JP2006224644A - Insulating sheet, metallic layer and insulating sheet laminate, and printed wiring board using same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an insulating sheet which can be preferably used for manufacturing a printed wiring board and the like, shows excellent adhesion to a metallic layer formed on a surface of the sheet even if the surface roughness of the sheet is small, has small coefficient of linear expansion and shows excellence in the uniformity of insulation thickness between layers and the reliability of insulation between layers in a fabricated multi-layered printed wiring board, and to provide its typical utilization technique. <P>SOLUTION: The insulating sheet is characterized in that a layer B containing a thermoplastic polyimide resin having a specific structure is formed on one surface of a non-thermoplastic polyimide film layer A, and in that a layer C containing a thermoplastic polyimide resin and a thermosetting component is formed on another surface of the film layer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an insulating sheet used for a printed wiring board, which is widely used in electrical / electronic devices and the like. More specifically, the surface of the insulating sheet is smooth, and when the metal layer is formed thereon, the adhesiveness with the metal layer is high, and the melt viscosity when laminated with the circuit surface is low, and the linear expansion after lamination hardening It relates to an insulating sheet having a small coefficient.

Printed wiring boards are widely used for mounting electronic components, semiconductor elements, and the like. With recent demands for downsizing and higher functionality of electronic devices, there is a strong demand for higher density and thinner wiring. In particular, establishment of a fine wiring forming method in which the line / space spacing is 25 μm / 25 μm or less is an important issue in the field of printed wiring boards.
The insulating layer used in the printed wiring board is preferably an insulating adhesive sheet having both a role for forming wiring thereon and a role for laminating on a circuit formed on a substrate or the like.
Such an insulating adhesive sheet is required to have high adhesion to the fine wiring and to be sufficiently smooth so that the surface roughness does not adversely affect the fine wiring formation in order to form the fine wiring. Further, in the case of fine wiring formation, the wiring shape, wiring width, wiring thickness and the like cannot be satisfactorily formed as designed unless the unevenness on the surface of the insulating adhesive sheet is made as small as possible. Therefore, the most preferable insulating adhesive sheet for forming fine wiring is an insulating layer having extremely small surface irregularities and sufficiently high adhesion to the fine wiring.
On the other hand, when manufacturing multilayer flexible printed wiring boards, build-up wiring boards, etc., an insulating adhesive sheet is laminated on a conductor circuit already formed on a substrate, but the insulating adhesive sheet flows during lamination. In addition, it is necessary to embed between the lines of the circuit wiring and to firmly bond the insulating adhesive sheet and the conductor circuit, and the insulating adhesive sheet and the insulating film on which the circuit is formed. That is, the insulating adhesive sheet is required to have fluidity that can fill the space between the circuit wirings together with excellent adhesion to the inner layer circuit, the substrate, and the like.

Furthermore, when manufacturing a printed wiring board, it is indispensable to form a via hole that conducts both sides of the wiring board. Therefore, such a printed wiring board is usually subjected to wiring formation through a laser via hole forming step, a desmear step, a catalyst application step, a step of applying electroless plated copper, and the like. In addition, fine wiring formation usually comprises a step of forming a resist film, an electrolytic copper plating step on the exposed portion of the electroless plating film, a step of removing the resist film, and an etching step of the extra electroless copper plating film. It is often produced by a so-called semi-additive process. Therefore, it is more preferable that the adhesion between the fine wiring and the insulating layer can withstand these processes.
It is believed that by using an insulating adhesive sheet that satisfies the above requirements, it is possible to provide a high-density printed wiring board for electronic equipment that requires high-speed, high-frequency electrical signals, and its appearance is strongly desired.
Here, conventionally, an epoxy-based adhesive material is generally used as the adhesive material used for the wiring board. The above-mentioned epoxy-based adhesive material is excellent in workability such as bonding between adherends under low temperature and low pressure conditions and embedding between circuit wiring lines, and excellent adhesion to adherends. Yes. However, the adhesion to the metal layer, that is, the adhesion between the epoxy adhesive material and the circuit wiring formed thereon was insufficient. In order to improve this problem, adhesiveness has been improved by surface irregularities called an anchor effect (see, for example, Patent Document 1). However, it has been difficult to obtain a sufficient adhesion force to the wiring without reducing the surface unevenness to be formed or without particularly forming the unevenness.
On the other hand, an interlayer insulating adhesion technique using an adhesive containing polyimide siloxane has been disclosed (for example, see Patent Document 2). However, Patent Document 2 does not disclose the configuration of the present invention having at least the outermost layer for forming the metal layer and the outermost layer for facing the formed circuit.

  In addition, when the performance and speed of a semiconductor element are increased, the strength of the semiconductor element may decrease (become easily broken). Furthermore, when the density of printed wiring boards is increased, higher precision is required for mounting the elements and the board, and the allowable range of positional deviation is becoming smaller.

At this time, if the linear expansion coefficients of the substrate and the element are greatly different, a change in temperature of the substrate on which the element is mounted causes a dimensional deviation between the substrate and the element, and stress is generated. Or the device breaks. In order to avoid such a trouble, a material having a linear expansion coefficient close to that of a semiconductor element, that is, a material having a small linear expansion coefficient, is required for the printed wiring board material.
From the viewpoint of reducing the linear expansion coefficient of a material, a technique for controlling the linear expansion coefficient and the viscosity by containing a filler in a sealing resin of a semiconductor device is disclosed. However, it does not relate to an interlayer insulating material for a printed wiring board, and has not yet provided a material suitable for a printed wiring board having both heat resistance and workability.
JP2000-198907 JP 2000-290606 A JP 07-66329 A

  The present invention is for solving the above-mentioned conventional problems, and its purpose is to provide flexible printed wiring boards, rigid printed wiring boards, multilayer flexible printed wiring boards, multilayer rigid wiring boards, build-up wiring boards, and the like. It can be suitably used for the manufacture of printed wiring boards, etc., has a small surface roughness, can form fine wiring, and can strongly form electroless plated copper on the surface, It is to provide an insulating sheet having a good laminate property and a small linear expansion coefficient and a typical application technique thereof.

As a result of intensive studies in view of the above problems, the present inventors have found that the above problems can be solved by the following novel insulating sheet. That is,
1) A layer B containing a thermoplastic polyimide resin having a siloxane structure is formed on one side of the polymer film layer A, and a layer C containing a thermoplastic polyimide resin and a thermosetting component is formed on the other side. An insulating sheet characterized by that.
2) The thermoplastic polyimide resin having the siloxane structure is a thermoplastic polyimide resin that uses an acid dianhydride component and a diamine component containing a diamine represented by the following general formula (1) as raw materials. 1) The insulating sheet as described.

（式中、ｇは１以上の整数を表す。また、Ｒ¹¹及びＲ²²は、それぞれ同一、または異なっていてよく、炭素数１〜６のアルキレン基またはフェニレン基を表す。Ｒ³³〜Ｒ⁶⁶は、それぞれ同一、または異なっていてよく、炭素数１〜６のアルキル基、またはアルコキシ基、またはフェニル基、またはフェノキシ基を表す。）
３） 前記層Ｂは、該層上に金属層を形成するための層であるとともに、前記層Ｃは、別途形成された回路と対向し積層させるための層であることを特徴とする１）または２）記載の絶縁シート。
４） 前記層Ｂの厚みが、前記層Ａの厚みの１倍以下であることを特徴とする１）〜３）のいずれか一項に記載の絶縁シート。
５） 前記層Ｂの引張弾性率が、前記層Ａの引張弾性率の１倍以下であることを特徴とする１）〜４）のいずれか一項に記載の絶縁シート。
６） 前記層Ｃがフィラーを５体積％以上含むことを特徴とする１）〜５）のいずれか一項に記載の絶縁シート
７） 前記フィラーが球状溶融シリカであることを特徴とする６）記載の絶縁シート。
８） 前記フィラーがシラン系またはチタン系のカップリング剤または表面処理剤で表面処理したフィラーであることを特徴とする６）または７）に記載の絶縁シート。
９）前記Ｃ層に含まれる熱硬化性成分がエポキシ樹脂成分を含むことを特徴とする１）〜８）のいずれか１項に記載の絶縁シート。
１０） 前記Ｃ層のＢ−ステージ状態での溶融粘度が２０，０００Ｐａ・ｓ以下であることを特徴とする１）〜９）のいずれか１項に記載の絶縁シート。
１１） 前記層Ｂのカットオフ値０.００２ｍｍで測定した算術平均粗さ（Ｒａ）が０.５μｍ未満であることを特徴とする１）〜１０）のいずれか１項に記載の絶縁シート。
１２） 前記金属層が、無電解銅メッキにより形成されることを特徴とする１）〜１１）のいずれか一項に記載の絶縁シート。
１３） 前記１）〜１１）のいずれか一項に記載の絶縁シートの層Ｂ上に金属層が形成された金属層／絶縁シート積層体であって、金属層の密着強度が５Ｎ/ｃｍ以上であることを特徴とする金属層／絶縁シート積層体。
１４） 前記金属層が、無電解銅メッキにより形成したものであることを特徴とする１３）記載の金属層／絶縁シート積層体。
１５） 前記金属層が、スパッタリング法、真空蒸着法、イオンプレーティング法または化学蒸着法のいずれかで形成されたものであることを特徴とする１３）記載の金属層／絶縁シート積層体。
１６） １）〜１５）のいずれか１項に記載の絶縁シートまたは金属層／絶縁シート積層体を用いることを特徴とするプリント配線板。
１７） 高分子フィルム層Ａの片面に、酸二無水物成分と、下記一般式（１）で表されるジアミンを含むジアミン成分を原料とする熱可塑性ポリイミド樹脂を含有する層Ｂが形成され、他方の面に、別途形成された回路と対向し積層させるための層が形成されたことを特徴とする絶縁シート。

(In the formula, g represents an integer of 1 or more. Further, R ¹¹ and R ²² may be the same or different and each represents an alkylene group or phenylene group having 1 to 6 carbon atoms. R ^{33 to} R ^66. May be the same or different and each represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group, a phenyl group, or a phenoxy group.)
3) The layer B is a layer for forming a metal layer on the layer, and the layer C is a layer for facing and laminating a separately formed circuit 1) Or the insulating sheet of 2) description.
4) The insulating sheet according to any one of 1) to 3), wherein the thickness of the layer B is not more than 1 times the thickness of the layer A.
5) The insulating sheet according to any one of 1) to 4), wherein the tensile modulus of the layer B is not more than 1 times the tensile modulus of the layer A.
6) The layer C contains 5% by volume or more of a filler. The insulating sheet 7) according to any one of 1) to 5), wherein the filler is spherical fused silica. 6) The insulating sheet described.
8) The insulating sheet according to 6) or 7), wherein the filler is a filler surface-treated with a silane-based or titanium-based coupling agent or surface treatment agent.
9) The insulating sheet according to any one of 1) to 8), wherein the thermosetting component contained in the C layer contains an epoxy resin component.
10) The insulating sheet according to any one of 1) to 9), wherein the melt viscosity in the B-stage state of the C layer is 20,000 Pa · s or less.
11) The insulating sheet according to any one of 1) to 10), wherein the arithmetic average roughness (Ra) measured at a cutoff value of 0.002 mm of the layer B is less than 0.5 μm.
12) The insulating sheet according to any one of 1) to 11), wherein the metal layer is formed by electroless copper plating.
13) A metal layer / insulating sheet laminate in which a metal layer is formed on the layer B of the insulating sheet according to any one of 1) to 11) above, wherein the adhesion strength of the metal layer is 5 N / cm or more. A metal layer / insulating sheet laminate characterized by the above.
14) The metal layer / insulating sheet laminate according to 13), wherein the metal layer is formed by electroless copper plating.
15) The metal layer / insulating sheet laminate according to 13), wherein the metal layer is formed by any one of a sputtering method, a vacuum deposition method, an ion plating method, and a chemical vapor deposition method.
16) A printed wiring board using the insulating sheet or the metal layer / insulating sheet laminate according to any one of 1) to 15).
17) On one side of the polymer film layer A, a layer B containing an acid dianhydride component and a thermoplastic polyimide resin made from a diamine component containing a diamine represented by the following general formula (1) is formed, An insulating sheet, wherein a layer for laminating and facing a separately formed circuit is formed on the other surface.

