JP2008255249A - Novel thermosetting resin composition and flexible printed wiring board using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin composition which can be suitably used as an electronic material, especially as a covering material for covering a conductor circuit pattern, is excellent in low-temperature curability and low stress property, has adhesiveness and flexibility, and is especially excellent in electric insulation reliance. <P>SOLUTION: The thermosetting resin composition at least contains (a) an amine-terminated imide oligomer having at least two amino groups per molecule at the terminals of its molecular chain, (b) a blocked isocyanate, and (c) a polyol compound. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a thermosetting resin composition that can be suitably used as a material for covering a circuit surface in an electronic material, and a flexible printed wiring board coated with the thermosetting resin composition.

  2. Description of the Related Art In recent years, electronic devices with high performance, high functionality, and miniaturization are rapidly progressing, and there is an increasing demand for miniaturization and weight reduction of electronic components used in electronic devices. Accordingly, various physical properties such as heat resistance, mechanical strength, electrical characteristics, and fine molding have been demanded more strongly than ever for materials for electronic components.

  In particular, for printed wiring boards, not only the substrate that holds the wiring but also the surface protection material used as the coating material for the wiring is required to have high characteristics, high insulation, environmental stability, and adhesion to the substrate. High heat resistance and mechanical strength are required. In particular, a coating material for a flexible printed wiring board having a polyimide film as a base material is desired to be a low-stress material that does not apply stress to the base material.

  However, epoxy-based resin compositions that have been widely used for wiring coating materials conventionally have a problem of lack of flexibility, poor flexibility, and only a few times of flexibility, and flexible printed wiring boards that require flexibility. There is a problem that cannot be used in the wiring coating material for use (see, for example, Patent Document 1).

On the other hand, in order to solve these problems, a urethane resin thermosetting resin composition mainly composed of polyols and blocked isocyanate has been proposed as a wiring coating material for flexible printed wiring boards. When used as a wiring coating material for a flexible wiring board, the electrical insulation reliability for a long time in a high-temperature and high-humidity environment was insufficient (see, for example, Patent Documents 2 to 3).
JP2002-40647 JP-A-11-61037 JP-A-11-61038

  INDUSTRIAL APPLICABILITY The present invention can be suitably used as a coating forming material for coating an electronic material, in particular, a conductor circuit pattern (particularly a flexible printed wiring board), has excellent low-temperature curability and low stress properties, adhesiveness and bending. Another object of the present invention is to provide a thermosetting resin composition that is also excellent in electrical insulation reliability.

  The present invention can solve the above problems by the following novel configuration.

  That is, the present invention is a thermosetting composition comprising at least (a) an amine-terminated imide oligomer having 2 or more amino groups per molecule at the end of a molecular chain, (b) a blocked isocyanate, and (c) a polyol compound. It is a resin composition.

  Furthermore, the thermosetting resin composition may contain (d) a thermosetting resin.

  Further, the (a) amine-terminated imide oligomer uses at least tetracarboxylic dianhydride and diamine as raw materials, and the ratio expressed by the number of moles of the raw material tetracarboxylic dianhydride / the number of moles of the raw material diamine. 0.01-0.99 may be sufficient.

  Furthermore, when the molar ratio of the component (a) amine-terminated imide oligomer, (b) blocked isocyanate, and (c) polyol compound is (a) is 1 mol, (b) is 0.1 to 10 mol. , (C) may be included in the range of 0.1 to 10 mol.

  Furthermore, the blending ratio of the (d) thermosetting resin includes 1 to 50 parts by weight when the total weight of (a), (b), and (c) is 100 parts by weight. Also good.

  Another invention is a flexible printed wiring board using the thermosetting resin composition as a coating material.

  Furthermore, when using the thermosetting resin composition as a coating material, the thermosetting resin composition may be cured and coated at a temperature of 200 ° C. or lower.

  The thermosetting resin of the present invention is a resin film having an excellent balance of physical properties required for use in electronic materials by coating and drying on the surface of a printed wiring board, and an optimal insulating film can be obtained. In particular, it is excellent in low-temperature curability, low stress, adhesiveness, flexibility, and electrical insulation reliability.

  The thermosetting resin composition of the present invention comprises (a) an amine-terminated imide oligomer having two or more amino groups per molecule at the end of a molecular chain, (b) a blocked isocyanate, and (c) a polyol compound. It is a thermosetting resin composition containing at least. Hereinafter, each component will be described in detail.

<(A) Amine-terminated imide oligomer>
The amine-terminated imide oligomer having (a) two or more amino groups per molecule at the end of the molecular chain according to the present invention has at least a number average molecular weight obtained by a reaction between a diamine and tetracarboxylic dianhydride. It is an imide compound having 500 or more in terms of polyethylene glycol and having two or more amino groups per molecule at the end of the molecular chain.

  The above compound can be obtained, for example, by reacting an excess amount of diamine with a small amount of tetracarboxylic dianhydride in a molar amount in a solvent. While the molar ratio (tetracarboxylic dianhydride moles / diamine moles) is 0.01 to 0.99, particularly preferably 0.40 to 0.80, the solubility in a solvent is improved, This is preferable because the number of amine groups which are reaction active points increases.

  Examples of diamines used as raw materials for amine-terminated imide oligomers include diamines represented by the following general formula (1).

