fragile. In addition, the solvent is preferably formulated in an amount that dissolves the polyamic acid as the component (A) and can be made into a solution state.
[黏度] 關於樹脂組成物的黏度，作為提高塗敷樹脂組成物時的處理性、容易形成均勻厚度的塗膜的黏度範圍，例如優選為設為3000 cps～100000 cps的範圍內，更優選為設為5000 cps～50000 cps的範圍內。若偏離所述黏度範圍，則在利用塗布機等進行的塗敷作業時，膜容易產生厚度不均、條紋等不良情況。[Viscosity] Regarding the viscosity of the resin composition, as a viscosity range for improving the handleability when applying the resin composition and easily forming a coating film of uniform thickness, for example, it is preferably set to be in the range of 3000 cps to 100,000 cps, and more preferably set to 5000 cps ~ 50000 cps range. If it deviates from the above-mentioned viscosity range, defects such as thickness unevenness and streaks are likely to occur in the film during coating work with a coater or the like.
[樹脂組成物的製造方法] 樹脂組成物優選為在使作為（A）成分的原料的四羧酸酐成分與二胺成分反應來合成聚醯胺酸的反應完成之前，添加作為（B）成分的LCP填料。在聚醯胺酸的合成反應完成之後，添加LCP填料也容易產生LCP填料的凝聚，另外，凝聚後的分散步驟也容易變得複雜。作為添加LCP填料的時間點的優選標準，例如，可在四羧酸酐成分與二胺成分的反應液的黏度達到1500 cps之前，添加並混合LCP填料。在反應液的黏度達到1500 cps之後，添加LCP填料也無法獲得均勻的混合狀態。[Manufacturing method of resin composition] In the resin composition, it is preferable to add the LCP filler as the component (B) before the reaction of the tetracarboxylic anhydride component as the raw material of the component (A) and the diamine component to synthesize the polyamide acid is completed. After the synthesis reaction of the polyamide acid is completed, the addition of the LCP filler is also likely to cause aggregation of the LCP filler, and the dispersion step after the aggregation is also likely to become complicated. As a preferred criterion for the time point of adding the LCP filler, for example, the LCP filler may be added and mixed before the viscosity of the reaction liquid of the tetracarboxylic anhydride component and the diamine component reaches 1500 cps. After the viscosity of the reaction solution reached 1500 cps, the addition of LCP fillers could not achieve a uniform mixing state.
就以上觀點而言，更優選為在使四羧酸酐成分與二胺成分反應之前的階段，對四羧酸酐成分和/或二胺成分添加LCP填料。 具體而言，也可在將四羧酸酐成分與二胺成分及LCP填料同時混合之後，使四羧酸酐成分與二胺成分反應來進行聚醯胺酸的合成反應。 另外，也可通過對在四羧酸酐成分中添加LCP填料而成的混合物添加並混合二胺成分，而開始聚醯胺酸的合成反應。 另外，也可通過對在二胺成分中添加LCP填料而成的混合物添加並混合四羧酸酐成分，而開始聚醯胺酸的合成反應。 在任一情況下，作為原料的四羧酸酐成分、二胺成分、LCP填料可一次投入總量，也可分為幾次且每次少量地添加。另外，也可使用預先分散有LCP填料的溶劑。From the above viewpoints, it is more preferable to add an LCP filler to the tetracarboxylic anhydride component and/or the diamine component in the stage before the tetracarboxylic anhydride component and the diamine component are reacted. Specifically, after mixing the tetracarboxylic anhydride component, the diamine component, and the LCP filler at the same time, the tetracarboxylic anhydride component and the diamine component may be reacted to perform the synthesis reaction of polyamide acid. In addition, by adding and mixing a diamine component to a mixture obtained by adding an LCP filler to a tetracarboxylic anhydride component, the synthesis reaction of polyamide acid can also be started. In addition, by adding and mixing a tetracarboxylic anhydride component to a mixture obtained by adding an LCP filler to a diamine component, the synthesis reaction of polyamide acid can also be started. In either case, the tetracarboxylic anhydride component, the diamine component, and the LCP filler as raw materials may be charged in the total amount at one time, or may be divided into several times and added in small amounts each time. In addition, a solvent in which the LCP filler is pre-dispersed can also be used.
[樹脂膜] 本實施形態的樹脂膜包含聚醯亞胺層（以下，有時記述為「含有LCP填料的聚醯亞胺層」），所述聚醯亞胺層含有聚醯亞胺、以及分散於聚醯亞胺中的LCP填料。含有LCP填料的聚醯亞胺層的基質樹脂為經醯亞胺化而成的聚醯亞胺，且呈其中分散有LCP填料的狀態。樹脂膜可為單層，也可由多層構成。即，樹脂膜整體可為含有LCP填料的聚醯亞胺層，也可包含含有LCP填料的聚醯亞胺層以外的樹脂層。其中，優選為含有LCP填料的聚醯亞胺層是樹脂膜的主要的層。此處，所謂「主要的層」，是指相對於樹脂膜的整體厚度而具有超過50%的厚度的層。[Resin Film] The resin film of this embodiment includes a polyimide layer (hereinafter, sometimes referred to as "polyimide layer containing LCP filler"), and the polyimide layer contains polyimide and dispersed in polyimide LCP filler in imines. The matrix resin of the polyimide layer containing the LCP filler is a polyimide formed by imidization, and the LCP filler is dispersed therein. The resin film may be a single layer, or may be composed of multiple layers. That is, the entire resin film may be a polyimide layer containing an LCP filler, or may include a resin layer other than the polyimide layer containing an LCP filler. Among them, it is preferable that the polyimide layer containing the LCP filler is the main layer of the resin film. Here, the "main layer" refers to a layer having a thickness exceeding 50% with respect to the entire thickness of the resin film.
考慮到電路基板材料的尺寸穩定性，樹脂膜中的含有LCP填料的聚醯亞胺層的熱膨脹係數優選為30 ppm/K以下，更優選為1 ppm/K～25 ppm/K的範圍內。In consideration of the dimensional stability of the circuit board material, the thermal expansion coefficient of the polyimide layer containing the LCP filler in the resin film is preferably 30 ppm/K or less, and more preferably in the range of 1 ppm/K to 25 ppm/K.
