JP2008197546A - New photosensitive resin composition, cured film and insulating film obtained from the same, and printed wiring board with insulating film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which exhibits high moisture-resistant insulation reliability when applied as a coating film on a surface of a printed wiring board, and to further provide a photosensitive resin composition which improves flexibility by using a urethane oligomer at the same time. <P>SOLUTION: The photosensitive resin composition comprises at least (A) a tetracarboxylic acid terminated siloxane imide oligomer freed of silicon-containing volatile portions under reduced pressure and heating, (B) a diamino compound, (C) a photosensitive resin, (D) a photopolymerization initiator and (E) a thermosetting resin. Moisture-resistant insulation reliability and flexibility are improved by this composition. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition using a polyimide resin from which silicon-based volatile components have been removed, which is the biggest problem of imide resins using siloxane diamine.

  Polyimide resins are used for electrical and electronic applications because of their excellent heat resistance, electrical insulation and chemical resistance, and excellent mechanical properties. For example, it is used to form insulating films and protective coatings on semiconductor devices, surface protective materials such as flexible circuit boards and integrated circuits, base resin, and fine circuit interlayer insulating films and protective films. . In particular, when used as a coating material for substrate wiring, a cover lay film obtained by applying an adhesive to a molded body such as a polyimide film or a liquid liquid cover coat ink composed of an epoxy resin or the like is used. Has been.

  However, as the liquid cover coat ink, a photosensitive cover coat ink (generally referred to as a solder resist) mainly composed of an epoxy resin or the like is used, but this ink is excellent in electrical insulation reliability as an insulating material. It is difficult to use for a flexible circuit board due to poor mechanical properties such as bending.

  In recent years, a liquid cover coat ink using a polyimide resin has been proposed.

  For example, a photosensitive resin composition containing a polyimide resin using siloxane diamine has been proposed (see, for example, Patent Documents 1 and 2).

Furthermore, a photosensitive resin composition or a plasma etching resist using a terminal half-esterified imidosiloxane oligomer has been proposed (see, for example, Patent Documents 3 to 6).
JP 9-100350 A JP 2002-162740 A JP 2000-212446 A JP 2001-89656 A JP 2001-125273 A JP 2001-215702 A

  However, in the photosensitive resin composition using the siloxane diamine of Patent Documents 1 to 6, the silicon-based volatile component contained in the siloxane diamine greatly affects the electrical insulation reliability. There was a problem that it could not be used in wiring board applications.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using the following photosensitive resin composition.

That is, the present invention
Containing at least (A) a terminal tetracarboxylic acid siloxane imide oligomer from which silicon-based volatile components have been removed under reduced pressure and heating, (B) a diamino compound, (C) a photosensitive resin, and (D) a photopolymerization initiator. It is the photosensitive resin composition characterized.

  The photosensitive resin composition further comprises (E) a thermosetting resin.

  The photosensitive resin composition according to claim 1, further comprising (F) a urethane oligomer.

Further, (A) a terminal tetracarboxylic acid siloxane imide oligomer from which silicon-based volatile components have been removed under reduced pressure and heating,
The following general formula (1)

（式中、Ｒ_１、Ｒ_２は炭素数１〜１２のアルキル基もしくは芳香族基であり、Ｒ_１、Ｒ_２は同一であっても異なっていても良い。ｍは１〜４０の整数、ｎは１〜２０の整数を示す。）
で示されるシロキサンジアミンと、
下記一般式（２）

(In the formula, R ₁ and R ₂ are an alkyl group having 1 to 12 carbon atoms or an aromatic group, and R ₁ and R ₂ may be the same or different. M is an integer of 1 to 40, n represents an integer of 1 to 20.)
A siloxane diamine represented by
The following general formula (2)

（式中、Ｒは４価の有機基を示す。）
で示されるテトラカルボン酸二無水物を、
モル比でシロキサンジアミンのモル数／テトラカルボン酸二無水物のモル数≦０.８０となるように反応した後に、減圧・加熱下でシリコン系揮発分を除去し水を反応させることにより得られることを特徴とする感光性樹脂組成物である。

(In the formula, R represents a tetravalent organic group.)
A tetracarboxylic dianhydride represented by
After reacting so that the molar ratio of siloxane diamine moles / tetracarboxylic dianhydride moles ≦ 0.80, it is obtained by removing silicon volatiles under reduced pressure and heating and reacting with water. It is the photosensitive resin composition characterized by the above-mentioned.

  Further, the (B) diamino compound is represented by the following general formula (3):

（式中、Ｒ’’は、２価の有機基である。）
で示される芳香族ジアミンであることを特徴とする感光性樹脂組成物である。

(In the formula, R ″ is a divalent organic group.)
It is the photosensitive resin composition characterized by the above-mentioned.

  The (C) photosensitive resin is a photosensitive resin composition having at least one unsaturated double bond in the molecule.

  Moreover, the said (E) thermosetting resin is an epoxy resin, It is the photosensitive resin composition characterized by the above-mentioned.

  The photosensitive resin composition is characterized in that the (F) urethane oligomer is a urethane oligomer obtained from a polyol, an isocyanate and an alcohol.

In addition, the component (A) and the component (B) in the photosensitive resin composition are as follows:
(A) the molar amount of the acid dianhydride of component (A),
(B) the molar amount of the siloxane diamine of component (A),
(C) When the molar amount of the diamine of component (B) is used, (a) / ((b) + (c)) is blended so as to be 0.80 or more and 1.20 or less. A photosensitive resin composition is preferably used.

Moreover, (A) component in the said photosensitive resin composition, (B) component, (C) component, and (D) component are as follows.
The component (C) is 10 to 200 parts by weight and the component (D) is 0.1 to 50 parts by weight with respect to 100 parts by weight of the solid content of the sum of the components (A) and (B). A photosensitive resin composition characterized by being blended is preferable.

  In addition, the blending ratio of the (E) thermosetting resin and (F) urethane oligomer is 100 parts by weight of the solid content in which the components (A), (B), (C) and (D) are combined. On the other hand, it is preferable that it is the photosensitive resin composition characterized by mix | blending so that (E) may be 0.5-100 weight part and (F) will be 0.1-50 weight part.

  Another invention of the present invention is a photosensitive resin composition solution obtained by dissolving a photosensitive resin composition in an organic solvent.

  Another invention of the present invention is a cured product obtained by curing a photosensitive resin composition.

  Another invention of the present invention is an insulating film obtained from a photosensitive resin composition.

  Another invention of the present invention is a printed wiring board with an insulating film obtained by coating a printed wiring board with a photosensitive resin composition.

  The photosensitive resin composition of the present invention is a photosensitive resin composition that can be cured at low temperature and exhibits various excellent properties when applied and molded on a wiring board.

  The constitution of the present invention consists of at least (A) a terminal tetracarboxylic acid siloxane imide oligomer from which silicon volatiles have been removed under reduced pressure and heating, (B) a diamino compound, (C) a photosensitive resin, and (D) a photopolymerization initiator. And (E) a photosensitive resin composition comprising a thermosetting resin.

  Each constituent material will be described.