（式中Ｒ’は２価の有機基である。）
上記ジアミンとして例えば、ｍ−フェニレンジアミン、ｏ−フェニレンジアミン、ｐ−フェニレンジアミン、ｍ−アミノベンジルアミン、ｐ−アミノベンジルアミン、ビス（３−アミノフェニル）スルフィド、（３−アミノフェニル）（４−アミノフェニル）スルフィド、ビス（４−アミノフェニル）スルフィド、ビス（３−アミノフェニル）スルホキシド、（３−アミノフェニル）（４−アミノフェニル）スルホキシド、ビス（４−アミノフェニル）スルホキシド、ビス（３−アミノフェニル）スルホン、（３−アミノフェニル）（４−アミノフェニル）スルホン、ビス（４−アミノフェニル）スルホン、３，４’−ジアミノベンゾフェノン、４，４’−ジアミノベンゾフェノン、３，３’−ジアミノベンゾフェノン、３，３’−ジアミノジフェニルメタン、３，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルエーテル、３，３’−ジアミノジフェニルエーテル、３，４’−ジアミノジフェニルエーテル、ビス［４−（３−アミノフェノキシ）フェニル］スルホキシド、ビス［４−（アミノフェノキシ）フェニル］スルホキシド、（４−アミノフェノキシフェニル）（３−アミノフェノキシフェニル）フェニル］スルホキシド、ビス［４−（３−アミノフェノキシ）フェニル］スルホン、ビス［４−（４−アミノフェノキシ）フェニル］スルホン、（４−アミノフェノキシフェニル）（３−アミノフェノキシフェニル）フェニル］スルホン、ビス［４−（３−アミノフェノキシ）フェニル］スルフィド、ビス［４−（アミノフェノキシ）フェニル］スルフィド、（４−アミノフェノキシフェニル）（３−アミノフェノキシフェニル）フェニル］スルフィド、３，３’−ジアミノベンズアニリド、３，４’−ジアミノベンズアニリド、４，４’−ジアミノベンズアニリド、ビス［４−（３−アミノフェノキシ）フェニル］メタン、ビス［４−（４−アミノフェノキシ）フェニル］メタン、[４−（４−アミノフェノキシフェニル）][４−（３−アミノフェノキシフェニル）]メタン、１，１−ビス［４−（３−アミノフェノキシ）フェニル］エタン、１，１−ビス［４−（４−アミノフェノキシ）フェニル］エタン、１，１−[４−（４−アミノフェノキシフェニル）][４−（３−アミノフェノキシフェニル）]エタン、１，２−ビス［４−（３−アミノフェノキシ）フェニル］エタン、１，２−ビス［４−（４−アミノフェノキシ）フェニル］エタン、１，２−[４−（４−アミノフェノキシフェニル）][４−（３−アミノフェノキシフェニル）]エタン、２，２−ビス［４−（３−アミノフェノキシ）フェニル］プロパン、２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン、２，２−[４−（４−アミノフェノキシフェニル）][４−（３−アミノフェノキシフェニル）] プロパン、２，２−ビス［３−（３−アミノフェノキシ）フェニル］−１，１，１，３，３，３−ヘキサフルオロプロパン、２，２−ビス［４−（４−アミノフェノキシ）フェニル］−１，１，１，３，３，３−ヘキサフルオロプロパン、２，２−[４−（４−アミノフェノキシフェニル）][４−（３−アミノフェノキシフェニル）] −１，１，１，３，３，３−ヘキサフルオロプロパン、１，３−ビス（３−アミノフェノキシ）ベンゼン、１，４−ビス（３−アミノフェノキシ）ベンゼン、１，４−ビス（４−アミノフェノキシ）ベンゼン、１，３−ビス（４−アミノフェノキシ）ベンゼン、４，４’−ビス（４−アミノフェノキシ）ビフェニル、４，４’−ビス（３−アミノフェノキシ）ビフェニル、ビス［４−（３−アミノフェノキシ）フェニル］ケトン、ビス［４−（４−アミノフェノキシ）フェニル］ケトン、ビス［４−（３−アミノフェノキシ）フェニル］エーテル、ビス［４−（４−アミノフェノキシ）フェニル］エーテル、ポリテトラメチレンオキシド−ジ−Ｐ−アミノベンゾエート、ポリ（テトラメチレン／３−メチルテトラメチレンエーテル）グリコールビス（４−アミノベンゾエート）、トリメチレン―ビス（４−アミノベンゾエート）、ｐ-フェニレン−ビス（４−アミノベンゾエート）、ｍ−フェニレン−ビス（４−アミノベンゾエート）、ビスフェノールＡ−ビス（４−アミノベンゾエート）、２，４−ジアミノ安息香酸、２，５−ジアミノ安息香酸、３，５−ジアミノ安息香酸、３，３’−ジアミノ−４，４’−ジカルボキシビフェニル、４，４’−ジアミノ−３，３’−ジカルボキシビフェニル、４，４’−ジアミノ−２，２’−ジカルボキシビフェニル、[ビス(４-アミノ-２-カルボキシ)フェニル]メタン、 [ビス(４-アミノ-３-カルボキシ)フェニル]メタン、[ビス(３-アミノ-４-カルボキシ)フェニル]メタン、 [ビス(３-アミノ-５-カルボキシ)フェニル]メタン、２，２−ビス[３−アミノ−４−カルボキシフェニル]プロパン、２，２−ビス[４−アミノ−３−カルボキシフェニル]プロパン、２，２−ビス[３−アミノ−４−カルボキシフェニル]ヘキサフルオロプロパン、２，２−ビス[４−アミノ−３−カルボキシフェニル]ヘキサフルオロプロパン、３，３’−ジアミノ−４，４’−ジカルボキシジフェニルエーテル、４，４‘−ジアミノ−３，３’−ジカルボキシジフェニルエーテル、４，４’−ジアミノ−２，２’−ジカルボキシジフェニルエーテル、３，３’−ジアミノ−４，４‘−ジカルボキシジフェニルスルフォン、４，４’−ジアミノ−３，３’−ジカルボキシジフェニルスルフォン、４，４’−ジアミノ−２，２’−ジカルボキシジフェニルスルフォン、２，３−ジアミノフェノール、２，４−ジアミノフェノール、２，５−ジアミノフェノール、３，５−ジアミノフェノール等のジアミノフェノール類、３，３’−ジアミノ−４，４’−ジヒドロキシビフェニル、４，４’−ジアミノ−３，３’−ジヒドロキシビフェニル、４，４’−ジアミノ−２，２’−ジヒドロキシビフェニル、４，４’−ジアミノ−２，２’，５，５’−テトラヒドロキシビフェニル等のヒドロキシビフェニル化合物類、３，３’−ジアミノ−４，４’−ジヒドロキシジフェニルメタン、４，４’−ジアミノ−３，３’−ジヒドロキシジフェニルメタン、４，４’−ジアミノ−２，２’−ジヒドロキシジフェニルメタン等のジヒドロキシジフェニルメタン類、２，２−ビス[３−アミノ−４−ヒドロキシフェニル]プロパン、２，２−ビス[４−アミノ−３−ヒドロキシフェニル]プロパン等のビス[ヒドロキシフェニル]プロパン類、２，２−ビス[３−アミノ−４−ヒドロキシフェニル]ヘキサフルオロプロパン、２，２−ビス[３−アミノ−４−ヒドロキシフェニル]ヘキサフルオロプロパン等のビス[ヒヒドロキシフェニル]ヘキサフルオロプロパン類、３，３’−ジアミノ−４，４’−ジヒドロキシジフェニルエーテル、４，４’−ジアミノ−３，３’−ジヒドロキシジフェニルエーテル、４，４’−ジアミノ−２，２’−ジヒドロキシジフェニルエーテル等のヒドロキシジフェニルエーテル類、３，３’−ジアミノ−４，４’−ジヒドロキシジフェニルスルフォン、４，４’−ジアミノ−３，３’−ジヒドロキシジフェニルスルフォン、４，４’−ジアミノ−２，２’−ジヒドロキシジフェニルスルフォン等のジヒドロキシジフェニルスルフォン類、３，３’−ジアミノ−４，４’−ジヒドロキシジフェニルスルフィド、４，４’−ジアミノ−３，３’−ジヒドロキシジフェニルスルフィド、４，４’−ジアミノ−２，２’−ジヒドロキシジフェニルスルフィド等のジヒドロキシジフェニルスルフィド類、３，３’−ジアミノ−４，４’−ジヒドロキシジフェニルスルホキシド、４，４’−ジアミノ−３，３’−ジヒドロキシジフェニルスルホキシド、４，４’−ジアミノ−２，２’−ジヒドロキシジフェニルスルホキシド等のジヒドロキシジフェニルスルホキシド類、２，２−ビス[４−（４−アミノ−３−ヒドロキシフェノキシ）フェニル]プロパン等のビス［（ヒドロキシフェニル）フェニル］アルカン化合物類、４，４’−ビス（４−アミノ−３−ヒドキシフェノキシ）ビフェニル等のビス（ヒドキシフェノキシ）ビフェニル化合物類、２，２−ビス[４−（４−アミノ−３−ヒドロキシフェノキシ）フェニル]スルフォン等のビス[（ヒドロキシフェノキシ）フェニル]スルフォン化合物、４，４’−ジアミノ−３，３’−ジハイドロキシジフェニルメタン、４，４’−ジアミノ−２，２’−ジハイドロキシジフェニルメタン、２，２−ビス[３−アミノ−４−カルボキシフェニル]プロパン、又は４，４’−ビス（４−アミノ−３−ヒドキシフェノキシ）ビフェニル等のビス（ヒドキシフェノキシ）ビフェニル化合物類をあげることができる。