另外，為了應對高頻訊號傳輸，含有LCP填料的聚醯亞胺層的10 GHz下的相對介電常數優選為2.0～3.8的範圍內，更優選為2.5～3.5的範圍內。另外，為了應對高頻訊號傳輸，含有LCP填料的聚醯亞胺層的10 GHz下的介電損耗正切優選為0.004以下，更優選為0.003以下。In addition, in order to cope with high-frequency signal transmission, the relative permittivity at 10 GHz of the polyimide layer containing the LCP filler is preferably in the range of 2.0 to 3.8, and more preferably in the range of 2.5 to 3.5. In addition, in order to cope with high-frequency signal transmission, the dielectric loss tangent at 10 GHz of the polyimide layer containing the LCP filler is preferably 0.004 or less, and more preferably 0.003 or less.
相對於含有LCP填料的聚醯亞胺層中的樹脂成分的合計量的、LCP填料的含量可根據使用目的而適宜設定，例如優選為1體積%～70體積%的範圍內，更優選為5體積%～65體積%的範圍內。若LCP填料的含量小於下限值，則有時無法充分獲得介電特性的改善效果及CTE減低效果，若超過上限值，則有時會因樹脂溶液的增黏而導致處理性降低或樹脂膜變脆弱。再者，含有LCP填料的聚醯亞胺層中的LCP填料的體積比率也可由利用三維穿透式電子顯微鏡（Transmission Electron Microscope，TEM）獲得的成像圖像來算出，也可由利用基於強鹼溶解的分解分析或熱分解分析法而獲得的重量比進行換算來求出。另外，也可由基於X射線繞射的相體積比率測量、剖面掃描式電子顯微鏡（Scanning Electron Microscope，SEM）圖像的面積比並通過計算來求出。The content of the LCP filler relative to the total amount of the resin components in the polyimide layer containing the LCP filler can be appropriately set according to the purpose of use, for example, it is preferably in the range of 1% by volume to 70% by volume, and more preferably 5 Within the range of vol% to 65 vol%. If the content of the LCP filler is less than the lower limit, the improvement effect of the dielectric properties and the CTE reduction effect may not be sufficiently obtained. If the content exceeds the upper limit, the handleability of the resin solution may be reduced or the resin may be reduced. The membrane becomes fragile. Furthermore, the volume ratio of the LCP filler in the polyimide layer containing the LCP filler can also be calculated from the imaging image obtained by using a three-dimensional transmission electron microscope (Transmission Electron Microscope, TEM), or it can be calculated by using a strong base-based dissolution method. The weight ratio obtained by the decomposition analysis or thermal decomposition analysis method is calculated by conversion. In addition, it can also be determined by calculation based on the phase volume ratio measurement based on X-ray diffraction and the cross-sectional scanning electron microscope (Scanning Electron Microscope, SEM) image area ratio.
在含有LCP填料的聚醯亞胺層中，優選為液晶聚合物分子的長邊方向進行配向。尤其是，就提高尺寸穩定性的觀點而言，優選為含有LCP填料的聚醯亞胺層的長邊方向（MD（縱向，Machine Direction）方向）與液晶聚合物分子的長邊方向為大致相同的方向。為此，如上所述，優選為以LCP填料的長軸方向與液晶聚合物分子的長邊方向大致一致的方式進行配向。In the polyimide layer containing the LCP filler, it is preferable that the liquid crystal polymer molecules are aligned in the longitudinal direction. In particular, from the viewpoint of improving dimensional stability, it is preferable that the longitudinal direction (MD (Machine Direction) direction) of the polyimide layer containing the LCP filler is substantially the same as the longitudinal direction of the liquid crystal polymer molecules. Direction. For this reason, as described above, it is preferable to perform the alignment so that the long axis direction of the LCP filler substantially coincides with the long side direction of the liquid crystal polymer molecules.
＜厚度＞ 樹脂膜的厚度可根據使用目的而適宜設定，例如優選為2 μm～150 μm的範圍內，更優選為10 μm～120 μm的範圍內。若樹脂膜的厚度不足2 μm，則有可能會產生在樹脂膜的製造等中的搬送時產生褶皺等不良情況，另一方面，若樹脂膜的厚度超過150 μm，則有可能會降低樹脂膜的生產性。＜Thickness＞ The thickness of the resin film can be appropriately set according to the purpose of use, and for example, it is preferably in the range of 2 μm to 150 μm, and more preferably in the range of 10 μm to 120 μm. If the thickness of the resin film is less than 2 μm, defects such as wrinkles may occur during transportation in the manufacture of the resin film. On the other hand, if the thickness of the resin film exceeds 150 μm, the resin film may be reduced. The productivity.
樹脂膜只要為膜（片）狀即可，可為積層於任意的基材、例如銅箔、玻璃板、聚醯亞胺系膜、聚醯胺系膜、聚酯系膜等上的狀態。The resin film may be in the form of a film (sheet), and may be in a state of being laminated on any substrate, for example, copper foil, glass plate, polyimide-based film, polyimide-based film, polyester-based film, and the like.
[樹脂膜的製造方法] 樹脂膜可通過如下方式來製造：對樹脂組成物進行熱處理，將聚醯胺酸醯亞胺化而形成含有LCP填料的聚醯亞胺層。對樹脂組成物進行熱處理來獲得含有LCP填料的聚醯亞胺層的方法並無特別限定，可採用公知的方法。[Manufacturing method of resin film] The resin film can be manufactured by heat-treating the resin composition to form a polyimide layer containing LCP filler by amidizing polyimide. The method of heat-treating the resin composition to obtain the polyimide layer containing the LCP filler is not particularly limited, and a known method can be adopted.
首先，將樹脂組成物直接流延塗布於任意的支撐基材上而形成塗布膜。接著，對於塗布膜，在150℃以下的溫度下，以某程度將溶劑乾燥去除。其後，為了聚醯胺酸的醯亞胺化，而對塗布膜在例如100℃～400℃、優選為130℃～380℃的溫度範圍內進行5分鐘～30分鐘左右的熱處理。如此，可在支撐基材上形成含有LCP填料的聚醯亞胺層。若用於醯亞胺化的熱處理溫度低於100℃，則聚醯亞胺的脫水閉環反應並未充分進行，相反，若超過400℃，則聚醯亞胺層有可能會劣化。First, the resin composition is directly cast-coated on an arbitrary supporting substrate to form a coating film. Next, for the coating film, the solvent is dried and removed to some extent at a temperature of 150°C or less. Thereafter, for the imidization of the polyamide acid, the coating film is heat-treated in a temperature range of, for example, 100°C to 400°C, preferably 130°C to 380°C, for about 5 minutes to 30 minutes. In this way, a polyimide layer containing LCP filler can be formed on the supporting substrate. If the heat treatment temperature for the imidization is lower than 100°C, the dehydration ring-closing reaction of the polyimide does not proceed sufficiently. On the contrary, if it exceeds 400°C, the polyimide layer may be degraded.