<(A) Terminal tetracarboxylic acid siloxane imide oligomer>
The terminal tetracarboxylic acid siloxane imide oligomer is
The following general formula (1)

（式中、Ｒ_１、Ｒ_２は炭素数１〜１２のアルキル基もしくは芳香族基であり、Ｒ_１、Ｒ_２は同一であっても異なっていても良い。ｍは１〜４０の整数、ｎは１〜２０の整数を示す。）
で示されるシロキサンジアミンと、
下記一般式（２）

(In the formula, R ₁ and R ₂ are an alkyl group having 1 to 12 carbon atoms or an aromatic group, and R ₁ and R ₂ may be the same or different. M is an integer of 1 to 40, n represents an integer of 1 to 20.)
A siloxane diamine represented by
The following general formula (2)

（式中、Ｒは４価の有機基を示す。）
で示されるテトラカルボン酸二無水物及び水を、
モル比でシロキサンジアミンのモル数／テトラカルボン酸二無水物のモル数≦０.８０となるように反応して得られる、内部はイミド環を有しており、末端がカルボン酸のシロキサンイミドオリゴマーである。より具体的には、本願発明に好適に用いられるシロキサンジアミンとテトラカルボン酸二無水物のモル比（シロキサンジアミンのモル数／テトラカルボン酸二無水物）は、１未満、より好ましくは、０.２０以上０.８０以下であり、特に好ましくは０.２５以上０.７０以下である。尚、上記範囲に添加量を制御して反応させることで、末端テトラカルボン酸シロキサンイミドオリゴマーの分子量を最適な範囲に制御することができるので好ましい。０．８０より大きい場合には、オリゴマーの分子量が大きくなり感光性樹脂組成物に用いた場合に、現像することが困難になるので好ましくない。また、本願発明の末端テトラカルボン酸シロキサンイミドオリゴマーの合成の際には、水を反応させることが必須である。

(In the formula, R represents a tetravalent organic group.)
Tetracarboxylic dianhydride and water represented by
A siloxane imide oligomer having an imide ring inside and having a carboxylic acid at the end, obtained by reacting such that the molar ratio is the number of moles of siloxane diamine / number of moles of tetracarboxylic dianhydride ≦ 0.80 It is. More specifically, the molar ratio of siloxane diamine and tetracarboxylic dianhydride suitably used in the present invention (number of moles of siloxane diamine / tetracarboxylic dianhydride) is less than 1, more preferably, 0.0. It is 20 or more and 0.80 or less, and particularly preferably 0.25 or more and 0.70 or less. In addition, since the molecular weight of the terminal tetracarboxylic acid siloxane imide oligomer can be controlled to an optimum range by controlling the addition amount within the above range, it is preferable. When it is larger than 0.80, the molecular weight of the oligomer becomes large, and it becomes difficult to develop when used in the photosensitive resin composition, which is not preferable. In addition, when synthesizing the terminal tetracarboxylic acid siloxane imide oligomer of the present invention, it is essential to react water.

  Preferred are terminal tetracarboxylic acid siloxane imide oligomers having an average molecular weight (weight average molecular weight in terms of polyethylene glycol) of 20,000 or less, particularly an average molecular weight of about 800 to 20,000.

  The reaction of the water will be described in detail. In the present invention, a terminal tetracarboxylic acid siloxane imide oligomer (internally has an imide ring and a terminal is a carboxylic acid) by reacting water at the time of imidation to open a terminal acid anhydride group. It is preferably used to obtain the following structure. However, after the imidation reaction, a method may be used in which water is reacted to open a terminal acid anhydride group to obtain a terminal tetracarboxylic acid siloxane imide oligomer.

  In addition, when the molar ratio of the tetracarboxylic dianhydride and the siloxane diamine in the present invention is less than 0.50, the tetracarboxylic acid in which the terminal anhydride group of the excess tetracarboxylic dianhydride is ring-opened coexists. However, in the present invention, there is no problem even if such tetracarboxylic acids coexist.

  Examples of the tetracarboxylic dianhydride used as a raw material for the above-mentioned (A) terminal tetracarboxylic acid siloxane imide oligomer include, for example, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride 3,3 ′, 4,4′-oxydiphthalic dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis (4-hydroxy Phenyl) propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4 '-Biphenyltetracarboxylic dianhydride, 2,3,3', 4-biphenyltetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3- It can be used tetracarboxylic acid dianhydride such as cyclohexene-1,2-dicarboxylic anhydride.

  Particularly preferably, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 In addition to improving the solubility of terminal tetracarboxylic acid siloxane imide oligomers obtained by using ', 4,4'-oxydiphthalic dianhydride in organic solvents, and improving the chemical resistance of polyimide resins Is preferable.

  It is particularly preferable to use 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride from the viewpoint of compatibility with a photosensitive resin or the like.

  The siloxane diamine used in the present invention is represented by the following general formula (1).

（式中、Ｒ_１、Ｒ_２は炭素数１〜１２のアルキル基もしくは芳香族基であり、Ｒ_１、Ｒ_２は同一であっても異なっていても良い。ｍは１〜４０の整数、ｎは１〜２０の整数を示す。）
で表されるシロキサンジアミン用いることが好ましく、
特に本願発明に用いられるシロキサンジアミンの構造は、Ｒ_１、Ｒ_２がメチル基、エチル基またはフェニル基であって、ｍは１〜４０の整数、ｎが２以上の整数であるものが好ましく用いられる。

(In the formula, R ₁ and R ₂ are an alkyl group having 1 to 12 carbon atoms or an aromatic group, and R ₁ and R ₂ may be the same or different. M is an integer of 1 to 40, n represents an integer of 1 to 20.)
It is preferable to use a siloxane diamine represented by
In particular, the structure of the siloxane diamine used in the present invention is preferably such that R ₁ and R ₂ are a methyl group, an ethyl group or a phenyl group, m is an integer of 1 to 40, and n is an integer of 2 or more. It is done.

Particularly preferably, R ₁ and R ₂ are methyl groups, m is 1 to 20, n is 3 siloxane diamine, or R ₁ and R ₂ are methyl groups or phenyl groups, and n = 3, m A siloxane diamine of 9 to 12 is preferably used. By using this diamine, the imidization temperature can be lowered and the electrical insulation reliability and the like of the polyimide resin can be improved.

  As a method for producing a terminal tetracarboxylic acid siloxane imide oligomer from which silicon-based volatile components have been removed under reduced pressure and heating, a general formula (1) is used in a solution in which tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent. A polyamic acid solution is prepared by adding and reacting with the siloxane diamine shown in FIG. This polyamic acid solution is imidized while removing the silicon-based volatiles by proceeding with the imidization reaction while removing the solvent under reduced pressure and heating so that the final heating temperature is 170 ° C. or higher and 250 ° C. or lower. The degree of vacuum at this time is preferably 50 mTorr or less. When the degree of vacuum is high, it is preferable because the solvent removal rate is increased and silicon volatiles can be efficiently removed.

  The organic solvent used in the above reaction is preferably a solvent having a boiling point lower than the final heating temperature and a high solubility of polyamic acid obtained by reacting tetracarboxylic dianhydride and siloxane diamine. As a preferable solvent, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, and acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide are preferably used.

  It was revealed that silicon-based volatile components can be efficiently removed by adopting a method of removing a solvent while imidizing in a vacuum oven. In the conventional method of vacuum distillation of siloxane diamine, if the heating temperature is too high, there is a problem that the siloxane diamine deteriorates by oxidation or a side reaction product is generated before the silicon-based volatilization is removed. However, it has become clear that the silicon-based volatile matter can be efficiently removed by employing the method of the present invention.

  In addition, the amount of water to be reacted is 2.0 to 300 times, more preferably 2.0 to 200 times the molar amount of tetracarboxylic dianhydride used. It is preferable to ring. It is preferable to include a large amount of water. However, there is no problem outside the above range depending on the reaction method. It is preferable to select an optimal amount as appropriate.

