JP5733778B2 - Polyimide resin for primer layer and laminate using the same - Google Patents
Polyimide resin for primer layer and laminate using the same Download PDFInfo
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本発明は、粗化処理の施されていない銅箔等の金属箔表面に、特定構造のポリイミド樹脂を塗布、乾燥してなるプライマー層を設けることにより、フレキシブルプリント配線板に用いられるポリイミド等の基材樹脂層と金属箔との良好な接着性を確保し、実用的なフレキシブルプリント配線板を得ることができるプライマー層用ポリイミド樹脂に関する。 The present invention provides a primer layer formed by applying and drying a polyimide resin having a specific structure on the surface of a metal foil such as a copper foil that has not been subjected to roughening treatment. It is related with the polyimide resin for primer layers which can ensure the favorable adhesiveness of a base resin layer and metal foil, and can obtain a practical flexible printed wiring board.
ポリイミド樹脂フィルムの一般的な用途としては、銅箔に代表される金属箔を貼り合わせた片面または両面フレキシブル積層板、フレキシブルプリント配線板用カバーレイ並びに多層基板用層間絶縁フィルム等が挙げられる。なかでも、ポリイミド樹脂と金属箔とをエポキシ系あるいはアクリル系の接着剤層を介さずに直接張り合わせた２層ＣＣＬと呼ばれる積層板は、配線の微細化や基板の耐熱性といった点で非常に有用であるが、ポリイミド樹脂と金属箔との剥離強度不足がしばしば問題となっている。２層ＣＣＬの製造方法としては、金属箔上に塗布したポリイミド前駆体を加熱によりイミド化するキャスト法が現在主流となっているが、接着層としての熱可塑性ポリイミドを介してポリイミドフィルムと金属箔とを加熱圧着するラミネート法や、ポリイミドフィルムの表面に設けられたスパッタ層に金属箔をメッキするスパッタ法等も知られている。
従来これらプリント配線板の製造には、銅箔の片面に微細な銅粒子を付着させる等の粗化処理を施すことにより、表面に凹凸が形成された銅箔が用いられてきた。粗化処理銅箔を用いた場合、張り合わせの際に銅箔表面の凹凸形状がプリプレグ等の基材樹脂内に埋まり込むことによってアンカー効果が得られるため、銅箔と基材樹脂との高い密着性が得られる。
Typical uses of the polyimide resin film include single-sided or double-sided flexible laminates bonded with metal foils typified by copper foils, coverlays for flexible printed wiring boards, and interlayer insulation films for multilayer boards. Among these, a laminate called a two-layer CCL, in which polyimide resin and metal foil are directly bonded together without using an epoxy or acrylic adhesive layer, is very useful in terms of miniaturization of wiring and heat resistance of the substrate. However, insufficient peel strength between the polyimide resin and the metal foil is often a problem. As a manufacturing method of the two-layer CCL, a casting method in which a polyimide precursor coated on a metal foil is imidized by heating is currently mainstream. However, a polyimide film and a metal foil via a thermoplastic polyimide as an adhesive layer. Also known are a laminating method in which heat and pressure bonding is performed, a sputtering method in which a metal foil is plated on a sputter layer provided on the surface of a polyimide film, and the like.
Conventionally, for the production of these printed wiring boards, copper foils having irregularities formed on the surface by applying a roughening process such as attaching fine copper particles to one side of the copper foil have been used. When roughened copper foil is used, the unevenness of the copper foil surface is embedded in the base resin such as prepreg during lamination, so the anchor effect is obtained, so the copper foil and base resin have high adhesion. Sex is obtained.
しかしながら、粗化処理銅箔の表面には、通常、防錆剤等としてのアミン化合物、長鎖アルキル化合物またはシリコーン系化合物等が表面処理剤として塗布されているため、銅箔の表面からこれらを除去せずにキャスト法でポリイミド前駆体を塗布すると、得られる２層ＣＣＬの銅箔とポリイミド樹脂層との剥離強度が低下してしまう。これら表面処理剤は、脱脂工程やソフトエッチングといった煩雑な工程を経ることにより除去可能ではあるが、表面処理剤を除去した銅箔表面は、大気やポリイミド前駆体にさらされることにより腐食酸化され易いことが問題であった。
近年、銅箔と基材樹脂である非熱可塑性ポリイミドフィルムの密着性を向上させる目的で、熱可塑性ポリイミドをプライマー層として用いる手法が検討されている（特許文献１、２及び３）。しかしながら、これらの多くは基材樹脂である非熱可塑性のポリイミドフィルムに熱可塑性ポリイミドのワニスを塗布して銅箔と熱圧着するラミネート法を用いており、初期ピール強度、耐熱ピール強度及び耐湿熱後ピール強度の全ての接着強度を満足するものは得られていない。また、該ワニスを用いたラミネート法は、寸法安定性が低くなる傾向にあり、しかも、非熱可塑性ポリイミドフィルムのガス透過性が低い場合には、ポリイミドフィルムと該ワニスとの界面で残留溶剤や分解物に由来する発泡が起こりやすいため、ガス透過性の高いポリイミドフィルムを基材に用いる必要があった。
However, since the surface of the roughened copper foil is usually coated with an amine compound, a long-chain alkyl compound, or a silicone compound as a rust preventive agent as a surface treating agent, these are removed from the surface of the copper foil. If the polyimide precursor is applied by a casting method without removing, the peel strength between the obtained two-layer CCL copper foil and the polyimide resin layer is lowered. Although these surface treatment agents can be removed through complicated steps such as a degreasing step and soft etching, the surface of the copper foil from which the surface treatment agent has been removed is easily corroded and oxidized by exposure to air or a polyimide precursor. That was the problem.
In recent years, methods for using thermoplastic polyimide as a primer layer have been studied for the purpose of improving the adhesion between a copper foil and a non-thermoplastic polyimide film that is a base resin (Patent Documents 1, 2, and 3). However, many of these use a laminate method in which a thermoplastic polyimide varnish is applied to a non-thermoplastic polyimide film, which is a base resin, and is thermocompression bonded to a copper foil, and the initial peel strength, heat peel strength, and moisture heat resistance Those satisfying all the adhesive strengths of the post peel strength have not been obtained. In addition, the laminating method using the varnish tends to have low dimensional stability, and when the gas permeability of the non-thermoplastic polyimide film is low, residual solvent or Since foaming derived from the decomposed product is likely to occur, it is necessary to use a polyimide film having high gas permeability for the base material.
粗化処理を施していない銅箔をプリント配線板の製造に用いることができれば、銅箔の粗化処理工程を省略することが可能となり、生産コストの大幅な低減が可能である。また、回路エッチングにおいて粗化処理部分を溶解するためのオーバーエッチングタイムを設ける必要がなくなることで、トータルエッチングコストの削減も可能である。 If a copper foil that has not been subjected to a roughening treatment can be used in the production of a printed wiring board, the copper foil roughening treatment step can be omitted, and the production cost can be greatly reduced. Further, it is not necessary to provide an over-etching time for dissolving the roughened portion in circuit etching, so that the total etching cost can be reduced.
しかも、粗化部分の厚みが無くなることによりプリント配線板の薄化が可能な上、凹凸部分に食い込んだ樹脂がエッチング残渣として残らないため、より微細な配線パターンの形成が可能となる。さらに、配線表面の電気抵抗も小さくなり、特に高周波電流を用いる場合、表皮効果により銅箔表面の電流密度が高くなる等、プリント配線板の特性も向上する。 In addition, since the thickness of the roughened portion is eliminated, the printed wiring board can be thinned, and the resin biting into the concavo-convex portion does not remain as an etching residue, so that a finer wiring pattern can be formed. Furthermore, the electrical resistance on the surface of the wiring is reduced, and particularly when a high-frequency current is used, the characteristics of the printed wiring board are improved, for example, the current density on the surface of the copper foil is increased by the skin effect.
本発明は、銅箔に代表される金属箔を粗化処理することなく、キャスト法で得られるフレキシブルプリント配線板用の樹脂基板において、金属箔と基材樹脂であるポリイミド樹脂との良好な接着性を確保すると共に、基材樹脂との界面での発泡を引き起こすことなく、しかも金属箔表面の腐食を防ぐことのできるプライマー層用ポリイミド樹脂、プライマー層用ポリイミド樹脂ワニス及びプライマー層用ポリイミド樹脂層を有する積層板を提供することを目的とする。 The present invention provides a good adhesion between a metal foil and a polyimide resin as a base resin in a resin substrate for a flexible printed wiring board obtained by a casting method without roughening a metal foil represented by a copper foil. The primer layer polyimide resin, the primer layer polyimide resin varnish, and the primer layer polyimide resin layer that can prevent the foaming at the interface with the base resin and prevent the metal foil surface from being corroded. It aims at providing the laminated board which has.
本発明者らは、上記課題を解決するため、鋭意研究の結果、特定構造のポリイミド樹脂をプライマー層として用いることにより、上記の課題が解決されることを見出し、本発明を完成するに至った。 As a result of diligent research, the present inventors have found that the above problems can be solved by using a polyimide resin having a specific structure as a primer layer, and have completed the present invention. .