在由兩層以上的聚醯亞胺層形成樹脂膜的情況下，在塗布第一聚醯胺酸的樹脂組成物並進行乾燥後，塗布第二聚醯胺酸的樹脂組成物並進行乾燥。其後，同樣地，以第三聚醯胺酸的樹脂組成物、接著是第四聚醯胺酸的樹脂組成物、…的方式，依次以所需的次數塗布聚醯胺酸的樹脂組成物並進行乾燥。其後，優選為一起進行熱處理而進行醯亞胺化。再者，只要其中的至少一層為含有LCP填料的聚醯亞胺層即可。 另外，通過對醯亞胺化後的任意的聚醯亞胺層進行適當的表面處理等，可進而重複經過樹脂組成物的塗布、乾燥及醯亞胺化的步驟，重新重疊層。在此情況下，無需完成中途步驟的醯亞胺化，可在最終步驟中一起完成醯亞胺化。 另外，醯亞胺化後的任意的聚醯亞胺層可與另外形成的樹脂膜加熱壓接。 再者，樹脂膜也可為帶支撐基材的狀態。In the case where the resin film is formed from two or more polyimide layers, after the resin composition of the first polyimide acid is applied and dried, the resin composition of the second polyimide acid is applied and dried. Thereafter, in the same manner, the resin composition of the third polyamide acid, followed by the resin composition of the fourth polyamide acid, ..., the resin composition of the polyamide acid was sequentially applied the required number of times And dry it. After that, it is preferable to perform heat treatment together to perform imidization. Furthermore, as long as at least one of the layers is a polyimide layer containing LCP filler. In addition, by performing appropriate surface treatment or the like on any polyimide layer after imidization, the steps of coating, drying, and imidization of the resin composition can be repeated, and the layers can be laminated again. In this case, there is no need to complete the imidization of the intermediate step, and the imidization can be completed together in the final step. In addition, any polyimide layer after imidization may be heat-compressed with a resin film formed separately. Furthermore, the resin film may be in a state with a supporting base material.
另外，列舉形成樹脂膜的其他例子。 首先，在任意的支撐基材上流延塗布樹脂組成物，進行膜狀成型。通過在支撐基材上對所述膜狀成型物進行加熱乾燥，而製成具有自支撐性的凝膠膜。將凝膠膜自支撐基材剝離後，例如在100℃～400℃、優選為130℃～380℃的溫度範圍內熱處理5分鐘～30分鐘左右，使聚醯胺酸醯亞胺化，從而可獲得包含含有LCP填料的聚醯亞胺層的樹脂膜。另外，視需要，也可使樹脂膜延伸。In addition, another example of forming a resin film is given. First, the resin composition is cast-coated on an arbitrary supporting substrate, and film-shaped molding is performed. By heating and drying the film-like molded article on a supporting substrate, a self-supporting gel film is produced. After peeling the gel film from the supporting substrate, for example, heat treatment at a temperature range of 100°C to 400°C, preferably 130°C to 380°C, for about 5 minutes to 30 minutes, to imidize the polyamide. A resin film including a polyimide layer containing LCP filler was obtained. In addition, if necessary, the resin film may be stretched.
[覆金屬積層板] 本實施形態的覆金屬積層板為包括絕緣樹脂層、以及積層於所述絕緣樹脂層的至少一面上的金屬層的覆金屬積層板，且絕緣樹脂層的至少一層包含利用所述方法製造的樹脂膜。覆金屬積層板可為僅在絕緣樹脂層的單面側具有金屬層的單面覆金屬積層板，也可為在絕緣樹脂層的兩面上具有金屬層的兩面覆金屬積層板。[Metal Clad Laminate] The metal-clad laminate of this embodiment is a metal-clad laminate including an insulating resin layer and a metal layer laminated on at least one surface of the insulating resin layer, and at least one layer of the insulating resin layer includes the resin manufactured by the method. membrane. The metal-clad laminate may be a single-sided metal-clad laminate having a metal layer on one side of the insulating resin layer, or a double-sided metal-clad laminate having metal layers on both sides of the insulating resin layer.
＜絕緣樹脂層＞ 絕緣樹脂層包含單層或多層，且含有包含所述樹脂膜的層。例如，所述樹脂膜也可形成用於保證機械特性或熱物性的作為絕緣樹脂層的主要的層的非熱塑性聚醯亞胺層。另外，所述樹脂膜也可形成負責與銅箔等金屬層的黏接強度的作為黏接劑層的熱塑性聚醯亞胺層。再者，所謂「主要的層」，是指占據絕緣樹脂層的總厚度的超過50%的厚度的層。＜Insulation resin layer＞ The insulating resin layer includes a single layer or multiple layers, and includes a layer including the resin film. For example, the resin film may form a non-thermoplastic polyimide layer as a main layer of the insulating resin layer for ensuring mechanical properties or thermal properties. In addition, the resin film may form a thermoplastic polyimide layer as an adhesive layer that is responsible for the adhesive strength with a metal layer such as copper foil. In addition, the "main layer" refers to a layer that occupies a thickness exceeding 50% of the total thickness of the insulating resin layer.
作為製造將樹脂膜設為絕緣樹脂層的覆金屬積層板的方法，例如可列舉：直接、或經由任意的黏接劑將金屬箔加熱壓接於樹脂膜上的方法；或利用金屬蒸鍍等方法在樹脂膜上形成金屬層的方法等。再者，兩面覆金屬積層板例如可利用如下方法等而獲得：在形成單面覆金屬積層板後，使聚醯亞胺層彼此相向並通過熱壓制進行壓接而形成的方法；或將金屬箔壓接於單面覆金屬積層板的聚醯亞胺層上而形成的方法。As a method of manufacturing a metal-clad laminate having a resin film as an insulating resin layer, for example, a method of heating and pressing a metal foil to the resin film directly or via an arbitrary adhesive; or using metal vapor deposition, etc. Method A method of forming a metal layer on a resin film, etc. Furthermore, a double-sided metal-clad laminate can be obtained, for example, by a method in which, after forming a single-sided metal-clad laminate, the polyimide layers are opposed to each other and pressure-bonded by hot pressing; or metal A method in which the foil is crimped on the polyimide layer of a single-sided metal-clad laminate.