(In the formula, R ′ is a divalent organic group.)
Examples of the diamine include m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, bis (3-aminophenyl) sulfide, (3-aminophenyl) (4- Aminophenyl) sulfide, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, (3-aminophenyl) (4-aminophenyl) sulfoxide, bis (4-aminophenyl) sulfoxide, bis (3- Aminophenyl) sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diamino Benzophenone, 3,3'-diaminodiphe Nylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, bis [4- (3-amino Phenoxy) phenyl] sulfoxide, bis [4- (aminophenoxy) phenyl] sulfoxide, (4-aminophenoxyphenyl) (3-aminophenoxyphenyl) phenyl] sulfoxide, bis [4- (3-aminophenoxy) phenyl] sulfone, Bis [4- (4-aminophenoxy) phenyl] sulfone, (4-aminophenoxyphenyl) (3-aminophenoxyphenyl) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (Aminophenoxy ) Phenyl] sulfide, (4-aminophenoxyphenyl) (3-aminophenoxyphenyl) phenyl] sulfide, 3,3′-diaminobenzanilide, 3,4′-diaminobenzanilide, 4,4′-diaminobenzanilide, Bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, [4- (4-aminophenoxyphenyl)] [4- (3-aminophenoxyphenyl)] Methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1- [4- (4-aminophenoxy) Phenyl)] [4- (3-aminophenoxyphenyl)] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, , 2-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2- [4- (4-aminophenoxyphenyl)] [4- (3-aminophenoxyphenyl)] ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2- [4- (4-aminophenoxyphenyl)] [4- ( 3-aminophenoxyphenyl)] propane, 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, 2,2- [4- (4-aminophenoxyphenyl)] [4- (3-aminophenoxyphenyl) ] -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, 1,3-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] ether, bis [4- (4-aminophenoxy) phenyl] ether, polytetramethylene Oxide-di-P-aminobenzoate, poly (tetramethylene / 3-methyltetramethylene ether) glycol bis (4-a Nobenzoate), trimethylene-bis (4-aminobenzoate), p-phenylene-bis (4-aminobenzoate), m-phenylene-bis (4-aminobenzoate), bisphenol A-bis (4-aminobenzoate), 2 , 4-Diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 3,3′-diamino-4,4′-dicarboxybiphenyl, 4,4′-diamino-3,3 ′ -Dicarboxybiphenyl, 4,4'-diamino-2,2'-dicarboxybiphenyl, [bis (4-amino-2-carboxy) phenyl] methane, [bis (4-amino-3-carboxy) phenyl] methane , [Bis (3-amino-4-carboxy) phenyl] methane, [Bis (3-amino-5-carboxy) phenyl] methane, 2,2-bis [3-amino-4-carboxypheny] ] Propane, 2,2-bis [4-amino-3-carboxyphenyl] propane, 2,2-bis [3-amino-4-carboxyphenyl] hexafluoropropane, 2,2-bis [4-amino-3] -Carboxyphenyl] hexafluoropropane, 3,3'-diamino-4,4'-dicarboxydiphenyl ether, 4,4'-diamino-3,3'-dicarboxydiphenyl ether, 4,4'-diamino-2,2 '-Dicarboxydiphenyl ether, 3,3'-diamino-4,4'-dicarboxydiphenyl sulfone, 4,4'-diamino-3,3'-dicarboxydiphenyl sulfone, 4,4'-diamino-2,2 '-Dicarboxydiphenylsulfone, 2,3-diaminophenol, 2,4-diaminophenol, 2,5-diaminophenol, 3,5- Diaminophenols such as aminophenol, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, 4,4′-diamino-2,2′- Hydroxybiphenyl compounds such as dihydroxybiphenyl, 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxybiphenyl, 3,3′-diamino-4,4′-dihydroxydiphenylmethane, 4,4′- Dihydroxy-3,3′-dihydroxydiphenylmethane, dihydroxydiphenylmethanes such as 4,4′-diamino-2,2′-dihydroxydiphenylmethane, 2,2-bis [3-amino-4-hydroxyphenyl] propane, 2,2 Bis [hydroxyphenyl] propanes such as bis [4-amino-3-hydroxyphenyl] propane, 2,2-bis [3 Bis [hyhydroxyphenyl] hexafluoropropanes such as amino-4-hydroxyphenyl] hexafluoropropane, 2,2-bis [3-amino-4-hydroxyphenyl] hexafluoropropane, 3,3′-diamino-4 , 4′-dihydroxydiphenyl ether, 4,4′-diamino-3,3′-dihydroxydiphenyl ether, hydroxydiphenyl ethers such as 4,4′-diamino-2,2′-dihydroxydiphenyl ether, 3,3′-diamino-4 , 4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, dihydroxydiphenyl sulfones such as 4,4'-diamino-2,2'-dihydroxydiphenyl sulfone, 3,3 '-Diamino-4,4'-dihydroxydiphenyls Dihydroxydiphenyl sulfides such as 4,4′-diamino-3,3′-dihydroxydiphenyl sulfide, 4,4′-diamino-2,2′-dihydroxydiphenyl sulfide, 3,3′-diamino-4,4 Dihydroxydiphenyl sulfoxides such as' -dihydroxydiphenyl sulfoxide, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfoxide, 4,4'-diamino-2,2'-dihydroxydiphenyl sulfoxide, 2,2-bis [ Bis [(hydroxyphenyl) phenyl] alkane compounds such as 4- (4-amino-3-hydroxyphenoxy) phenyl] propane, bis such as 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl (Hydroxyphenoxy) biphenyl compounds, 2,2-bis [4- (4- Bis [(hydroxyphenoxy) phenyl] sulfone compounds such as amino-3-hydroxyphenoxy) phenyl] sulfone, 4,4′-diamino-3,3′-dihydroxydiphenylmethane, 4,4′-diamino-2,2 ′ Bis (hydroxyphenoxy) biphenyl such as dihydroxydiphenylmethane, 2,2-bis [3-amino-4-carboxyphenyl] propane, or 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl Compounds can be listed.