すなわち本発明は
（１）表面粗さ（Ｒｚ）が２μｍ以下である金属箔（ａ）と該金属箔（ａ）上にキャスト法により形成されるポリイミド前駆体から得られるポリイミド樹脂層（ｂ）との間の接着性を確保するためのプライマー層用ポリイミド樹脂であって、下記式（１）
That is, the present invention includes (1) a polyimide resin layer (b) obtained from a metal foil (a) having a surface roughness (Rz) of 2 μm or less and a polyimide precursor formed on the metal foil (a) by a casting method. A polyimide resin for a primer layer for ensuring adhesion between the following formula (1)
（式（１）中、Ｒ1は下記式（２） (In the formula (1), R 1 represents the following formula (2)
で表される４価の芳香族基からなり、Ｒ2は下記式（３） R 2 is represented by the following formula (3):
並びに３，３’−ジアミノ−４，４’−ジヒドロキシジフェニルエーテル、３，３’−ジアミノ−４，４’−ジヒドロキシビフェニル、３，３’−ジヒドロキシ−４，４’−ジアミノビフェニル、２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパン、１，３−ヘキサフルオロ−２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパン、１，３−ビス（４−アミノ−３−ヒドロキシフェノキシ）ベンゼン及び９，９’−ビス（３−アミノ−４−ヒドロキシフェニル）フルオレンからなる群から選ばれる１種以上のアミノフェノール類から誘導される２価の芳香族基であり、ｎは繰り返し数を表す。）で表されるプライマー層用ポリイミド樹脂（Ａ）、
（２）末端官能基がアミノ基または酸無水物基である、前項（１）に記載のプライマー層用ポリイミド樹脂（Ａ）、
（３）前項（１）または（２）に記載のプライマー層用ポリイミド樹脂（Ａ）を有機溶剤に溶解してなるポリイミド樹脂ワニス、
（４）表面粗さ（Ｒｚ）が２μｍ以下である金属箔（ａ）、該金属箔（ａ）上にキャスト法により形成されるポリイミド前駆体から得られるポリイミド樹脂層（ｂ）及び前項（１）または（２）に記載のプライマー層用ポリイミド樹脂（Ａ）の層を有するフレキシブルプリント配線板用積層板、
（５）表面粗さ（Ｒｚ）が２μｍ以下である金属箔（ａ）が、メッキ層を備えていても良い銅箔であることを特徴とする前項（４）に記載のフレキシブルプリント配線板用積層板、
（６）キャスト法により形成されるポリイミド前駆体から得られるポリイミド樹脂層（ｂ）が、金属箔（ａ）上に設けられたプライマー層上にポリアミック酸樹脂を塗布後、該ポリアミック酸樹脂を熱閉環させて得られたポリイミド樹脂層であることを特徴とする前項（４）または（５）に記載のフレキシブルプリント配線板用積層板、
（７）前項（４）〜（６）のいずれか一項に記載のフレキシブルプリント配線板用積層板を用いて作られるフレキシブルプリント配線板、
（８）表面粗さ（Ｒｚ）が２μｍ以下である金属箔（ａ）上に、前項（３）記載のポリイミド樹脂ワニスを塗布した後に有機溶剤を乾燥させてプライマー層用ポリイミド樹脂（Ａ）からなるプライマー層を設ける工程、該プライマー層上にポリアミック酸樹脂をキャスト法により塗布する工程、及び加熱によりポリアミック酸樹脂をイミド化してポリイミド樹脂層（ｂ）を設ける工程を含むフレキシブルプリント配線板用積層板の製造方法、
に関する。
3,3′-diamino-4,4′-dihydroxydiphenyl ether, 3,3′-diamino-4,4′-dihydroxybiphenyl, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 2,2- Bis (3-amino-4-hydroxyphenyl) propane, 1,3-hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane, 1,3-bis (4-amino-3-hydroxy) A divalent aromatic group derived from one or more aminophenols selected from the group consisting of phenoxy) benzene and 9,9′-bis (3-amino-4-hydroxyphenyl) fluorene, and n is a repeating group. Represents a number. Polyimide resin for primer layer (A) represented by
(2) The polyimide resin for primer layer (A) according to (1) above, wherein the terminal functional group is an amino group or an acid anhydride group,
(3) A polyimide resin varnish obtained by dissolving the polyimide resin (A) for the primer layer described in (1) or (2) above in an organic solvent,
(4) Metal foil (a) having a surface roughness (Rz) of 2 μm or less, a polyimide resin layer (b) obtained from a polyimide precursor formed on the metal foil (a) by a casting method, and the preceding item (1 ) Or a laminate for a flexible printed wiring board having a layer of the polyimide resin for primer layer (A) according to (2),
(5) The metal foil (a) having a surface roughness (Rz) of 2 μm or less is a copper foil which may be provided with a plating layer, for the flexible printed wiring board as described in (4) above Laminated board,
(6) After the polyimide resin layer (b) obtained from the polyimide precursor formed by the casting method has applied the polyamic acid resin on the primer layer provided on the metal foil (a), the polyamic acid resin is heated. The laminate for flexible printed wiring boards according to (4) or (5) above, which is a polyimide resin layer obtained by ring-closing,
(7) A flexible printed wiring board made using the laminate for flexible printed wiring board according to any one of (4) to (6) above,
(8) From the polyimide resin (A) for the primer layer by drying the organic solvent after applying the polyimide resin varnish described in (3) above on the metal foil (a) having a surface roughness (Rz) of 2 μm or less. A layer for a flexible printed wiring board including a step of providing a primer layer, a step of applying a polyamic acid resin on the primer layer by a casting method, and a step of imidizing the polyamic acid resin by heating to provide a polyimide resin layer (b) Board manufacturing method,
About.
本発明のプライマー層用ポリイミド樹脂（Ａ）（以下単に「ポリイミド樹脂（Ａ）」と記載する）は、イミド化された溶媒可溶性ポリイミド樹脂であって、ポリイミド前駆体ではないため、表面粗さ（Ｒｚ）が２μｍ以下である金属箔（ａ）（以下単に「金属箔（ａ）」と記載する）上に塗布した後の硬化工程を必要としない。また、柔軟なエーテル結合と適切な繰り返し長さを有するため、金属箔（ａ）表面とポリイミド樹脂（Ａ）中のイミド基及び芳香環との相互作用点が多くなり、あらゆる条件において安定した接着強度が得られる。また、ポリイミド樹脂（Ａ）の骨格中に特定構造のアミノフェノールを導入することで、ガス透過性の低い基材樹脂との界面における残溶剤及び分解反応に起因する発泡を大幅に抑制することができる。しかも、金属箔（ａ）の防錆処理層としての効果をも有する。さらにフレキシブルプリント配線板用積層板において、キャスト法により形成されるポリイミド前駆体溶液から得られるポリイミド樹脂層（ｂ）（以下単に「ポリイミド樹脂層（ｂ）」と記載する）とポリイミド樹脂（Ａ）との間の接着強度は、ポリイミド前駆体溶液中の溶剤によるプライマー層の溶融及びポリイミド前駆体硬化時のプライマー層の溶融により高められるため、電気電子材料分野で極めて有用である。 The polyimide resin for primer layer (A) of the present invention (hereinafter simply referred to as “polyimide resin (A)”) is an imidized solvent-soluble polyimide resin and not a polyimide precursor. Rz) does not require a curing step after coating on metal foil (a) (hereinafter simply referred to as “metal foil (a)”) having a thickness of 2 μm or less. In addition, since it has a flexible ether bond and an appropriate repeating length, the number of interaction points between the surface of the metal foil (a) and the imide group and aromatic ring in the polyimide resin (A) increases, and stable adhesion under all conditions. Strength is obtained. Moreover, by introducing aminophenol having a specific structure into the skeleton of the polyimide resin (A), it is possible to significantly suppress foaming caused by residual solvent and decomposition reaction at the interface with the base resin having low gas permeability. it can. And it also has the effect as a rust prevention process layer of metal foil (a). Furthermore, in the laminated board for flexible printed wiring boards, a polyimide resin layer (b) (hereinafter simply referred to as “polyimide resin layer (b)”) obtained from a polyimide precursor solution formed by a casting method and a polyimide resin (A) The adhesion strength between the two is enhanced by melting of the primer layer by the solvent in the polyimide precursor solution and melting of the primer layer at the time of curing the polyimide precursor, and thus is extremely useful in the field of electrical and electronic materials.
本発明のポリイミド樹脂（Ａ）は、通常、下記式（５） The polyimide resin (A) of the present invention is usually represented by the following formula (5).
で表されるテトラカルボン酸二無水物から選ばれる１種以上と、下記式（６） One or more selected from tetracarboxylic dianhydrides represented by the following formula (6)
で表されるジアミン化合物から選ばれる１種以上及び３，３’−ジアミノ−４，４’−ジヒドロキシジフェニルエーテル、３，３’−ジアミノ−４，４’−ジヒドロキシビフェニル、３，３’−ジヒドロキシ−４，４’−ジアミノビフェニル、２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパン、１，３−ヘキサフルオロ−２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパン、１，３−ビス（４−アミノ−３−ヒドロキシフェノキシ）ベンゼン及び９，９’−ビス（３−アミノ−４−ヒドロキシフェニル）フルオレンからなる群から選ばれる１種以上のアミノフェノール類との付加反応により得られたポリアミック酸を、更に脱水閉環させることにより得ることが出来る。これら一連の反応は１ポットで行うことが好ましい。 And one or more selected from diamine compounds represented by: 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 3,3′-diamino-4,4′-dihydroxybiphenyl, 3,3′-dihydroxy- 4,4′-diaminobiphenyl, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 1,3-hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane, , 3-bis (4-amino-3-hydroxyphenoxy) benzene and 9,9′-bis (3-amino-4-hydroxyphenyl) fluorene addition reaction with one or more aminophenols selected from the group consisting of Can be obtained by further dehydrating and ring-closing the polyamic acid obtained by the above. These series of reactions are preferably performed in one pot.
本発明のポリイミド樹脂（Ａ）は、溶媒に溶解したポリイミド樹脂ワニスとして金属箔（ａ）に塗布されるが、該樹脂ワニスの濃度は、通常溶媒中に５〜５０質重量％、好ましくは１０〜３０質量％である。該樹脂ワニスとしては、合成終了後、合成に用いた溶媒に溶解したポリイミド樹脂（Ａ）をそのまま用いることが出来るが、必要により該樹脂ワニスを濃縮又は更に溶媒を加えて希釈して用いても良い。従って、前記付加反応及び脱水閉環反応は、合成の中間体であるポリアミック酸および本発明のポリイミド樹脂（Ａ）を溶解する溶媒中、例えばＮ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルアセトアミドまたはγ−ブチロラクトンより選ばれる１種以上を含有する溶媒中で行うことが好ましい。 Although the polyimide resin (A) of this invention is apply | coated to metal foil (a) as a polyimide resin varnish melt | dissolved in the solvent, the density | concentration of this resin varnish is 5-50 mass% normally in a solvent, Preferably it is 10 -30 mass%. As the resin varnish, the polyimide resin (A) dissolved in the solvent used for the synthesis can be used as it is after the synthesis is finished, but if necessary, the resin varnish may be concentrated or further diluted by adding a solvent. good. Therefore, the addition reaction and dehydration ring-closing reaction are carried out in a solvent that dissolves the polyamic acid that is a synthetic intermediate and the polyimide resin (A) of the present invention, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide or It is preferably carried out in a solvent containing one or more selected from γ-butyrolactone.
前記脱水閉環反応の際には、脱水剤として、トルエン、キシレン、ヘキサン、シクロヘキサンまたはヘプタン等の比較的低沸点の無極性溶媒を少量使用し、反応時に副生する水を反応系から除去しながら実施するのが好ましい。また、触媒としてピリジンを少量添加することも好ましい。付加反応及び脱水閉環反応時の反応温度は通常１５０〜２２０℃、好ましくは１８０〜２００℃であり、反応時間は通常２〜１０時間、好ましくは５〜８時間である。脱水剤の添加量は反応液に対し通常５〜２０質量％、触媒の添加量は反応液に対し通常０．１〜５質量％である。 In the dehydration cyclization reaction, a small amount of a nonpolar solvent having a relatively low boiling point such as toluene, xylene, hexane, cyclohexane or heptane is used as a dehydrating agent, while removing water generated as a by-product during the reaction from the reaction system. It is preferable to carry out. It is also preferable to add a small amount of pyridine as a catalyst. The reaction temperature during the addition reaction and dehydration ring-closing reaction is usually 150 to 220 ° C., preferably 180 to 200 ° C., and the reaction time is usually 2 to 10 hours, preferably 5 to 8 hours. The addition amount of the dehydrating agent is usually 5 to 20% by mass with respect to the reaction solution, and the addition amount of the catalyst is usually 0.1 to 5% by mass with respect to the reaction solution.
