JP2008261921A - 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 has good photosensitive function and basic properties as an electrical insulating material and ensures small warpage of a flexible printed wiring board when applied on one surface of a soft substrate of the printed wiring board or the like. <P>SOLUTION: The photosensitive resin composition includes at least (A) a siloxane imide oligomer terminated by a tetracarboxylic acid, (B) a diamino compound, (C) a photosensitive resin and (D) an oxime ester base photopolymerization initiator. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition which can be cured at low temperature and can be suitably used as an insulating material for electrical and electronic applications, and which can be developed with an alkaline aqueous solution, and a cured film, an insulating film and an insulating film obtained therefrom. The present invention relates to a printed wiring board with a film.

  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 coverlay film obtained by applying an adhesive to a molded body such as a polyimide film, or a liquid covercoat ink composed of an epoxy resin or the like has been used. It was.

  The cover lay film is obtained by applying an adhesive to a polyimide film, and has excellent various electrical characteristics and chemical resistance. However, in order to adapt to fine substrate wiring, the method of thermocompression bonding after fine processing of the coverlay film is taken, but there is a limit to the fine pattern, and a photosensitive function is required to perform finer processing. It has been.

  On the other hand, the liquid cover coat ink uses a photosensitive cover coat ink (generally also referred to as a solder resist) mainly composed of an epoxy resin or the like, and is excellent in fine workability because it has photosensitivity. However, this ink has excellent electrical insulation reliability as an insulating material, but has poor mechanical properties such as flexibility and is difficult to use for a flexible circuit board. In particular, there is a problem that the film is warped when applied to one side of a flexible and flexible film base material such as a polyimide film used for flexible printed wiring boards.

  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).

  Moreover, the photosensitive resin composition which consists of a polyamic-acid solution which is a precursor of a polyimide is proposed (for example, refer patent documents 3-4).

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 5 to 8).
JP 9-100350 A JP 2002-162740 A JP-A-2-50161 JP-A-2005-148611 JP 2000-212446 A JP 2001-89656 A JP 2001-125273 A JP 2001-215702 A

However, in the above Patent Documents 1 to 3, the polyimide type and its polyamic acid type cover coat ink have a high curing temperature, and the cured film has a high elastic modulus. There was a problem that the printed wiring board was warped when it was worked. Further, in Patent Document 4, in addition to the above problems, an acrylic resin is reacted with the side chain of the polyamic acid, and a high temperature (300 ° C. or higher) is required to remove the functional group. There was also a problem that it could not be used as an insulating protective film on the surface of a printed wiring board.
Moreover, when the terminal half-esterified imide siloxane oligomer described in Patent Documents 5 to 8 is used, the elastic modulus of the cured product of the terminal half-esterified imide siloxane oligomer is high, and warping is large when applied to the surface of a printed wiring board. It was a problem.

  In view of the above situation, an object of the present invention is a photosensitive resin composition having a good photosensitive function and basic characteristics as an electrically insulating material, and further, on one side of a soft substrate such as a flexible printed wiring board. An object of the present invention is to provide a photosensitive resin composition having a small warp of a printed wiring board when coated.

  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 includes at least (A) a terminal tetracarboxylic acid siloxane imide oligomer, (B) a diamino compound, (C) a photosensitive resin, and (D) an oxime ester photopolymerization start represented by the following general formula (1). It is a photosensitive resin composition characterized by containing an agent.

（式中、Ｒ_１、Ｒ_２は同一でも異なっていてもよく、炭素数が１〜６のアルキレン基である。）
また、前記感光性樹脂組成物が更に、（Ｅ）熱硬化性樹脂を含有することを特徴とする感光性樹脂組成物である。

(In formula, R < ₁ >, R < ₂ > may be same or different and is a C1-C6 alkylene group.)
The photosensitive resin composition further comprises (E) a thermosetting resin.