＜金屬層＞ 金屬層的材質並無特別限制，例如可列舉：銅、不銹鋼、鐵、鎳、鈹、鋁、鋅、銦、銀、金、錫、鋯、鉭、鈦、鉛、鎂、錳及這些的合金等。這些中，特別優選為銅或銅合金。金屬層可為包含金屬箔的層，也可為對膜進行金屬蒸鍍而成的層、印刷糊等而成的層。另外，無論是金屬箔還是金屬板，均可使用，優選為銅箔或銅板。＜Metal layer＞ The material of the metal layer is not particularly limited. Examples include copper, stainless steel, iron, nickel, beryllium, aluminum, zinc, indium, silver, gold, tin, zirconium, tantalum, titanium, lead, magnesium, manganese, and alloys of these Wait. Among these, copper or copper alloys are particularly preferred. The metal layer may be a layer containing a metal foil, a layer formed by metal vapor-depositing a film, a layer formed by printing paste, or the like. In addition, it can be used regardless of whether it is a metal foil or a metal plate, and it is preferably a copper foil or a copper plate.
金屬層的厚度是根據覆金屬積層板的使用目的而適宜設定，因此並無特別限定，例如優選為5 μm～3 mm的範圍內，更優選為12 μm～1 mm的範圍內。若金屬層的厚度不足5 μm，則有可能會產生在覆金屬積層板的製造等中的搬送時產生褶皺等不良情況。相反，若金屬層的厚度超過3 mm，則硬而加工性變差。The thickness of the metal layer is appropriately set according to the purpose of use of the metal-clad laminate, and therefore is not particularly limited. For example, it is preferably in the range of 5 μm to 3 mm, and more preferably in the range of 12 μm to 1 mm. If the thickness of the metal layer is less than 5 μm, defects such as wrinkles may occur during transportation in the manufacture of the metal-clad laminate. On the contrary, if the thickness of the metal layer exceeds 3 mm, it becomes hard and the workability deteriorates.
如以上那樣進行而獲得的樹脂膜及覆金屬積層板因在聚醯亞胺中分散有LCP填料，而兼顧了優異的介電特性與尺寸穩定性。因此，樹脂膜及覆金屬積層板由於可減低高頻訊號傳輸中的損失，還可維持尺寸穩定性，因此可適宜地用作各種電子設備中的FPC等的電路基板材料。 [實施例]The resin film and the metal-clad laminate obtained as described above have both excellent dielectric properties and dimensional stability due to the dispersion of the LCP filler in the polyimide. Therefore, the resin film and the metal-clad laminate can reduce the loss in high-frequency signal transmission and maintain dimensional stability, so they can be suitably used as circuit board materials such as FPC in various electronic devices. [Example]
以下示出實施例，更具體地說明本發明的特徵。其中，本發明的範圍並不限定於實施例。再者，在以下的實施例中，只要沒有特別說明，則各種測定、評價均是依照下述內容進行。Examples are shown below to more specifically explain the characteristics of the present invention. However, the scope of the present invention is not limited to the examples. In addition, in the following examples, unless otherwise specified, various measurements and evaluations were performed in accordance with the following contents.
[黏度的測定] 使用E型黏度計（博勒菲（Brookfield）公司製造，商品名：DV-II+Pro），對25℃下的黏度進行測定。以使扭矩（torque）成為10%～90%的方式設定轉數，開始測定起經過1分鐘後，讀取黏度穩定時的值。[Determination of Viscosity] Using an E-type viscometer (manufactured by Brookfield, trade name: DV-II+Pro), the viscosity at 25°C was measured. Set the number of revolutions so that the torque becomes 10% to 90%. After 1 minute has passed since the start of the measurement, read the value when the viscosity is stable.
[熱膨脹係數（CTE）的測定] 將聚醯亞胺膜切出為TD（橫向，Transverse Direction）方向3 mm×MD方向20 mm的尺寸，使用熱機械分析儀（布魯克（Bruker）公司製造，商品名：4000SA），一邊在MD方向上施加5.0 g的負荷，一邊以一定的升溫速度自30℃升溫至260℃，進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（熱膨脹係數）。[Determination of Coefficient of Thermal Expansion (CTE)] The polyimide film was cut out to a size of 3 mm in the TD (Transverse Direction) direction and 20 mm in the MD direction, using a thermomechanical analyzer (manufactured by Bruker, trade name: 4000SA), with one side in the MD direction A load of 5.0 g is applied to the upper part, while the temperature is raised from 30°C to 260°C at a constant temperature rise rate, and then kept at the temperature for 10 minutes, and then cooled at a rate of 5°C/min to obtain the value from 250°C to 100°C The average thermal expansion coefficient (coefficient of thermal expansion) so far.
[熔點的測定] 使用差示掃描量熱分析裝置（DSC（差示掃描量熱儀，Differential Scanning Calorimetry），SII公司製造，商品名：DSC-6200），在惰性氣體環境中，以1.5℃/min自室溫升溫至450℃，進行熔點的測定。[Determination of melting point] Using a differential scanning calorimetry device (DSC (Differential Scanning Calorimetry), manufactured by SII, trade name: DSC-6200), in an inert gas environment, the temperature is raised from room temperature to 1.5°C/min At 450°C, the melting point was measured.
[拉伸彈性模量的測定] （樹脂膜） 使用張力試驗器（奧立恩泰科（orientec）製造，商品名：滕喜龍（Tensilon）），由樹脂膜製作試驗片（寬度12.7 mm×長度127 mm）。使用所述試驗片，以50 mm/min進行拉伸試驗，求出25℃下的拉伸彈性模量。 （填料） 隨機取出10根填料加工前的長纖維，將各長纖維加工成200 mm的長度，依據日本工業標準（Japanese Industrial Standards，JIS）L 1013（2010）的標準時試驗，使用拉伸試驗機（島津製作所公司製，商品名：AGS-500NX），在拉伸速度200 mm/min下，對各長纖維求出拉伸彈性模量，並以平均值來表示。[Determination of Tensile Modulus of Elasticity] (Resin film) Using a tensile tester (manufactured by Orientec, trade name: Tensilon), a test piece (width 12.7 mm × length 127 mm) was made from a resin film. Using the test piece, a tensile test was performed at 50 mm/min, and the tensile elastic modulus at 25°C was determined. (filler) Randomly take out 10 long fibers before filler processing, and process each long fiber into a length of 200 mm. Test according to the standard time of Japanese Industrial Standards (JIS) L 1013 (2010), using a tensile testing machine (Shimadzu Corporation) The company’s product, trade name: AGS-500NX), at a tensile speed of 200 mm/min, the tensile elastic modulus of each long fiber is calculated and expressed as an average value.