本発明のポリイミド樹脂（Ａ）としては、前記式（１）で表される構造の閉環型イミドセグメントを含有していれば特に制限は無いが、式（１）におけるｎの値が小さすぎる場合には、本来ポリイミドのもつ耐熱性と機械強度が発現し難くなるとともに、金属箔の表面がポリイミド樹脂（Ａ）の有する末端アミノ基またはカルボキシル基の影響を受けやすくなる。また、ｎの値が大きすぎる場合には、溶媒中における粘度が高くなることでプライマー層の薄膜を形成することが困難になると共に、金属箔表面とプライマー層との接着性が低下する。これらのことから、式（１）におけるｎの値は、通常１０〜１０００．好ましくは５０〜５００である。 The polyimide resin (A) of the present invention is not particularly limited as long as it contains a closed imide segment having a structure represented by the formula (1), but the value of n in the formula (1) is too small. Therefore, the heat resistance and mechanical strength inherent to polyimide are difficult to develop, and the surface of the metal foil is easily affected by the terminal amino group or carboxyl group of the polyimide resin (A). Moreover, when the value of n is too large, it becomes difficult to form a primer layer thin film due to an increase in viscosity in the solvent, and the adhesion between the metal foil surface and the primer layer decreases. From these things, the value of n in Formula (1) is 10-1000. Preferably it is 50-500.
本発明の式（１）で表されるポリイミド樹脂（Ａ）の繰り返し数ｎは、テトラカルボン酸二無水物成分（前記式（５）で表されるテトラカルボン酸二無水物から選ばれる１種以上）とジアミン成分（前記式（６）で表されるジアミン化合物から選ばれる１種以上及び前記群から選ばれる１種以上のアミノフェノール類）とのモル比で制御可能であり、例えばｎ＝１００のポリイミド樹脂（Ａ）は、テトラカルボン酸二無水物成分とジアミン成分とを１．００：１．０１〜１．０１：１．００の範囲で用いることにより得られる。
尚、式（１）にはポリイミド樹脂（Ａ）の末端構造は記載されていないが、テトラカルボン酸二無水物に対してジアミン成分を過剰に用いた場合は式（１）の両末端がアミノ基となり、テトラカルボン酸二無水物を過剰に用いた場合は両末端が酸無水物基となる。
The repeating number n of the polyimide resin (A) represented by the formula (1) of the present invention is a tetracarboxylic dianhydride component (one kind selected from tetracarboxylic dianhydrides represented by the formula (5)). Or more) and a diamine component (one or more selected from the diamine compounds represented by the formula (6) and one or more aminophenols selected from the above group) can be controlled, for example, n = 100 polyimide resin (A) is obtained by using a tetracarboxylic dianhydride component and a diamine component in the range of 1.00: 1.01 to 1.01: 1.00.
In addition, although the terminal structure of polyimide resin (A) is not described in Formula (1), when a diamine component is used excessively with respect to tetracarboxylic dianhydride, both ends of Formula (1) are amino. When the tetracarboxylic dianhydride is used in excess, both ends are acid anhydride groups.
本発明のポリイミド樹脂（Ａ）の平均分子量は、数平均分子量で１，０００〜５０，０００、重量平均分子量で５，０００〜５００，０００程度が好ましい。平均分子量がこの範囲を下回る場合は、本来ポリイミド樹脂のもつ耐熱性と機械強度が発現し難くなるとともに、金属箔の表面がポリイミド樹脂（Ａ）の有する末端アミノ基または酸無水物基の影響を受けやすくなる。また、この範囲を超える場合は、溶媒中における粘度が高くなることでプライマー層の薄膜を形成することが困難になると共に、金属箔表面とプライマー層との接着性が低下する。尚、本発明でいう平均分子量とは、ゲルパーミエイションクロマトグラフィーの測定結果を元に、ポリスチレン換算で算出した分子量を表す。 The average molecular weight of the polyimide resin (A) of the present invention is preferably about 1,000 to 50,000 in terms of number average molecular weight and about 5,000 to 500,000 in terms of weight average molecular weight. If the average molecular weight is below this range, the heat resistance and mechanical strength inherently possessed by the polyimide resin are difficult to develop, and the influence of the terminal amino group or acid anhydride group of the polyimide resin (A) on the surface of the metal foil is affected. It becomes easy to receive. Moreover, when exceeding this range, while the viscosity in a solvent becomes high, while it becomes difficult to form the thin film of a primer layer, the adhesiveness of the metal foil surface and a primer layer falls. In addition, the average molecular weight as used in the field of this invention represents the molecular weight computed in polystyrene conversion based on the measurement result of gel permeation chromatography.
本発明のポリイミド樹脂（Ａ）は、アミノフェノール類から誘導される２価の芳香族基をその構造中に一部導入したことにより、金属箔とポリイミド樹脂（Ａ）との界面で起こる発泡を抑制する効果を付与したものである。アミノフェノール類から誘導される２価の芳香族基は、本発明のポリイミド樹脂（Ａ）の水酸基当量の計算値が、通常、２００〜３，０００ｇ／ｅｑ．、好ましくは３００〜２，０００ｇ／ｅｑ．となる量が導入されるが、基材の種類により得られる効果が異なるのでこの限りではない。 The polyimide resin (A) of the present invention introduces foaming that occurs at the interface between the metal foil and the polyimide resin (A) by partially introducing a divalent aromatic group derived from aminophenols into the structure. The effect of suppressing is given. The divalent aromatic group derived from aminophenols has a calculated hydroxyl equivalent weight of the polyimide resin (A) of the present invention of usually 200 to 3,000 g / eq. , Preferably 300 to 2,000 g / eq. However, this is not the case because the effect obtained varies depending on the type of substrate.
通常、熱可塑性ポリイミド樹脂をプライマー層として用いて銅張積層板を作成する場合、その前駆体であるポリアミック酸を金属箔上に塗布、乾燥後、３２０〜４００℃の加熱処理によって前駆体を脱水閉環させてプライマー層を形成するが、本発明のポリイミド樹脂（Ａ）はポリアミック酸が脱水閉環したものなので、ポリイミド樹脂（Ａ）を含有するポリイミド樹脂ワニスを金属箔上に直接塗布した後、溶媒を乾燥させるだけでプライマー層を形成することができる。 Usually, when creating a copper clad laminate using a thermoplastic polyimide resin as a primer layer, the precursor polyamic acid is applied on a metal foil, dried, and then the precursor is dehydrated by heat treatment at 320 to 400 ° C. The primer layer is formed by ring closure. Since the polyimide resin (A) of the present invention is a polyamic acid dehydrated ring-closing, the polyimide resin varnish containing the polyimide resin (A) is directly applied on the metal foil, The primer layer can be formed simply by drying.
本発明のポリイミド樹脂（Ａ）には、金属箔（ａ）及びポリイミド樹脂層（ｂ）への接着強度並びに金属箔（ａ）の防錆効果を損なわない範囲内であれば、種々の添加剤を加えることができる。該添加剤としては、例えば、芳香族ポリアミド樹脂、エポキシ樹脂及びフェノール樹脂等の有機添加剤、シリカ化合物等の無機添加剤、顔料、染料、ハレーション防止剤、蛍光増白剤、界面活性剤、レベリング剤、可塑剤、難燃剤、酸化防止剤、充填剤、静電防止剤、粘度調整剤、促進剤、光安定剤、光触媒、低誘電体、導電体、磁性体並びに熱分解性化合物等が挙げられる。 The polyimide resin (A) of the present invention has various additives as long as it does not impair the adhesive strength to the metal foil (a) and the polyimide resin layer (b) and the rust preventive effect of the metal foil (a). Can be added. Examples of the additives include organic additives such as aromatic polyamide resins, epoxy resins and phenol resins, inorganic additives such as silica compounds, pigments, dyes, antihalation agents, brightening agents, surfactants, and leveling. Agents, plasticizers, flame retardants, antioxidants, fillers, antistatic agents, viscosity modifiers, accelerators, light stabilizers, photocatalysts, low dielectric materials, conductors, magnetic materials, and thermally decomposable compounds. It is done.
本発明のポリイミド樹脂（Ａ）を用いたプライマー層は、粗化処理の施されていない金属箔（ａ）の片面に、乾燥後の厚さが１〜５μｍとなるように本発明のポリイミド樹脂ワニスを塗布して乾燥することにより得られるが、例えば金属箔（ａ）上に、ポリイミド樹脂（Ａ）を２０質量％含有する本発明のポリイミド樹脂ワニスを１５μｍの厚さになるよう塗布し、通常８０〜２００℃で５〜６０分間、好ましくは１３０〜１５０℃で１０〜３０分間乾燥させることにより、およそ３μｍの厚さのプライマー層が得られる。
乾燥時の熱源は熱風でも遠赤外線ヒーターでもよいが、気化した溶媒の滞留防止および樹脂内部まで加熱を施せる点で、熱風と遠赤外線ヒーターとを併用することが好ましい。
The primer layer using the polyimide resin (A) of the present invention has the polyimide resin of the present invention so that the thickness after drying is 1 to 5 μm on one side of the metal foil (a) not subjected to the roughening treatment. It is obtained by applying and drying the varnish, for example, on the metal foil (a), the polyimide resin varnish of the present invention containing 20% by mass of the polyimide resin (A) is applied to a thickness of 15 μm, Usually, a primer layer having a thickness of about 3 μm is obtained by drying at 80 to 200 ° C. for 5 to 60 minutes, preferably 130 to 150 ° C. for 10 to 30 minutes.
The heat source during drying may be hot air or a far-infrared heater, but it is preferable to use hot air and a far-infrared heater in combination in order to prevent the vaporized solvent from staying and to heat the inside of the resin.
本発明のポリイミド樹脂（Ａ）は、銅箔に代表される一般的な金属箔に用いた場合でもプライマーとしての効果を発現するが、表面粗さ（Ｒｚ）が２μｍ以下である金属箔（ａ）、特に金属箔（ａ）が粗化処理を施されていない場合に、従来公知のプライマーとの顕著な効果の差を発現する。金属箔（ａ）の金属種としては銅が好ましく、また、該銅箔の表面にはニッケル、鉄、亜鉛、金、錫又はクロム等のメッキ層が備えられていても良い。 The polyimide resin (A) of the present invention exhibits an effect as a primer even when used for a general metal foil typified by a copper foil, but has a surface roughness (Rz) of 2 μm or less. ), Particularly when the metal foil (a) is not subjected to roughening treatment, a significant difference in effect from the conventionally known primer is developed. The metal species of the metal foil (a) is preferably copper, and the surface of the copper foil may be provided with a plating layer such as nickel, iron, zinc, gold, tin or chrome.