  The (A) terminal tetracarboxylic acid siloxane imide oligomer is a siloxane diamine represented by the following general formula (2):

（式中、Ｒ_３、Ｒ_４はそれぞれ同一でも異なっていてもよく、炭素数１〜１２のアルキル基もしくは芳香族基を示す。ｍは１〜４０の整数、ｎは１〜２０の整数を示す。）
下記一般式（３）で示されるテトラカルボン酸二無水物及び水を、

_(Wherein, R 3, _{R 4} may be different from each other in the same, integer .m 1 to 40 represents an alkyl group or an aromatic group having 1 to 12 carbon atoms, n represents an integer of from 1 to 20 Show.)
Tetracarboxylic dianhydride and water represented by the following general formula (3)

（式中、Ｒ_５は４価の有機基を示す。）
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ことを特徴とする感光性樹脂組成物である。

(In the formula, R ₅ represents a tetravalent organic group.)
It is a photosensitive resin composition obtained by reacting such that the molar ratio is the number of moles of siloxane diamine / the number of moles of tetracarboxylic dianhydride ≦ 0.80.

  The (B) diamino compound is a photosensitive resin composition characterized by using an aromatic diamine represented by the following general formula (4) as a raw material.

（式中、Ｒ_６は、２価の有機基である。）
また、前記、（Ｃ）感光性樹脂が、分子内に不飽和二重結合を少なくとも１つ有する感光性樹脂組成物である。

(In the formula, R ₆ is a divalent organic group.)
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.

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. The photosensitive resin composition.

  Further, the component (A), the component (B), the component (C), and the component (D) in the photosensitive resin composition have a solid content of 100 parts by weight, which is the sum of the components (A) and (B). On the other hand, the photosensitive resin composition is characterized in that the component (C) is blended so as to be 10 to 100 parts by weight and the component (D) is 0.1 to 50 parts by weight.

  Moreover, the blending ratio of the (E) thermosetting resin is 0.5 to 100 parts by weight based on the total solid content of the (A) component, (B) component, (C) component, and (D) component. It is a photosensitive resin composition, which is blended so as to be 100 parts by weight.

  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 film 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 having a good photosensitive function and basic characteristics as an electrically insulating material, and is further applied to one side of a soft substrate such as a flexible printed wiring board. It is a photosensitive resin composition with a small warp of a printed wiring board when processed.

  The composition of the present invention consists of at least (A) a terminal tetracarboxylic acid siloxane imide oligomer, (B) a diamino compound, (C) a photosensitive resin, and (D) an oxime ester photopolymerization represented by the following general formula (1). It is a photosensitive resin composition characterized by containing an initiator.

（式中、Ｒ_１、Ｒ_２は同一でも異なっていてもよく、炭素数が１〜６のアルキレン基である。）
それぞれの構成材料について説明を行う。

(In formula, R < ₁ >, R < ₂ > may be same or different and is a C1-C6 alkylene group.)
Each constituent material will be described.

<(A) Terminal tetracarboxylic acid siloxane imide oligomer>
The terminal tetracarboxylic acid siloxane imide oligomer of the present invention is an oligomer having a tetracarboxylic acid at the terminal, a siloxane structure inside, and an imide ring closed. Although it will not specifically limit if it is these structures, Preferably, the siloxane diamine shown by following General formula (2),

（式中、Ｒ_３、Ｒ_４はそれぞれ同一でも異なっていてもよく、炭素数１〜１２のアルキル基もしくは芳香族基を示す。ｍは１〜４０の整数、ｎは１〜２０の整数を示す。）
下記一般式（３）で示されるテトラカルボン酸二無水物及び水を、

_(Wherein, R 3, _{R 4} may be different from each other in the same, integer .m 1 to 40 represents an alkyl group or an aromatic group having 1 to 12 carbon atoms, n represents an integer of from 1 to 20 Show.)
Tetracarboxylic dianhydride and water represented by the following general formula (3)

（式中、Ｒ_５は４価の有機基を示す。）
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場合がある。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 ₅ represents a tetravalent organic group.)
The inside obtained by reacting so that the molar ratio of the number of moles of siloxane diamine / the number of moles of tetracarboxylic dianhydride ≦ 0.80 has an imide ring, and the terminal is a siloxane imide oligomer having a carboxylic acid. is there. More specifically, the molar ratio of siloxane diamine and tetracarboxylic dianhydride suitably used in the present invention is less than 1, more preferably 0.20 or more and 0.80 or less, and particularly preferably 0.8. It is 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. If the molecular weight is larger than 0.80, the molecular weight of the oligomer becomes large, and it may be difficult to develop when used in the photosensitive resin composition. 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.

  Furthermore, in the present invention, the terminal tetracarboxylic acid siloxane imide oligomer (with an imide ring inside and a terminal carboxyl group) is formed by reacting water during the imidation to open the terminal acid anhydride group. It is preferably used to obtain an acid 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.