  In particular, m-phenylenediamine, bis (3-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, bis [ 4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis (4-aminophenoxy) benzene, or 1,3-bis ( Preference is given to using 3-aminophenoxy) benzene. It is preferable to use the aromatic diamine because the heat resistance of the thermosetting resin composition is improved.

  The said diamine can use 1 type (s) or 2 or more types.

  The tetracarboxylic dianhydride used as a raw material for the amine-terminated imide oligomer is not particularly limited, but 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, pyromellitic tetracarboxylic dianhydride 3,3 ′, 4,4′-oxydiphthaltetracarboxylic dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′ , 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4-biphenyltetracarboxylic dianhydride, or 5- (2,5-dioxotetrahydro-3-furanyl) It is preferable to use 3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride.

  In particular, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4 , 4'-oxydiphthaltetracarboxylic dianhydride or 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride However, it is preferable for improving the solubility of the resulting amine-terminated imide oligomer in an organic solvent and improving the chemical resistance of the thermosetting resin composition.

  The said tetracarboxylic dianhydride can use 1 type (s) or 2 or more types.

  The mixing ratio of the diamine and the tetracarboxylic dianhydride is 0.01 to 0.99, particularly preferably 0.40 to 0.80, as the molar ratio (tetracarboxylic dianhydride moles / diamine moles). It is. Such a blending ratio is preferable because the molecular weight of the amine-terminated imide oligomer does not become too large, the solubility in a solvent is improved, and the number of amine groups that are reaction active points increases.

  As a manufacturing method of an amine terminal imide oligomer, the following method is mentioned, for example.

  Method 1: A polyamic acid solution is prepared by adding and reacting the diamine represented by the general formula (1) in a solution in which the tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent. Add an imidization catalyst (preferably tertiary amines such as pyridine, picoline, isoquinoline, trimethylamine, triethylamine, tributylamine, etc.) and a dehydrating agent (acetic anhydride, etc.) to this polyamic acid solution at 60 ° C. or higher. By heating to 180 ° C. or less to perform imidization, the amine-terminated imide oligomer solution is added with alcohols (for example, methanol, ethanol, butanol, propanol, etc.) or water, or is added to the alcohol or water. Amine-terminated imide oligomers are precipitated. The oligomer can be obtained by washing the amine-terminated imide oligomer and drying it by heating.

  Method 2: A polyamic acid solution is prepared by adding and reacting the diamine represented by the general formula (1) in a solution in which the tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent. An amine-terminated imide oligomer can be obtained by placing this polyamic acid solution in a vacuum oven heated to 100 ° C. or more and 300 ° C. or less and drawing it under vacuum while heating and drying to perform imidization.

  The above method is preferably used, but any method may be used as long as it is a method capable of obtaining an imide oligomer having an amine at the end and imidized at the center, regardless of the above method.