ポリイミド樹脂層（ｂ）は、テトラカルボン酸二無水物とジアミン化合物とを、Ｎ−メチル−２−ピロリドンやＮ，Ｎ−ジメチルアセトアミド等の極性溶媒中で反応させて得られるポリアミック酸樹脂ワニスを、金属箔（ａ）上に設けられたポリイミド樹脂（Ａ）のプライマー層上に塗布して乾燥した後、２５０〜４００℃で０．５〜２０時間の条件で脱水閉環させることにより得られる。この際、ポリアミック酸樹脂ワニスには、テトラカルボン酸二無水物にメタノールやエタノールを反応させたエステル塩を含有していても良い。尚、ポリイミド樹脂層（ｂ）の原料となるテトラカルボン酸二無水物とジアミン化合物との組み合わせには何ら制限は無く、従来公知の組み合わせにより得られるポリイミド樹脂を用いることができる。ポリアミック酸樹脂ワニスの市販品としては、ＫＡＹＡＦＬＥＸ ＫＰＩ−１２０（日本化薬株式会社製）等が挙げられる。 The polyimide resin layer (b) is a polyamic acid resin varnish obtained by reacting a tetracarboxylic dianhydride and a diamine compound in a polar solvent such as N-methyl-2-pyrrolidone or N, N-dimethylacetamide. It is obtained by applying and drying on the primer layer of the polyimide resin (A) provided on the metal foil (a), followed by drying and ring-closing at 250 to 400 ° C. for 0.5 to 20 hours. At this time, the polyamic acid resin varnish may contain an ester salt obtained by reacting tetracarboxylic dianhydride with methanol or ethanol. In addition, there is no restriction | limiting in the combination of the tetracarboxylic dianhydride used as the raw material of a polyimide resin layer (b), and a diamine compound, The polyimide resin obtained by a conventionally well-known combination can be used. Examples of commercially available polyamic acid resin varnish include KAYAFLEX KPI-120 (manufactured by Nippon Kayaku Co., Ltd.).
本発明のフレキシブルプリント配線板用積層板は、金属箔（ａ）とポリイミド樹脂層（ｂ）との間にポリイミド樹脂（Ａ）からなるプライマー層が介在するフレキシブルプリント配線板用積層板である。該積層版におけるプライマー層と金属箔（ａ）及びポリイミド樹脂層（ｂ）との接着強度は、実用上、０．８Ｎ／ｍｍ以上であることが好ましい。 The laminated board for flexible printed wiring boards of the present invention is a laminated board for flexible printed wiring boards in which a primer layer made of a polyimide resin (A) is interposed between a metal foil (a) and a polyimide resin layer (b). In practice, the adhesive strength between the primer layer, the metal foil (a) and the polyimide resin layer (b) in the laminated plate is preferably 0.8 N / mm or more.
以下に実施例によって本発明を更に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
実施例１
温度計、環流冷却器、ディーンスターク装置、粉体導入口、窒素導入装置及び攪拌装置のついた５００ｍｌの反応器に、ジアミン化合物としてＡＰＢ−Ｎ（１，３−ビス−（３−アミノフェノキシ）ベンゼン、三井化学株式会社製、分子量２９２．３３）１９．７１ｇ（０．０６７モル）及びＨＡＢ（３，３’−ジアミノ−４，４’−ジヒドロキシビフェニル、日本化薬株式会社製、分子量２１６．２４）１０．２２ｇ（０．０４７モル）を仕込み、乾燥窒素を流しながら溶剤としてγ−ブチロラクトン５５．５９ｇを加え、７０℃で３０分間撹拌した。その後、テトラカルボン酸二無水物としてＯＤＰＡ(４，４’−オキシジフタル酸無水物、マナック株式会社製、分子量３１０．２２)３３．５７ｇ（０．１１モル）、溶剤としてγ−ブチロラクトン６２．３４ｇ、触媒としてピリジン１．７１ｇ及び脱水剤としてトルエン２６．５８ｇを添加して反応器内を１８０℃まで昇温した。ディーンスターク装置を用いてイミド化反応により発生する水を除去しながら、１８０℃で３時間加熱閉環反応を行った後、更に２時間加熱を行いピリジン及びトルエンを除去した。反応終了後、８０℃以下に冷却した反応液に孔径３μｍのテフロン（登録商標）製フィルターを用いて加圧濾過を施すことにより、ポリイミド樹脂（Ａ）を３４質量％含有する本発明のポリイミド樹脂ワニス（Ａ−１）を１７５ｇ得た。ポリイミド樹脂ワニス（Ａ−１）中のポリイミド樹脂（Ａ）の数平均分子量は１０，８００、重量平均分子量は３９，９００であり（いずれもゲルパーミエイションクロマトグラフィーの測定結果を元に、ポリスチレン換算で算出した、以下同じ）、原料の仕込み量から算出した理論水酸基当量は、６３０．２７ｇ／ｅｑ．であった。
Example 1
APB-N (1,3-bis- (3-aminophenoxy) as a diamine compound was added to a 500 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a powder inlet, a nitrogen inlet and a stirring device. Benzene, manufactured by Mitsui Chemicals, Inc., molecular weight 292.33) 19.71 g (0.067 mol) and HAB (3,3′-diamino-4,4′-dihydroxybiphenyl, Nippon Kayaku Co., Ltd., molecular weight 216. 24) 10.22 g (0.047 mol) was charged, 55.59 g of γ-butyrolactone was added as a solvent while flowing dry nitrogen, and the mixture was stirred at 70 ° C. for 30 minutes. Thereafter, 33.57 g (0.11 mol) of ODPA (4,4′-oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22) as tetracarboxylic dianhydride, 62.34 g of γ-butyrolactone as a solvent, 1.71 g of pyridine as a catalyst and 26.58 g of toluene as a dehydrating agent were added, and the temperature in the reactor was increased to 180 ° C. While removing water generated by the imidization reaction using a Dean-Stark apparatus, a heat ring-closing reaction was performed at 180 ° C. for 3 hours, followed by further heating for 2 hours to remove pyridine and toluene. After completion of the reaction, the reaction solution cooled to 80 ° C. or lower is subjected to pressure filtration using a Teflon (registered trademark) filter having a pore size of 3 μm, so that the polyimide resin of the present invention containing 34% by mass of the polyimide resin (A) is obtained. 175 g of varnish (A-1) was obtained. The number average molecular weight of the polyimide resin (A) in the polyimide resin varnish (A-1) is 10,800, and the weight average molecular weight is 39,900 (both are based on the measurement results of gel permeation chromatography, polystyrene The theoretical hydroxyl equivalent calculated from the raw material charge was 630.27 g / eq. Met.
実施例２
温度計、環流冷却器、ディーンスターク装置、粉体導入口、窒素導入装置及び攪拌装置のついた５００ｍｌの反応器に、ジアミン化合物としてＡＰＢ−Ｎ（１，３−ビス−（３−アミノフェノキシ）ベンゼン、三井化学株式会社製、分子量２９２．３３）１７．９６ｇ（０．０６１モル）及びＢＡＦＡ（１，３−ヘキサフルオロ−２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパン、日本化薬株式会社製、分子量３６６．２６）１９．５１ｇ（０．０５３モル）を仕込み、乾燥窒素を流しながら溶剤としてγ−ブチロラクトン６９．５８ｇを加え、７０℃で３０分間撹拌した。その後、テトラカルボン酸二無水物としてＯＤＰＡ(４，４’−オキシジフタル酸無水物 マナック株式会社製、分子量３１０．２２)３３．５７ｇ（０．１１モル）、溶剤としてγ−ブチロラクトン６２．３４ｇ、触媒としてピリジン１．７１ｇ及び脱水剤としてトルエン２８．５２ｇを添加して反応器内を１８０℃まで昇温した。ディーンスターク装置を用いてイミド化反応により発生する水を除去しながら、１８０℃で３時間加熱閉環反応を行った後、更に２時間加熱を行いピリジン及びトルエンを除去した。反応終了後、８０℃以下に冷却した反応液に孔径３μｍのテフロン（登録商標）製フィルターを用いて加圧濾過を施すことにより、ポリイミド樹脂（Ａ）を３４質量％含有する本発明のポリイミド樹脂ワニス（Ａ−２）を１７５ｇ得た。ポリイミド樹脂ワニス（Ａ−２）中のポリイミド樹脂（Ａ）の数平均分子量は１０，６００、重量平均分子量は４４，３００であり、原料の仕込み量から算出した理論水酸基当量は、６３０．２７ｇ／ｅｑ．であった。
Example 2
APB-N (1,3-bis- (3-aminophenoxy) as a diamine compound was added to a 500 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a powder inlet, a nitrogen inlet and a stirring device. Benzene, manufactured by Mitsui Chemicals, Inc., molecular weight 292.33) 17.96 g (0.061 mol) and BAFA (1,3-hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane, Japan 19.51 g (0.053 mol) manufactured by Kayaku Co., Ltd. was charged, 69.58 g of γ-butyrolactone was added as a solvent while flowing dry nitrogen, and the mixture was stirred at 70 ° C. for 30 minutes. Thereafter, 33.57 g (0.11 mol) of ODPA (4,4′-oxydiphthalic anhydride Manac Co., Ltd., molecular weight 310.22) as tetracarboxylic dianhydride, 62.34 g of γ-butyrolactone as catalyst, catalyst Was added with 1.71 g of pyridine and 28.52 g of toluene as a dehydrating agent, and the temperature in the reactor was increased to 180 ° C. While removing water generated by the imidization reaction using a Dean-Stark apparatus, a heat ring-closing reaction was performed at 180 ° C. for 3 hours, followed by further heating for 2 hours to remove pyridine and toluene. After completion of the reaction, the reaction solution cooled to 80 ° C. or lower is subjected to pressure filtration using a Teflon (registered trademark) filter having a pore size of 3 μm, so that the polyimide resin of the present invention containing 34% by mass of the polyimide resin (A) is obtained. 175 g of varnish (A-2) was obtained. The number average molecular weight of the polyimide resin (A) in the polyimide resin varnish (A-2) is 10,600, the weight average molecular weight is 44,300, and the theoretical hydroxyl equivalent calculated from the raw material charge is 630.27 g / eq. Met.