  In particular, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride is most preferably used from the viewpoint of compatibility with a photosensitive resin or the like.

  The siloxane diamine used in the present invention is preferably a siloxane diamine represented by the following general formula (2),

（式中、Ｒ_３、Ｒ_４はそれぞれ同一でも異なっていてもよく、炭素数１〜１２のアルキル基もしくは芳香族基を示す。ｍは１〜４０の整数、ｎは１〜２０の整数を示す。）
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_３、Ｒ_４がメチル基、エチル基、フェニル基のいずれかであって、ｍは１〜４０、ｎが２以上であるものが好ましく用いられる。

_(Wherein, R 3, _{R 4} may be different from each other in the same, integer .m 1 to 40 represents an alkyl group or an aromatic group having 1 to 12 carbon atoms, n represents an integer of from 1 to 20 Show.)
In particular, the structure of the siloxane diamine used in the present invention is preferably one in which R ₃ and R ₄ are any one of a methyl group, an ethyl group, and a phenyl group, m is 1 to 40, and n is 2 or more. .

Particularly preferably, R ₃ and R ₄ are methyl groups, m is 1 to 20, n is 3 siloxane diamine, or R ₃ and R ₄ 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, the electrical insulation reliability of the polyimide resin can be improved, and good alkaline solution developability can be imparted.

  Various methods are mentioned as a manufacturing method of a terminal tetracarboxylic-acid siloxane imide oligomer. The typical method is illustrated below.

  Method 1: A polyamic acid solution is prepared by adding and reacting a siloxane diamine represented by the general formula (2) in a solution in which tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent. After the reaction of tetracarboxylic dianhydride and siloxane diamine is completed, the resulting polyamic acid solution is heated to 100 ° C. or higher and 300 ° C. or lower, more preferably 150 ° C. or higher and 250 ° C. or lower to perform dehydration and imidization Subsequently, the reaction solution is cooled to 150 ° C. or lower and water is added. More preferably, it is 20 degreeC or more and 150 degrees C or less, Most preferably, they are 40 degreeC or more and 100 degrees C or less. In the imidation, it can be removed from the reaction system while azeotropically boiling with a solvent such as toluene or hexane. The input amount of water is preferably larger than the molar amount of tetracarboxylic dianhydride used.

  In addition, it is preferable to use the solvent whose boiling point is 100 degreeC or more as a solvent used by this method. In addition, since the reaction time of each process changes with the raw material to be used, it is preferable to select suitably.

  Method 2: A polyamic acid solution is prepared by adding and reacting a siloxane diamine represented by the general formula (2) in a solution in which 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. Heat to 180 ° C. or less to imidize. Water is added to the solution that has undergone imidization, or the solution that has undergone imidization is poured into water to cause precipitation. The terminal tetracarboxylic acid siloxane imide oligomer can be obtained by precipitating, filtering and drying the precipitated particles. In addition, when it does not precipitate, it can manufacture by removing a solvent with a vacuum dryer etc.

  Method 3: A polyamic acid solution is prepared by adding and reacting a siloxane diamine represented by the general formula (2) in a solution in which tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent. The polyamic acid solution is placed in a vacuum reduced pressure dryer heated to 100 ° C. or more and 250 ° C. or less, and imidation is performed by drawing a vacuum while heating and drying. A terminal tetracarboxylic acid siloxane imide oligomer can be obtained by reacting this resin with water.

  The above method is preferably used. Regardless of the above method, any method can be used as long as it is a method capable of obtaining a terminal tetracarboxylic acid siloxane imide oligomer having an imide ring inside and a terminal carboxylic acid. There is no problem using it.

  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 open the 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.

Examples of the solvent used for the synthesis of the terminal tetracarboxylic acid siloxane imide oligomer include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, and formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide. Acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o-, m- or p -Phenol solvents such as cresol, xylenol, halogenated phenol, catechol, or hexamethylphosphoramide, γ-butyrolactone, methylmonoglyme (1,2-dimethoxyethane), methyldiglyme (bis (2-methoxyether) Ether), methyltriglyme (1,2-bis (2-methoxyethoxy) ethane), methyltetraglyme (bis [2- (2-methoxyethoxyethyl)] ether), ethyl monoglyme (1,2-diethoxy) Ethane), ethyl diglyme (bis (2-ethoxyethyl) ether), symmetric glycol diethers such as butyl diglyme (bis (2-butoxyethyl) ether), γ-butyrolactone and 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-butyl acetate) Xyloxy) ethyl)), 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 Acetates such as 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, 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 them, symmetric glycol diethers are particularly preferable because of high solubility of oligomers.