（式中、ｇは１以上の整数を表す。また、Ｒ¹¹及びＲ²²は、それぞれ同一、または異なっていてよく、炭素数１〜６のアルキレン基またはフェニレン基を表す。Ｒ³³〜Ｒ⁶⁶は、それぞれ同一、または異なっていてよく、炭素数１〜６のアルキル基、またはアルコキシ基、またはフェニル基、またはフェノキシ基を表す。）
１８） 高分子フィルムが非熱可塑性ポリイミドであることを特徴とする１）〜１７）に記載の絶縁シートならびに金属層／絶縁シート積層体またはプリント配線板。

(In the formula, g represents an integer of 1 or more. Further, R ¹¹ and R ²² may be the same or different and each represents an alkylene group or phenylene group having 1 to 6 carbon atoms. R ^{33 to} R ^66. May be the same or different and each represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group, a phenyl group, or a phenoxy group.)
18) The insulating sheet and the metal layer / insulating sheet laminate or printed wiring board according to 1) to 17), wherein the polymer film is a non-thermoplastic polyimide.

  In the present invention, by using a thermoplastic polyimide resin having a specific structure for the layer B, even when the surface roughness of the layer is small, the adhesive strength with the metal layer when the metal layer is formed on the layer B The effect is high.

  Furthermore, by providing the layer C, it is possible to bond the insulating sheet according to the present invention and the inner layer circuit board (formed circuit) under low temperature and low pressure conditions and to embed circuit wiring between lines. Excellent in properties.

  Furthermore, by setting the layer B on one side of the polymer film layer A and the layer C on the other side, the overall linear expansion coefficient can be kept small.

  As described above, the insulating sheet of the present invention has excellent workability, fine circuit formability, and features such as prevention of element destruction when a semiconductor element is mounted. It can be used appropriately for high-density printed wiring boards. In addition, it has excellent adhesion, workability, and heat resistance to resin materials and conductor materials, which are necessary as materials for printed wiring boards. Flexible printed wiring boards, build-up wiring boards, multilayer flexible printed wiring boards, and coreless packages The effect that it can be used suitably for manufacture of a board | substrate is also show | played.

One embodiment of the present invention will be described in detail below, but the present invention is not limited to the following description.
(Characteristics and material configuration of the insulating sheet of the present invention)
The insulating sheet of the present invention is a diamine component in which at least one polymer film layer A and a layer B formed on one surface thereof contain an acid dianhydride component and a diamine represented by the following general formula (1) The insulating sheet is characterized in that a layer C containing a thermoplastic polyimide resin and a thermosetting component is formed on the other surface.

（式中、ｇは１以上の整数を表す。また、Ｒ¹¹及びＲ²²は、それぞれ同一、または異なっていてよく、炭素数１〜６のアルキレン基またはフェニレン基を表す。Ｒ³³〜Ｒ⁶⁶は、それぞれ同一、または異なっていてよく、炭素数１〜６のアルキル基、またはアルコキシ基、またはフェニル基、またはフェノキシ基を表す。）
上記式中、ｇは、１以上２０以下であることが好ましい。
さらに前記の層Ｂは該層上に金属層を形成するための層であるとともに、層Ｃが別途形成された回路と対向し積層させるための層であることを特徴とする。すなわち金属層を形成するための層に特定の構造を有する熱可塑性ポリイミド樹脂を用いることにより、表面粗度が小さい場合でも金属層との接着強度が高く、層Ｃすなわち形成された回路と対向させるための層を設けることにより、本発明にかかる絶縁シートと内層回路基板との低温・低圧条件下での貼り合わせや回路配線の線間埋め込みが可能である等の加工性に優れた絶縁シートを得ることが可能である。
また、層Ｂの厚みが層Ａの厚みの１倍以下であることを特徴とし、また、層Ｂの引張弾性率が層Ａの引張弾性率の１倍以下であることを特徴とする。これらにより、層Ａの低線膨張係数の特徴を発現することが可能となる。
また、層Ｃが低線膨張係数の溶融シリカのフィラーを５体積％以上含むことにより層Ｃの線膨張係数を小さくすることができるため系全体の線膨張係数を小さくすることができる。
さらに、フィラーに球状のものを用い、シラン系またはチタン系のカップリング剤または表面処理剤で表面処理すること、また、熱硬化性成分がエポキシ樹脂成分を含むことにより層ＣのＢ−ステージ状態での溶融粘度を２０００Ｐａ・ｓ以下とし、別途形成された回路と対向し積層させるために十分な樹脂流れ性を発現することができる。
また、層Ｂのカットオフ値０.００２ｍｍで測定した算術平均粗さ（Ｒａ）が０.５μｍ未満であることを特徴とする。このことにより、微細回路形成に際してエッチング残りが発生するなどの問題を解決できる。この表面平滑な層Ｂとその上に金属層を形成した場合の積層体における金属層との密着強度が５Ｎ/ｃｍ以上とすることが可能である。金属層としては、無電解銅めっき、あるいは、スパッタリング法、真空蒸着法、イオンプレーティング法または化学蒸着法で形成されたものであることが好ましい。

(In the formula, g represents an integer of 1 or more. Further, R ¹¹ and R ²² may be the same or different and each represents an alkylene group or phenylene group having 1 to 6 carbon atoms. R ^{33 to} R ^66. May be the same or different and each represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group, a phenyl group, or a phenoxy group.)
In the above formula, g is preferably 1 or more and 20 or less.
Further, the layer B is a layer for forming a metal layer on the layer, and a layer for facing and laminating a circuit in which the layer C is separately formed. That is, by using a thermoplastic polyimide resin having a specific structure as a layer for forming the metal layer, even when the surface roughness is small, the adhesive strength with the metal layer is high, and the layer C, that is, the formed circuit is made to face. By providing a layer for this purpose, an insulating sheet excellent in workability such as bonding of the insulating sheet according to the present invention and the inner circuit board under a low temperature / low pressure condition and embedding of the wiring of the circuit wiring is possible. It is possible to obtain.
In addition, the thickness of the layer B is 1 time or less of the thickness of the layer A, and the tensile elastic modulus of the layer B is 1 time or less of the tensile elastic modulus of the layer A. By these, it becomes possible to express the characteristic of the low linear expansion coefficient of the layer A.
In addition, since the layer C contains 5% by volume or more of a fused silica filler having a low linear expansion coefficient, the linear expansion coefficient of the layer C can be reduced, so that the linear expansion coefficient of the entire system can be reduced.
Further, a spherical material is used as the filler, surface treatment is performed with a silane-based or titanium-based coupling agent or surface treatment agent, and the thermosetting component contains an epoxy resin component, so that the B-stage state of the layer C In this case, the resin has a melt viscosity of 2000 Pa · s or less, and can exhibit a sufficient resin flow property to be laminated opposite to a separately formed circuit.
Further, the arithmetic average roughness (Ra) measured at a cutoff value of 0.002 mm of the layer B is less than 0.5 μm. As a result, problems such as the occurrence of etching residue when forming a fine circuit can be solved. The adhesion strength between the smooth surface layer B and the metal layer in the laminate when the metal layer is formed thereon can be 5 N / cm or more. The metal layer is preferably formed by electroless copper plating, sputtering, vacuum deposition, ion plating, or chemical vapor deposition.

Moreover, this invention is the layer B containing the thermoplastic polyimide resin which uses as a raw material the diamine component containing the diamine represented by the acid dianhydride component and following General formula (1) on the single side | surface of the polymer film layer A. The insulating sheet is characterized in that a layer for facing and laminating a separately formed circuit is formed on the other surface.
Moreover, this invention can obtain the printed wiring board suitable for high-density mounting by producing a printed wiring board using the said insulating sheet or laminated body.

Furthermore, since the adhesive strength is high after an environmental test such as a pressure cooker test (PCT) as well as a normal state, the reliability is excellent.
Here, the arithmetic average roughness Ra is defined in JIS B 0601 (revised on February 1, 1994). In particular, the numerical value of the arithmetic average roughness Ra of the present invention is a numerical value obtained by observing the surface with an optical interference type surface structure analyzer. The cutoff value of the present invention is described in the above JIS B 0601, and indicates a wavelength set when a roughness curve is obtained from a cross-sectional curve (measured data). That is, the value Ra measured with a cut-off value of 0.002 mm is an arithmetic average roughness calculated from a roughness curve obtained by removing irregularities having a wavelength longer than 0.002 mm from measured data.

The insulating sheet of the present invention is preferable because the structure of layer B / layer A / layer C is the simplest, but each layer may be further multilayered.
An example for obtaining such an insulating sheet will be described.
(Polymer film layer A)
The polymer film used in the laminate of the present invention is used for realizing a low thermal expansion coefficient of the insulating sheet. The thermal expansion coefficient of the insulating sheet of the present invention can be controlled by controlling the balance between the thermal expansion coefficient and thickness of the polymer film, and the thermal expansion coefficient and thickness of layers B and C. It is easy and preferable to make it small.