実施例３
温度計、環流冷却器、ディーンスターク装置、粉体導入口、窒素導入装置及び攪拌装置のついた５００ｍｌの反応器に、ジアミン化合物としてＡＰＢ−Ｎ（１，３−ビス−（３−アミノフェノキシ）ベンゼン、三井化学株式会社製、分子量２９２．３３）１９．５４ｇ（０．０６７モル）及びＡＤＰＥ（３，３’−ジアミノ−４，４’−ジヒドロキシジフェニルエーテル、日本化薬株式会社製、分子量２３２．２４）１１．１１ｇ（０．０４８モル）を仕込み、乾燥窒素を流しながら溶剤としてγ−ブチロラクトン５６．９３ｇを加え、７０℃で３０分間撹拌した。その後、テトラカルボン酸二無水物としてＯＤＰＡ(４，４’−オキシジフタル酸無水物、マナック株式会社製、分子量３１０．２２)３３．５７ｇ（０．１１モル）、溶剤としてγ−ブチロラクトン６２．３４ｇ、触媒としてピリジン１．７１ｇ及び脱水剤としてトルエン２６．７７ｇを添加して反応器内を１８０℃まで昇温した。ディーンスターク装置を用いてイミド化反応により発生する水を除去しながら、１８０℃で３時間加熱閉環反応を行った後、更に２時間加熱を行いピリジン及びトルエンを除去した。反応終了後、８０℃以下に冷却した反応液に孔径３μｍのテフロン（登録商標）製フィルターを用いて加圧濾過を施すことにより、ポリイミド樹脂（Ａ）を３４質量％含有する本発明のポリイミド樹脂ワニス（Ａ−３）を１７６ｇ得た。ポリイミド樹脂ワニス（Ａ−３）中のポリイミド樹脂（Ａ）の数平均分子量は１０，１００、重量平均分子量は４０，３００であり、原料の仕込み量から算出した理論水酸基当量は、６３０．２７ｇ／ｅｑ．であった。
Example 3
APB-N (1,3-bis- (3-aminophenoxy) as a diamine compound was added to a 500 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a powder inlet, a nitrogen inlet and a stirring device. Benzene, Mitsui Chemicals, Inc., molecular weight 292.33) 19.54 g (0.067 mol) and ADPE (3,3′-diamino-4,4′-dihydroxydiphenyl ether, Nippon Kayaku Co., Ltd., molecular weight 232. 24) 11.11 g (0.048 mol) was charged, 56.93 g of γ-butyrolactone was added as a solvent while flowing dry nitrogen, and the mixture was stirred at 70 ° C. for 30 minutes. Thereafter, 33.57 g (0.11 mol) of ODPA (4,4′-oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22) as tetracarboxylic dianhydride, 62.34 g of γ-butyrolactone as a solvent, 1.71 g of pyridine as a catalyst and 26.77 g of toluene as a dehydrating agent were added, and the temperature in the reactor was increased to 180 ° C. While removing water generated by the imidization reaction using a Dean-Stark apparatus, a heat ring-closing reaction was performed at 180 ° C. for 3 hours, followed by further heating for 2 hours to remove pyridine and toluene. After completion of the reaction, the reaction solution cooled to 80 ° C. or lower is subjected to pressure filtration using a Teflon (registered trademark) filter having a pore size of 3 μm, so that the polyimide resin of the present invention containing 34% by mass of the polyimide resin (A) is obtained. 176 g of varnish (A-3) was obtained. The number average molecular weight of the polyimide resin (A) in the polyimide resin varnish (A-3) is 10,100, the weight average molecular weight is 40,300, and the theoretical hydroxyl equivalent calculated from the raw material charge is 630.27 g / eq. Met.
実施例４
温度計、環流冷却器、ディーンスターク装置、粉体導入口、窒素導入装置及び攪拌装置のついた５００ｍｌの反応器に、ジアミン化合物としてＡＰＢ−Ｎ（１，３−ビス−（３−アミノフェノキシ）ベンゼン、三井化学株式会社製、分子量２９２．３３）１８．４９ｇ（０．０６３モル）及びＡＨＰＢ（１，３−ビス（４−アミノ−３−ヒドロキシフェノキシ）ベンゼン、日本純良薬品株式会社製、分子量３２４．３３）１６．６８ｇ（０．０５１モル）を仕込み、乾燥窒素を流しながら溶剤としてγ−ブチロラクトン６５．３３ｇを加え、７０℃で３０分間撹拌した。その後、テトラカルボン酸二無水物としてＯＤＰＡ(４，４’−オキシジフタル酸無水物、マナック株式会社製、分子量３１０．２２)３３．５７ｇ（０．１１モル）、溶剤としてγ−ブチロラクトン６２．３４ｇ、触媒としてピリジン１．７１ｇ及び脱水剤としてトルエン２７．９３ｇを添加して反応器内を１８０℃まで昇温した。ディーンスターク装置を用いてイミド化反応により発生する水を除去しながら、１８０℃で３時間加熱閉環反応を行った後、更に２時間加熱を行いピリジン及びトルエンを除去した。反応終了後、８０℃以下に冷却した反応液に孔径３μｍのテフロン（登録商標）製フィルターを用いて加圧濾過を施すことにより、ポリイミド樹脂（Ａ）を３４質量％含有する本発明のポリイミド樹脂ワニス（Ａ−４）を１７６ｇ得た。ポリイミド樹脂ワニス（Ａ−４）中のポリイミド樹脂（Ａ）の数平均分子量は１４，８００、重量平均分子量は５７，４００であり、原料の仕込み量から算出した理論水酸基当量は、６３０．２７ｇ／ｅｑ．であった。
Example 4
APB-N (1,3-bis- (3-aminophenoxy) as a diamine compound was added to a 500 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a powder inlet, a nitrogen inlet and a stirring device. Benzene, manufactured by Mitsui Chemicals, Inc., molecular weight 292.33) 18.49 g (0.063 mol) and AHPB (1,3-bis (4-amino-3-hydroxyphenoxy) benzene, manufactured by Nippon Pure Chemicals Co., Ltd., molecular weight 32.33) 16.68 g (0.051 mol) was charged, 65.33 g of γ-butyrolactone was added as a solvent while flowing dry nitrogen, and the mixture was stirred at 70 ° C. for 30 minutes. Thereafter, 33.57 g (0.11 mol) of ODPA (4,4′-oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22) as tetracarboxylic dianhydride, 62.34 g of γ-butyrolactone as a solvent, 1.71 g of pyridine as a catalyst and 27.93 g of toluene as a dehydrating agent were added, and the temperature in the reactor was increased to 180 ° C. While removing water generated by the imidization reaction using a Dean-Stark apparatus, a heat ring-closing reaction was performed at 180 ° C. for 3 hours, followed by further heating for 2 hours to remove pyridine and toluene. After completion of the reaction, the reaction solution cooled to 80 ° C. or lower is subjected to pressure filtration using a Teflon (registered trademark) filter having a pore size of 3 μm, so that the polyimide resin of the present invention containing 34% by mass of the polyimide resin (A) is obtained. 176 g of varnish (A-4) was obtained. The number average molecular weight of the polyimide resin (A) in the polyimide resin varnish (A-4) is 14,800, the weight average molecular weight is 57,400, and the theoretical hydroxyl equivalent calculated from the raw material charge is 630.27 g / eq. Met.
実施例５
温度計、環流冷却器、ディーンスターク装置、粉体導入口、窒素導入装置及び攪拌装置のついた５００ｍｌの反応器に、ジアミン化合物としてＡＰＢ−Ｎ（１，３−ビス−（３−アミノフェノキシ）ベンゼン、三井化学株式会社製、分子量２９２．３３）３０．０２ｇ（０．１０３モル）及びＨＡＢ（３，３’−ジアミノ−４，４’−ジヒドロキシビフェニル、日本化薬株式会社製、分子量２１６．２４）４．８５ｇ（０．０２２モル）を仕込み、乾燥窒素を流しながら溶剤としてＮ−メチル−２−ピロリドン６４．７６ｇを加え、７０℃で３０分間撹拌した。その後、テトラカルボン酸二無水物として、ＯＤＰＡ(４，４’−オキシジフタル酸無水物、マナック株式会社製、分子量３１０．２２)３６．６２ｇ（０．１１８モル）、溶剤としてＮ−メチル−２−ピロリドン６８．００ｇ、触媒としてピリジン１．８７ｇ及び脱水剤としてトルエン２８．６６ｇを添加して反応器内を１８０℃まで昇温した。ディーンスターク装置を用いてイミド化反応により発生する水を除去しながら、１８０℃で３時間加熱閉環反応を行った後、更に２時間加熱を行いピリジン及びトルエンを除去した。反応終了後、８０℃以下に冷却した反応液に孔径３μｍのテフロン（登録商標）製フィルターを用いて加圧濾過を施すことにより、ポリイミド樹脂（Ａ）を３４質量％含有する本発明のポリイミド樹脂ワニス（Ａ−５）を１９５ｇ得た。ポリイミド樹脂ワニス（Ａ−５）中のポリイミド樹脂（Ａ）の数平均分子量は１１，０００、重量平均分子量は３８，３００であり、原料の仕込み量から算出した理論水酸基当量は、１，５００ｇ／ｅｑ．であった。
Example 5
APB-N (1,3-bis- (3-aminophenoxy) as a diamine compound was added to a 500 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a powder inlet, a nitrogen inlet and a stirring device. Benzene, manufactured by Mitsui Chemicals, Inc., molecular weight 292.33) 30.02 g (0.103 mol) and HAB (3,3′-diamino-4,4′-dihydroxybiphenyl, Nippon Kayaku Co., Ltd., molecular weight 216. 24) 4.85 g (0.022 mol) was charged, 64.76 g of N-methyl-2-pyrrolidone was added as a solvent while flowing dry nitrogen, and the mixture was stirred at 70 ° C. for 30 minutes. Then, 36.62 g (0.118 mol) of ODPA (4,4′-oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22) as tetracarboxylic dianhydride, N-methyl-2- 68.00 g of pyrrolidone, 1.87 g of pyridine as a catalyst, and 28.66 g of toluene as a dehydrating agent were added, and the temperature in the reactor was increased to 180 ° C. While removing water generated by the imidization reaction using a Dean-Stark apparatus, a heat ring-closing reaction was performed at 180 ° C. for 3 hours, followed by further heating for 2 hours to remove pyridine and toluene. After completion of the reaction, the reaction solution cooled to 80 ° C. or lower is subjected to pressure filtration using a Teflon (registered trademark) filter having a pore size of 3 μm, so that the polyimide resin of the present invention containing 34% by mass of the polyimide resin (A) is obtained. 195g of varnish (A-5) was obtained. The number average molecular weight of the polyimide resin (A) in the polyimide resin varnish (A-5) is 11,000, the weight average molecular weight is 38,300, and the theoretical hydroxyl equivalent calculated from the charged amount of raw material is 1,500 g / eq. Met.