<(B) Diamino Compound>
In the present invention, the (B) diamino compound is a compound having two or more amino groups. Preferably, it is an aromatic diamine represented by the following general formula (4).

（式中、Ｒ_６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 ₆ 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. .

  By making it within the above range, the chain extension reaction of the terminal tetracarboxylic acid siloxane imide oligomer easily proceeds by the diamine compound, and it becomes easy to produce a high molecular weight polyimide resin in the photosensitive resin composition, and the photosensitive resin composition. This is preferable because the heat resistance, chemical resistance and flex resistance after curing of the resin are improved.

<(C) Photosensitive resin>
The photosensitive resin (C) in the present invention is a resin in which a chemical bond is formed by a photopolymerization initiator. Among these, a resin having at least one unsaturated double bond in the molecule is preferable. 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. In addition, stress hardly remains in the cured film obtained by curing the photosensitive resin composition. For example, among printed wiring boards, when laminated on a flexible printed wiring board based on a polyimide resin, the printed wiring board warps. Features such as being able to be suppressed.

  In particular, it is particularly preferable to use the EO-modified diacrylate or dimethacrylate together with an acrylic resin having 3 or more acryl groups or methacryl groups in order to improve developability. Ethoxylated isocyanuric acid EO modified trimethacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol Triacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ditrimethylol B bread tetraacrylate, ditrimethylolpropane tetraacrylate, propoxylated pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, acrylic resins such as dipentaerythritol hexaacrylate is preferably used.

  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.

<(D) Oxime ester photopolymerization initiator>
The (D) oxime ester photopolymerization initiator in the present invention is a compound represented by the following general formula (1).

（式中、Ｒ_１、Ｒ_２は同一でも異なっていてもよく、炭素数が１〜６のアルキレン基である。）
上記構造を有するオキシムエステル系光重合開始剤を用いることで驚くべきことに芳香族系化合物が多量に含まれる感光性樹脂組成物においても良好な感光性や解像性が発現することが分かった。

(In formula, R < ₁ >, R < ₂ > may be same or different and is a C1-C6 alkylene group.)
Surprisingly, it has been found that by using the oxime ester photopolymerization initiator having the above structure, good photosensitivity and resolution are exhibited even in a photosensitive resin composition containing a large amount of an aromatic compound. .

  Particularly, the blending amount of the component (D) in the photosensitive resin composition of the present invention is 0.1 to 50 parts by weight with respect to 100 parts by weight of the total solid content of the components (A) and (B). It is preferable that it is blended for efficiently photocuring the photosensitive resin composition. It is particularly preferable that the amount is 0.1 to 10 parts by weight. When the component (D) is less than the above range, the curing reaction of the acrylic resin at the time of light irradiation hardly occurs, and the curing becomes insufficient. In addition, when the amount is large, it is difficult to adjust the amount of light irradiation, and an overexposure state is obtained, and good resolution cannot be obtained. Therefore, in order to advance the photocuring reaction efficiently, it is preferable to adjust within the above range.

  Moreover, in this invention, although the said oxime ester system photoinitiator can be used independently, you may use together another photoinitiator. Examples of such a photopolymerization initiator include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 4,4 ′, 4 ″ -tris (dimethylamino) triphenylmethane, and 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, benzine Rudimethylketal, 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-hydride) Xyloxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl 2-dimethylamino-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 -Cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) thi Ni, 1,2-octanonedione, 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-carbazole -3-yl]-, 1- (O-acetyloxyome) and the like.

  Although the compounding quantity of the other photoinitiator used together with the said oxime ester system photopolymerization is not specifically limited, With respect to 100 weight part of solid content which totaled (A) component and (B) component, It is preferable that it is mix | blended so that it may be 0.1-50 weight part, It is preferable that it is mix | blended with 0.1-10 weight part especially preferably. If the other photopolymerization initiator used in combination with the oxime ester photopolymerization is less than the above range, the sensitization effect of the oxime ester photopolymerization initiator during light irradiation may be difficult to obtain, In many cases, the photopolymerization reaction may proceed excessively, and thus warpage after curing may increase.