Moreover, when using the laminated body of this invention as a flexible printed wiring board, dimensional stability is desired.
Therefore, a polymer film having a thermal expansion coefficient of 20 ppm or less is desirable. Furthermore, a polymer film having high heat resistance and low water absorption is desirable so that defects such as swelling due to volatile components do not occur due to heat during processing. In addition, the thickness of the polymer film is preferably 50 μm or less, more preferably 35 μm or less, and even more preferably 25 μm or less for the formation of small diameter via holes. Preferably it is 1 micrometer or more, More preferably, it is 2 micrometers or more. A polymer film that is not so thick and ensures sufficient electrical insulation is desirable. Such a polymer film may be composed of a single layer or may be composed of two or more layers. For example, in the case of a single layer, polyolefin such as polyethylene, polypropylene, polybutene; polyester such as ethylene-vinyl alcohol copolymer, polystyrene, polyethylene terephthalate, polybutylene terephthalate, ethylene-2,6-naphthalate; and nylon-6 , Nylon-11, aromatic polyamide, polyamideimide resin, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyketone resin, polysulfone resin, polyphenylene sulfide resin, polyetherimide resin, fluorine resin, polyarylate resin, liquid crystal polymer resin And films of polyphenylene ether resin and non-thermoplastic polyimide resin.
In addition, in order to improve the adhesion with the layer A, a thermosetting resin or a thermoplastic resin is provided on one side or both sides of the single layer film, or various organic substances such as an organic monomer and a coupling agent are used. Can be processed. Here, when a thermoplastic polyimide resin is used, the adhesiveness with the layer A is further improved, which is preferably used. Furthermore, a plurality of layers may be laminated on the film exemplified by the single layer film via an adhesive.
A non-thermoplastic polyimide film is suitable as the polymer film that satisfies the above-mentioned properties. Hereinafter, the non-thermoplastic polyimide film will be described.

  The non-thermoplastic polyimide film used for the layer A of the present invention can be produced by a known method. That is, it can be obtained by casting and coating polyamic acid on a support and imidizing chemically or thermally. Among them, the polyamic acid organic solvent solution is represented by chemical conversion agents (dehydrating agents) represented by acid anhydrides such as acetic anhydride, and tertiary amines such as isoquinoline, β-picoline, and pyridine. From the viewpoints of film toughness, breaking strength, and productivity, a method of allowing a catalyst to act, that is, a chemical imidization method is preferable. Further, a method of using a thermal curing method in combination with the chemical imidization method is more preferable.

  Basically, any known polyamic acid can be used as the polyamic acid. Usually, at least one aromatic dianhydride and at least one diamine are substantially equimolar amounts in an organic solvent. The polyamic acid organic solvent solution obtained by dissolving is produced by stirring under controlled temperature conditions until the polymerization of the acid dianhydride and diamine is completed.

  Suitable acid dianhydrides for synthesis on the non-thermoplastic polyimides according to the present invention are pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, bis (3, 4-dicarboxyphenyl) sulfone dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, oxydiphthalic acid Anhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2-bis (3,4-dicarboxyphenyl) ethane dianhydride, 2,2-bis (3,4- Dicarboxypheny ) Propane dianhydride, 1,3-bis (3,4-dicarboxyphenyl) propane dianhydride, 4,4′-hexafluoroisopropylidenediphthalic anhydride, 1,2,5,6-naphthalenetetra Carboxylic dianhydride, 2,3,4,7-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, p-phenylenebis (trimellitic acid monoester anhydride Product), ethylenebis (trimellitic acid monoester anhydride), bisphenol A bis (trimellitic acid monoester anhydride), 4,4 '-(4,4'-isopropylidenediphenoxy) bis (phthalic anhydride) Acid), aromatic tetracarboxylic dianhydrides such as p-phenylenediphthalic anhydride and the like.

  In the acid dianhydride used for the synthesis of the non-thermoplastic polyimide according to the present invention, pyromellitic dianhydride, oxydiphthalic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3 , 3 ′, 4,4′-biphenyltetracarboxylic dianhydride and p-phenylenebis (trimellitic acid monoester acid anhydride) are preferable, and these are used alone or in a mixture of any ratio.

  Examples of the diamine that can be used for the synthesis of the non-thermoplastic polyimide according to the present invention include 1,4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene, 1,2-diaminobenzene, 3,3 ′. -Dichlorobenzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-dihydroxybenzidine, 3,3 ', 5,5'-tetramethylbenzidine, 4,4'-diaminodiphenylpropane 4,4′-diaminodiphenylhexafluoropropane, 1,5-diaminonaphthalene, 4,4′-diaminodiphenyldiethylsilane, 4,4′-diaminodiphenylsilane, 4,4′-diaminodiphenylethylphosphine oxide, 4 , 4'-diaminodiphenyl N-methylamine, 4,4'-diaminodiph Nyl N-phenylamine, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl thioether, 3,4′-diaminodiphenyl thioether, 3, 3'-diaminodiphenylthioether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3 , 3'-diaminodiphenylsulfone, 4,4'-diaminobenzanilide, 3,4'-diaminobenzanilide, 3,3'-diaminobenzanilide, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone 3 3′-diaminobenzophenone, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (3-aminophenoxy) phenyl ] Ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4- Aminophenoxy) phenyl] ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4 -(3-aminophenoxy) phenyl] butane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2 -Bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3 -Aminophenoxy) benzene, 1,4'-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, bis [ 4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) Phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [ -(3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4 -(3-aminophenoxy) benzoyl] benzene, 4,4'-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, 4 , 4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, Bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone, 1,4-bis [4- (4-aminopheno) Xyl) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 4,4′-diaminodiphenylethylphosphine oxide, and the like Including analogs of

  Among these diamines used in the non-thermoplastic polyimide film of the present invention, 4,4′-diaminodiphenyl ether, 4,4′-diaminobenzanilide and p-phenylenediamine are preferable, and these may be used alone or in a mixture of any ratio. Preferably used.

Preferred combinations of acid dianhydride and diamines for the present invention are a combination of pyromellitic dianhydride and 4,4′-diaminodiphenyl ether, pyromellitic dianhydride, 4,4′-diaminodiphenyl ether and p-phenylene. Combination of diamine, pyromellitic dianhydride, p-phenylenebis (trimellitic acid monoester anhydride), 4,4'-diaminodiphenyl ether and p-phenylenediamine, pyromellitic dianhydride, p- Combination of phenylenebis (trimellitic acid monoester anhydride), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-diaminodiphenyl ether and p-phenylenediamine, pyromellitic acid Dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid Objects and oxydianiline, a combination of p- phenylenediamine and 2,2-bis [4- (3-aminophenoxy) phenyl] propane. Non-thermoplastic polyimides synthesized by combining these monomers exhibit excellent properties such as moderate elastic modulus, dimensional stability, and low water absorption, and are suitable for use in various laminates of the present invention.

Preferred solvents for synthesizing the polyamic acid are amide solvents, ie N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like, and N, N-dimethylformamide is particularly preferred. Preferably used.
When imidization is performed by a chemical cure method, the chemical conversion agent added to the polyamic acid composition according to the present invention is, for example, an aliphatic acid anhydride, an aromatic acid anhydride, N, N′-dialkylcarbodiimide, Examples thereof include lower aliphatic halides, halogenated lower aliphatic halides, halogenated lower fatty acid anhydrides, arylphosphonic acid dihalides, thionyl halides, and mixtures of two or more thereof. Of these, aliphatic anhydrides such as acetic anhydride, propionic anhydride, and lactic anhydride are used alone or a mixture of two or more thereof is preferably used. These chemical conversion agents are preferably added in an amount of 1 to 10 times, preferably 1 to 7 times, more preferably 1 to 5 times the number of moles of the polyamic acid moiety in the polyamic acid solution. Moreover, in order to perform imidation effectively, it is preferable to use a catalyst simultaneously with a chemical conversion agent. As the catalyst, aliphatic tertiary amine, aromatic tertiary amine, heterocyclic tertiary amine and the like are used. Among them, those selected from heterocyclic tertiary amines can be particularly preferably used. Specifically, quinoline, isoquinoline, β-picoline, pyridine and the like are preferably used. These catalysts are added in an amount of 1/20 to 10 times, preferably 1/15 to 5 times, more preferably 1/10 to 2 times the number of moles of the chemical conversion agent. If the amount of these chemical conversion agents and catalysts is small, imidization does not proceed effectively. Conversely, if the amount is too large, imidization is accelerated and handling becomes difficult.

  Non-thermoplastic polyimide films obtained by the above-mentioned various known methods may be added with plasticizers and antioxidants such as inorganic or organic fillers and organic phosphorus compounds by known methods. At least one surface can be subjected to a known physical surface treatment such as corona discharge treatment, plasma discharge treatment or ion gun treatment, or a chemical surface treatment such as primer treatment, so that even better characteristics can be imparted.

      The thickness of the non-thermoplastic polyimide film is preferably 2 μm or more and 125 μm or less, and more preferably 5 μm or more and 75 μm or less. If it is thinner than this range, not only the rigidity of the laminate is insufficient, but also the film becomes difficult to handle. On the other hand, if the film is too thick, it is necessary to widen the circuit width in terms of impedance control when manufacturing the printed wiring board, which goes against the demand for miniaturization and higher density of the printed wiring board. Further, the non-thermoplastic polyimide film used for layer A preferably has a low coefficient of linear expansion, and a polyimide film of 10 to 40 ppm, more preferably a polyimide film of 10 to 20 ppm is industrially produced and can be obtained and applied. It is. In order to control the linear expansion coefficient, in addition to combining monomers with a rigid structure and monomers with a flexible structure in an appropriate ratio, the order of adding an acid anhydride component and a diamine component when synthesizing a polyamic acid solution The linear expansion coefficient of the non-thermoplastic polyimide film obtained can also be controlled by selection of chemical imidization and thermal imidization, temperature conditions when converting polyamic acid to polyimide, and the like.

  In the present invention, the diamine having a rigid structure is

式中のＲ２は

R2 in the formula is

一般式群（１）
で表される２価の芳香族基からなる群から選択される基であり、式中のＲ３は同一または異なって，ＣＨ３−、−ＯＨ、−ＣＦ３、−ＳＯ４、−ＣＯＯＨ、−ＣＯ-ＮＨ２、Ｃｌ−、Ｂｒ−、Ｆ−、及びＣＨ３Ｏ−からなる群より選択される何れかの１つの基である）
で表されるものをいう。
また、柔構造を有するジアミンとは、エーテル基、スルホン基、ケトン基、スルフィド基などの柔構造を有するジアミンであり、好ましくは、下記一般式（２）で表されるものである。

General formula group (1)
In which R 3 is the same or different and is represented by CH 3 —, —OH, —CF 3, —SO 4, —COOH, —CO—NH 2, or a group selected from the group consisting of divalent aromatic groups. And any one group selected from the group consisting of Cl-, Br-, F-, and CH3O-)
The one represented by
The diamine having a flexible structure is a diamine having a flexible structure such as an ether group, a sulfone group, a ketone group, or a sulfide group, and is preferably represented by the following general formula (2).