実施例６
温度計、環流冷却器、ディーンスターク装置、粉体導入口、窒素導入装置及び攪拌装置のついた５００ｍｌの反応器に、ジアミン化合物としてＡＰＢ−Ｎ（１，３−ビス−（３−アミノフェノキシ）ベンゼン、三井化学株式会社製、分子量２９２．３３）７．４１ｇ（０．０２５モル）及びＨＡＢ（３，３’−ジアミノ−４，４’−ジヒドロキシビフェニル、日本化薬株式会社製、分子量２１６．２４）２４．１４ｇ（０．１１２モル）を仕込み、乾燥窒素を流しながら溶剤としてＮ−メチル−２−ピロリドン５８．５８ｇを加え、７０℃で３０分間撹拌した。その後、テトラカルボン酸二無水物としてＯＤＰＡ(４，４’−オキシジフタル酸無水物、マナック株式会社製、分子量３１０．２２)４０．０８ｇ（０．１２９モル）、溶剤としてＮ−メチル−２−ピロリドン７４．４４ｇ、触媒としてピリジン２．０４ｇ及び脱水剤としてトルエン２８．７２ｇを添加して反応器内を１８０℃まで昇温した。ディーンスターク装置を用いてイミド化反応により発生する水を除去しながら、１８０℃で３時間加熱閉環反応を行った後、更に２時間加熱を行いピリジン及びトルエンを除去した。反応終了後、８０℃以下に冷却した反応液に孔径３μｍのテフロン（登録商標）製フィルターを用いて加圧濾過を施すことにより、ポリイミド樹脂（Ａ）を３４質量％含有する本発明のポリイミド樹脂ワニス（Ａ−６）を１９５ｇ得た。ポリイミド樹脂ワニス（Ａ−６）中のポリイミド樹脂（Ａ）の数平均分子量は１２，２００、重量平均分子量は４９，８００であり、原料の仕込み量から算出した理論水酸基当量は、３００ｇ／ｅｑ．であった。
Example 6
APB-N (1,3-bis- (3-aminophenoxy) as a diamine compound was added to a 500 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a powder inlet, a nitrogen inlet and a stirring device. Benzene, Mitsui Chemicals, Inc., molecular weight 292.33) 7.41 g (0.025 mol) and HAB (3,3′-diamino-4,4′-dihydroxybiphenyl, Nippon Kayaku Co., Ltd., molecular weight 216. 24) 24.14 g (0.112 mol) was charged, 58.58 g of N-methyl-2-pyrrolidone was added as a solvent while flowing dry nitrogen, and the mixture was stirred at 70 ° C. for 30 minutes. Thereafter, 40.08 g (0.129 mol) of ODPA (4,4′-oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22) as tetracarboxylic dianhydride, N-methyl-2-pyrrolidone as solvent 74.44 g, 2.04 g of pyridine as a catalyst, and 28.72 g of toluene as a dehydrating agent were added, and the temperature in the reactor was increased to 180 ° C. While removing water generated by the imidization reaction using a Dean-Stark apparatus, a heat ring-closing reaction was performed at 180 ° C. for 3 hours, followed by further heating for 2 hours to remove pyridine and toluene. After completion of the reaction, the reaction solution cooled to 80 ° C. or lower is subjected to pressure filtration using a Teflon (registered trademark) filter having a pore size of 3 μm, so that the polyimide resin of the present invention containing 34% by mass of the polyimide resin (A) is obtained. 195g of varnish (A-6) was obtained. The number average molecular weight of the polyimide resin (A) in the polyimide resin varnish (A-6) is 12,200, the weight average molecular weight is 49,800, and the theoretical hydroxyl equivalent calculated from the charged amount of raw material is 300 g / eq. Met.
比較例１
温度計、環流冷却器、ディーンスターク装置、粉体導入口、窒素導入装置及び攪拌装置のついた５００ｍｌの反応器に、ジアミン化合物としてＡＰＢ−Ｎ（１，３−ビス−（３−アミノフェノキシ）ベンゼン、三井化学株式会社製、分子量２９２．３３）３５．７１ｇ（０．１２２モル）を仕込み、乾燥窒素を流しながら溶剤としてγ−ブチロラクトン６６．３１ｇを加え、７０℃で３０分間撹拌した。その後、テトラカルボン酸二無水物としてＯＤＰＡ(４，４’−オキシジフタル酸無水物、マナック株式会社製、分子量３１０．２２)３５．７５ｇ（０．１１５モル）、溶剤としてγ−ブチロラクトン６６．３９ｇ、触媒としてピリジン１．８２ｇ及び脱水剤としてトルエン２８．５４ｇを添加して反応器内を１８０℃まで昇温した。ディーンスターク装置を用いてイミド化反応により発生する水を除去しながら、１８０℃で３時間加熱閉環反応を行った後、更に２時間加熱を行いピリジン及びトルエンを除去した。反応終了後、８０℃以下に冷却した反応液に孔径３μｍのテフロン（登録商標）製フィルターを用いて加圧濾過を施すことにより、比較用ポリイミド樹脂を３４質量％含有する比較用のポリイミド樹脂ワニス（Ｂ−１）を１９５ｇ得た。ポリイミド樹脂ワニス（Ｂ−１）中の比較用ポリイミド樹脂の数平均分子量は１０，９００、重量平均分子量は３８，２００であった。尚、該比較用ポリイミド樹脂中には、水酸基は存在しない。
Comparative Example 1
APB-N (1,3-bis- (3-aminophenoxy) as a diamine compound was added to a 500 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a powder inlet, a nitrogen inlet and a stirring device. Benzene, manufactured by Mitsui Chemicals, Inc., molecular weight 292.33) 35.71 g (0.122 mol) was charged, 66.31 g of γ-butyrolactone was added as a solvent while flowing dry nitrogen, and the mixture was stirred at 70 ° C. for 30 minutes. Then, 35.75 g (0.115 mol) of ODPA (4,4′-oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22) as tetracarboxylic dianhydride, 66.39 g of γ-butyrolactone as a solvent, 1.82 g of pyridine as a catalyst and 28.54 g of toluene as a dehydrating agent were added, and the temperature in the reactor was increased to 180 ° C. While removing water generated by the imidization reaction using a Dean-Stark apparatus, a heat ring-closing reaction was performed at 180 ° C. for 3 hours, followed by further heating for 2 hours to remove pyridine and toluene. After completion of the reaction, the reaction solution cooled to 80 ° C. or lower is subjected to pressure filtration using a Teflon (registered trademark) filter having a pore size of 3 μm, so that a comparative polyimide resin varnish containing 34% by mass of a comparative polyimide resin is obtained. 195 g of (B-1) was obtained. The number average molecular weight of the comparative polyimide resin in the polyimide resin varnish (B-1) was 10,900, and the weight average molecular weight was 38,200. In the comparative polyimide resin, there is no hydroxyl group.
比較例２
温度計、環流冷却器、ディーンスターク装置、粉体導入口、窒素導入装置及び攪拌装置のついた５００ｍｌの反応器に、ジアミン化合物としてＢＡＰＰ（２，２−ビス（４−（４−アミノフェノキシ）フェニル）プロパン、和歌山精化工業株式会社製、分子量４１０．５１）２５．００ｇ（０．０６１モル）及びＨＡＢ（３，３’−ジアミノ−４，４’−ジヒドロキシビフェニル、日本化薬株式会社製、分子量２１６．２４）１１．５８ｇ（０．０５４モル）を仕込み、乾燥窒素を流しながら溶剤としてγ−ブチロラクトン６７．９３ｇを加え、７０℃で３０分間撹拌した。その後、テトラカルボン酸二無水物としてＢＴＤＡ(３，３’，４，４’−ベンゾフェノンテトラカルボン酸無水物、ダイセル化学工業株式会社製、分子量３２２．２３)３４．７９ｇ（０．１０８モル）、溶剤としてγ−ブチロラクトン６４．６０ｇ、触媒としてピリジン１．７１ｇ及び脱水剤としてトルエン２８．５０ｇを添加して反応器内を１８０℃まで昇温した。ディーンスターク装置を用いてイミド化反応により発生する水を除去しながら、１８０℃で３時間加熱閉環反応を行った後、更に２時間加熱を行いピリジン及びトルエンを除去した。反応終了後、８０℃以下に冷却した反応液に孔径３μｍのテフロン（登録商標）製フィルターを用いて加圧濾過を施すことにより、比較用ポリイミド樹脂を３４質量％含有する比較用のポリイミド樹脂ワニス（Ｂ−２）を１７５ｇ得た。ポリイミド樹脂ワニス（Ｂ−２）中の比較用ポリイミド樹脂の数平均分子量は１４，０００、重量平均分子量は４２，６００であり、原料の仕込み量から算出した理論水酸基当量は、６３０．２７ｇ／ｅｑ．であった。
Comparative Example 2
BAPP (2,2-bis (4- (4-aminophenoxy)) as a diamine compound was added to a 500 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a powder inlet, a nitrogen introduction device and a stirring device. Phenyl) propane, manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 410.51) 25.00 g (0.061 mol) and HAB (3,3′-diamino-4,4′-dihydroxybiphenyl, manufactured by Nippon Kayaku Co., Ltd. , Molecular weight 216.24) 11.58 g (0.054 mol) was added, 67.93 g of γ-butyrolactone was added as a solvent while flowing dry nitrogen, and the mixture was stirred at 70 ° C. for 30 minutes. Then, 34.79 g (0.108 mol) of BTDA (3,3 ′, 4,4′-benzophenone tetracarboxylic anhydride, manufactured by Daicel Chemical Industries, Ltd., molecular weight 322.23) as tetracarboxylic dianhydride, 64.60 g of γ-butyrolactone as a solvent, 1.71 g of pyridine as a catalyst, and 28.50 g of toluene as a dehydrating agent were added, and the temperature in the reactor was increased to 180 ° C. While removing water generated by the imidization reaction using a Dean-Stark apparatus, a heat ring-closing reaction was performed at 180 ° C. for 3 hours, followed by further heating for 2 hours to remove pyridine and toluene. After completion of the reaction, the reaction solution cooled to 80 ° C. or lower is subjected to pressure filtration using a Teflon (registered trademark) filter having a pore size of 3 μm, so that a comparative polyimide resin varnish containing 34% by mass of a comparative polyimide resin is obtained. 175 g of (B-2) was obtained. The number average molecular weight of the comparative polyimide resin in the polyimide resin varnish (B-2) is 14,000, the weight average molecular weight is 42,600, and the theoretical hydroxyl equivalent calculated from the raw material charge is 630.27 g / eq. . Met.