[平均長軸徑及平均短軸徑的測定方法] 隨機取出10個填料，使用體視顯微鏡，獨立地進行觀察，對所取出的各填料測定長軸徑及短軸徑，並以平均值的形式來求出。[Method for measuring average major axis diameter and average minor axis diameter] Ten fillers were taken out at random and observed independently using a stereo microscope. The major axis diameter and the minor axis diameter of each filler were measured, and the average value was calculated.
[真比重的測定] 使用連續自動粉體真密度測定裝置（清新（seishin）企業公司製造，商品名：自動真密度（AUTO TRUE DENSER）MAT-7000），進行基於比重計（pycnometer）法（液相置換法）的真比重的測定。[Determination of true specific gravity] A continuous automatic powder true density measuring device (manufactured by Seishin Enterprise Co., Ltd., trade name: AUTO TRUE DENSER MAT-7000) was used to perform the true density measurement based on the pycnometer method (liquid phase displacement method). Determination of specific gravity.
[凝聚評價] 確認在對支撐體塗布清漆時，使500 mL的清漆通過500 μm的間隙塗布機時，有無非通過固形物的存在。[Cohesion Evaluation] When applying the varnish to the support, it was confirmed whether there were any non-passing solids when 500 mL of the varnish was passed through a 500 μm gap coater.
[相對介電常數及介電損耗正切的測定] （樹脂膜） 使用向量網路分析儀（Vector Network Analyzer）（安捷倫（Agilent）公司製造，商品名：向量網路分析儀（Vector Network Analyzer）E8363C）以及分離介質諧振器（Split Post Dielectric Resonator，SPDR），測定頻率10 GHz下的樹脂膜（硬化後的樹脂膜）的相對介電常數（ε1）及介電損耗正切（Tanδ1）。再者，測定時所使用的樹脂膜是在溫度：24℃～26℃、濕度：45%～55%的條件下放置24小時的樹脂膜。 （液晶聚合物） 使用向量網路分析儀（安捷倫（Agilent）公司製造，商品名：向量網路分析儀（Vector Network Analyzer）E8363C）以及SPDR，測定使液晶聚合物熔融成型為板狀而成的樣品的頻率1 GHz下的相對介電常數（ε1）及介電損耗正切（Tanδ1）。再者，測定時所使用的樣品是在溫度：24℃～26℃、濕度：45%～55%的條件下放置24小時的樣品。[Measurement of relative permittivity and dielectric loss tangent] (Resin film) Use Vector Network Analyzer (manufactured by Agilent, trade name: Vector Network Analyzer E8363C) and Split Post Dielectric Resonator (SPDR) to measure the frequency Relative permittivity (ε1) and dielectric loss tangent (Tanδ1) of the resin film (resin film after curing) at 10 GHz. In addition, the resin film used in the measurement is a resin film left for 24 hours under the conditions of temperature: 24° C. to 26° C. and humidity: 45% to 55%. (Liquid Crystal Polymer) Using a vector network analyzer (manufactured by Agilent, trade name: Vector Network Analyzer (Vector Network Analyzer) E8363C) and SPDR, the frequency of a sample obtained by melting and molding a liquid crystal polymer into a plate shape is measured at 1 GHz Relative permittivity (ε1) and dielectric loss tangent (Tanδ1) below. In addition, the sample used in the measurement is a sample left for 24 hours under the conditions of temperature: 24°C to 26°C and humidity: 45% to 55%.
[剖面觀察] 1）測定用樣品的製作 以覆銅積層板（TD：10 mm×MD：10 mm）的、樣品的觀察面（厚度方向上的剖面）成為MD方向的方式，利用環氧系樹脂包埋樣品後，使用旋轉板型研磨機，進行利用多張砂紙（emery paper）（至#1200）的研磨及拋光研磨（至金剛石粒子糊的1 μm為止）以及利用藥液的化學研磨，製作測定用樣品。 2）測定用樣品的觀察。 使用掃描電子顯微鏡（SEM），以200倍～3000倍的倍率觀察測定用樣品的觀察面。[Profile Observation] 1) Preparation of samples for measurement The observation surface of the sample (cross section in the thickness direction) of the copper-clad laminate (TD: 10 mm×MD: 10 mm) is in the MD direction. After embedding the sample with epoxy resin, it is polished using a rotary plate The machine performs grinding and polishing (up to 1 μm of the diamond particle paste) with multiple emery paper (up to #1200) and chemical grinding with chemical solution to prepare samples for measurement. 2) Observation of the sample for measurement. Using a scanning electron microscope (SEM), the observation surface of the measurement sample is observed at a magnification of 200 to 3000 times.