（式中のＲ４は、

(R4 in the formula is

で表される２価の有機基からなる群から選択される基であり、式中のＲ５は同一または異なって、ＣＨ３−、−ＯＨ、−ＣＦ３、−ＳＯ４、−ＣＯＯＨ、−ＣＯ-ＮＨ２、Ｃｌ−、Ｂｒ−、Ｆ−、及びＣＨ３Ｏ−からなる群より選択される１つの基である。）
非熱可塑性ポリイミドフィルムの引っ張り弾性率は、ＡＳＴＭ Ｄ８８２−８１に準拠し測定される。弾性率が低いとフィルムの剛性が低下し取り扱いが困難になる、一方高すぎると、フィルムの柔軟性が損なわれるためロール・ツー・ロールの加工が困難になる、フィルムが脆くなるなどの不具合が生じる場合がある。弾性率３〜１０ＧＰａのポリイミドフィルム、より好ましくは４〜７ＧＰａのポリイミドフィルムが工業的に生産されており、入手、適用可能である。引っ張り弾性率も線膨張係数と同様、剛直な構造のモノマーと柔軟な構造のモノマーを適切な割合で組み合わせ、ポリアミド酸溶液を合成する際に酸無水物成分とジアミン成分を添加する順序、化学的イミド化と熱的イミド化の選択、ポリアミド酸をポリイミドに転化する際の温度条件などによって制御できる。

R5 in the formula is the same or different and is CH3-, -OH, -CF3, -SO4, -COOH, -CO-NH2, or a group selected from the group consisting of divalent organic groups One group selected from the group consisting of Cl-, Br-, F-, and CH3O-. )
The tensile elastic modulus of the non-thermoplastic polyimide film is measured according to ASTM D882-81. If the elastic modulus is low, the rigidity of the film decreases and handling becomes difficult. On the other hand, if it is too high, the flexibility of the film is impaired, making roll-to-roll processing difficult, and the film becoming brittle. May occur. A polyimide film having a modulus of elasticity of 3 to 10 GPa, more preferably a polyimide film of 4 to 7 GPa, is industrially produced and can be obtained and applied. Similar to the linear expansion coefficient, the tensile modulus is a combination of a rigid structure monomer and a flexible structure monomer at an appropriate ratio, and the order in which an acid anhydride component and a diamine component are added when synthesizing a polyamic acid solution. It can be controlled by selection of imidization and thermal imidization, temperature conditions when converting polyamic acid to polyimide, and the like.

(Layer B)
The layer B is characterized by containing a polyimide resin having a siloxane structure.
The polyimide resin having a siloxane structure of the present invention may be any polyimide resin as long as it has a siloxane structure. For example, (1) using a dianhydride component having a siloxane structure or a diamine component having a siloxane structure, a polyamic acid that is a precursor of a polyimide resin is produced, and this is imidized to produce a polyimide resin; (2) A polyamic acid having a functional group is produced using an acid dianhydride component having a functional group or a diamine component having a functional group, and the functional group capable of reacting with the functional group and a compound having a siloxane structure are reacted. A polyamic acid having a siloxane structure introduced, and imidizing it to produce a polyimide resin; (3) functionalization using an acid dianhydride component having a functional group or a diamine component having a functional group; A polyamic acid having a functional group, imidized to produce a polyimide having a functional group, and reacting with the functional group. That functional group, and by reacting a compound having a siloxane structure, a method of producing a polyimide resin siloxane structure is introduced, and the like. Here, since the diamine having a siloxane structure can be obtained relatively easily, among them, the acid dianhydride component and the diamine having a siloxane structure are reacted to produce a target polyimide resin. It is preferable to use a diamine represented by the following general formula (1) as the diamine having a siloxane structure.

（式中、ｇは１以上の整数を表す。また、Ｒ¹¹及びＲ²²は、それぞれ同一、または異なっていてよく、アルキレン基またはフェニレン基を表す。Ｒ³³〜Ｒ⁶⁶は、それぞれ同一、または異なっていてよく、アルキル基、またはフェニル基、またはフェノキシ基、またはアルコキシ基を表す。好ましくは、ｇは１以上２０以下である。またＲ¹¹及びＲ²²は、炭素数が１〜２０のアルキレン基またはフェニレン基であることが好ましい。さらにＲ³³〜Ｒ⁶⁶は、炭素数１〜６のアルキル基、またはフェニル基、またはフェノキシ基、またはアルコキシ基であることが好ましい。）
本発明における熱可塑性ポリイミドとは、圧縮モード（プローブ径３ｍｍφ、荷重５ｇ）の熱機械分析測定（ＴＭＡ）において、１０〜４００℃（昇温速度：１０℃／ｍｉｎ）の温度範囲で永久圧縮変形を起こすものをいう。

(In the formula, g represents an integer of 1 or more. R ¹¹ and R ²² may be the same or different and each represents an alkylene group or a phenylene group. R ^{33 to} R ⁶⁶ are the same or May be different and represents an alkyl group, a phenyl group, a phenoxy group, or an alkoxy group, preferably g is 1 or more and 20 or less, and R ¹¹ and R ²² are alkylene having 1 to 20 carbon atoms. And R ^{33 to} R ⁶⁶ are preferably an alkyl group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group, or an alkoxy group.
The thermoplastic polyimide in the present invention is a permanent compression deformation in a temperature range of 10 to 400 ° C. (temperature increase rate: 10 ° C./min) in a thermomechanical analysis measurement (TMA) in a compression mode (probe diameter 3 mmφ, load 5 g). It is something that causes

  A polyimide resin is obtained by reacting an acid dianhydride component and a diamine component. Hereinafter, the acid dianhydride component will be described.

  The acid dianhydride component is not particularly limited, and pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetra Carboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 4,4′-oxydiphthalic anhydride, 3, 3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl Propanic acid dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, p-phenylenediphthalic anhydride Such Aromatic tetracarboxylic dianhydride, 4,4′-hexafluoroisopropylidenediphthalic anhydride, 4,4′-oxydiphthalic anhydride, 3,4′-oxydiphthalic anhydride, 3,3′-oxydiphthalate Acid anhydride, 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic anhydride), 4,4′-hydroquinonebis (phthalic anhydride), 2,2-bis (4-hydroxyphenyl) ) Propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride, 1,2-ethylenebis (trimellitic acid monoester anhydride), p-phenylenebis (trimellitic acid monoester anhydride) And the like. These may be used alone or in combination of two or more.

  Subsequently, the diamine component will be described. In this invention, it is preferable that the diamine component represented by following General formula (1) is included as a diamine component.

（式中、ｇは１以上の整数を表す。また、Ｒ¹¹及びＲ²²は、それぞれ同一、または異なっていてよく、アルキレン基またはフェニレン基を表す。Ｒ³³〜Ｒ⁶⁶は、それぞれ同一、または異なっていてよく、アルキル基、またはフェニル基、またはフェノキシ基、またはアルコキシ基を表す。好ましくは、ｇは１以上２０以下である。またＲ¹¹及びＲ²²は、炭素数が１〜６のアルキレン基またはフェニレン基であることが好ましい。さらにＲ³³〜Ｒ⁶⁶は、炭素数１〜６のアルキル基、またはフェニル基、またはフェノキシ基、またはアルコキシ基であることが好ましい。）
一般式（１）で表されるジアミン成分を用いることにより、得られるポリイミド樹脂は、無電解めっき層と強固に接着するという特徴を有するようになる。

(In the formula, g represents an integer of 1 or more. R ¹¹ and R ²² may be the same or different and each represents an alkylene group or a phenylene group. R ^{33 to} R ⁶⁶ are the same or May be different and represents an alkyl group, a phenyl group, a phenoxy group, or an alkoxy group, preferably g is 1 or more and 20 or less, and R ¹¹ and R ²² are alkylene having 1 to 6 carbon atoms. And R ^{33 to} R ⁶⁶ are preferably an alkyl group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group, or an alkoxy group.
By using the diamine component represented by the general formula (1), the obtained polyimide resin has a characteristic of being firmly bonded to the electroless plating layer.

  Examples of the diamine represented by the general formula (1) include 1,1,3,3-tetramethyl-1,3-bis (4-aminophenyl) disiloxane and 1,1,3,3-tetraphenoxy. -1,3-bis (4-aminoethyl) disiloxane, 1,1,3,3,5,5-hexamethyl-1,5-bis (4-aminophenyl) trisiloxane, 1,1,3,3 , -Tetraphenyl-1,3-bis (2-aminophenyl) disiloxane, 1,1,3,3-tetraphenyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,5 , 5, -tetraphenyl-3,3-dimethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,5,5, -tetraphenyl-3,3-dimethoxy-1,5-bis (3-Aminobutyl) trisiloxane, 1,1,5,5,- Traphenyl-3,3-dimethoxy-1,5-bis (3-aminopentyl) trisiloxane, 1,1,3,3, -tetramethyl-1,3-bis (2-aminoethyl) disiloxane, , 1,3,3-Tetramethyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (4-aminobutyl) disiloxane 1,3-dimethyl-1,3-dimethoxy-1,3-bis (4-aminobutyl) disiloxane, 1,1,5,5, -tetramethyl-3,3-dimethoxy-1,5-bis (2-Aminoethyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane, 1,1,5,5,- Tetramethyl-3,3-dimethoxy-1,5-bis (5- Aminopentyl) trisiloxane, 1,1,3,3,5,5-hexamethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5-hexaethyl-1, Examples include 5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5-hexapropyl-1,5-bis (3-aminopropyl) trisiloxane, and the like. In addition, as relatively easily available diamines represented by the general formula (1), KF-8010, X-22-161A, X-22-161B, X-22-1660B-3 manufactured by Shin-Etsu Chemical Co., Ltd. , KF-8008, KF-8012, X-22-9362, and the like. The said diamine may be used independently and may mix 2 or more types.

  For the purpose of improving the heat resistance of the layer B, it is also preferable to use a combination of the above diamine and another diamine. As the other diamine component, any diamine can be used, and m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, bis (3-amino). Phenyl) sulfide, (3-aminophenyl) (4-aminophenyl) sulfide, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, (3-aminophenyl) (4-aminophenyl) sulfoxide, Bis (3-aminophenyl) sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3, 3'-diaminodiphenylmethane, 3,4'-di Minodiphenylmethane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, bis [4- (3-aminophenoxy) phenyl] sulfoxide, bis [4- (Aminophenoxy) phenyl] sulfoxide, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenylthioether, 3,4′-diamino Diphenylthioether, 3,3'-diaminodiphenylthioether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfur 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminobenzanilide, 3,4'-diaminobenzanilide, 3,3'-diaminobenzanilide, 4, 4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) ) Phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 2,2-bis [4- (3-aminophenyl) Enoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [3- (3-Aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3 3,3-hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4′-bis (4-aminophenoxy) benzene, 4, 4′-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3- Minophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-Aminophenoxy) benzoyl] benzene, 4,4′-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] ben Phenone, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone, 1,4 -Bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 3,3′- Examples thereof include dihydroxy-4,4′-diaminobiphenyl.