<(B) Diamino Compound>
In this invention, the (B) diamino compound is an aromatic diamine represented by the general formula (3).

（式中、Ｒ’’は、２価の有機基である。）
上記ジアミノ化合物の中で、より具体的には、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、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.)
Among the diamino compounds, more specifically, 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-amino) Phenyl) sulfoxide, bis (3-aminophenyl) sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3,4'-diaminobenzophenone, 4,4'-diamino Benzophenone, 3,3′-diaminobenzophenone, 3,3 ′ -Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, bis [4- (3 -Aminophenoxy) phenyl] sulfoxide, bis [4- (aminophenoxy) phenyl] sulfoxide, (4-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′-diaminobenz Anilide, 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- Aminophenoxyphenyl)] [4- (3-aminophenoxyphenyl)] ethane, 1,2-bis [4- (3-aminophenoxy) fur Nyl] ethane, 1,2-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 -Aminophenoxypheny )]-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) glyco Rubis (4-aminobenzoate), trimethylene-bis (4-aminobenzoate), p-phenylene-bis (4-aminobenzoate), m-phenylene-bis (4-aminobenzoate), bisphenol A-bis (4-amino) Benzoate), 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- Ruboxyphenyl] 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 , Diaminophenols such as 3,5-diaminophenol, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, 4,4′- Hydroxybiphenyl compounds such as diamino-2,2′-dihydroxybiphenyl, 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxybiphenyl, 3,3′-diamino-4,4′-dihydroxy Dihydroxydiphenylmethanes such as diphenylmethane, 4,4′-diamino-3,3′-dihydroxydiphenylmethane, 4,4′-diamino-2,2′-dihydroxydiphenylmethane, 2,2-bis [3-amino-4-hydroxy Bis [hydroxyphenyl] propanes such as phenyl] propane and 2,2-bis [4-amino-3-hydroxyphenyl] propane Bis [hyhydroxyphenyl] hexafluoropropanes such as 2,2-bis [3-amino-4-hydroxyphenyl] hexafluoropropane, 2,2-bis [3-amino-4-hydroxyphenyl] hexafluoropropane, Hydroxydiphenyl ethers such as 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 4,4′-diamino-3,3′-dihydroxydiphenyl ether, 4,4′-diamino-2,2′-dihydroxydiphenyl ether, Dihydroxy such as 3,3′-diamino-4,4′-dihydroxydiphenyl sulfone, 4,4′-diamino-3,3′-dihydroxydiphenyl sulfone, 4,4′-diamino-2,2′-dihydroxydiphenyl sulfone Diphenyl sulfones, 3,3′-diamino-4,4′-dihydro Dihydroxydiphenyl sulfides such as sidiphenyl sulfide, 4,4′-diamino-3,3′-dihydroxydiphenyl sulfide, 4,4′-diamino-2,2′-dihydroxydiphenyl sulfide, 3,3′-diamino-4 , 4'-dihydroxydiphenyl sulfoxide, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfoxide, dihydroxydiphenyl sulfoxides such as 4,4'-diamino-2,2'-dihydroxydiphenyl sulfoxide, 2,2- Bis [(hydroxyphenyl) phenyl] alkane compounds such as bis [4- (4-amino-3-hydroxyphenoxy) phenyl] propane, 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl, etc. Bis (hydroxyphenoxy) biphenyl compounds, 2,2 Bis [(hydroxyphenoxy) phenyl] sulfone compounds such as bis [4- (4-amino-3-hydroxyphenoxy) phenyl] sulfone, 4,4′-diamino-3,3′-dihydroxydiphenylmethane, 4,4 ′ -Bis such as diamino-2,2'-dihydroxydiphenylmethane, 2,2-bis [3-amino-4-carboxyphenyl] propane, 4,4'-bis (4-amino-3-hydroxyphenoxy) biphenyl (Hydroxyphenoxy) biphenyl compounds can be mentioned.

  In particular, diamines that can be suitably used in the photosensitive resin composition of the present invention include m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, bis (3-aminophenyl) sulfone, and bis (4-aminophenyl). Sulfone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] Sulfone, bis [4- (3-amino Enoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-amino) Phenoxy) 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 -Aminopheno B) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 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- Aminobenzoate), trimethylene-bis (4-aminobenzoate), p-phenylene-bis (4-aminobenzoate), m-phenylene-bis (4-aminobenzoate), bisphenol A-bis (4-aminobenzoate) are preferred. Used for. It is preferable to use the aromatic diamine because the heat resistance of the photosensitive resin composition is improved.

The compounding amount of the diamino compound in the present invention is such that (A) component and (B) component in the photosensitive resin composition are:
(A) the molar amount of the acid dianhydride of component (A),
(B) the molar amount of the siloxane diamine of component (A),
(C) It is preferable that (a) / ((b) + (c)) is blended so as to be 0.80 or more and 1.20 or less when the molar amount of the component (B) diamine is used. .

  Within the above range, the imidization reaction of the cured film of the photosensitive resin composition is likely to proceed, and a high molecular weight polyimide resin can be obtained.

<(C) Photosensitive resin>
The photosensitive resin (C) in the present invention is a resin that is polymerized by radicals generated by light or heat. More preferred is a resin having at least one unsaturated double bond. Furthermore, the unsaturated double bond is preferably an acrylic group (CH2 = CH-group), a methacryloyl group (CH = C (CH3) -group) or a vinyl group (-CH = CH-group). .