實施例及比較例中所使用的簡稱是表示以下的化合物。 PMDA：均苯四甲酸二酐 BPDA：3,3',4,4'-聯苯基四羧酸二酐 m-TB：2,2'-二甲基-4,4'-二胺基聯苯 DMAc：N,N-二甲基乙醯胺 填料1：具有聚酯結構的液晶聚合物，短纖維狀，平均短軸徑：28 μm，平均長軸徑：1000 μm，熔點（Tm）：350℃，真比重：1.4，拉伸彈性模量：85 GPa，相對介電常數：3.1，介電損耗正切：0.0010 填料2：具有聚酯結構的液晶聚合物，短纖維狀，平均短軸徑：28 μm，平均長軸徑：500 μm，熔點（Tm）：350℃，真比重：1.4，拉伸彈性模量：85 GPa，相對介電常數：3.1，介電損耗正切：0.0010 填料3：具有聚酯結構的液晶聚合物，短纖維狀，平均短軸徑：28 μm，平均長軸徑：1000 μm，熔點（Tm）：330℃，真比重：1.4，拉伸彈性模量：160 GPa，相對介電常數：3.4，介電損耗正切：0.0020 填料4：具有聚酯結構的液晶聚合物，短纖維狀，平均短軸徑：14 μm，平均長軸徑：1000 μm，熔點（Tm）：330℃，真比重：1.4，拉伸彈性模量：140 GPa，相對介電常數：3.4，介電損耗正切：0.0020 填料5：具有聚酯結構的液晶聚合物粒子，不定形形狀，平均短軸徑：8 μm，平均長軸徑：14 μm，熔點（Tm）：320℃，真比重：1.4，相對介電常數：3.4，介電損耗正切：0.0010The abbreviations used in Examples and Comparative Examples indicate the following compounds. PMDA: Pyromellitic dianhydride BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride m-TB: 2,2'-dimethyl-4,4'-diaminobiphenyl DMAc: N,N-Dimethylacetamide Filler 1: Liquid crystal polymer with polyester structure, short fiber shape, average minor axis diameter: 28 μm, average major axis diameter: 1000 μm, melting point (Tm): 350°C, true specific gravity: 1.4, tensile elastic modulus ：85 GPa, relative dielectric constant: 3.1, dielectric loss tangent: 0.0010 Filler 2: Liquid crystal polymer with polyester structure, short fiber shape, average minor axis diameter: 28 μm, average major axis diameter: 500 μm, melting point (Tm): 350°C, true specific gravity: 1.4, tensile modulus of elasticity ：85 GPa, relative dielectric constant: 3.1, dielectric loss tangent: 0.0010 Filler 3: Liquid crystal polymer with polyester structure, short fiber shape, average minor axis diameter: 28 μm, average major axis diameter: 1000 μm, melting point (Tm): 330°C, true specific gravity: 1.4, tensile modulus of elasticity : 160 GPa, relative dielectric constant: 3.4, dielectric loss tangent: 0.0020 Filler 4: Liquid crystal polymer with polyester structure, short fiber shape, average minor axis diameter: 14 μm, average major axis diameter: 1000 μm, melting point (Tm): 330°C, true specific gravity: 1.4, tensile modulus of elasticity : 140 GPa, relative permittivity: 3.4, dielectric loss tangent: 0.0020 Filler 5: Liquid crystal polymer particles with polyester structure, irregular shape, average minor axis diameter: 8 μm, average major axis diameter: 14 μm, melting point (Tm): 320°C, true specific gravity: 1.4, relative permittivity : 3.4, Dielectric loss tangent: 0.0010
[實施例1] 在300 ml的可分離式燒瓶中，投入17 g的m-TB（82 mmol）、230 g的DMAc，在室溫、氮氣流下進行攪拌。完全溶解後，添加4.5 g的PMDA（20 mmol）及18 g的BPDA（62 mmol）、4.2 g的填料1，在室溫下攪拌18小時，製備樹脂溶液1（黏度：30,000 cps，填料1相對於不揮發性成分的含有率：10體積%）。[Example 1] Put 17 g of m-TB (82 mmol) and 230 g of DMAc into a 300 ml separable flask, and stir at room temperature under nitrogen flow. After completely dissolved, add 4.5 g of PMDA (20 mmol), 18 g of BPDA (62 mmol), 4.2 g of filler 1, and stir at room temperature for 18 hours to prepare resin solution 1 (viscosity: 30,000 cps, filler 1 is relatively The content of non-volatile components: 10% by volume).
在銅箔（電解銅箔，厚度：12 μm）上以約350 μm的厚度塗布樹脂溶液1，在130℃下乾燥5分鐘而形成樹脂層。其後，自150℃至380℃，歷時20分鐘，階段性地進行熱處理，完成醯亞胺化，製備覆銅積層板1。 蝕刻去除覆銅積層板1的銅箔，製備樹脂膜1（厚度：48 μm）。樹脂膜1的CTE為13 ppm/K，相對介電常數為3.1，介電損耗正切為0.0039。The resin solution 1 was coated with a thickness of about 350 μm on copper foil (electrolytic copper foil, thickness: 12 μm), and dried at 130° C. for 5 minutes to form a resin layer. Thereafter, from 150° C. to 380° C., for 20 minutes, heat treatment was performed step by step to complete the imidization, and the copper-clad laminate 1 was prepared. The copper foil of the copper-clad laminate 1 was etched away to prepare a resin film 1 (thickness: 48 μm). The CTE of the resin film 1 is 13 ppm/K, the relative dielectric constant is 3.1, and the dielectric loss tangent is 0.0039.
[實施例2] 將實施例1中的填料1的添加量代替為17 g，添加填料1後進而追加添加94 g的DMAc，除此以外，與實施例1同樣地製備樹脂溶液2（黏度：34,000 cps，填料1相對於不揮發性成分的含有率：30體積%）。[Example 2] The addition amount of the filler 1 in Example 1 was replaced with 17 g, and after the filler 1 was added, 94 g of DMAc was additionally added, except that the resin solution 2 was prepared in the same manner as in Example 1 (viscosity: 34,000 cps, filler 1 Relative to the content of non-volatile components: 30% by volume).
在銅箔（電解銅箔，厚度：12 μm）上以約350 μm的厚度塗布樹脂溶液2，在130℃下乾燥5分鐘而形成樹脂層。其後，自150℃至380℃，歷時20分鐘，階段性地進行熱處理，完成醯亞胺化，製備覆銅積層板2。 蝕刻去除覆銅積層板2的銅箔，製備樹脂膜2（厚度：37 μm）。樹脂膜2的CTE為3 ppm/K，相對介電常數為2.3，介電損耗正切為0.0035。The resin solution 2 was coated with a thickness of about 350 μm on copper foil (electrolytic copper foil, thickness: 12 μm), and dried at 130° C. for 5 minutes to form a resin layer. Thereafter, from 150° C. to 380° C. for 20 minutes, heat treatment was performed step by step to complete the imidization, and the copper-clad laminate 2 was prepared. The copper foil of the copper-clad laminate 2 was etched away to prepare a resin film 2 (thickness: 37 μm). The CTE of the resin film 2 is 3 ppm/K, the relative dielectric constant is 2.3, and the dielectric loss tangent is 0.0035.
[實施例3] 代替實施例1中的4.2 g的填料1而添加4.3 g的填料2，及添加填料2後進而追加添加25 g的DMAc，除此以外，與實施例1同樣地製備樹脂溶液3（黏度：28,000 cps，填料2相對於不揮發性成分的含有率：10體積%）。[Example 3] Instead of 4.2 g of filler 1 in Example 1, 4.3 g of filler 2 was added, and after filler 2 was added, 25 g of DMAc was added. Resin solution 3 was prepared in the same manner as in Example 1 (viscosity: 28,000). cps, the content rate of the filler 2 with respect to the non-volatile component: 10% by volume).