  2-100 mol% is preferable with respect to all the diamine components, and, as for the diamine represented by General formula (1), More preferably, it is 5-100 mol%. When the diamine represented by the general formula (1) is lower than 2 mol% with respect to the total diamine component, the adhesive strength between the layer B and the electroless plating film is lowered.

  The polyimide is obtained by dehydrating and ring-closing the corresponding precursor polyamic acid polymer. The polyamic acid polymer is obtained by reacting an acid dianhydride component and a diamine component in substantially equimolar amounts.

  A typical procedure for the reaction is a method in which one or more diamine components are dissolved or dispersed in an organic polar solvent, and then one or more acid dianhydride components are added to obtain a polyamic acid solution. The order of addition of each monomer is not particularly limited, and the acid dianhydride component may be added to the organic polar solvent in advance, and the diamine component may be added to form a polyamic acid polymer solution, or the diamine component may be added to the organic polar solvent. A suitable amount of the acid dianhydride component may be added first, and then an excess amount of the dianhydride component may be added, and a diamine component corresponding to the excess amount may be added to form a polyamic acid polymer solution. There are various other addition methods known to those skilled in the art. Specifically, the following method is mentioned.

The term “dissolved” as used herein refers to a state in which the solute is uniformly dissolved or dispersed in the solvent in addition to the case where the solvent completely dissolves the solute. Including cases. The reaction time and reaction temperature are not particularly limited.
1) A method in which an aromatic diamine is dissolved in an organic polar solvent and this is reacted with a substantially equimolar amount of an aromatic tetracarboxylic dianhydride for polymerization.
2) An aromatic tetracarboxylic dianhydride is reacted with a small molar amount of an aromatic diamine compound in an organic polar solvent to obtain a prepolymer having acid anhydride groups at both ends. Then, the method of superposing | polymerizing using an aromatic diamine compound so that an aromatic tetracarboxylic dianhydride and an aromatic diamine compound may become substantially equimolar in all the processes.
3) An aromatic tetracarboxylic dianhydride is reacted with an excess molar amount of an aromatic diamine compound in an organic polar solvent to obtain a prepolymer having amino groups at both ends. Subsequently, after adding an aromatic diamine compound here, using the aromatic tetracarboxylic dianhydride so that the aromatic tetracarboxylic dianhydride and the aromatic diamine compound are substantially equimolar in all steps. How to polymerize.
4) A method in which an aromatic tetracarboxylic dianhydride is dissolved and / or dispersed in an organic polar solvent and then polymerized using an aromatic diamine compound so as to be substantially equimolar.
5) A method in which a substantially equimolar mixture of aromatic tetracarboxylic dianhydride and aromatic diamine is reacted in an organic polar solvent for polymerization.

  Examples of the organic polar solvent used for the polyamic acid polymerization reaction include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, N, N- Acetamide solvents such as dimethylacetamide and N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o-, m- or p-cresol, xylenol, Examples thereof include phenol solvents such as halogenated phenols and catechols, hexamethylphosphoramide, and γ-butyrolactone. Further, if necessary, these organic polar solvents can be used in combination with an aromatic hydrocarbon such as xylene or toluene.

  The polyamic acid solution obtained by the above method is dehydrated and cyclized by a thermal or chemical method to obtain a polyimide, and a thermal method in which the polyamic acid solution is subjected to heat treatment for dehydration, a chemical method for dehydration using a dehydrating agent. Any of these can be used. Moreover, the method of imidating by heating under reduced pressure can also be used. Each method will be described below.

  As a method of thermally dehydrating and cyclizing, a method of evaporating the solvent at the same time that the polyamic acid solution is subjected to an imidation reaction by heat treatment can be exemplified. By this method, a solid polyimide resin can be obtained. The heating conditions are not particularly limited, but it is preferably performed at a temperature of 200 ° C. or lower for a time range of 1 second to 200 minutes.

  Further, as a method of chemically dehydrating and cyclizing, a method of causing a dehydration reaction by adding a dehydrating agent and a catalyst having a stoichiometric amount or more to the polyamic acid solution and evaporating the organic solvent can be exemplified. Thereby, a solid polyimide resin can be obtained. Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride and aromatic acid anhydrides such as benzoic anhydride. Examples of the catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic rings such as pyridine, α-picoline, β-picoline, γ-picoline, and isoquinoline. And tertiary amines of the formula. The conditions for chemically dehydrating and cyclizing are preferably 100 ° C. or less, and the organic solvent is preferably evaporated at a temperature of 200 ° C. or less for a period of about 5 minutes to 120 minutes.

  Further, as another method for obtaining a polyimide resin, there is a method in which the solvent is not evaporated in the thermal or chemical dehydration ring closure method. Specifically, a polyimide solution obtained by performing a thermal imidization treatment or a chemical imidization treatment with a dehydrating agent is put into a poor solvent, a polyimide resin is precipitated, and unreacted monomers are removed and purified and dried. And obtaining a solid polyimide resin. As the poor solvent, a solvent that is well mixed with the solvent but is difficult to dissolve polyimide is selected. Illustrative examples include, but are not limited to, acetone, methanol, ethanol, isopropanol, benzene, methyl cellosolve, methyl ethyl ketone, and the like.

  Next, although it is the method of imidating by heating under reduced pressure, according to this imidization method, water generated by imidization can be actively removed out of the system, so that hydrolysis of polyamic acid is suppressed. And a high molecular weight polyimide is obtained. In addition, according to this method, one-sided or both-side ring-opened products existing as impurities in the raw acid dianhydride are closed again, so that a further improvement in molecular weight can be expected.

  The heating condition of the method of heating imidization under reduced pressure is preferably 80 to 400 ° C., more preferably 100 ° C. or more, more preferably 120 ° C. or more, in which imidization is efficiently performed and water is efficiently removed. is there. The maximum temperature is preferably equal to or lower than the thermal decomposition temperature of the target polyimide, and a normal imidation completion temperature, that is, about 250 to 350 ° C. is usually applied.

The conditions for pressure reduction are preferably smaller, but specifically, 9 × 10 ↑ 4 to 1 × 10 ↑ 2 Pa, preferably 8 × 10 ↑ 4 to 1 × 10 ↑ 2 Pa, more preferably 7 × 10 ↑. 4 to 1 × 10 ↑ 2 Pa.

Although the polyimide resin has been described above, a commercially available polyimide resin having a siloxane structure may also be used. Examples of polyimide resins containing a relatively easily available siloxane structure that can be used for layer B of the laminate of the present invention include X-22-8915, X-22-8904, X-manufactured by Shin-Etsu Chemical Co., Ltd. 22-8951, X-22-8756, X-22-8984, X-22-8985, and the like. These are polyimide solutions.

  Although the polyimide resin has been described above, the layer B of the laminate of the present invention can contain other components for the purpose of improving heat resistance. As other components, resins such as thermoplastic resins and thermosetting resins can be used as appropriate.

Thermoplastic resins include polysulfone resins, polyethersulfone resins, polyphenylene ether resins, phenoxy resins, and thermoplastic polyimides comprising an acid dianhydride component and a diamine component containing a diamine represented by the general formula (1) Examples of the resin include thermoplastic polyimide resins having different structures, and these can be used alone or in appropriate combination.
Thermosetting resins include bismaleimide resin, bisallyl nadiimide resin, phenol resin, cyanate resin, epoxy resin, acrylic resin, methacrylic resin, triazine resin, hydrosilyl cured resin, allyl cured resin, unsaturated polyester resin, etc. These can be used alone or in appropriate combination. In addition to the thermosetting resin, a side chain reactive group type thermosetting having a reactive group such as an epoxy group, an allyl group, a vinyl group, an alkoxysilyl group or a hydrosilyl group at the side chain or terminal of the polymer chain. It is also possible to use a functional polymer.

  In addition, for the purpose of further improving the adhesion between the layer B and the electroless plating film, various additives may be added to the polymer material and may be present on the surface of the polymer material by a method such as coating. Specific examples include organic thiol compounds, but are not limited thereto.

  In addition, various organic fillers and inorganic fillers can be added for the purpose of forming a surface roughness on the surface of the layer B that does not inhibit the formation of fine wiring and enhancing the adhesion to the electroless plating film.

  It is important to combine the above-mentioned other components within a range that does not increase the surface roughness of the layer B to such an extent that the fine wiring formation is adversely affected, and does not deteriorate the adhesion between the layer B and the electroless plating film. This point needs attention.

  Here, for the formation of fine wiring, the surface roughness of the layer B of the present invention is preferably such that the arithmetic average roughness of the layer B measured at a cutoff value of 0.002 mm is 0.5 μm or less.

  In order to reduce the overall linear expansion coefficient, the thickness of the layer B is preferably thinner, specifically, not more than 1 times that of the layer A, more preferably not more than 1/2. Specifically, the thickness of the layer B is preferably 5 μm or less, more preferably 3 μm or less. Further, as for the elastic modulus, if the elastic modulus of the layer B is high, the overall linear expansion coefficient is dominated by the characteristics of the layer B, so that the elastic modulus is preferably low. Specifically, it is preferably 1 times or less, more preferably 1/2 or less of layer A. Specifically, the elastic modulus of the layer B is preferably 4 GPa or less, more preferably 3 GPa or less.

(Layer C)
Details of the components used in the layer C according to the present invention will be described. When the insulating sheet of the present invention is laminated on the uneven surface on which the circuit is formed, the layer C needs to have excellent workability so that the layer C flows between the circuits and the circuit can be embedded. is there. In general, the thermosetting resin is excellent in the processability, and the layer C of the present invention preferably contains a thermosetting resin. As this thermosetting resin, epoxy resin, phenol resin, thermosetting polyimide resin, cyanate ester resin, hydrosilyl cured resin, bismaleimide resin, bisallyl nadiimide resin, acrylic resin, methacrylic resin, allyl resin, unsaturated polyester A thermosetting resin such as a resin; a side chain reactive group type thermosetting polymer having a reactive group such as an allyl group, a vinyl group, an alkoxysilyl group, or a hydrosilyl group at the side chain or terminal of the polymer chain is appropriately used. It can be applied as a thermosetting resin composition in combination with a thermosetting agent and a curing catalyst.