  For example, bisphenol F EO modified (n = 2-50) diacrylate, bisphenol A EO modified (n = 2-50) diacrylate, bisphenol S EO modified (n = 2-50) diacrylate, bisphenol F EO modified (n = 2-50) dimethacrylate, bisphenol A EO modified (n = 2-50) dimethacrylate, bisphenol S EO modified (n = 2-50) dimethacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, Ethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tetramethylolpropane tetraacrylate Tetraethylene glycol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexamethacrylate, tetramethylol Propane tetramethacrylate, tetraethylene glycol dimethacrylate, methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, β-methacryloyloxyethyl hydrogen phthalate, β-methacryloyloxyethyl hydrogen succinate, 3-chloro-2-hydroxypropyl methacrylate, Allyl methacrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy polyethylene glycol acrylate, β-acryloyloxyethyl hydrogen succinate, lauryl acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1 , 3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2-hydroxy-1,3-dimethacryloxypropane, 2,2-bis [4- ( Methacryloxyethoxy) phenyl] propane, 2,2-bi [4- (methacryloxy / diethoxy) phenyl] propane, 2,2-bis [4- (methacryloxy / polyethoxy) phenyl] propane, polyethylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2- Bis [4- (acryloxy-diethoxy) phenyl] propane, 2,2-bis [4- (acryloxy-polyethoxy) phenyl] propane, 2-hydroxy-1-acryloxy-3-methacryloxypropane, trimethylolpropane trimethacrylate, Tetramethylol methane triacrylate, tetramethylol methane tetraacrylate, methoxydipropylene glycol methacrylate, methoxytriethylene glycol acrylate, nonylphenol Xylethylene glycol acrylate, nonylphenoxy polypropylene glycol acrylate, 1-acryloyloxypropyl-2-phthalate, isostearyl acrylate, polyoxyethylene alkyl ether acrylate, nonylphenoxyethylene glycol acrylate, polypropylene glycol dimethacrylate, 1,4-butanediol di Methacrylate, 3-methyl-1,5-pentanediol dimethacrylate, 1,6-mexanediol dimethacrylate, 1,9-nonanediol methacrylate, 2,4-diethyl-1,5-pentanediol dimethacrylate, 1, 4-cyclohexanedimethanol dimethacrylate, dipropylene glycol diacrylate, tricyclodecane dimethanol dia Chryrate, 2,2-hydrogenated bis [4- (acryloxy polyethoxy) phenyl] propane, 2,2-bis [4- (acryloxy polypropoxy) phenyl] propane, 2,4-diethyl-1,5-pentane Diol diacrylate, ethoxylated totimethylolpropane triacrylate, propoxylated tomethylolpropane triacrylate, isocyanuric acid tri (ethane acrylate), pentathritol tetraacrylate, ethoxylated pentathritol tetraacrylate, propoxylated pentathritol tetraacrylate, Ditrimethylolpropane tetraacrylate, dipentaerythritol polyacrylate, triallyl isocyanurate, glycidyl methacrylate, glycidyl allyl ether, 1,3,5-triac Liloylhexahydro-s-triazine, triallyl 1,3,5-benzenecarboxylate, triallylamine, triallyl citrate, triallyl phosphate, allobarbital, diallylamine, diallyldimethylsilane, diallyl disulfide, diallyl ether, zalyl sialate Diallyl isophthalate, diallyl terephthalate, 1,3-dialyloxy-2-propanol, diallyl sulfide diallyl maleate, 4,4′-isopropylidene diphenol dimethacrylate, 4,4′-isopropylidene diphenol diacrylate, etc. Although preferable, it is not limited to these. In particular, the repeating unit of EO (ethylene oxide) contained in one molecule of diacrylate or methacrylate is preferably in the range of 2-50, more preferably 2-40. By using a product having an EO repeating unit in the range of 2 to 50, the solubility in an aqueous developer typified by an alkaline aqueous solution is improved, and the development time is shortened. Furthermore, it is difficult for stress to remain in the cured film obtained by curing the photosensitive resin composition. For example, among the printed wiring boards, when laminated on a flexible printed wiring board based on a polyimide resin, curling of the printed wiring board is prevented. Features such as being able to be suppressed.

  In addition, hydroxyl groups in the molecular structure skeleton such as 2-hydroxy-3-phenoxypropyl acrylate, monohydroxyethyl acrylate phthalate, ω-carboxy-polycaprolactone monoacrylate, acrylic acid dimer, pentaerythritol tri and tetraacrylate, Those having a carbonyl group are also preferably used.

  In addition, any photosensitive resin such as an epoxy-modified acrylic (methacrylic) resin, a urethane-modified acrylic (methacrylic) resin, or a polyester-modified acrylic (methacrylic) resin may be used.

  In addition, although it is also possible to use 1 type as a photosensitive resin, using 2 or more types together is preferable when improving the heat resistance of the cured film after photocuring.

<(D) Photopolymerization initiator>
(D) As the photopolymerization initiator, for example, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 4,4 ′, 4 ″ -tris (dimethylamino) triphenylmethane, 2,2′- Bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-diimidazole, acetophenone, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin Isopropyl ether, benzoin isobutyl ether, 2-t-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, methylanthraquinone, thioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 1-hydroxy Cyclohexyl phenyl ketone, diacetylbenzyl, benzyldimethylketa , Benzyldiethylketal, 2 (2′-furylethylidene) -4,6-bis (trichloromethyl) -S-triazine, 2 [2 ′ (5 ″ -methylfuryl) ethylidene] -4,6- Bis (trichloromethyl) -S-triazine, 2 (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,6-di (p-azidobenzal) -4-methylcyclohexanone, 4, 4'-diazidochalcone, di (tetraalkylammonium) -4,4'-diazidostilbene-2,2'-disulfonate, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1 -Hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -pheny ] -2-Hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethyl Amino-1- (4-morpholinophenyl) -butane-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl -Pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, bis (n5-2,4-cyclopentadiene- 1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 1,2-octa Dione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], iododium, (4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate (1 -), Ethyl-4-dimethylaminobenzoate, 2-ethylhexyl-4-dimethylaminobenzoate, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1 -(O-acetyloxyome) etc. are mentioned. The photopolymerization initiator is preferably selected as appropriate, and one or more types are preferably mixed and used.

In the present invention, the (A) component, (B) component, (C) component and (D) component in the photosensitive resin composition are:
The component (C) is 10 to 200 parts by weight and the component (D) is 0.1 to 50 parts by weight with respect to 100 parts by weight of the solid content of the sum of the components (A) and (B). It is preferable that it is blended.

The blending ratio is preferable because various properties (such as electrical insulation reliability) of the cured product and insulating film finally obtained are improved.
(C) When the photosensitive resin is less than the above range, the heat resistance of the cured film after photo-curing the photosensitive resin is lowered, and the contrast when exposed and developed is difficult to be obtained. For this reason, it is possible to set the resolution at the time of exposure / development to an optimal range by setting the value within the above range.

  (D) When there are few photoinitiators than the said range, the hardening reaction of the acrylic resin at the time of light irradiation hardly occurs, and hardening becomes inadequate in many cases. Moreover, when there is too much, adjustment of light irradiation amount becomes difficult and may be in an overexposure state. Therefore, in order to advance the photocuring reaction efficiently, it is preferable to adjust within the above range.

<(E) Thermosetting resin>
The thermosetting resin used in the photosensitive resin composition of the present invention is epoxy resin, isocyanate resin, block isocyanate resin, bismaleimide resin, bisallyl nadiimide resin, acrylic resin, methacrylic resin, hydrosilyl cured resin, allyl cured resin. Thermosetting resins such as unsaturated polyester resins; side chain reactive group type thermosetting resins having reactive groups such as allyl group, vinyl group, alkoxysilyl group, hydrosilyl group, etc. at the side chain or terminal of the polymer chain A polymer or the like can be used. 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 the naphthalene type tetrafunctional epoxy resin manufactured by Dainippon Ink Chemical Co., Ltd., the product name Epicron HP-7200 of the cyclopentadiene type epoxy resin, and the product of the phenol novolac type epoxy resin. The name Epicron N-740, Epicron EXA-7240, which is a high heat resistance epoxy resin, Epicron N-660, N-665, N-670, N-680, N-655-, which is a cresol novolac type polyfunctional epoxy resin EXP, trade name of phenol novolac type epoxy resin Epicron N-740, trade name of tetraphenylethane type epoxy resin, Epicron ETePE, trade name of triphenylmethane type epoxy resin, Epicron ETrPM, trade name of Japan Epoxy Resin Co., Ltd. Bisphenol A type epoxy resin such as Tote Kasei Co., Ltd., Bisphenol F type epoxy resin such as YDF-170, manufactured by Toto Kasei Co., Ltd., Epicoat 152, 154 manufactured by Japan Epoxy Resin Co., Ltd., Nippon Kayaku ( Phenol novolac type epoxy resin such as trade name EPPN-201 manufactured by Dow Chemical Co., Ltd., and trade name EOCN-125S, 103S, 104S manufactured by Nippon Kayaku Co., Ltd. Novolac type epoxy resin, trade name Epon 1031S manufactured by Japan Epoxy Resins Co., Ltd., trade name Araldite 0163 manufactured by Ciba Specialty Chemicals Co., Ltd., trade names Denacol EX-611, EX-614 manufactured by Nagase Chemical Co., Ltd. EX-614B, EX-622, EX-512, EX-521, EX 421, EX-411, EX-321 and other polyfunctional epoxy resins, Japan Epoxy Resin Co., Ltd. trade name Epicoat 604, Toto Kasei Co., Ltd. trade name YH434, Mitsubishi Gas Chemical Co., Ltd. trade name TETRAD-X, TERRAD-C, Nippon Kayaku Co., Ltd. trade name GAN, Sumitomo Chemical Co., Ltd. trade name ELM-120, etc. Amine type epoxy resin, Ciba Specialty Chemicals Co., Ltd. Heterocycle-containing epoxy resins such as the name Araldite PT810, and alicyclic epoxy resins such as ERL4234, 4299, 4221, and 4206 manufactured by UCC, and the like can be used alone or in combination of two or more.