在銅箔（電解銅箔，厚度：12 μm）上以約350 μm的厚度塗布樹脂溶液3，在130℃下乾燥5分鐘而形成樹脂層。其後，自150℃至380℃，歷時20分鐘，階段性地進行熱處理，完成醯亞胺化，製備覆銅積層板3。 蝕刻去除覆銅積層板3的銅箔，製備樹脂膜3（厚度：55 μm）。樹脂膜3的CTE為15 ppm/K，相對介電常數為2.8，介電損耗正切為0.0037。The resin solution 3 was coated with a thickness of about 350 μm on copper foil (electrolytic copper foil, thickness: 12 μm), and dried at 130° C. for 5 minutes to form a resin layer. Thereafter, from 150° C. to 380° C. for 20 minutes, heat treatment was performed in stages to complete the imidization, and the copper-clad laminate 3 was prepared. The copper foil of the copper-clad laminate 3 was etched away to prepare a resin film 3 (thickness: 55 μm). The CTE of the resin film 3 is 15 ppm/K, the relative dielectric constant is 2.8, and the dielectric loss tangent is 0.0037.
[實施例4] 代替實施例2的填料1而使用填料2，除此以外，與實施例2同樣地製備樹脂溶液4（黏度：30,000 cps，填料2相對於不揮發性成分的含有率：30體積%）。[Example 4] Except that the filler 2 was used instead of the filler 1 of Example 2, the resin solution 4 (viscosity: 30,000 cps, content rate of filler 2 with respect to the nonvolatile component: 30 volume%) was prepared similarly to Example 2 except this.
在銅箔（電解銅箔，厚度：12 μm）上以約350 μm的厚度塗布樹脂溶液4，在130℃下乾燥5分鐘而形成樹脂層。其後，自150℃至380℃，歷時20分鐘，階段性地進行熱處理，完成醯亞胺化，製備覆銅積層板4。 蝕刻去除覆銅積層板4的銅箔，製備樹脂膜4（厚度：67 μm）。樹脂膜4的CTE為8 ppm/K，相對介電常數為2.5，介電損耗正切為0.0034。The resin solution 4 was coated with a thickness of about 350 μm on copper foil (electrolytic copper foil, thickness: 12 μm), and dried at 130° C. for 5 minutes to form a resin layer. Thereafter, from 150° C. to 380° C. for 20 minutes, heat treatment was performed in stages to complete the imidization, and the copper-clad laminate 4 was prepared. The copper foil of the copper-clad laminated board 4 was removed by etching, and the resin film 4 (thickness: 67 μm) was prepared. The CTE of the resin film 4 is 8 ppm/K, the relative dielectric constant is 2.5, and the dielectric loss tangent is 0.0034.
[實施例5] 代替實施例1中的4.2 g的填料1而添加34 g的填料2，及添加填料2後進而添加180 g的DMAc，除此以外，與實施例1同樣地製備樹脂溶液5（黏度：45,000 cps，填料2相對於不揮發性成分的含有率：60體積%）。[Example 5] Instead of 4.2 g of filler 1 in Example 1, 34 g of filler 2 was added, and after filler 2 was added, 180 g of DMAc was added. Resin solution 5 was prepared in the same manner as in Example 1 (viscosity: 45,000 cps). , Filler 2 with respect to the content of non-volatile components: 60% by volume).
在銅箔（電解銅箔，厚度：12 μm）上以約350 μm的厚度塗布樹脂溶液5，在130℃下乾燥5分鐘而形成樹脂層。其後，自150℃至380℃，歷時20分鐘，階段性地進行熱處理，完成醯亞胺化，製備覆銅積層板5。 蝕刻去除覆銅積層板5的銅箔，製備樹脂膜5（厚度：67 μm）。樹脂膜5的CTE為2 ppm/K，相對介電常數為3.0，介電損耗正切為0.0029。The resin solution 5 was coated with a thickness of about 350 μm on copper foil (electrolytic copper foil, thickness: 12 μm), and dried at 130° C. for 5 minutes to form a resin layer. Thereafter, from 150° C. to 380° C. for 20 minutes, heat treatment was performed in stages to complete the imidization, and the copper-clad laminate 5 was prepared. The copper foil of the copper-clad laminate 5 was etched away to prepare a resin film 5 (thickness: 67 μm). The CTE of the resin film 5 is 2 ppm/K, the relative dielectric constant is 3.0, and the dielectric loss tangent is 0.0029.
[實施例6] 代替實施例1的填料1而使用填料3，除此以外，與實施例1同樣地製備樹脂溶液6（黏度：30,000 cps，填料3相對於不揮發性成分的含有率：10體積%）。[Example 6] Except that the filler 3 was used instead of the filler 1 of Example 1, the resin solution 6 (viscosity: 30,000 cps, content rate of filler 3 with respect to the non-volatile component: 10 volume%) was prepared similarly to Example 1 except this.
在銅箔（電解銅箔，厚度：12 μm）上以約350 μm的厚度塗布樹脂溶液6，在130℃下乾燥5分鐘而形成樹脂層。其後，自150℃至380℃，歷時20分鐘，階段性地進行熱處理，完成醯亞胺化，製備覆銅積層板6。 蝕刻去除覆銅積層板6的銅箔，製備樹脂膜6（厚度：50 μm）。樹脂膜6的CTE為18 ppm/K，相對介電常數為3.1，介電損耗正切為0.0039。The resin solution 6 was coated with a thickness of about 350 μm on copper foil (electrolytic copper foil, thickness: 12 μm), and dried at 130° C. for 5 minutes to form a resin layer. Thereafter, from 150° C. to 380° C. for 20 minutes, heat treatment was performed in stages to complete the imidization, and the copper-clad laminate 6 was prepared. The copper foil of the copper-clad laminate 6 was etched away to prepare a resin film 6 (thickness: 50 μm). The CTE of the resin film 6 is 18 ppm/K, the relative dielectric constant is 3.1, and the dielectric loss tangent is 0.0039.
[實施例7] 代替實施例1的填料1而使用填料4，除此以外，與實施例1同樣地製備樹脂溶液7（黏度：28,000 cps，填料4相對於不揮發性成分的含有率：10體積%）。[Example 7] Except that the filler 4 was used instead of the filler 1 of Example 1, the resin solution 7 (viscosity: 28,000 cps, content rate of filler 4 with respect to the non-volatile component: 10 volume %) was prepared similarly to Example 1 except this.