<(E) Thermosetting resin>
The photosensitive resin composition of the present invention preferably further contains (E) a thermosetting resin in addition to the components (A) to (D). (E) It is preferable to contain a thermosetting resin since the heat resistance is further improved, and particularly the solder heat resistance is improved.

  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 Thermosetting resins such as resins and unsaturated polyester resins; side chain reactive group type thermosetting having reactive groups such as allyl group, vinyl group, alkoxysilyl group, hydrosilyl group at the side chain or terminal of the polymer chain 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.

  The amount of the thermosetting resin used in the present invention is such that the component (E) is 0.1 to 50 parts by weight with respect to 100 parts by weight of the solid content of the components (A) and (B). It is preferable to do. Particularly preferred is 1.0 to 30 parts by weight. It is preferable to add it in the above range since the heat resistance, chemical resistance and electrical insulation reliability of the cured film of the photosensitive resin composition can be improved.

  In the photosensitive resin composition of the present invention, examples of the thermosetting resin curing agent include phenol resins such as phenol novolac type phenol resins, cresol novolac type phenol resins, and naphthalene type phenol resins, amino resins, and urea resins. Melamine resins, dicyandiamide, dihydrazine compounds, imidazole compounds, Lewis acids, Bronsted acid salts, polymercaptan compounds, isocyanates 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.

<The mixing method of (A)-(D) or (A)-(E)>
The photosensitive resin composition of this invention is obtained by uniformly mixing the components (A) to (D) or (A) to (E). 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 filler, an adhesion assistant, a leveling agent, a polymerization inhibitor, an antioxidant, a silane coupling agent, and an antifoaming agent are further added to the photosensitive resin composition of the present invention as necessary. Can do. 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.

  A photosensitive resin composition solution within this range is preferable because the film reduction rate after coating and drying is reduced.

<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 having high heat resistance can be obtained by subjecting the terminal carboxylic acid siloxane imide oligomer to chain extension with a diamino compound by performing heat curing 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 heat curing 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 desirable.

  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 converted into 154 g of 1,2-bis (2-methoxyethoxy) ethane. Dispersed and kept at 80 ° C. To this, 159 g (0 from Shin-Etsu Chemical Co., Ltd .: product name KF8010, molecular weight 830, R ₃ and R ₄ in the general formula (2) are methyl groups, n = 3, m = 6 to 11). 192 mol) and stirred uniformly for 30 minutes. Next, the mixture was heated to 140 ° C. and stirred uniformly for 1 hour, heated to 180 ° C. and heated to reflux for 3 hours to carry out an imidization reaction. After cooling to 80 ° C., 27.7 g (1.54 mol) of water was added, and the mixture was heated to reflux for 5 hours. In this way, a terminal tetracarboxylic acid resin containing a terminal tetracarboxylic acid siloxane imide oligomer was obtained. The solid content concentration of this solution was 66% by weight, and the viscosity of the solution was 100 poise at 23 ° C. This terminal tetracarboxylic acid resin solution was a stable solution with little change in viscosity even when it was allowed to stand at room temperature for 1 month. This synthetic resin is abbreviated as resin A.

(Synthesis Example 2)
200 g (0.384 mol) of BPADA was dispersed in 184 g of 1,2-bis (2-methoxyethoxy) ethane and kept at 80 ° C. To this, siloxane diamine (manufactured by Shin-Etsu Chemical Co., Ltd .: product name X-22-9409S, molecular weight 1492, R ₃ and R ₄ in the general formula (2) are methyl groups or phenyl groups, n = 3, m = 9 to 12 229 g (0.154 mol) was added and stirred uniformly for 30 minutes. Next, the mixture was heated to 140 ° C. and stirred uniformly for 1 hour, heated to 180 ° C. and heated to reflux for 3 hours to carry out an imidization reaction. After cooling to 80 ° C., 27.7 g (1.54 mol) of water was added. After stirring uniformly for 30 minutes, the mixture was heated to 80 ° C. and refluxed for 5 hours. In this way, a terminal tetracarboxylic acid resin containing a terminal tetracarboxylic acid siloxane imide oligomer was obtained. The solid content concentration of this solution was 67% by weight, and the viscosity of the solution was 90 poise at 23 ° C. This terminal tetracarboxylic acid resin solution was a stable solution with little change in viscosity even when it was allowed to stand at room temperature for 1 month. This synthetic resin is abbreviated as resin B.