  Among these epoxy resins, an epoxy resin having two or more epoxy groups in one molecule is particularly preferable from the viewpoint of improving the heat resistance, solvent resistance, chemical resistance and moisture resistance of the photosensitive resin composition.

  The epoxy resin used in the resin composition of the present invention is an epoxy compound having only one epoxy group in one molecule, such as n-butyl glycidyl ether, phenyl glycidyl ether, dibromophenyl glycidyl ether, dibromocresyl glycidyl ether, etc. There is. In addition, alicyclic epoxy compounds such as 3,4-epoxycyclohexyl and methyl (3,4-epoxycyclohexane) carboxylate can be used in combination.

  In the photosensitive resin composition of the present invention, as a curing agent for the photosensitive resin, for example, phenol resins such as phenol novolac type phenol resin, cresol novolac type phenol resin, naphthalene type phenol resin, amino resins, urea resins Melamine resins, dicyandiamide, dihydrazine compounds, imidazole compounds, Lewis acids, Bronsted acid salts, polymercaptan compounds, isocyanate and blocked isocyanate compounds, and the like can be used in combination.

  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. When an amino group is contained in the urethane resin, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2,4-diamino-6- [ It is preferable to use imidazoles such as 2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine.

<(F) Urethane oligomer>
The urethane oligomer in the present invention is a polyol represented by the following general formula (4):

（式中、Ｒ_３は、ポリカーボネート骨格及び／もしくはポリアルキレン骨格を示し、ｌは１〜２０の整数である。）
下記一般式（５）で示されるイソシアネート、

(In the formula, R ₃ represents a polycarbonate skeleton and / or a polyalkylene skeleton, and 1 is an integer of 1 to 20.)
Isocyanate represented by the following general formula (5),

（式中、Ｘ１は２価の有機基を示す。）
及び、下記一般式（６）で示されるアルコール性ＯＨを有するアルコールを、

(In the formula, X1 represents a divalent organic group.)
And an alcohol having an alcoholic OH represented by the following general formula (6):

（式中、Ｒ_４はアルキル基もしくは、アリレン基である。）
反応させてなるウレタンオリゴマーであることが好ましい。
上記反応は、一般式（４）のポリオールと一般式（５）のイソシアネートを、モル比（イソシアネートのモル量／ポリオールのモル量）を、１．２０以上２．２０以下の割合で反応させてイソシアネート基末端のウレタンオリゴマーを合成し、一般式（６）のアルコールを一般式（５）のイソシアネートのモル数以上のアルコールを反応させてウレタンオリゴマーを得ることができる。

(In the formula, R ₄ is an alkyl group or an arylene group.)
A urethane oligomer obtained by reaction is preferable.
In the above reaction, the polyol of the general formula (4) and the isocyanate of the general formula (5) are reacted in a molar ratio (molar amount of isocyanate / mole amount of polyol) at a ratio of 1.20 or more and 2.20 or less. A urethane oligomer can be obtained by synthesizing an isocyanate group-terminated urethane oligomer and reacting the alcohol of the general formula (6) with an alcohol having a molar number of the isocyanate of the general formula (5) or more.

  As the above polyol,

の式中のＲ３が、下記一般式群（１）より選ばれる２価の有機基である。

R3 in the formula is a divalent organic group selected from the following general formula group (1).

（式中、Ｚは−ＣＨ_２−、−ＣＨ_２Ｃ（ＣＨ_３）_２ＣＨ_２−、−ＣＨ_２ＣＨ（ＣＨ_３）ＣＨ_２−、−ＣＨ_２ＣＨ（ＣＨ_３）ＣＨ_２ＣＨ_２−、から選ばれる１種以上の基であり、ｑ、ｓは１〜３０の整数であり、ｒは１以上の整数である。ｔ1，ｔ２は１以上の整数である。）
例えば上記ポリオールの製品名としては、旭化成（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、２２０ＨＬとして市販されているのものが挙げられ、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。

(Wherein, Z is _{-CH 2 -, - CH 2 C} (CH 3) 2 CH 2 -, - CH 2 CH (CH 3) CH 2 -, - CH 2 CH (CH 3) CH 2 CH 2 -, And q and s are integers of 1 to 30, r is an integer of 1 or more, and t1 and t2 are integers of 1 or more.)
For example, as a product name of the above polyol, trade names of PCDL, T6002, T6001, T5652, T5651, T5650J, T4672, T4671, T4692, T4691, manufactured by Asahi Kasei Co., Ltd., trade names PLACEL and CD- The thing marketed as 205,205PL, 205HL, 210,210PL, 210HL, 220,220PL, 220HL is mentioned, These can be used individually or in combination of 2 or more types.

  Furthermore, as a product name of the said polyalkylene diol, Asahi Kasei Co., Ltd. brand name PTMG series, PTXG1000, PTXG1500, PTXG1800, FAS PTMG-1000, FAS PTMG-1800, FAS PTMG-2000 are mentioned.

  Use of polycarbonate diol is preferable because it can improve the adhesion to the substrate and improve chemical resistance. In addition, it is preferable to use an alkylene diol in combination because the cured product can be given flexibility.

  Examples of the isocyanate include diphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3'- or 5,2'- or 5,3'-. Or 6,2'- or 6,3'-dimethyldiphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3'- or 5,2 ' -Or 5,3'- or 6,2'- or 6,3'-diethyldiphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3 '-Or 5,2'- or 5,3'- or 6,2'- or 6,3'-dimethoxydiphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-3,3 '-Diisocyanate, diphe Lumethane-3,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, benzophenone-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6 -Use of aromatic diisocyanates such as diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, naphthalene-2,6-diisocyanate, 4,4 '-[2,2-bis (4-phenoxyphenyl) propane] diisocyanate It is preferable to increase the heat resistance. These can be used alone or in combination of two or more. Among these, for use in combination with the photosensitive resin composition, tolylene-2,6-diisocyanate, tolylene-2,4-diisocyanate, and 1,6-hexamethylene diisocyanate are preferably used.

  Moreover, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isopropanol, phenol etc. are used as alcohol which has alcoholic OH. In particular, methanol, ethanol, 2-propanol and the like are suitably used as alcohols that do not affect alkali developability.

  The reaction amount of the polyol and isocyanate in the above reaction is preferably a molar ratio (molar amount of isocyanate / mole amount of polyol), and is preferably reacted at a ratio of 1.20 or more and 2.20 or less. The reaction is preferably performed at a rate of 80 or more and 2.10 or less. By making it react in this range, since the molecular weight of the urethane oligomer of the isocyanate group terminal can be kept small, it is preferable.

  The alcohol is preferably reacted in an amount equal to or greater than the number of moles of the isocyanate. A particularly preferable reaction amount is preferably 1.5 to 5.0 times the number of moles of isocyanate. In this way, the terminal isocyanate group can be completely blocked by reacting the alcohol.