  Examples of the solvent used for polymerization in the present invention include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, and N, N-dimethylacetamide. , Acetamide solvents such as N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o-, m- or p-cresol, xylenol, halogenated Phenol solvents such as phenol and catechol, or hexamethylphosphoramide, γ-butyrolactone, methyl monoglyme (1,2-dimethoxyethane), methyl diglyme (bis (2-methoxyether) ether), methyl triglyme ( 1,2-bis (2 -Methoxyethoxy) ethane), methyltetraglyme (bis [2- (2-methoxyethoxyethyl)] ether), ethyl monoglyme (1,2-diethoxyethane), ethyldiglyme (bis (2-ethoxyethyl)) Ether), butyl diglyme (bis (2-butoxyethyl) ether), symmetric glycol diethers, γ-butyrolactone, N-methyl-2-pyrrolidone, methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate , Butyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate (also known as carbitol acetate, 2- (2-butoxyethoxy) ethyl acetate)), diethylene glycol Acetate monobutyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, Dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripylene glycol n-propyl ether, propylene glycol Phenyl ether, dipropylene glycol dimethyl ether 1,3-dioxolane, ethylene glycol monobutyl ether, can be used diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, or ethers solvent such as ethylene glycol monoethyl ether. The said solvent can be used by 1 type (s) or 2 or more types. If necessary, low-boiling hexane, acetone, toluene, xylene and the like can be used in combination.

<(B) Blocked isocyanate>
The (b) blocked isocyanate of the present invention is a compound obtained by reacting a blocking agent with an isocyanate having two or more isocyanate groups in the molecule. Examples of the isocyanate include 1,6-hexane diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate. Xylylene diisocyanate, 4,4'dicyclohexylmethane diisocyanate, 4,4'-hydroxylated diisocyanate, isophorone diisocyanate, 1,5-naphthalenediisocyanate, 4,4-diphenyl Diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, phenylene 1,4-diisocyanate, phenylene 2,6-diisocyanate, 1,3,6-hexamethylene triisocyanate, or And hexamethylene diisocyanate. Blocking agents include alcohols, phenols, ε-caprolactam, oximes, active methylenes, mercaptans, amines, imides, acid amides, imidazoles, ureas, carbamates , Imines, sulfites, and the like are used. As a more specific product of the above-mentioned blocked isocyanate compound, for example, hexamethylene diisocyanate (hereinafter also referred to as HDI) block isocyanate, trade names Duranate 17B-60PX, TPA-B80E manufactured by Asahi Kasei Chemicals Corporation, TPA-B80X, MF-B60X, E402-B80T, ME20-B80S, MF-K60X, K6000, trade name Takenate B-882N manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., Mitsui Chemicals Polyurethane, which is a tolylene diisocyanate block isocyanate ( Trade name Takenate B-830, 4,4'-diphenylmethane diisocyanate block isocyanate manufactured by Mitsui Chemicals Polyurethane Co., Ltd., trade name Takenate B-815N, 1,3-bis (isocyanate) Nate methyl) cyclohexane block isocyanate, trade name Takenate B-846N manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., trade name Coronate AP-M, 2503, 2515, 2507, 2513 manufactured by Nippon Polyurethane Industry Co., Ltd., or Millionate MS What is marketed, such as -50, is mentioned, These can be used individually or in combination of 2 or more types.

  In order to develop low temperature curability at 200 ° C. or lower, it is preferable to use an HDI-based blocked isocyanate having a low curing temperature.

<(C) Polyol>
The (c) polyol compound of the present invention is a compound having two or more hydroxyl groups per molecule. Examples of polyol compounds include ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene. Glycols having two alcoholic hydroxyl groups such as glycols, carbondiols, neopentyl glycols, alkylene oxide adducts of bisphenols, alkylene oxide adducts of hydrogenated bisphenols, etc. Polyether glycols such as polyethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene adipate, polypropylene adipate, polybutylene adipate, poly Tetramethylene adipate, polypentamethylene adipate, polyhexamethylene adipate, Polyester diols such as licaprolactone diol, polyhydric alcohols having three or more alcoholic hydroxyl groups such as trimethylol ethane, trimethylol propane, glycerin and pentaestriol, or polycarbonate diol Etc. These can be used alone or in combination of two or more.

  Among these polyols, polycarbonate diol can be preferably used. Furthermore, it is preferable to use a polycarbonate diol represented by the following general formula (2) as the polycarbonate diol. Use of these polycarbonate diols is preferable since the electrical insulation reliability of the resulting thermosetting resin film is improved and the adhesiveness is improved.

（式中、Ｒ^１、Ｒ^２は同一であっても異種であってもよく、ＣＨ_２、ＣＨ_２Ｃ（ＣＨ_３）_２ＣＨ_２、ＣＨ_２ＣＨ（ＣＨ_３）ＣＨ_２、及びＣＨ_２ＣＨ（ＣＨ₃）ＣＨ_２ＣＨ_２からなる群から選ばれる少なくとも１種以上の基であり、ｌ、ｎは１〜３０の整数であり、ｍは１以上の整数である。）
上記ポリカーボネートジオールのより具体的な製品としては、例えば、旭化成ケミカルズ（株）製の商品名ＰＣＤＬ、Ｔ６００２、Ｔ６００１、Ｔ５６５２、Ｔ５６５１、Ｔ５６５０Ｊ、Ｔ４６７２、Ｔ４６７１、Ｔ４６９２、Ｔ４６９１、ダイセル化学（株）製の商品名ＰＬＡＣＣＥＬ、ＣＤ−２０５、２０５ＰＬ、２０５ＨＬ、２１０、２１０ＰＬ、２１０ＨＬ、２２０、２２０ＰＬ、または２２０ＨＬなどの市販されているものが挙げられ、これらを単独で又は２種類以上を組み合わせて使用できる。

(In the formula, R ¹ and R ² may be the same or different, CH ₂ , CH ₂ C (CH ₃ ) ₂ CH ₂ , CH ₂ CH (CH ₃ ) CH ₂ , and CH ₂ CH. (CH ₃ ) At least one group selected from the group consisting of CH ₂ CH ₂ , l and n are integers of 1 to 30, and m is an integer of 1 or more.
As a more specific product of the polycarbonate diol, for example, trade names PCDL, T6002, T6001, T5652, T5651, T5650J, T4672, T4671, T4692, T4691, manufactured by Asahi Kasei Chemicals Corporation, manufactured by Daicel Chemical Industries, Ltd. Commercially available products such as trade names PLACEL, CD-205, 205PL, 205HL, 210, 210PL, 210HL, 220, 220PL, or 220HL can be used, and these can be used alone or in combination of two or more.