  Among these, it is preferable to use an epoxy resin from the viewpoints of heat resistance and workability. It is also possible to preferably add a thermoplastic polymer to these thermosetting resin compositions. Examples of the thermoplastic polymer include phenoxy resin, thermoplastic polyimide resin, polyether sulfone resin, and polyphenylene ether resin. Can be mentioned. Preferred combinations include a thermosetting resin composition containing an epoxy resin and a phenoxy resin, a thermosetting resin composition containing an epoxy resin and a thermoplastic polyimide resin, and a thermosetting resin composition containing a cyanate resin and a thermoplastic polyimide resin. Is mentioned. Among these, the thermosetting resin composition containing the epoxy resin and thermoplastic polyimide resin which are excellent in the various property balance requested | required as a printed wiring board material is the most preferable.

  In addition, various fillers can be combined for low thermal expansion. The amount of filler added at this time may vary depending on the desired coefficient of linear expansion, but is specifically in the range of 5 to 80% by volume, preferably 10 to 50%. When a filler is added to the resin, the melt fluidity of the resin usually decreases. In the present invention, by combining fillers, it is possible to reduce the melt fluidity of the resin, that is, to ensure sufficient circuit embedding properties, even though the filler is added. For example, sufficient circuit embedding can be ensured by using spherical fused silica, or by surface-treating the filler with a silane-based or titanium-based surface treatment agent or coupling agent. The melt viscosity of the layer C in the B-stage state is 20000 Pas or less, more preferably 2000 Pas or less. Methods for controlling the viscosity within the above range include 1) using a spherical filler shape, 2) applying a surface treatment to the filler, and 3) using a filler having a wide particle size distribution. ) To 3) may be combined. As for the thickness of the layer C, there is an insulating layer thickness necessary from the viewpoints of facing circuit height, remaining copper ratio, and impedance control. In general, it is preferably about 1/2 to 1 times the circuit height of the opposing circuit. Specifically, a range of 5 to 100 μm is preferable.

(Other layers)
In the present invention, the configuration of layer B / layer A / layer C is the simplest configuration and is therefore preferable. The configuration has mainly been described, but another layer may be provided between the layers. .

(Metal layer)
As a metal layer formed on the layer B of the insulating sheet according to the present invention, a metal layer formed by wet plating such as electroless plating on the layer B of the insulating sheet, or dry plating such as sputtering is formed. A metal layer formed by laminating a metal foil such as a copper foil or an aluminum foil, or a metal formed by previously forming the insulating sheet of the present invention on the metal foil so that the metal foil and the layer B are in contact with each other. A metal layer formed by wet plating such as electroless plating is preferable in consideration of fine wiring formability, manufacturing efficiency, cost, and the like. The metal layer is also preferably formed by sputtering, vacuum deposition, ion plating, or chemical vapor deposition from the viewpoints of adhesion, uniformity, appearance, and the like.

  Examples of electroless plating include electroless copper plating, electroless nickel plating, electroless gold plating, electroless silver plating, electroless tin plating, and the like. From the viewpoints of electrical characteristics such as a general viewpoint and migration resistance, electroless copper plating and electroless nickel plating are preferable, and electroless copper plating is particularly preferable.

(Use of insulating sheet according to the present invention)
Although the insulating sheet concerning this invention can be used suitably for various uses, it can be used suitably as a material of printed wiring boards, such as a flexible printed wiring board and a buildup wiring board, especially. Specifically, it is suitably used as a protective material for protecting the printed circuit board and the patterned circuit on the printed circuit board, an interlayer insulation material for ensuring insulation between layers in a multilayer printed circuit board, and the like. Can be used.

(Insulating sheet manufacturing method according to the present invention)
Next, although the manufacturing method of the insulating sheet concerning this invention is demonstrated, it is not limited to this. First, the thermoplastic polyimide resin contained in the layer B and other components as necessary are added to an appropriate solvent and stirred to obtain a uniformly dissolved and dispersed layer B resin solution. This is cast-coated on one side of the non-thermoplastic polyimide film layer A, and then the layer B resin solution is dried. Subsequently, the layer C resin solution prepared in the same manner was casted on the other surface of the layer A, and then the resin solution was dried, whereby the insulating sheet of the present invention composed of layer B / layer A / layer C was obtained. Obtainable.
Here, since the layer C plays a role of embedding an inner layer circuit, the thermosetting resin composition as a component thereof is in a semi-cured state (B stage state), and a drying temperature to obtain a semi-cured state. It is important to properly control the time.

<Printed wiring board>
The insulating sheet and the interlayer adhesive material for printed wiring board of the present invention can be preferably used for printed wiring board applications.

  When the printed wiring board of the present invention is manufactured using the insulating sheet of the present invention, the inner layer substrate on which the metal foil, the insulating sheet, and the circuit pattern are formed is sequentially laminated so that the layer C and the circuit pattern face each other. It is possible to obtain a printed wiring board of the present invention by embedding a pattern mainly with the layer C and then performing a pattern etching process by a subtractive method to form a desired conductor circuit pattern.

  As another method for producing the printed wiring board of the present invention using the insulating sheet of the present invention, an insulating sheet with an easily peelable resin film substrate that protects the layer B, and an inner layer substrate on which a circuit pattern is formed are sequentially provided. The circuit pattern is laminated with the circuit pattern facing the layer C side, and the circuit pattern is mainly filled with the layer C, and then the electroless plating is performed on the surface of the layer B resin exposed by peeling off the resin film substrate. It is also possible to obtain a metal layer for use. This method can be preferably applied to a circuit pattern forming method by an additive method, and is particularly preferably performed when fine wiring formation is necessary.

  In the above, when a flexible printed wiring board is used for the inner layer board, a multilayer flexible wiring board is manufactured, and when a printed wiring board using a glass-epoxy base material is used, a multilayer rigid wiring board or build An up-wiring board will be manufactured. In addition, since the insulating sheet of the present invention has a layer A made of a tough non-thermoplastic polyimide film, it is also suitably used for manufacturing a coreless laminated substrate and a coreless package substrate by laminating the insulating sheets. It is done. In addition, vias must be formed on the multilayer printed wiring board for vertical electrical connection. In the printed wiring board of the present invention, vias are formed by a known method such as laser, mechanical drilling or punching. In addition, it can be made conductive by a known method such as electroless plating, conductive paste, direct plating, etc., and is preferably carried out.

  At least the layer C of the insulating sheet of the present invention has appropriate fluidity in a semi-cured state. For this reason, the pattern circuit line is mainly used by performing thermocompression bonding such as heat pressing, vacuum pressing, laminating (thermal laminating), vacuum laminating, hot roll laminating, and vacuum hot roll laminating. The layer C can be embedded well. Among these, processing under vacuum, that is, vacuum press processing, vacuum laminating processing, and vacuum hot roll laminating processing can be preferably performed without voids between the circuits, and can be preferably performed.

  Although the processing temperature in the said thermocompression bonding process is not specifically limited, It is preferable to exist in the range of 50 degreeC or more and 250 degrees C or less, It is more preferable to exist in the range of 60 degreeC or more and 200 degrees C or less, 80 degreeC It is preferably within the range of 180 ° C. or lower. When the said processing temperature exceeds 250 degreeC, the insulating sheet of this invention will harden | cure at the time of a thermocompression bonding process, and there exists a possibility that favorable lamination | stacking cannot be performed. On the other hand, when the treatment temperature is less than 50 ° C., the fluidity of the layer C is low, and it is difficult to embed a conductor circuit pattern.

  The processing time and processing pressure in the thermocompression treatment are not particularly limited, and should be appropriately set according to the characteristics of the apparatus used and the fluidity of the layer C. Usually, the treatment time is preferably several seconds to 3 hours, and the treatment pressure is preferably 0.1 MPa to 5 MPa.

The layer C provided on the conductor circuit pattern serves as a protective material for protecting the conductor circuit pattern or an interlayer insulating material in a multilayer printed wiring board. Therefore, it is preferable that the pattern circuit is embedded and then completely cured by performing heat curing or the like. The specific method of heat curing is not particularly limited, and it is preferably performed under conditions that allow the thermosetting resin composition of layer C of the insulating sheet to be sufficiently cured.
In the case of curing the layer C, it is preferable to perform a post heat treatment after or simultaneously with the laminating step in order to sufficiently advance the curing reaction of the thermosetting resin composition. The conditions for the post heat treatment are not particularly limited, but it is preferable to perform the heat treatment for 10 minutes to 3 hours under temperature conditions in the range of 150 ° C. to 200 ° C.

  Thus, the printed wiring board concerning this invention is equipped with the resin layer containing the insulating sheet mentioned above. Therefore, it is possible to maintain excellent fine circuit formability, and furthermore, various properties such as processability / handleability, heat resistance, and resin fluidity can be imparted in a balanced manner. Thereby, it becomes possible to manufacture a printed wiring board suitably.

  Further, for the purpose of improving the adhesion between the layer B and the electroless plating layer, it is possible to perform a heat treatment after forming the electroless plating layer.

  The present invention will be described more specifically based on examples, but the present invention is not limited to this. Those skilled in the art can make various changes, modifications, and alterations without departing from the scope of the present invention. In addition, as a characteristic of the insulating sheet concerning this invention, the adhesiveness with electroless-plated copper, surface roughness Ra, and lamination | stacking property were evaluated or calculated as follows.

(Preparation of non-thermoplastic polyimide film)
Pyromellitic dianhydride / p-phenylenebis (trimellitic acid monoester anhydride) / p-phenylenediamine / 4,4′-diaminodiphenyl ether was synthesized at a 1/1/1/1 molar ratio. 90 g of a 17 wt% N, N-dimethylacetamide solution of polyamic acid is mixed with a conversion agent consisting of 17 g of acetic anhydride and 2 g of isoquinoline, stirred, defoamed by centrifugation, and cast onto aluminum foil at a thickness of 150 μm. did. The process from stirring to defoaming was performed while cooling to 0 ° C. The laminate of the aluminum foil and the polyamic acid solution was heated at 110 ° C. for 4 minutes to obtain a gel film having self-supporting properties. This gel film had a residual volatile content of 30 wt% and an imidization ratio of 90%. This gel film was peeled off from the aluminum foil and fixed to the frame. This gel film was heated at 300 ° C., 400 ° C., and 500 ° C. for 1 minute each to produce a non-thermoplastic polyimide film (a) having a thickness of 13 μm. The obtained non-thermoplastic polyimide film had an average linear expansion coefficient of 12 ppm at 100 ° C. to 200 ° C. and a tensile elastic modulus at room temperature of 6 GPa.