<(E) Mixing ratio of thermosetting resin and (F) urethane oligomer>
The blending ratio of (E) thermosetting resin and (F) urethane oligomer in the present invention is as follows: (A) terminal tetracarboxylic acid siloxane imide oligomer from which silicon-based volatile components are removed under reduced pressure and heating, (B) diamino compound, (E) is 0.5 to 100 parts by weight, and (F) is 0.1 to 50 parts by weight with respect to 100 parts by weight of the total solid content of (C) the photosensitive resin and (D) the photopolymerization initiator. It is preferable to mix | blend so that it may become. Particularly preferably, (E) is 1.0 to 50 parts by weight and (F) is 0.5 to 25% by weight. It is preferable to add it in the above range since the heat resistance, chemical resistance, electrical insulation reliability, and flexibility of the cured film of the photosensitive resin composition can be improved without affecting the photosensitive function.

<Method of mixing (A) to (E) and (F)>
The photosensitive resin composition of this invention is obtained by uniformly mixing the components (A) to (E) and (F). As a method of uniformly mixing, for example, a general kneading apparatus such as a three roll or bead mill apparatus may be used for mixing. Moreover, when the viscosity of a solution is low, you may mix using a general stirring apparatus.

<Other ingredients>
Various additives such as a flame retardant, an antifoaming agent, a coupling agent, a filler, an adhesion aid, a leveling agent, and a polymerization inhibitor can be added to the photosensitive resin composition of the present invention as necessary. . As the filler, a fine inorganic filler such as silica, mica, talc, barium sulfate, wollastonite, calcium carbonate, or a fine organic polymer filler may be contained. It is preferable to select the content appropriately.

<Photosensitive resin composition solution>
The photosensitive resin composition of the present invention is highly soluble in various organic solvents, such as sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, and formamide systems such as N, N-dimethylformamide and N, N-diethylformamide. Solvents, acetamide solvents such as N, N-dimethylacetamide, N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o-, m- or Phenolic solvents such as p-cresol, xylenol, halogenated phenol, catechol, or hexamethylphosphoramide, γ-butyrolactone, methylmonoglyme (1,2-dimethoxyethane), methyldiglyme (bis (2-methoxyether) ) Ether), Methyl Trigura (1,2-bis (2-methoxyethoxy) ethane), methyltetraglyme (bis [2- (2-methoxyethoxyethyl)] ether), ethyl monoglyme (1,2-diethoxyethane), ethyldigig Symmetric glycol diethers such as lime (bis (2-ethoxyethyl) ether), butyldiglyme (bis (2-butoxyethyl) ether), 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)) Acetates such as diethylene glycol 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 Methyl ether, 1,3-dioxolane, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, a solvent may be used ethers such as ethyl ether also ethylene glycol. If necessary, low-boiling hexane, acetone, toluene, xylene and the like can be used in combination.

  Among these, symmetric glycol diethers are particularly preferable because the solubility of the photosensitive resin composition is high.

  The photosensitive resin composition solution of the present invention comprises (A) component, (B) component, (C) component, (D) component, and (E) component with respect to 100 parts by weight of the total solid content, It is preferable that 10 to 100 parts by weight is blended.

  It is preferable to use a photosensitive resin composition solution within this range because the film reduction rate after drying becomes small.

<Usage method of photosensitive resin composition>
The pattern can be formed as follows, either directly with the photosensitive resin composition of the present invention or after preparing the photosensitive resin composition solution. First, the photosensitive resin composition is applied to a substrate and dried to remove the organic solvent. The substrate can be applied by screen printing, curtain roll, river roll, spray coating, spin coating using a spinner, or the like. Drying of the coating film (preferably thickness: 5 to 100 μm, particularly 10 to 100 μm) is performed at 120 ° C. or less, preferably 40 to 100 ° C. After drying, a negative photomask is placed on the dried coating film and irradiated with actinic rays such as ultraviolet rays, visible rays, and electron beams. Next, the relief pattern can be obtained by washing out the unexposed portion with a developer using various methods such as shower, paddle, immersion, or ultrasonic wave. Since the time until the pattern is exposed varies depending on the spraying pressure and flow velocity of the developing device and the temperature of the etching solution, it is preferable to find optimal apparatus conditions as appropriate.

  As the developer, an alkaline aqueous solution is preferably used. This developer may contain a water-soluble organic solvent such as methanol, ethanol, n-propanol, isopropanol, or N-methyl-2-pyrrolidone. Examples of the alkaline compound that gives the alkaline aqueous solution include hydroxides, carbonates, hydrogen carbonates, amine compounds, and the like of alkali metals, alkaline earth metals, or ammonium ions, specifically sodium hydroxide. , Potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium Hydroxide, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylethanolamine, triethanolamine, triisopropanolamine, trii Such as propylamine can be mentioned, the aqueous solution is a compound other than this as long as it exhibits basicity can also be naturally used. The concentration of the alkaline compound that can be suitably used in the development step of the photosensitive resin composition of the present invention is preferably 0.01 to 20% by weight, particularly preferably 0.02 to 10% by weight. Further, the temperature of the developer depends on the composition of the photosensitive resin composition and the composition of the alkali developer, and is generally 0 ° C. or higher and 80 ° C. or lower, more generally 10 ° C. or higher and 60 ° C. or lower. Is preferably used.

  The relief pattern formed by the development process is rinsed to remove unnecessary residues. Examples of the rinsing liquid include water and acidic aqueous solutions.

Next, a cured film rich in heat resistance can be obtained by imidizing the terminal carboxylic acid siloxane imide oligomer and the diamino compound by performing a heat treatment. Although a cured film is determined in consideration of wiring thickness etc., it is preferable that thickness is about 2-50 micrometers. It is desired that the final curing temperature at this time can be imidized by heating at a low temperature for the purpose of preventing oxidation of the wiring and the like and not reducing the adhesion between the wiring and the substrate.
The imidization temperature applied at this time is preferably 100 ° C. or higher and 250 ° C. or lower, more preferably 120 ° C. or higher and 200 ° C. or lower, and particularly preferably 130 ° C. or higher and 190 ° C. or lower. If the final heating temperature is high, the wiring is oxidatively deteriorated, which is not preferable.

  A pattern comprising a cured film formed from the photosensitive resin composition of the present invention is excellent in heat resistance, electrical and mechanical properties, and particularly excellent in flexibility. For example, the insulating film of the present invention preferably has a thickness of about 2 to 50 μm and a resolution of at least 10 μm after photocuring, particularly a resolution of about 10 to 1000 μm. Therefore, the insulating film of the present invention is particularly suitable as an insulating material for a high-density flexible substrate. Furthermore, it is used for various photo-curing wiring coating protective agents, photosensitive heat-resistant adhesives, electric wire / cable insulation coatings, and the like.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

(Synthesis Example 1)
200 g (0.384 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride (hereinafter abbreviated as BPADA) was dispersed in 200 g of N, N-dimethylformamide and heated to 80 ° C. Kept. 128 g (0) of siloxane diamine (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name KF8010, molecular weight 830, R ₁ and R ₂ in the general formula (1) are methyl groups, n = 3, m = 6 to 11). 154 mol), and stirred uniformly for 30 minutes. Next, the mixture was heated to 140 ° C. and stirred uniformly for 1 hour to completely dissolve it. Next, the reaction solution was transferred to a vat coated with fluororesin, heated in a vacuum oven from 30 ° C. to 210 ° C. over 2 hours, and maintained at 210 ° C. for 5 hours. During drying, N, N-dimethylformamide, water and silicon-based volatiles were removed. Next, the taken-out resin was dissolved in 140 g of 1,2-bis (2-methoxyethoxy) ethane, heated again to 140 ° C., cooled to 80 ° C., and 27.7 g (1.54 mol) of water was added. . After the charging, the mixture was heated and refluxed for 5 hours. Thus, the terminal tetracarboxylic acid siloxane imide oligomer solution containing the terminal tetracarboxylic acid siloxane imide oligomer was obtained. This terminal tetracarboxylic acid siloxane imide oligomer is abbreviated as resin A.