<Combination ratio>
The blending ratio of the component (a) amine-terminated imide oligomer, (b) blocked isocyanate and (c) polyol compound is such that (b) is 0.1 to 10 moles when (a) is 1 mole. , (C) is preferably contained in the range of 0.1 to 10 mol. By setting it as such a range, while being able to improve the electrical insulation reliability of a thermosetting resin composition, the brittleness of a coating film can be improved. Furthermore, the blending ratio of the present invention is preferably such that (b) is 0.3 to 3.0 moles and (c) is 0.3 to 3.0 when (a) is 1 mole in terms of molar ratio. The reaction is preferably carried out at a molar ratio, and the value of (b) / (c) is preferably 0.90 or more in terms of improving low stress properties and further improving electrical insulation reliability.

<Thermosetting resin>
The resin composition of the present invention may further contain a thermosetting resin. By including a thermosetting resin, the adhesiveness, chemical resistance, and electrical insulation reliability of the thermosetting resin composition can be improved.

  Thermosetting resins used in the resin composition of the present invention include epoxy resins, isocyanate resins, bismaleimide resins, bisallyl nadiimide resins, acrylic resins, methacrylic resins, hydrosilyl cured resins, allyl cured resins, unsaturated polyester resins, etc. Use of a side chain reactive group type thermosetting polymer having a reactive group such as an allyl group, a vinyl group, an alkoxysilyl group, a hydrosilyl group, etc. at the side chain or terminal of the polymer chain Can do. The thermosetting component may be used alone or in combination of two or more.

  Among these, it is preferable to use an epoxy resin. By containing an epoxy resin component, heat resistance can be imparted to a cured resin obtained by curing a thermosetting resin composition, and adhesion to a conductor such as a metal foil or a circuit board can be imparted. .

  The epoxy resin contains at least two epoxy groups in the molecule, and is bisphenol A type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, bisphenol A novolac type epoxy resin. , Water added bisphenol A type epoxy resin, ethylene oxide adduct bisphenol A type epoxy resin, propylene oxide adduct bisphenol A type epoxy resin, novolac type epoxy resin, glycidyl ester type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, Alkylphenol novolac type epoxy resin, polyglycol type epoxy resin, cycloaliphatic epoxy resin, cyclopentadiene type epoxy resin, dicyclopentadiene Type epoxy resins, cresol novolak type epoxy resins, glycidyl amine type epoxy resins, naphthalene type epoxy resins, urethane modified epoxy resins, rubber-modified epoxy resin, an epoxy resin such as epoxy-modified polysiloxane. These epoxy resins may be used alone or in combination of two or more at any ratio.

  Examples of the epoxy resin include, for example, the product name Epicron HP-4700 of a naphthalene type tetrafunctional epoxy resin manufactured by Dainippon Ink and Chemicals Co., Ltd. The name Epicron N-740, Epicron EXA-7240, which is a highly heat-resistant epoxy resin, Epicron N-660, N-665, N-670, N-680, N-665, which is a cresol novolac type polyfunctional epoxy resin EXP, tetraphenylethane type epoxy resin trade name Epicron ETePE, triphenylmethane type epoxy resin trade name Epicron ETrPM, Japan Epoxy Resin Co., Ltd. trade name Epicoat 828, etc. Bisphenol A type epoxy resin, Toto Kasei Co., Ltd. ) Made Bisphenol F type epoxy resin such as YDF-170, product name Epicoat 152, 154 manufactured by Japan Epoxy Resin Co., Ltd., product name EPPN-201 manufactured by Nippon Kayaku Co., Ltd., product name manufactured by Dow Chemical Co., Ltd. Phenol novolac type epoxy resins such as DEN-438, trade names EOCN-125S, 103S and 104S manufactured by Nippon Kayaku Co., Ltd., trade names Epon 1031S manufactured by Japan Epoxy Resin Co., Ltd. Product names Araldite 0163 manufactured by Ciba Specialty Chemicals Co., Ltd., product names Denacol EX-611, EX-614, EX-614B, EX-622, EX-512, EX-521, EX manufactured by Nagase Kasei Co., Ltd. -421, EX-411, EX-321, etc. Product name Epicoat 604 manufactured by Nepoxy Resin Co., Ltd., product name YH434 manufactured by Toto Kasei Co., Ltd., product names TETRAD-X and TERRAD-C manufactured by Mitsubishi Gas Chemical Co., Ltd., manufactured by Nippon Kayaku Co., Ltd. Amine type epoxy resin such as trade name GAN, trade name ELM-120 manufactured by Sumitomo Chemical Co., Ltd., heterocycle-containing epoxy resin such as trade name Araldite PT810 manufactured by Ciba Specialty Chemicals, ERL4234 manufactured by UCC , 4299, 4221, 4206 and the like, and these can be used alone or in combination of two or more.

  Among these epoxy resins, the use of an epoxy resin having two or more epoxy groups in one molecule can improve the heat resistance of the thermosetting resin, and further improve the adhesion and electrical insulation reliability. Therefore, it is preferably used. In addition, chemical resistance can also be provided by using an epoxy resin together.

  In addition, the epoxy resin used for the thermosetting resin composition of this invention may contain the epoxy compound which has only one epoxy group in 1 molecule. Examples of such epoxy compounds include n-butyl glycidyl ether, phenyl glycidyl ether, dibromophenyl glycidyl ether, and dibromocresyl glycidyl ether. In addition, alicyclic epoxy compounds such as 3,4-epoxycyclohexyl and methyl (3,4-epoxycyclohexane) carboxylate can be used.

  The blending ratio of the thermosetting resin in the present invention is a ratio of 1 to 50 parts by weight when the total weight of (a) amine-terminated imide oligomer, (b) blocked isocyanate, and (c) polyol compound is 100 parts by weight. It is preferable to contain. By controlling to the said range, since the said characteristic can be provided and it does not reduce the brittleness of a thermosetting resin, it is preferable.

<Other ingredients>
In the thermosetting resin composition of the present invention, if necessary, a thermosetting component, a photochromic agent such as tribromophenylsulfone or leucocrystal violet, a thermochromic inhibitor, a plasticizer such as p-toluenesulfonamide, Colorants such as dyes such as malachite green, phthalocyanine-based phthalocyanine green or phthalocyanine blue, organic pigments such as azo-based or inorganic pigments such as titanium dioxide, fillers such as silica, alumina, talc, calcium carbonate or barium sulfate, Various additives such as antifoaming agents, flame retardants, stabilizers, azole compounds, leveling agents, antioxidants, curing agents for epoxy resin components, and the reaction between epoxy resin components and curing agents For example, a thermosetting component such as a curing accelerator may be contained.