(Synthesis example 1 of thermoplastic polyimide)
In a glass flask with a capacity of 2000 ml, 1,4.7 g (0.15 mol) of 1,1,3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane and N, N-dimethylformamide ( (Hereinafter referred to as DMF) was added and dissolved while stirring, and 78.1 g (0.15 mol) of 4,4 ′-(4,4′-isopropylidenediphenoxy) bisphthalic anhydride was added for about 1 hour. The mixture was stirred to obtain a DMF solution of polyamic acid with a solid content concentration of 30%. The polyamic acid solution was placed in a vat coated with Teflon (registered trademark) and heated in a vacuum oven at 200 ° C. for 120 minutes at 665 Pa to obtain a thermoplastic polyimide resin (b1).
The obtained thermoplastic polyimide resin (b1) was subjected to permanent compression deformation at 40 ° C. in a thermomechanical analysis measurement (TMA, heating rate: 10 ° C./min) in a compression mode (probe diameter 3 mmφ, load 5 g).
Moreover, after melt | dissolving the obtained thermoplastic polyimide resin (b1) in dioxolane, it cast-coated on PET film, and the tensile elasticity modulus of the thermoplastic polyimide film obtained by drying for 2 minutes at 150 degreeC is 0.5 GPa. Met.

(Synthesis example 2 of thermoplastic polyimide)
In a glass flask with a volume of 2000 ml, 62.3 g (0.075 mol) of 1,1,3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane and 4,4′-diaminodiphenyl ether 15.0 g (0.075 mol) and DMF were added and dissolved while stirring to obtain 78.1 g (0.15 mol) of 4,4 ′-(4,4′-isopropylidenediphenoxy) bisphthalic anhydride. The mixture was added and stirred for about 1 hour to obtain a DMF solution of polyamic acid having a solid content concentration of 30%. The polyamic acid solution was placed in a Teflon (registered trademark) -coated vat and heated in a vacuum oven at 200 ° C. for 120 minutes at 665 Pa to obtain a thermoplastic polyimide resin (b2).
The obtained thermoplastic polyimide resin (b2) was subjected to permanent compression deformation at 90 ° C. in a thermomechanical analysis measurement (TMA, heating rate: 10 ° C./min) in a compression mode (probe diameter 3 mmφ, load 5 g). Moreover, after melt | dissolving the obtained thermoplastic polyimide resin (b2) in dioxolane, it cast-coated on PET film, and the tensile elasticity modulus of the thermoplastic polyimide film obtained by drying for 2 minutes at 150 degreeC is 1.0 GPa. Met.

(Synthesis example 3 of thermoplastic polyimide)
In a glass flask with a capacity of 2000 ml, 37.4 g (0.045 mol) of 1,1,3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane and 4,4′-diaminodiphenyl ether 21.0 g (0.105 mol) and DMF were added and dissolved while stirring to obtain 78.1 g (0.15 mol) of 4,4 ′-(4,4′-isopropylidenediphenoxy) bisphthalic anhydride. The mixture was added and stirred for about 1 hour to obtain a DMF solution of polyamic acid having a solid content concentration of 30%. The polyamic acid solution was placed in a vat coated with Teflon (registered trademark) and heated in a vacuum oven at 200 ° C. for 120 minutes at 665 Pa to obtain a thermoplastic polyimide resin (b3).

  The obtained thermoplastic polyimide resin (b3) was subjected to permanent compression deformation at 150 ° C. in a thermomechanical analysis measurement (TMA, heating rate: 10 ° C./min) in a compression mode (probe diameter 3 mmφ, load 5 g). Moreover, after melt | dissolving the obtained thermoplastic polyimide resin (b3) in dioxolane, it cast-coated on PET film, and the tensile elasticity modulus of the thermoplastic polyimide film obtained by drying for 2 minutes at 150 degreeC is 1.4 GPa. Met.

(Synthesis example 4 of thermoplastic polyimide)
In a glass flask having a capacity of 2000 ml, 37.4 g (0.045 mol) of 1,1,3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane and 1,3-bis (3 -Aminophenoxy) benzene (30.7 g, 0.105 mol) and DMF were added and dissolved while stirring to give 78 g (0. 4) of 4,4 '-(4,4'-isopropylidenediphenoxy) bisphthalic anhydride. 15 mol) was added and stirred for about 1 hour to obtain a DMF solution of polyamic acid with a solid content concentration of 30%. The polyamic acid solution was placed in a Teflon (registered trademark) -coated vat and heated under reduced pressure in a vacuum oven at 200 ° C. for 120 minutes at 665 Pa to obtain a thermoplastic polyimide resin (b4).
The obtained thermoplastic polyimide resin (b4) was subjected to permanent compression deformation at 140 ° C. in a thermomechanical analysis measurement (TMA, heating rate: 10 ° C./min) in a compression mode (probe diameter 3 mmφ, load 5 g). Further, the thermoplastic polyimide resin (b4) obtained was dissolved in dioxolane, and then cast on a PET film and dried at 150 ° C. for 2 minutes, and the tensile modulus of the thermoplastic polyimide film obtained was 1.2 GPa. Met.

(Synthesis example 5 of thermoplastic polyimide)
Into a glass flask having a capacity of 2000 ml, 41 g (0.15 mol) of 1,3-bis (3-aminophenoxy) benzene and DMF were added and dissolved while stirring, and 4,4 ′-(4,4′- 78 g (0.15 mol) of isopropylidenediphenoxy) bisphthalic anhydride was added and stirred for about 1 hour to obtain a DMF solution of 30% solid content polyamic acid. The polyamic acid solution was placed in a Teflon (registered trademark) -coated vat and heated in a vacuum oven at 200 ° C. for 180 minutes at 665 Pa to obtain a thermoplastic polyimide resin (b5).
The obtained thermoplastic polyimide resin (b5) was subjected to permanent compression deformation at 160 ° C. in a thermomechanical analysis measurement (TMA, heating rate: 10 ° C./min) in a compression mode (probe diameter 3 mmφ, load 5 g). Moreover, after melt | dissolving the obtained thermoplastic polyimide resin (b5) in dioxolane, it cast-coated on PET film, and the tensile elasticity modulus of the thermoplastic polyimide film obtained by drying for 2 minutes at 150 degreeC is 2.0 GPa. Met.

(Formulation example of layer B resin solution)
The thermoplastic polyimide resin obtained above was dissolved and dispersed in dioxolane to obtain a layer B resin solution. The solid content concentration was 15% by weight.

(Preparation of layer C resin solution)
50 g of the thermoplastic polyimide resin (b5) obtained above, 32.1 g of biphenyl type epoxy resin YX4000H manufactured by Japan Epoxy Resin Co., Ltd., 17.9 g of bis [4- (3-aminophenoxy) phenyl] sulfone, 0.2 g of 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine was dissolved in a mixed solution of dioxolane and toluene in a weight ratio of 7 to 3, A layer C resin solution was obtained by dispersing 50 g of spherical fused silica filler having an average particle size of 1.5 μm, which was surface-treated with silazane by a dry method. The solid content concentration was set to 30% by weight.

(Production of laminate)
A fluororesin film (trade name Aflex, manufactured by Asahi Glass Co., Ltd.) is disposed on the layer B side as a protective film, and layer C is a glass epoxy substrate (trade name RISHOLITE, CS-3665, manufactured by Risho Co., Ltd .; copper foil thickness 18 μm, The whole sheet is 0.6 mm thick, and heated and pressurized for 60 minutes under conditions of a temperature of 180 ° C., a pressure of 3 MPa, and a vacuum, and then the fluororesin film is peeled off to form an insulating sheet / glass epoxy substrate laminate. Got.
(Formation of metal layer 1 on layer B, desmear, electroless plating + electrolytic copper plating)
The exposed surface of the insulating sheet / glass epoxy substrate laminate obtained above is subjected to desmearing and electroless copper plating under the conditions of (Table 1) and (Table 2), and then thickened on the electroless plated copper. An electrolytically plated copper layer having a thickness of 18 μm was formed.

（層Ｂ上への金属層の形成２、スパッタリング＋電解銅メッキ）
上記で得られた絶縁シート／ガラスエポキシ基板積層体の露出する層Ｂ表面に昭和真空社製スパッタリング装置ＮＳＰ−６を用い、銅２００ｎｍを（スパッタ圧０.２Ｐａ、ＤＣ出力２００Ｗ、スパッタ時間２４分間）の条件でスパッタリングにより銅薄膜を形成し、スパッタ銅薄膜上に厚さ１８μｍの電解銅メッキ層を形成した。
（接着強度の測定）
上記得られた、層Ｂ表面に金属層を形成した絶縁シート／ガラスエポキシ基板積層体を、１８０℃、３０分の乾燥処理を行った後、ＪＰＣＡ−ＢＵ０１−１９９８（社団法人日本プリント回路工業会発行）に従い、常態、及びプレッシャークッカー試験（ＰＣＴ）後の接着強度を測定した。尚、デスミアおよび無電解銅めっきは以下実施した。
常態接着強度：２５℃、５０％の雰囲気下、２４時間放置した後に測定した接着強度。
ＰＣＴ後接着強度：１２１℃、１００％の雰囲気下、９６時間放置した後に測定した接着強度。

(Metal layer formation on layer B, sputtering + electrolytic copper plating)
Using the sputtering apparatus NSP-6 manufactured by Showa Vacuum Co., Ltd. on the surface of the exposed layer B of the insulating sheet / glass epoxy substrate laminate obtained above, copper 200 nm (sputtering pressure 0.2 Pa, DC output 200 W, sputtering time 24 minutes) ), A copper thin film was formed by sputtering, and an electrolytic copper plating layer having a thickness of 18 μm was formed on the sputtered copper thin film.
(Measurement of adhesive strength)
After the obtained insulating sheet / glass epoxy substrate laminate having a metal layer formed on the surface of layer B was subjected to a drying treatment at 180 ° C. for 30 minutes, JPCA-BU01-1998 (Japan Printed Circuit Industries Association) The bond strength after the normal state and pressure cooker test (PCT) was measured according to (Issuance). Note that desmear and electroless copper plating were performed as follows.
Normal-state adhesive strength: Adhesive strength measured after standing for 24 hours in an atmosphere of 25 ° C. and 50%.
Adhesive strength after PCT: Adhesive strength measured after standing for 96 hours in an atmosphere of 121 ° C. and 100%.

[Surface roughness Ra measurement]
The surface roughness Ra of the layer B was measured using a sample in a state where the desmear was performed in the sample preparation procedure in the above adhesiveness measurement item. In the measurement, the arithmetic average roughness of the layer B was measured under the following conditions using a light wave interference type surface roughness meter (New View 5030 system manufactured by ZYGO).