(Synthesis Example 2)
200 g (0.384 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride (hereinafter abbreviated as BPADA) was converted to 140 g of 1,2-bis (2-methoxyethoxy) ethane. Dispersed and kept at 80 ° C. 128 g (0) of siloxane diamine (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name KF8010, molecular weight 830, R ₁ and R ₂ in the general formula (1) are methyl groups, n = 3, m = 6 to 11). 154 mol), and stirred uniformly for 30 minutes. Next, the mixture was heated to 140 ° C. and stirred uniformly for 1 hour, then heated to 180 ° C. and heated to reflux for 3 hours to carry out an imidization reaction. Next, the mixture was cooled to 80 ° C., 27.7 g (1.54 mol) of water was added, and the mixture was heated to reflux for 5 hours. Thus, the terminal tetracarboxylic acid siloxane imide oligomer solution containing the terminal tetracarboxylic acid siloxane imide oligomer was obtained. This terminal tetracarboxylic acid siloxane imide oligomer is abbreviated as resin B.

(Synthesis Example 3)
Polyol (manufactured by Asahi Kasei Corporation PTXG-1800: molecular weight 1800, R ₃ in the general formula (3) is a divalent organic group represented by the following general formula (7), where t ₁ and t ₂ are (0.100 mol) is dissolved in 1,2-bis (2-methoxyethoxy) ethane, and tolylene diisocyanate (toluene-2,4-diisocyanate 80% and toluene-2,6- A mixture of 20% diisocyanate) (0.200 mol) was reacted at 80 ° C. for 5 hours, then cooled and reacted with 0.200 mol of methanol to synthesize a urethane oligomer. The urethane oligomer was synthesized by reacting so that the solid content concentration of the urethane oligomer was 50% by weight. This urethane oligomer is abbreviated as Resin C.

（実施例１）
合成例１で得られた末端テトラカルボン酸シロキサンイミドオリゴマーにジアミノ化合物、感光性樹脂、光重合開始剤、熱硬化性樹脂、有機溶剤を表１記載の割合で添加して感光性樹脂組成物溶液を作製した。
感光性樹脂組成物ははじめに一般的な攪拌翼のついた攪拌装置で混合し、その溶液を３本ロールミルで２回パスし均一な溶液とした。グラインドメーターにて粒子径を測定したところ、いずれも１０μｍ以下であった。混合溶液を脱泡装置で溶液中の泡を完全に脱泡して下記評価を実施した。

(Example 1)
A diamino compound, a photosensitive resin, a photopolymerization initiator, a thermosetting resin, and an organic solvent are added to the terminal tetracarboxylic acid siloxane imide oligomer obtained in Synthesis Example 1 in the proportions shown in Table 1, and the photosensitive resin composition solution is added. Was made.
The photosensitive resin composition was first mixed with a general stirring device equipped with a stirring blade, and the solution was passed twice with a three-roll mill to obtain a uniform solution. When the particle size was measured with a grindometer, all were 10 μm or less. The following evaluation was carried out by completely defoaming the foam in the solution with a defoaming device.

  The evaluation results are shown in Table 2.

(Moisture resistance)
A comb-shaped pattern of line width / space width = 25 μm / 25 μm on a flexible copper-laminated laminate (copper foil thickness 9 μm, polyimide film is Apical 25 NPI manufactured by Kaneka Co., Ltd., copper foil is bonded with polyimide adhesive) After being prepared and immersed in a 10% by volume sulfuric acid aqueous solution for 1 minute, the surface of the copper foil was treated by washing with pure water.

Thereafter, the photosensitive resin composition solution was cast and applied onto the comb pattern using a Baker type applicator so that the final dry thickness was 25 μm, and dried at 80 ° C. for 20 minutes. A negative photomask capable of completely exposing the comb-shaped electrode portion was placed and exposed to ultraviolet light at 300 mJ / cm ² in a nitrogen atmosphere for exposure. This photosensitive film was subjected to spray development for 30 seconds at a discharge pressure of 1.0 kgf / mm ² using a solution obtained by heating a 0.2 wt% sodium carbonate aqueous solution to 30 ° C. After development, the film was thoroughly washed with pure water, and then dried by heating in an oven at 170 ° C. for 60 minutes to prepare a cured film of the photosensitive resin composition.

A cured film of the photosensitive resin composition was prepared on the comb pattern by the same method as the method of preparing the cured film on the polyimide film, and the test piece was adjusted. A 100 V direct current was applied to both terminal portions of the test piece in an environmental test machine at 85 ° C. and 85% RH, and the insulation resistance value and occurrence of migration after 100 hours were observed. The case where migration did not occur was marked as ◯, and the case where migration occurred was marked as x. In addition, the measurement lower limit of the apparatus is 1.0 × 10 ³ Ω.

(Preparation of coating film for evaluating various physical properties)
The above photosensitive resin composition was cast and applied to an area of 100 mm × 100 mm on a 75 μm polyimide film (manufactured by Kaneka Corporation: trade name 75 NPI) using a Baker type applicator so that the final dry thickness was 25 μm. And dried at 80 ° C. for 20 minutes. Ten sheets of this dry film were prepared. Nine sheets have a negative photomask with a completely transparent area of 50 mm × 50 mm, and one sheet has a negative photomask with a line width / space width = 100 μm / 100 μm (30 mm length × 100 μm width). A photomask with 10 lines left) was placed and exposed to UV light at 300 mJ / cm ² in a nitrogen atmosphere. This photosensitive film was subjected to spray development for 30 seconds at a discharge pressure of 1.0 kgf / mm 2 using a solution obtained by heating a 1.0 wt% sodium carbonate aqueous solution to 30 ° C. After development, the film was thoroughly washed with pure water, and then dried by heating in an oven at 170 ° C. for 60 minutes to prepare a cured film of the photosensitive resin composition.

(Photosensitivity evaluation)
Evaluation of the photosensitivity of the photosensitive resin composition is based on the above (manufacture of coating film for evaluating various physical properties), negative photomask (line of 30 mm length × 100 μm width) of line width / space width = 100 μm / 100 μm. The surface of the cured film obtained by placing 10 remaining photomasks) was observed and judged.
◯: Clear line width / space width = 100 / 100μm photosensitive pattern is drawn on the polyimide film surface, no line shaking occurs due to peeling of the line part, and there is no residual residue in the space part thing.
Δ: A clear photosensitive pattern having a line width / space width = 100/100 μm is drawn, and the line portion is shaken due to peeling, but there is no undissolved residue in the space portion.
X: A clear line width / space width = 100/100 μm photosensitive pattern was not drawn, the line portion was peeled off, and a dissolution residue was generated in the space portion.