比較例３
温度計、環流冷却器、ディーンスターク装置、粉体導入口、窒素導入装置及び攪拌装置のついた５００ｍｌの反応器に、ジアミン化合物としてＡＰＢ−Ｎ（１，３−ビス−（３−アミノフェノキシ）ベンゼン、三井化学株式会社製、分子量２９２．３３）１７．２９ｇ（０．０５９モル）及びＡＢＰＳ（３，３’−ジアミノ−４，４’−ジヒドロキシジフェニルスルホン、日本化薬株式会社製、分子量２８０．３０）１３．０８ｇ（０．０４７モル）を仕込み、乾燥窒素を流しながら溶剤としてＮ−メチル−２−ピロリドン５６．４１ｇを加え、７０℃で３０分間撹拌した。その後、テトラカルボン酸二無水物として、ＯＤＰＡ(４，４’−オキシジフタル酸無水物、マナック株式会社製、分子量３１０．２２)３２．１８ｇ（０．１０４モル）、溶剤としてＮ−メチル−２−ピロリドン５９．７７ｇ、触媒としてピリジン１．６４ｇ及び脱水剤としてトルエン２６．２３ｇを添加して反応器内を１８０℃まで昇温した。ディーンスターク装置を用いてイミド化反応により発生する水を除去しながら、１８０℃で３時間加熱閉環反応を行った後、更に２時間加熱を行いピリジン及びトルエンを除去した。反応終了後、８０℃以下に冷却した反応液に孔径３μｍのテフロン（登録商標）製フィルターを用いて加圧濾過を施すことにより、比較用ポリイミド樹脂を３４質量％含有する比較用ポリイミド樹脂ワニス（Ｂ−３）を１７３ｇ得た。ポリイミド樹脂ワニス（Ｂ−３）中の比較用ポリイミド樹脂の数平均分子量は１７，６００、重量平均分子量は９１，０００であり、原料の仕込み量から算出した理論水酸基当量は、６３０．２７ｇ／ｅｑ．であった。
Comparative Example 3
APB-N (1,3-bis- (3-aminophenoxy) as a diamine compound was added to a 500 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a powder inlet, a nitrogen inlet and a stirring device. Benzene, manufactured by Mitsui Chemicals, Inc., molecular weight 292.33) 17.29 g (0.059 mol) and ABPS (3,3′-diamino-4,4′-dihydroxydiphenylsulfone, manufactured by Nippon Kayaku Co., Ltd., molecular weight 280 .30) 13.08 g (0.047 mol) was charged, 56.41 g of N-methyl-2-pyrrolidone was added as a solvent while flowing dry nitrogen, and the mixture was stirred at 70 ° C. for 30 minutes. Thereafter, ODPA (4,4′-oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22) 32.18 g (0.104 mol) as tetracarboxylic dianhydride, N-methyl-2- 59.77 g of pyrrolidone, 1.64 g of pyridine as a catalyst and 26.23 g of toluene as a dehydrating agent were added, and the temperature in the reactor was increased to 180 ° C. While removing water generated by the imidization reaction using a Dean-Stark apparatus, a heat ring-closing reaction was performed at 180 ° C. for 3 hours, followed by further heating for 2 hours to remove pyridine and toluene. After completion of the reaction, the reaction solution cooled to 80 ° C. or lower is subjected to pressure filtration using a Teflon (registered trademark) filter having a pore diameter of 3 μm, whereby a comparative polyimide resin varnish containing 34% by mass of a comparative polyimide resin ( 173 g of B-3) was obtained. The number average molecular weight of the comparative polyimide resin in the polyimide resin varnish (B-3) is 17,600, the weight average molecular weight is 91,000, and the theoretical hydroxyl equivalent calculated from the raw material charge is 630.27 g / eq. . Met.
（ｉ）本発明のポリイミド樹脂（Ａ）及び比較用ポリイミド樹脂の物性評価
実施例１〜６及び比較例１〜３で得られた各樹脂ワニス（Ａ−１）〜（Ａ−６）及び（Ｂ−１）〜（Ｂ−３）を、乾燥後の膜厚が２０μｍになるようにオートマチックアプリケーター（株式会社安田精機製作所製）を用いてＰＥＴフィルム上に塗布し、塗膜を１３０℃で３０分間乾燥した。その後、ＰＥＴフィルムから剥離して得られた樹脂膜を、ＳＵＳ製の型枠にイミドテープで固定して２００℃で１時間追加乾燥させ、残存溶剤を完全に除去することで本発明のポリイミド樹脂（Ａ）及び比較用ポリイミド樹脂のフィルムを得た。得られたフィルムについて、パーキンエルマー社製ＴＭＡ７（Ｔｈｒｍｏｍｅｃｈａｎｉｃａｌ Ａｎａｌｙｚｅｒ）を用いて、４ｍｍ幅に切ったフィルムを２００ｍＮの加重で引っ張りながら５０℃から３５０℃まで加熱し、線膨張係数の変移温度（ガラス転移温度、Ｔｇ）及び５０〜１５０℃間の線膨張係数（ＣＴＥ）を測定した。結果を表１及び表２に示した。
(I) Physical property evaluation of polyimide resin (A) of the present invention and comparative polyimide resin Each resin varnish (A-1) to (A-6) obtained in Examples 1 to 6 and Comparative Examples 1 to 3 and ( B-1) to (B-3) were applied onto a PET film using an automatic applicator (manufactured by Yasuda Seiki Seisakusyo Co., Ltd.) so that the film thickness after drying was 20 μm, and the coating film was 30 ° C. at 30 ° C. Dried for minutes. Thereafter, the resin film obtained by peeling from the PET film is fixed to an SUS mold with an imide tape and further dried at 200 ° C. for 1 hour, and the residual solvent is completely removed to completely remove the polyimide resin ( A) and a comparative polyimide resin film were obtained. The obtained film was heated from 50 ° C. to 350 ° C. while pulling a film cut to a width of 4 mm with a load of 200 mN using TMA7 (Through Mechanical Analyzer) manufactured by PerkinElmer Co., Ltd. Temperature, Tg) and linear expansion coefficient (CTE) between 50-150 ° C. were measured. The results are shown in Tables 1 and 2.
実施例７〜１２、比較例４〜８
実施例１〜６及び比較例１〜３で得られた各樹脂ワニス（Ａ−１）〜（Ａ−６）及び（Ｂ−１）〜（Ｂ−３）を、乾燥後の膜厚が２μｍになるようにオートマチックアプリケーター（株式会社安田精機製作所製）を用いて表面粗さ（Ｒｚ）が２μｍ以下である厚さ１８μｍの圧延銅箔上に塗布し、塗膜を１３０℃で１０分間乾燥することで本発明のポリイミド樹脂（Ａ）及び比較用ポリイミド樹脂からなるプライマー層の設けられた銅箔を得た。次いで、ＫＡＹＡＦＬＥＸ ＫＰＩ−１２０（商品名、日本化薬株式会社製、ポリアミック酸樹脂ワニス）を、イミド化後の膜厚が２５μｍになるようにキャスト法によりこれらプライマー層上に塗布し、塗膜を１３０℃で１０分間乾燥した後、更に３５０℃で２時間イミド化を行うことで、実施例７〜１２及び比較例４〜６のフレキシブルプリント配線板用積層板を得た。
また、プライマー層を形成せず、銅箔上に直接ＫＡＹＡＦＬＥＸ ＫＰＩ−１２０（商品名、日本化薬株式会社製、ポリアミック酸樹脂ワニス）を塗布したこと以外は実施例７〜１２と同様の操作を行うことで、比較例７のフレキシブルプリント配線板用積層板を得た。
Examples 7-12, Comparative Examples 4-8
Each of the resin varnishes (A-1) to (A-6) and (B-1) to (B-3) obtained in Examples 1 to 6 and Comparative Examples 1 to 3 has a thickness of 2 μm after drying. Using an automatic applicator (manufactured by Yasuda Seiki Seisakusho Co., Ltd.), the surface roughness (Rz) is applied onto a rolled copper foil having a thickness of 2 μm or less and a thickness of 18 μm, and the coating film is dried at 130 ° C. for 10 minutes. Thus, a copper foil provided with a primer layer made of the polyimide resin (A) of the present invention and a comparative polyimide resin was obtained. Next, KAYAFLEX KPI-120 (trade name, manufactured by Nippon Kayaku Co., Ltd., polyamic acid resin varnish) was applied onto these primer layers by a casting method so that the film thickness after imidization was 25 μm. After drying at 130 ° C. for 10 minutes, imidization was further performed at 350 ° C. for 2 hours to obtain laminates for flexible printed wiring boards of Examples 7 to 12 and Comparative Examples 4 to 6.
Further, the same operation as in Examples 7 to 12 was performed except that KAYAFLEX KPI-120 (trade name, manufactured by Nippon Kayaku Co., Ltd., polyamic acid resin varnish) was directly applied on the copper foil without forming a primer layer. By performing, the laminated board for flexible printed wiring boards of the comparative example 7 was obtained.
更に、ポリイミド樹脂層（ｂ）をラミネート法で形成した場合との比較のために、実施例１で得られた樹脂ワニス（Ａ−１）を、乾燥後の膜厚が２μｍになるようにオートマチックアプリケーター（株式会社安田精機製作所製）を用いてアピカルＮＰＩ（商品名、株式会社カネカ製、ポリイミドフィルム、厚さ２５μｍ）に塗布し、塗膜を１３０℃で１０分間乾燥することでプライマー層の設けられたポリイミドフィルムを得た。次いで、該プライマー層が挟み込まれるように実施例７〜１２で用いたのと同じ圧延銅箔を重ね合わせ、２５０℃、７０ｋｇ／ｃｍ2の条件で熱プレスを行うことで、比較例８のフレキシブルプリント配線板用積層板を得た。 Further, for comparison with the case where the polyimide resin layer (b) is formed by the laminating method, the resin varnish (A-1) obtained in Example 1 is automatically adjusted so that the film thickness after drying becomes 2 μm. Using a applicator (manufactured by Yasuda Seiki Seisakusho Co., Ltd.), it is applied to apical NPI (trade name, manufactured by Kaneka Corporation, polyimide film, thickness 25 μm), and the coating layer is dried at 130 ° C. for 10 minutes to provide a primer layer The obtained polyimide film was obtained. Next, the same rolled copper foil as used in Examples 7 to 12 was overlaid so that the primer layer was sandwiched, and hot pressing was performed under the conditions of 250 ° C. and 70 kg / cm 2. A laminate for a printed wiring board was obtained.
（ｉｉ）本発明及び比較用のフレキシブルプリント配線板用積層板の評価
実施例７〜１２及び比較例４〜８で得られたフレキシブルプリント配線板用積層板を用いて、下記の評価を行った。
(Ii) Evaluation of the present invention and a laminate for flexible printed wiring board for comparison The following evaluation was performed using the laminate for flexible printed wiring board obtained in Examples 7 to 12 and Comparative Examples 4 to 8. .