The epoxy curing agent is not particularly limited, but phenolic resins such as phenol novolac type phenol resin, cresol novolac type phenol resin, naphthalene type phenol resin; dodecyl succinic anhydride, polyadipic anhydride, polyazeline Aliphatic acid anhydrides such as acid anhydrides; alicyclic acid anhydrides such as hexahydrophthalic anhydride and methylhexahydrophthalic acid; phthalic anhydride, trimellitic anhydride, benzophenone tetracarboxylic acid, ethylene glycol bistrimellitate, Aromatic acid anhydrides such as glycerol tristrimate; amino resins, urea resins, melamine resins, dicyandiamide, dihydrazine compounds, imidazole compounds, Lewis acids, Bronsted acid salts, polymercaptan compounds, etc. The Can it gel.
The said hardening | curing agent should just be used combining 1 type (s) or 2 or more types, and it is preferable to use within the range of 1 weight part-100 weight part with respect to 100 weight part of all the epoxy resins.

  Further, the curing accelerator is not particularly limited, but for example, phosphine compounds such as triphenylphosphine; amine compounds such as tertiary amine, trimethanolamine, triethanolamine and tetraethanolamine; 1,8- Borate compounds such as diaza-bicyclo [5,4,0] -7-undecenium tetraphenylborate, imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-un Imidazoles such as decylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole; 2-methylimidazoline, 2- Ethyl imidazoline, 2 Imidazolines such as isopropylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline; 2,4-diamino-6- [2′-methylimidazolyl- ( 1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2 ′ And azine-based imidazoles such as -ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine.

  Since the thermosetting resin composition of the present invention is excellent in low-temperature curability, for example, when it is applied and dried on a printed wiring board, it does not oxidize a conductor (metal such as copper) and has low stress properties. Therefore, curling of the printed wiring board can be reduced. From the above, the thermosetting resin composition of the present invention is suitably used for flexible printed wiring boards. Furthermore, since the thermosetting resin composition of the present invention is excellent in low-temperature curability, low stress, and electrical insulation reliability, for example, interlayer insulation in the field of semiconductor device and overcoat materials for various electronic components, rigid or flexible substrates, etc. Sheet, varnish for sheet combined with base materials such as film, surface protective film, solder resist layer, adhesive layer, liquid sealing material, varnish for enamel wire, impregnating varnish for electrical insulation, casting varnish, mica, glass cloth, It can be used for varnishes for MCL laminates and friction materials. The film forming material in the present invention can be used for a semiconductor element, a flexible circuit board, a laminate, an enameled wire, etc. having a film formed by using the above composition.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited only to these Examples.

  Evaluation items and evaluation methods performed in the examples are as follows.

(Adhesion evaluation)
The thermosetting resin composition solution was applied to a 25 μm polyimide film (Akane 25NPI manufactured by Kaneka Corporation) and cured at 120 ° C. for 90 minutes to form a 20 μm thick film on the polyimide film surface. The adhesive strength of this coating film was evaluated by a cross-cut tape method according to JIS K-5400.
○: No peeling by cross-cut tape method.
Δ: 80% or more of the cells remain.
X: The remaining amount of the mesh is less than 80%.

(Flexibility evaluation)
A thermosetting resin composition solution is applied to the surface of a 25 μm-thick polyimide film (Apical 25NPI manufactured by Kaneka Corporation) so that the final film thickness is 20 μm, and cured at 120 ° C. for 90 minutes to obtain a polyimide film laminate. It was. This polyimide film laminate was cut into 30 mm × 10 mm strips, bent 10 times at 180 ° at 15 mm, and the coating film was visually confirmed to check for cracks.
○: The cured film has no cracks.
Δ: The cured film has some cracks.
X: The cured film has cracks.

(warp)
A 25 μm thick polyimide film (Akane 25NPI manufactured by Kaneka Corporation) was coated with a thermosetting resin composition solution to a final coating thickness of 20 μm and cured at 120 ° C. for 90 minutes to obtain a polyimide film laminate. Obtained. The polyimide film laminate was cut into a 50 mm × 50 mm square film, and the warp height of the edge was evaluated with the coated surface facing up. In addition, since the warpage increases when the residual stress of the coating film is large, in the present invention, instead of measuring the stress, the stress is calculated by the amount of warpage of the film. Especially in this invention, it is preferable that it will be less than 5 mm, and the following determination was performed.
○: Warpage height is 0 mm.
Δ: Warpage height is 5 mm or less.
X: Warpage height is 5 mm or more.

(Moisture resistance)
A comb-shaped pattern of L / S = 100/100 μm was created on the flexible copper-clad laminate, immersed in a 10 vol% sulfuric acid solution for 1 minute, washed with pure water, and subjected to a copper foil surface treatment. Thereafter, a thermosetting resin composition solution is applied onto the comb pattern so that the final coating thickness is 20 μm, and cured at 120 ° C. for 90 minutes to form a thermosetting resin composition film and to prepare a test piece. Went. A 100 V direct current was applied to both terminals of the test piece in an environmental test machine at 85 ° C. and 85% RH, and changes in the insulation resistance value and occurrence of migration were observed.
A: A resistance value of 10 9 or more in 500 hours or more and no occurrence of migration or dendrite.
X: A resistance value of 10 9 or less in 500 hours or more, or the occurrence of migration, dendrite or the like.