(Synthesis Example 3)
The water charged after the reaction in Synthesis Example 1 was changed to methanol and half-esterified. This synthetic resin is abbreviated as resin C.

(Examples 1-9)
Addition of diamino compound, oxime ester photopolymerization initiator, other photopolymerization initiator, photosensitive resin, epoxy resin, filler, organic solvent to the terminal tetracarboxylic acid resin obtained in Synthesis Examples 1-2 A resin composition was prepared. Tables 1 and 2 describe the blending amounts of the constituent raw materials in the resin solid content and the types of raw materials. In addition, 1,2-bis (2-methoxyethoxy) ethane which is a solvent in the table is the total amount of solvent including the solvent and the like contained in the above synthetic resin solution and the like.

  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 diameter 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 Tables 3 and 4.

※１ 新中村化学社製 製品名ＮＫエステルＡ−９３００ エトキシ化イソシアヌル酸トリアクリレート
※２ 新中村化学社製 製品名ＮＫエステルＢＰＥ−５００ ビスフェノールＡ ＥＯ変性ジアクリレート 分子量が５００
※３ 上記一般式（１）中、Ｒ_１がエチル基、Ｒ_２がメチル基 チバスペシャルティケミカルズ社製 製品名ＩＲＧＡＣＵＲＥ ＯＸＥ−０２
※４ 日本化薬社製 製品名ＫＡＹＡＣＵＲＥ ＤＥＴＸ−Ｓ ２，４−ジエチルチオキサントン
※５ 日本化薬社製 製品名ＫＡＹＡＣＵＲＥ ＥＰＡ エチル−４−ジメチルアミノベンゾエート
※６ チバスペシャルティケミカルズ社製 製品名ＩＲＧＡＣＵＲＥ ９０７ ２−メチル−１−[４−（メチルチオ）フェニル]−２−モルフォリノプロパン−１−オン
※７ 大日本インキ株式会社製 クレゾールノボラック型の多官能エポキシ樹脂
※８ 日本アエロジル株式会社製 シリカ粒子。

* 1 Shin-Nakamura Chemical Co., Ltd. Product name NK Ester A-9300 Ethoxylated isocyanuric acid triacrylate * 2 Shin-Nakamura Chemical Co., Ltd. product name NK Ester BPE-500 Bisphenol A EO-modified diacrylate Molecular weight 500
* 3 In the above general formula (1), R ₁ is an ethyl group and R ₂ is a methyl group. Product name IRGACURE OXE-02 manufactured by Ciba Specialty Chemicals
* 4 Nippon Kayaku Co., Ltd. product name KAYACURE DETX-S 2,4-diethylthioxanthone * 5 Nippon Kayaku Co., Ltd. product name KAYACURE EPA ethyl-4-dimethylaminobenzoate * 6 Ciba Specialty Chemicals product name IRGACURE 907 2- Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one * 7 A cresol novolac type polyfunctional epoxy resin manufactured by Dainippon Ink Co., Ltd. * 8 Silica particles manufactured by Nippon Aerosil Co., Ltd.

(Preparation of coating film on polyimide film)
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. After drying at 80 ° C. for 20 minutes, a negative photomask having an area of 50 mm × 50 mm line width / space width = 100 μm / 100 μm was placed and exposed to UV light at 300 mJ / cm 2 in a nitrogen atmosphere. This photosensitive film was spray-developed 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 the development, it was washed purely and sufficiently, 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)
The evaluation of the photosensitivity of the photosensitive resin composition was determined by observing the surface of the cured film obtained in the above item (Preparation of coating film on polyimide film).
◯: Clear line width / space width = 100/100 μm photosensitive pattern is drawn on the polyimide film surface, there is no fluctuation of the line due to peeling of the line part, and there is no residual residue in the space part thing.
Δ: A clear line width / space width = 100/100 μm photosensitive pattern is drawn, and the line portion is shaken due to peeling, but the space portion has no undissolved residue.
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.

(Coating film adhesion)
The adhesive strength of the cured film of the photosensitive resin composition obtained in the above item (Preparation of coating film on polyimide 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.

(Solvent resistance)
The solvent resistance of the cured film of the photosensitive resin composition obtained in the above item (preparation of coating film on polyimide film) 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 obtained in the above item (Preparation of coating film on polyimide film) 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 obtained in the above item (preparation of coating film on polyimide film) 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.