(Measurement condition)
Objective lens: 50x Mirau Image zoom: 2
FDA Res: Normal
Analysis conditions:
Remove: Cylinder
Filter: High Pass
Filter Low Wave: 0.002mm
[Lamination evaluation]
A glass epoxy substrate having a circuit formed with a height of 18 μm, a circuit width of 50 μm, and a distance between circuits of 50 μm (trade name RISHOITE, CS-3665, manufactured by Rishosha; copper foil thickness of 18 μm, overall thickness 0.6 mm) circuit formation surface and the layer C side of the insulating sheet having a fluororesin film (trade name Aflex, manufactured by Asahi Glass Co., Ltd.) as a protective film on the layer B side are opposed to each other at a temperature of 180 ° C., a pressure of 3 MPa, and a vacuum After heating and pressing for 60 minutes under the above conditions, the fluororesin film was peeled off to obtain an insulating sheet / glass epoxy substrate laminate. The exposed resin surface was visually observed using an optical microscope (magnification 50 times), and the presence or absence of bubbles in between the circuits was confirmed. The stacking property when the encroachment of bubbles between the circuits (the portion where the resin does not enter between the circuits) is not confirmed is accepted (O), and the laminating property when the entrapment of bubbles is confirmed is rejected ( Evaluation was carried out as x).

(Measurement of linear expansion coefficient)
Insulating sheet consisting of layer B / layer A / layer C is cured by thermosetting the thermosetting component by hot pressing (180 ° C. for 1 hour) to prepare a cured sheet, and further dried at 180 ° C. for 30 minutes as a sample. The temperature was raised from room temperature to 200 ° C with the equipment (TMA120C manufactured by Seiko Instruments Inc.), sample shape (15 mm length x 5 mm width), temperature increase rate (10 ° C / min), and tensile load (3 g). Cool once. By this operation, the residual stress in the sample is released, and the temperature is again raised from room temperature to 270 ° C. and measured. In this second measurement, the temperature at the inflection point of the temperature-dimension curve was the glass transition temperature (Tg), and the average linear expansion coefficient in the temperature range from room temperature to Tg-10 ° C. was the linear expansion coefficient of the sample.

(Measurement of melt viscosity)
The resin sheet made of the material of the layer C in the B-stage state is measured with a measuring device (Rheometer CVO manufactured by BOHLIN), a sample size (25 mmφ, 0.5 mm thickness), and a temperature rising rate (12 ° C./min). The temperature is raised from 60 ° C. to 180 ° C. and then held at 180 ° C. for 1 hour. The time change of the complex viscosity coefficient of the sample from the start of temperature increase was observed, and the lowest value was taken as the melt viscosity of the sample.

(Measurement of elastic modulus)
The tensile modulus was measured according to ASTM D882-81.

[Example 1]
The non-thermoplastic polyimide film (a) obtained by the above-mentioned method was used as layer A, and the solution of the thermoplastic polyimide resin (b1) obtained above was cast on one surface thereof. Thereafter, it was heated and dried for 2 minutes at 60 ° C., 100 ° C., and 150 ° C. in a hot air oven to obtain a layer B having a thickness of 5 μm. Subsequently, the layer C resin solution obtained by the above method was cast and applied to the other surface of layer A so that the thickness of layer C after drying was 40 μm, and was heated at 80 ° C., 100 ° C., 120 ° C. in a hot air oven. The insulating sheet of the present invention consisting of layer B (5 μm) / layer A (13 μm) / layer C (40 μm) was obtained by heating and drying at a temperature of 150 ° C. for 1 minute each. Using the obtained sheet, an insulating sheet / glass epoxy substrate laminate was prepared, and a metal layer was formed on layer B by the method of desmear / electroless plating + electrolytic plating by the method described above, and the adhesion was evaluated.
Further, various evaluation items of the obtained insulating sheet / glass epoxy substrate laminate and insulating sheet were evaluated according to the above-described evaluation procedure. The evaluation results are shown in Table 3.

[Examples 2 to 4]
The insulating sheet of this invention was obtained in the procedure similar to Example 1 except using the thermoplastic polyimide resin (b2)-(b4) obtained by the said method for the layer B resin solution, respectively. The obtained sheet or insulating sheet / glass epoxy substrate laminate was evaluated in the same manner as in Example 1 according to the evaluation procedures for various evaluation items. The evaluation results are shown in Table 3.

(Example 5)
Using the insulating sheet / glass epoxy substrate laminate obtained in the same manner as in Example 3, a metal layer was formed on layer B by the sputtering + electrolytic plating method as described above, and the adhesion was evaluated. The results are shown in Table 3.
(Examples 6 to 8)
The layer B resin solution is the same as in Example 3 except that the thermoplastic polyimide resin (b3) is used, the fused silica filler is not added to the layer C, and the thicknesses are 15, 20, and 40 μm, respectively. An insulating sheet was obtained. The obtained sheet or insulating sheet / glass epoxy substrate laminate was evaluated in the same manner as in Example 1 according to the evaluation procedures for various evaluation items. The evaluation results are shown in Table 3.

(Comparative Example 1)
An insulating sheet of the present invention was obtained in the same procedure as in Example 1 except that the layer B resin solution was not used. The obtained sheet or insulating sheet / glass epoxy substrate laminate was evaluated in the same manner as in Example 1 according to the evaluation procedures for various evaluation items. The evaluation results are shown in (Table 3).

（比較例２）
層Ｂ樹脂溶液をそれぞれ上記方法で得た熱可塑性ポリイミド樹脂（ｂ５）を用いる以外は実施例１と同様の手順で本発明の絶縁シートを得た。得られたシートや絶縁シート／ガラスエポキシ基板積層体を実施例１と同様に各種評価項目の評価手順に従い評価した。評価結果を（表３）に示す。

(Comparative Example 2)
The insulating sheet of the present invention was obtained in the same procedure as in Example 1 except that the thermoplastic polyimide resin (b5) obtained by the above method was used for each of the layer B resin solutions. The obtained sheet or insulating sheet / glass epoxy substrate laminate was evaluated in the same manner as in Example 1 according to the evaluation procedures for various evaluation items. The evaluation results are shown in (Table 3).

表４に示すように、一般式（１）で表されるジアミンを含まない熱可塑性ポリイミド樹脂を用いた比較例１は金属層の接着強度が低い。

As shown in Table 4, Comparative Example 1 using a thermoplastic polyimide resin containing no diamine represented by the general formula (1) has a low adhesive strength of the metal layer.

(Examples 9 to 11)
An insulating sheet was obtained in the same manner as in Example 3 except that the thickness of the layer C was 15 μm, 20 μm, and 30 μm, respectively. The linear expansion coefficient of the obtained insulating sheet is shown in Table 5 (Reference Example 1)
Without using a non-thermoplastic film for layer A, apply the resin of layer B made of the supporting PET film thermoplastic polyimide resin (b3), and further apply the resin of layer C and dry it. An insulating sheet was produced. The linear expansion coefficient of the obtained sheet was evaluated. The results are shown in Table 5.

Note that the present invention is not limited to the configurations described above, and various modifications are possible within the scope of the claims, and technical means disclosed in different embodiments and examples respectively. Embodiments obtained by appropriate combinations are also included in the technical scope of the present invention.

  The insulating sheet according to the present invention has a feature of high adhesive strength with a circuit even when the surface roughness of a layer forming the circuit is small, and therefore has excellent fine wiring formability.

Furthermore, it has a laminated structure with a non-thermoplastic polyimide film, and is excellent in uniformity of interlayer insulation thickness and reliability of interlayer insulation when processed as a multilayer printed wiring board. Further, the non-thermoplastic polyimide film has a small coefficient of linear expansion and can exhibit excellent characteristics for forming fine wiring. Therefore, the present invention can be suitably used not only in the material processing industry such as resin compositions and adhesives and various chemical industries, but also in the industrial field of various electronic components.

Claims (18)

  A layer B containing a thermoplastic polyimide resin having a siloxane structure was formed on one side of the polymer film layer A, and a layer C containing a thermoplastic polyimide resin and a thermosetting component was formed on the other side. Insulating sheet characterized by The thermoplastic polyimide resin having the siloxane structure is a thermoplastic polyimide resin that uses an acid dianhydride component and a diamine component containing a diamine represented by the following general formula (1) as raw materials. The insulating sheet according to 1.

(In the formula, g represents an integer of 1 or more. Further, R ¹¹ and R ²² may be the same or different and each represents an alkylene group or phenylene group having 1 to 6 carbon atoms. R ^{33 to} R ^66. May be the same or different and each represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group, a phenyl group, or a phenoxy group.)   2. The layer B is a layer for forming a metal layer on the layer, and the layer C is a layer for stacking facing a separately formed circuit. 2. The insulating sheet according to 2.   The thickness of the said layer B is 1 times or less of the thickness of the said layer A, The insulating sheet as described in any one of Claims 1-3 characterized by the above-mentioned.   The insulating sheet according to any one of claims 1 to 4, wherein the tensile modulus of the layer B is not more than one times the tensile elastic modulus of the layer A.   The said layer C contains 5 volume% or more of fillers, The insulating sheet as described in any one of Claims 1-5 characterized by the above-mentioned.   The insulating sheet according to claim 6, wherein the filler is spherical fused silica.   The insulating sheet according to claim 6 or 7, wherein the filler is a filler surface-treated with a silane-based or titanium-based coupling agent or a surface treatment agent. The insulating sheet according to any one of claims 1 to 8, wherein the thermosetting component contained in the C layer contains an epoxy resin component.   The insulating sheet according to any one of claims 1 to 9, wherein a melt viscosity of the C layer in a B-stage state is 20,000 Pa · s or less.   The insulating sheet according to any one of claims 1 to 10, wherein the arithmetic average roughness (Ra) measured at a cutoff value of 0.002 mm of the layer B is less than 0.5 µm.   The insulating sheet according to any one of claims 1 to 11, wherein the metal layer is formed by electroless copper plating.   A metal layer / insulating sheet laminate in which a metal layer is formed on the insulating sheet layer B according to any one of claims 1 to 11, wherein the adhesion strength of the metal layer is 5 N / cm or more. A metal layer / insulating sheet laminate characterized by the above.   The metal layer / insulating sheet laminate according to claim 13, wherein the metal layer is formed by electroless copper plating.   The metal layer / insulating sheet laminate according to claim 13, wherein the metal layer is formed by any one of a sputtering method, a vacuum vapor deposition method, an ion plating method, and a chemical vapor deposition method.   A printed wiring board using the insulating sheet or metal layer / insulating sheet laminate according to claim 1. On one side of the polymer film layer A is formed a layer B containing a thermoplastic polyimide resin made from a diamine component containing a diamine component represented by the following general formula (1) and an acid dianhydride component. An insulating sheet, characterized in that a layer is formed on a surface to be opposed to a separately formed circuit.

(In the formula, g represents an integer of 1 or more. Further, R ¹¹ and R ²² may be the same or different and each represents an alkylene group or phenylene group having 1 to 6 carbon atoms. R ^{33 to} R ^66. May be the same or different and each represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group, a phenyl group, or a phenoxy group.)   18. The insulating sheet, metal layer / insulating sheet laminate or printed wiring board according to claim 1, wherein the polymer film is a non-thermoplastic polyimide.