(Synthesis Example 1)
In a 500 ml separable flask equipped with a nitrogen inlet tube, a condenser and a stirrer, 100 g (0.342 mol) of 1,3-bis (3-aminophenoxy) benzene was dispersed in 70 g of N, N-dimethylformamide and placed in an oil bath. The temperature was raised to 50 ° C. and stirred for 30 minutes while maintaining the temperature to obtain a uniform solution. Next, 89 g (0.171 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride was added, the temperature was raised to 140 ° C., and the mixture was stirred for 1 hour while maintaining the temperature. A homogeneous solution was obtained. Next, the temperature was lowered to 5 ° C. with ice cooling, and the mixture was stirred for 2 hours while maintaining the temperature to obtain a polyamide solution. The polyamide solution is then transferred to a polytetrafluoroethylene vat, placed in a vacuum oven, heated to 239 ° C. under reduced pressure, and subjected to an imidization reaction for 6 hours while trapping N, N-dimethylformamide and water. An amine-terminated imide oligomer was obtained. This synthetic resin is abbreviated as synthetic resin A. The number average molecular weight of this synthetic resin was 1200 in terms of polyethylene glycol.

(Synthesis Example 2)
Disperse 100 g (0.403 mol) of bis (3-aminophenyl) sulfone in 137 g of N, N-dimethylformamide in a 500 ml separable flask equipped with a nitrogen inlet tube, a condenser and a stirrer, and raise the temperature to 50 ° C. in an oil bath. The mixture was warmed and stirred for 30 minutes while maintaining the temperature to obtain a uniform solution. Next, 105 g (0.201 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride was added, the temperature was raised to 140 ° C., and the mixture was stirred for 1 hour while maintaining the temperature. A homogeneous solution was obtained. Next, the temperature was lowered to 5 ° C. with ice cooling, and the mixture was stirred for 2 hours while maintaining the temperature to obtain a polyamide solution. The polyamide solution is then transferred to a polytetrafluoroethylene vat, placed in a vacuum oven, heated to 239 ° C. under reduced pressure, and subjected to an imidization reaction for 6 hours while trapping N, N-dimethylformamide and water. An amine-terminated imide oligomer was obtained. This synthetic resin is abbreviated as synthetic resin B. The number average molecular weight of this synthetic resin was 1100 in terms of polyethylene glycol.

(Examples 1-3)
A thermosetting resin composition was prepared by adding the amine-terminated imide oligomer (synthetic resin A) obtained in Synthesis Example 1, a blocked isocyanate, a polyol compound, and a thermosetting resin. Table 1 shows the blending amount of each constituent raw material in the resin solid content and the kind of the raw material. This thermosetting resin composition was diluted with 1,2-bis (2-methoxyethoxy) ethane to obtain a thermosetting resin composition solution having a nonvolatile content of 50% by weight. The following evaluation was performed using this solution. The evaluation results are shown in Table 2.
Example 4
A thermosetting resin composition was prepared by adding the amine-terminated imide oligomer (synthetic resin B) obtained in Synthesis Example 2, a blocked isocyanate, a polyol compound, and a thermosetting resin. Table 1 shows the blending amount of each constituent raw material in the resin solid content and the kind of the raw material. This thermosetting resin composition was diluted with 1,2-bis (2-methoxyethoxy) ethane to obtain a thermosetting resin composition solution having a nonvolatile content of 50% by weight. The following evaluation was performed using this solution. The evaluation results are shown in Table 2.

※１：旭化成ケミカルズ製ＨＤＩ系ブロックイソシアネート、ＮＣＯ当量６３８ｇ/ｅｑ
※２：旭化成ケミカルズ製ＨＤＩ系ブロックイソシアネート、ＮＣＯ当量７００ｇ/ｅｑ
※３：旭化成ケミカルズ製ＨＤＩ系ブロックイソシアネート、ＮＣＯ当量５２５ｇ/ｅｑ
※４：旭化成ケミカルズ製Ｃ５／Ｃ６系コポリマータイプポリカーボネートジオール、Ｍｎ：２０００、水酸基当量９８６ｇ／ｅｑ
※５：大日本インキ製フェノールノボラック型エポキシ樹脂、エポキシ当量１８０ｇ／ｅｑ
（比較例１）
合成例１のジアミン末端イミドオリゴマーを用いない以外は実施例２と同様の方法で熱硬化性樹脂組成物を調合して物性評価を実施した。

* 1: HDI block isocyanate manufactured by Asahi Kasei Chemicals, NCO equivalent 638 g / eq
* 2: HDI block isocyanate manufactured by Asahi Kasei Chemicals, NCO equivalent 700g / eq
* 3: HDI block isocyanate manufactured by Asahi Kasei Chemicals, NCO equivalent 525g / eq
* 4: C5 / C6 copolymer type polycarbonate diol manufactured by Asahi Kasei Chemicals, Mn: 2000, hydroxyl equivalent 986 g / eq
* 5: Dainippon Ink's phenol novolac epoxy resin, epoxy equivalent 180g / eq
(Comparative Example 1)
A thermosetting resin composition was prepared in the same manner as in Example 2 except that the diamine-terminated imide oligomer of Synthesis Example 1 was not used, and physical properties were evaluated.

Claims (7)

  (A) A thermosetting resin composition comprising at least an amine-terminated imide oligomer having two or more amino groups per molecule at the end of the molecular chain, (b) a blocked isocyanate, and (c) a polyol compound.   The thermosetting resin composition according to claim 1, further comprising (d) a thermosetting resin.   The (a) amine-terminated imide oligomer uses at least tetracarboxylic dianhydride and diamine as raw materials, and the ratio expressed by the number of moles of raw material tetracarboxylic dianhydride / number of moles of raw material diamine is 0.00. The thermosetting resin composition according to claim 1, which is 01 to 0.99.   When the molar ratio of (a) amine-terminated imide oligomer, (b) blocked isocyanate, and (c) polyol compound is (a) being 1 mol, (b) is 0.1 to 10 mol, (c ) In a range of 0.1 to 10 mol, the thermosetting resin composition according to any one of claims 1 to 3.   The blending ratio of the (d) thermosetting resin includes 1 to 50 parts by weight when the total weight of (a), (b), and (c) is 100 parts by weight. The thermosetting resin composition according to any one of claims 1 to 4.   The flexible printed wiring board which used the thermosetting resin composition of any one of Claims 1-5 as a coating | covering material.   The flexible printed wiring board according to claim 6, wherein the thermosetting resin composition is cured and coated at a temperature of 200 ° C. or lower when the thermosetting resin composition is used as a coating material.