（１）銅箔の剥離強度
実施例７〜１２及び比較例４〜８で得られたフレキシブルプリント配線板用積層板の銅箔側に、マスキングテープ（商品名 クリアーラインテープ Ｎｏ．５５７、ニチバン株式会社製、）を貼り付けた後、４０℃に加熱したエッチング液（塩化第二鉄水溶液４５°ボーメ）中で３０分間エッチングを行い、マスキングテープを剥離することで１０ｍｍ幅の銅箔パターンを形成した。次いで、ボンディングシートを用いてポリイミド樹脂層側を補強板に貼り付け、カッターナイフを用いて１０ｍｍ幅の銅箔の端部をポリイミド樹脂から剥がし、テンシロン試験機（ＡアンドＤ：オリエンテック製）を用いて１８０°方向での銅箔とポリイミド樹脂層との剥離強度を測定し、これを常態ピール強度とした。また、該積層板を１５０℃で１６８時間保持した後の剥離強度を耐熱ピール強度、４０℃、９５％ＲＨで９６時間保持した後の剥離強度を耐湿熱ピール強度とした。結果を表１及び表２に示した。
(1) Peel strength of copper foil On the copper foil side of the laminates for flexible printed wiring boards obtained in Examples 7-12 and Comparative Examples 4-8, a masking tape (trade name Clear Line Tape No. 557, Nichiban Co., Ltd.) After affixing a product made in the company, etching is performed for 30 minutes in an etching solution heated to 40 ° C. (ferric chloride aqueous solution 45 ° Baume), and a 10 mm wide copper foil pattern is formed by peeling the masking tape. did. Next, the polyimide resin layer side is attached to the reinforcing plate using a bonding sheet, and the end of the 10 mm wide copper foil is peeled off from the polyimide resin using a cutter knife, and a Tensilon tester (A and D: manufactured by Orientec) is used. The peel strength between the copper foil and the polyimide resin layer in the 180 ° direction was measured and used as the normal peel strength. Further, the peel strength after the laminate was held at 150 ° C. for 168 hours was defined as heat-resistant peel strength, and the peel strength after retained at 40 ° C. and 95% RH for 96 hours was defined as moisture-heat peel strength. The results are shown in Tables 1 and 2.
（２）発泡の確認
実施例７〜１２及び比較例４〜８で得られたフレキシブルプリント配線板用積層板の外観を目視で観察し、下記の基準で評価した。結果を表１及び表２に示した。
○ 発泡がなく外観上問題なし
× 発泡があり外観上問題有り
(2) Confirmation of foaming The external appearance of the laminated board for flexible printed wiring boards obtained in Examples 7-12 and Comparative Examples 4-8 was visually observed and evaluated according to the following criteria. The results are shown in Tables 1 and 2.
○ No foaming and no problems in appearance × Foaming and problems in appearance
（３）防錆効果の確認
実施例７〜１２及び比較例４〜８で得られたフレキシブルプリント配線板用積層板の外観を目視で観察し、下記の基準で評価した。結果を表１及び表２に示した。
○ 目視により銅箔の酸化が見られない
× 目視により銅箔の酸化による変色が確認される
(3) Confirmation of rust prevention effect The appearance of the laminates for flexible printed wiring boards obtained in Examples 7 to 12 and Comparative Examples 4 to 8 was visually observed and evaluated according to the following criteria. The results are shown in Tables 1 and 2.
○ No oxidation of copper foil is observed by visual observation × Discoloration due to oxidation of copper foil is confirmed by visual inspection
（４）耐熱性試験
実施例７〜１２及び比較例４〜８で得られたフレキシブルプリント配線板用積層板を２６０℃のハンダ浴に浮かべて外観を目視で観察し、下記の基準で評価した。結果を表１及び表２に示した。
○ 外観の変化なし
× 膨れ、変色等の外観異常が見られる
(4) Heat resistance test The laminates for flexible printed wiring boards obtained in Examples 7 to 12 and Comparative Examples 4 to 8 were floated on a 260 ° C. solder bath, the appearance was visually observed, and the following criteria were evaluated. . The results are shown in Tables 1 and 2.
○ No change in appearance × Abnormal appearance such as swelling or discoloration
ポリイミド樹脂ワニス（Ａ−１）〜（Ａ−６）をプライマー層に用いた実施例７〜１２の積層板は、水酸基を含有しない比較用のポリイミド樹脂ワニス（Ｂ−１）をプライマー層に用いた比較例４の積層板と比べて発泡がなく、耐熱性に優れていた。また、本願の特定構造のポリイミド樹脂（Ａ）以外の水酸基を有する比較用ポリイミドを含有する樹脂ワニス（Ｂ−２）及び（Ｂ−３）をプライマー層に用いた比較例５及び６では、発泡は無かったものの、ピール強度は実施例７〜１２の１／３程度であった。更に、ポリイミド樹脂ワニス（Ａ−１）を用いた場合でも、ポリイミド樹脂層（ｂ）をラミネート法で形成した比較例８のピール強度は、ポリイミド樹脂層（ｂ）をキャスト法で形成した実施例７の１／２程度であった。これらのことから、本発明のプライマー層用ポリイミド樹脂（Ａ）は、合成が容易であり、それを用いた銅張積層板は、剥離強度、発泡の抑制、防錆効果及び耐熱性に優れ、銅張積層板として有用であることは明らかである。 The laminates of Examples 7 to 12 using the polyimide resin varnishes (A-1) to (A-6) as the primer layer were prepared using the comparative polyimide resin varnish (B-1) containing no hydroxyl group as the primer layer. Compared to the laminate of Comparative Example 4, there was no foaming and the heat resistance was excellent. Moreover, in Comparative Examples 5 and 6 in which the resin varnishes (B-2) and (B-3) containing a comparative polyimide having a hydroxyl group other than the polyimide resin (A) having a specific structure of the present application were used as a primer layer, foaming was performed. The peel strength was about 1/3 that of Examples 7-12. Further, even when the polyimide resin varnish (A-1) was used, the peel strength of Comparative Example 8 in which the polyimide resin layer (b) was formed by the laminate method was the example in which the polyimide resin layer (b) was formed by the cast method. It was about 1/2 of 7. From these, the polyimide resin for primer layer (A) of the present invention is easy to synthesize, and the copper-clad laminate using the same is excellent in peel strength, suppression of foaming, rust prevention effect and heat resistance, It is clear that it is useful as a copper clad laminate.
本発明のプライマー層用ポリイミド樹脂（Ａ）は、金属箔（ａ）上に塗布した後の硬化工程を必要とせず、あらゆる条件において安定した接着強度が得られる。また、骨格中に特定構造のアミノフェノールを導入することで、ガス透過性の低い基材樹脂との界面における残溶剤及び分解反応に起因する発泡を大幅に抑制することができ、しかも、金属箔の防錆処理層としての効果をも有する。従って、電気電子材料分野で極めて有用である。 The polyimide resin (A) for primer layer of the present invention does not require a curing step after coating on the metal foil (a), and a stable adhesive strength can be obtained under all conditions. In addition, by introducing aminophenol having a specific structure into the skeleton, foaming caused by residual solvent and decomposition reaction at the interface with the base resin having low gas permeability can be greatly suppressed, and metal foil It also has an effect as a rust preventive treatment layer. Therefore, it is extremely useful in the field of electrical and electronic materials.
Claims (8)
Ｒ1は下記式（２）
Ｒ2は下記式（３）
３，３’−ジアミノ−４，４’−ジヒドロキシジフェニルエーテル、３，３’−ジアミノ−４，４’−ジヒドロキシビフェニル、２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパン、１，３−ヘキサフルオロ−２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパン、１，３−ビス（４−アミノ−３−ヒドロキシフェノキシ）ベンゼン及び９，９’−ビス（３−アミノ−４−ヒドロキシフェニル）フルオレンからなる群から選ばれる１種以上のアミノフェノール類から誘導される２価の芳香族基、であり、ｎは繰り返し数を表す。）
で表されるプライマー層用ポリイミド樹脂（Ａ）。 Adhesion between a metal foil (a) having a surface roughness (Rz) of 2 μm or less and a polyimide resin layer (b) obtained from a polyimide precursor formed on the metal foil (a) by a casting method A polyimide resin for a primer layer for securing the following formula (1)
R 1 is the following formula (2)
R 2 is the following formula (3)
3,3′-diamino-4,4′-dihydroxydiphenyl ether, 3,3′-diamino-4,4′-dihydroxybiphenyl, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 1,3 Hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane, 1,3-bis (4-amino-3-hydroxyphenoxy) benzene and 9,9′-bis (3-amino-4) -Hydroxyphenyl) a divalent aromatic group derived from one or more aminophenols selected from the group consisting of fluorenes, and n represents the number of repetitions. )
A polyimide resin for primer layer (A) represented by:
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| JP2010189510A (en) * | 2009-02-17 | 2010-09-02 | Hitachi Cable Ltd | Insulating coating and insulated wire |
| US9462688B2 (en) | 2011-09-07 | 2016-10-04 | Lg Chem, Ltd. | Flexible metal laminate containing fluoropolymer |
| US20160194542A1 (en) * | 2013-10-23 | 2016-07-07 | Nippon Kayaku Kabushiki Kaisha | Polyimide resin composition, and heat-conductive adhesive film produced using same |
| JP6232605B2 (en) * | 2016-05-10 | 2017-11-22 | メック株式会社 | Film-forming composition, method for producing surface-treated metal member, and method for producing metal-resin composite |
| JP7052384B2 (en) * | 2018-01-31 | 2022-04-12 | 東レ株式会社 | A resin composition for a temporary protective film, and a method for manufacturing a semiconductor electronic component using the resin composition. |
| DE102019206559A1 (en) * | 2019-05-07 | 2020-11-26 | Aktiebolaget Skf | Imide composition and protectant composition with the imide composition |
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| JP4102051B2 (en) * | 2001-10-12 | 2008-06-18 | 株式会社カネカ | Laminated body and multilayer printed wiring board |
| JP2003136631A (en) * | 2001-11-02 | 2003-05-14 | Kanegafuchi Chem Ind Co Ltd | Flexible copper-clad laminated sheet |
| JP4071958B2 (en) * | 2001-11-19 | 2008-04-02 | 株式会社カネカ | Polyimide resin composition |
| JP2007077308A (en) * | 2005-09-15 | 2007-03-29 | Toray Ind Inc | Polyimide resin, heat-resistant resin laminated film using the same and metal layer-attached laminated film |
| TWI417311B (en) * | 2005-10-21 | 2013-12-01 | Nippon Kayaku Kk | Thermosetting resin composition and uses thereof |
| WO2007148666A1 (en) * | 2006-06-20 | 2007-12-27 | Nippon Kayaku Kabushiki Kaisha | Copper foil with primer resin layer and laminate using the same |
| WO2008126818A1 (en) * | 2007-04-10 | 2008-10-23 | Nippon Kayaku Kabushiki Kaisha | Photosensitive resin composition |
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