在銅箔（電解銅箔，厚度：12 μm）上以約350 μm的厚度塗布樹脂溶液7，在130℃下乾燥5分鐘而形成樹脂層。其後，自150℃至380℃，歷時20分鐘，階段性地進行熱處理，完成醯亞胺化，製備覆銅積層板7。將所獲得的覆銅積層板7的剖面結構示於圖1中。確認在聚醯亞胺中進行配向的填料4的短軸方向上的剖面。 蝕刻去除覆銅積層板7的銅箔，製備樹脂膜7（厚度：45 μm）。樹脂膜7的CTE為16 ppm/K，相對介電常數為3.0，介電損耗正切為0.0040。The resin solution 7 was coated with a thickness of about 350 μm on copper foil (electrolytic copper foil, thickness: 12 μm), and dried at 130° C. for 5 minutes to form a resin layer. Thereafter, from 150° C. to 380° C. for 20 minutes, heat treatment was performed in stages to complete the imidization, and the copper-clad laminate 7 was prepared. The cross-sectional structure of the obtained copper-clad laminated board 7 is shown in FIG. 1. The cross section in the minor axis direction of the filler 4 aligned in the polyimide was confirmed. The copper foil of the copper-clad laminate 7 was removed by etching, and a resin film 7 (thickness: 45 μm) was prepared. The CTE of the resin film 7 is 16 ppm/K, the relative dielectric constant is 3.0, and the dielectric loss tangent is 0.0040.
（比較例1） 在銅箔（電解銅箔，厚度：12 μm）上以約500 μm的厚度塗布聚醯胺酸溶液1，在130℃下乾燥5分鐘而形成樹脂層。其後，自150℃至380℃，歷時20分鐘，階段性地進行熱處理，完成醯亞胺化，製備覆銅積層板8。 蝕刻去除覆銅積層板8的銅箔，製備樹脂膜8（厚度：41 μm）。樹脂膜8的CTE為19 ppm/K，相對介電常數為3.4，介電損耗正切為0.0041，真比重為1.4，拉伸彈性模量為8 GPa。(Comparative example 1) The polyamide acid solution 1 was coated with a thickness of about 500 μm on copper foil (electrolytic copper foil, thickness: 12 μm), and dried at 130° C. for 5 minutes to form a resin layer. Thereafter, from 150° C. to 380° C. for 20 minutes, heat treatment was performed in stages to complete the imidization, and the copper-clad laminate 8 was prepared. The copper foil of the copper-clad laminate 8 was etched away to prepare a resin film 8 (thickness: 41 μm). The CTE of the resin film 8 is 19 ppm/K, the relative dielectric constant is 3.4, the dielectric loss tangent is 0.0041, the true specific gravity is 1.4, and the tensile modulus of elasticity is 8 GPa.
（比較例2） 將140 g的聚醯胺酸溶液1及8.3 g的填料3混合並攪拌，製備樹脂溶液9（填料3相對於不揮發性成分的含有率：30體積%）。(Comparative example 2) 140 g of polyamide acid solution 1 and 8.3 g of filler 3 were mixed and stirred to prepare resin solution 9 (content rate of filler 3 with respect to nonvolatile components: 30% by volume).
在銅箔（電解銅箔，厚度：12 μm）上以約350 μm的厚度塗布樹脂溶液9，結果，填料凝聚而成的固形物堵塞於塗布機間隙間。即便擴大到500 μm的間隙，也同樣產生固形物的堵塞。The resin solution 9 was applied to the copper foil (electrolytic copper foil, thickness: 12 μm) to a thickness of about 350 μm. As a result, the solid matter formed by agglomeration of the filler was clogged between the gaps of the coater. Even if the gap is enlarged to 500 μm, it also causes blockage of solids.
（參考例1） 代替實施例1的填料1而使用7 g的填料5，除此以外，與實施例1同樣地製備樹脂溶液10（黏度：28000 cps，填料5相對於不揮發性成分的含有率：30體積%）。(Reference example 1) Except that 7 g of filler 5 was used instead of filler 1 of Example 1, a resin solution 10 was prepared in the same manner as in Example 1 (viscosity: 28000 cps, content rate of filler 5 with respect to non-volatile components: 30% by volume ).
在銅箔（電解銅箔，厚度：12 μm）上以約350 μm的厚度塗布樹脂溶液10，在130℃下乾燥5分鐘而形成樹脂層。其後，自150℃至380℃，歷時20分鐘，階段性地進行熱處理，完成醯亞胺化，製備覆銅積層板10。 蝕刻去除覆銅積層板10的銅箔，製備樹脂膜10（厚度：45 μm）。樹脂膜10的CTE為33 ppm/K，相對介電常數為3.3，介電損耗正切為0.0030。The resin solution 10 was coated with a thickness of about 350 μm on copper foil (electrolytic copper foil, thickness: 12 μm), and dried at 130° C. for 5 minutes to form a resin layer. Thereafter, from 150° C. to 380° C., for 20 minutes, heat treatment is performed step by step to complete the imidization, and the copper-clad laminate 10 is prepared. The copper foil of the copper-clad laminated board 10 was etched and removed, and the resin film 10 (thickness: 45 μm) was prepared. The CTE of the resin film 10 is 33 ppm/K, the relative dielectric constant is 3.3, and the dielectric loss tangent is 0.0030.
將以上的結果一起示於表1中。The above results are shown in Table 1 together.
[表1]
根據實施例1～實施例7、比較例1的結果，確認到：通過添加填料1～填料4，可抑制CTE的上升，同時可減低介電常數及介電損耗正切。在比較例2（調配法）中，在樹脂液中，填料彼此纏繞而產生凝聚，無法塗敷。另外，參考例1中，介電損耗正切降低，但CTE顯著上升。According to the results of Examples 1 to 7 and Comparative Example 1, it was confirmed that by adding fillers 1 to 4, the increase in CTE can be suppressed, and the dielectric constant and the dielectric loss tangent can be reduced. In Comparative Example 2 (mixing method), in the resin liquid, the fillers were entangled with each other to cause aggregation, and the coating could not be performed. In addition, in Reference Example 1, the dielectric loss tangent decreased, but the CTE increased significantly.
以上，以例示的目的詳細地說明瞭本發明的實施形態，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, the embodiment of the present invention has been described in detail for the purpose of illustration, but the present invention is not restricted by the above-mentioned embodiment, and various modifications can be made.
無。without.
圖1是實施例7中所製作的覆銅積層板的樹脂層的外觀照片。FIG. 1 is a photograph of the appearance of the resin layer of the copper-clad laminate produced in Example 7. FIG.
無。without.
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