(Adhesion)
The adhesive strength of the cured film of the photosensitive resin composition of 50 mm × 50 mm obtained in the above item (preparation of coating film for evaluating various physical properties) was evaluated by a cross-cut tape method according to JIS K5400.
○ The one that does not peel off by the cross-cut tape method
△, if 95% or more of the cells remain
The case where the residual amount of the mesh was less than 80% was evaluated as x.

(Solvent resistance)
The solvent resistance of the cured film of the photosensitive resin composition of 50 mm × 50 mm obtained in the above item (Preparation of coating film for evaluating various physical properties) was evaluated. In the evaluation method, the film was dipped in isopropanol at 25 ° C. for 15 minutes and then air-dried, and the state of the film surface was observed.
○: There is no abnormality in the coating film.
X: Abnormality occurs in the coating film.

(Acid resistance)
The acid resistance of the cured film of the photosensitive resin composition of 50 mm × 50 mm obtained in the above item (Preparation of coating film for evaluating various physical properties) was evaluated. In the evaluation method, the film was immersed in a 2N hydrochloric acid solution at 25 ° C. for 15 minutes and then air-dried, and the state of the film surface was observed.
○: The coating film has no abnormality (whitening or peeling).
X: Abnormality (whitening or peeling) occurs in the coating film.

(Alkali resistance)
The alkali resistance of the cured film of the photosensitive resin composition of 50 mm × 50 mm obtained in the above item (Preparation of coating film for evaluating various physical properties) was evaluated. In the evaluation method, the film was dipped in a 2N sodium hydroxide solution at 25 ° C. for 15 minutes and then air-dried, and the state of the film surface was observed.
○: There is no abnormality (whitening or peeling) in the coating film.
X: Abnormality (whitening or peeling) occurs in the coating film.

(Solder heat resistance)
Curing of the photosensitive resin composition in a solder bath in which the coating film of the photosensitive resin composition of 50 mm × 50 mm obtained in the above item (Preparation of coating film for evaluating various physical properties) is completely dissolved at 260 ° C. It floated so that the surface on which the film was applied was in contact, and was pulled up 10 seconds later. The operation was performed three times, and the adhesive strength of the cured film was evaluated by a cross-cut tape method according to JIS K5400.
○ The one that does not peel off by the cross-cut tape method
△, when 95% or more of the cells remain
The case where the residual amount of the mesh was less than 80% was evaluated as x.

(Example 2)
Photosensitivity is obtained by adding a urethane oligomer to the terminal tetracarboxylic acid siloxane imide oligomer obtained in Synthesis Example 1 in addition to a diamino compound, a photosensitive resin, a photopolymerization initiator, a thermosetting resin, and an organic solvent in the proportions shown in Table 1. A conductive resin composition solution was prepared.
First, the photosensitive resin composition solution was mixed with a general stirring device with a stirring blade, and the solution was passed twice with a three-roll mill to obtain a uniform solution. When the particle size was measured with a grindometer, all were 10 μm or less. The mixed solution was subjected to the same evaluation as in Example 1 by completely defoaming bubbles in the solution with a defoaming apparatus. In addition to the evaluation items of Example 1, the following flexibility test was also conducted. The evaluation results are shown in Table 2.

(Flexibility)
Photosensitive resin on the surface of a 25 μm-thick polyimide film (Apical 25NPI manufactured by Kaneka Corporation) in the same manner as the method for preparing a cured film of 50 mm × 50 mm obtained in the above item (Preparation of coating film for evaluating various physical properties) A cured film laminated film of the composition was prepared. The cured film laminated film was cut into a 30 mm × 10 mm strip, 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.

(Reference Example 1)
A diamino compound, a photosensitive resin, a photopolymerization initiator, a thermosetting resin, and an organic solvent are added to the terminal tetracarboxylic acid siloxane imide oligomer obtained in Synthesis Example 2 in the proportions shown in Table 1, and the photosensitive resin composition solution is added. Was made.
The photosensitive resin composition was first mixed with a general stirring device equipped with a stirring blade, and the solution was passed twice with a three-roll mill to obtain a uniform solution. When the particle size was measured with a grindometer, all were 10 μm or less. The following evaluation was carried out by completely defoaming the foam in the solution with a defoaming device.

  The evaluation results are shown in Table 2.

Claims (14)

  At least (A) a terminal tetracarboxylic acid siloxane imide oligomer from which silicon-based volatiles have been removed under reduced pressure and heating, (B) a diamino compound, (C) a photosensitive resin, (D) a photopolymerization initiator, and (E) heat A photosensitive resin composition comprising a curable resin.   The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition further contains (F) a urethane oligomer. The terminal tetracarboxylic acid siloxane imide oligomer from which (A) the silicon-based volatile component has been removed under reduced pressure and heating,
The following general formula (1)

(In the formula, R ₁ and R ₂ are an alkyl group having 1 to 12 carbon atoms or an aromatic group, and R ₁ and R ₂ may be the same or different. M is an integer of 1 to 40, n represents an integer of 1 to 20.)
A siloxane diamine represented by
The following general formula (2)

(In the formula, R represents a tetravalent organic group.)
A tetracarboxylic dianhydride represented by
After reacting so that the molar ratio of siloxane diamine moles / tetracarboxylic dianhydride moles ≦ 0.80, it is obtained by removing silicon volatiles under reduced pressure and heating and reacting with water. The photosensitive resin composition of Claim 1 or 2 characterized by the above-mentioned. The (B) diamino compound is represented by the following general formula (3):

(In the formula, R ″ is a divalent organic group.)
The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is an aromatic diamine represented by the formula:   The photosensitive resin composition according to claim 1, wherein the (C) photosensitive resin has at least one unsaturated double bond in the molecule.   The said (E) thermosetting resin is an epoxy resin, The photosensitive resin composition of any one of Claims 1-5 characterized by the above-mentioned.   The said (F) urethane oligomer is a urethane oligomer obtained from a polyol, isocyanate, and alcohol, The photosensitive resin composition of any one of Claims 2-6 characterized by the above-mentioned. The component (A) and the component (B) in the photosensitive resin composition are
(A) the molar amount of the acid dianhydride of component (A),
(B) the molar amount of the siloxane diamine of component (A),
(C) When the molar amount of the diamine of component (B) is used, (a) / ((b) + (c)) is blended so as to be 0.80 or more and 1.20 or less. The photosensitive resin composition according to any one of claims 1 to 7. The component (A), the component (B), the component (C) and the component (D) in the photosensitive resin composition are as follows:
The component (C) is 10 to 200 parts by weight and the component (D) is 0.1 to 50 parts by weight with respect to 100 parts by weight of the solid content of the sum of the components (A) and (B). It mix | blends, The photosensitive resin composition of any one of Claims 1-8 characterized by the above-mentioned.   The blending ratio of the (E) thermosetting resin and the (F) urethane oligomer is based on 100 parts by weight of the solid content of the sum of the component (A), the component (B), the component (C), and the component (D). (E) is mix | blended so that it may become 0.5-100 weight part and (F) will be 0.1-50 weight part, It is any one of Claims 2-9 characterized by the above-mentioned. Photosensitive resin composition.   The photosensitive resin composition solution obtained by melt | dissolving the photosensitive resin composition of any one of Claims 1-10 in the organic solvent.   Hardened | cured material obtained by hardening the photosensitive resin composition of any one of Claims 1-10.   The insulating film obtained from the photosensitive resin composition of any one of Claims 1-10.   The printed wiring board with an insulating film which coat | covered the photosensitive resin composition of any one of Claims 1-10 on the printed wiring board.