(Flexibility)
A cured film laminated film of a photosensitive resin composition was prepared on the surface of a 25 μm-thick polyimide film (Apical 25NPI manufactured by Kaneka Corporation) in the same manner as the above item (Preparation of a coating film on a polyimide film). 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

(Solder heat resistance)
The 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. After drying at 80 ° C. for 20 minutes, a negative photomask having an area of 50 mm × 50 mm line width / space width = 100 μm / 100 μm was placed and exposed to UV light at 300 mJ / cm 2 in a nitrogen atmosphere. This photosensitive film was spray-developed 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 the development, it was washed purely and sufficiently, and then dried by heating in an oven at 170 ° C. for 60 minutes to prepare a cured film of the photosensitive resin composition.
The coated film was floated so that the surface coated with the cured film of the photosensitive resin composition was in contact with a solder bath completely dissolved at 260 ° C., and then 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.

(Moisture resistance)
A comb-shaped pattern of line width / space width = 100 μm / 100 μm on a flexible copper-laminated laminate (copper foil thickness 12 μm, polyimide film is Apical 25 NPI manufactured by Kaneka Corporation, and copper foil is bonded with a 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. Then, the cured film of the photosensitive resin composition was produced on the comb pattern by the method similar to the production method of the cured film on a polyimide film, and the test piece was adjusted. 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 resistance value of 10 6 or more after 500 hours or more after the start of the test, and no occurrence of migration, dendrite, etc. ×: The occurrence of migration, dendrite, etc. after 500 hours or more after the start of the test.

(Warpage amount)
Using the Baker type applicator, the photosensitive resin composition was cast and applied to a 25 μm-thick polyimide film (Apical 25NPI manufactured by Kaneka Corporation) to an area of 100 mm × 100 mm so that the final dry thickness was 25 μm. Dry at 80 ° C. for 20 minutes. The entire surface was exposed to 300 mJ / cm 2 of ultraviolet light in a nitrogen atmosphere. This photosensitive film was spray-developed 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. However, since the entire surface was exposed, no change in the film area was observed. After the development, it was washed purely and sufficiently, and then dried by heating in an oven at 170 ° C. for 60 minutes to prepare a cured film of the photosensitive resin composition.
The cured film was cut into a film having an area of 50 mm × 50 mm and placed on a smooth table so that the coating film was on the upper surface, and the warp height of the film edge was measured. A schematic diagram of the measurement site is shown in FIG. The smaller the amount of warpage on the polyimide film surface, the smaller the stress on the surface of the printed wiring board and the lower the amount of warping of the printed wiring board. The amount of warp is preferably 10 mm or less.

(Comparative Example 1)
Using the half-esterified resin obtained in Synthesis Example 3, the oxime ester photopolymerization initiator used was 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Ciba A photosensitive resin composition was prepared in the same manner as in Example 1 except that the product was changed to Specialty Chemicals, trade name IRGACURE907), and evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 4. Since the photopolymerization reaction was insufficient, the cured part was dissolved in a 1.0% by weight sodium carbonate aqueous solution during development. Moreover, imidation did not fully advance and the obtained photosensitive resin composition became a thing with very bad moisture-proof insulation.

Schematic diagram measuring the amount of warping of the film

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Polyimide film which laminated the photosensitive resin composition 2 Warpage amount 3 Smooth stand

Claims (13)

It contains at least (A) terminal tetracarboxylic acid siloxane imide oligomer, (B) diamino compound, (C) photosensitive resin, and (D) an oxime ester photopolymerization initiator represented by the following general formula (1). A photosensitive resin composition characterized by the above.

(In formula, R < ₁ >, R < ₂ > may be same or different and is a C1-C6 alkylene group.)   The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition further comprises (E) a thermosetting resin. The (A) terminal tetracarboxylic acid siloxane imide oligomer is a siloxane diamine represented by the following general formula (2):

_(Wherein, R 3, _{R 4} may be different from each other in the same, integer .m 1 to 40 represents an alkyl group or an aromatic group having 1 to 12 carbon atoms, n represents an integer of from 1 to 20 Show.)
Tetracarboxylic dianhydride and water represented by the following general formula (3)

(In the formula, R ₅ represents a tetravalent organic group.)
3. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is obtained by reacting such that the molar ratio is the number of moles of siloxane diamine / the number of moles of tetracarboxylic dianhydride ≦ 0.80. The said (B) diamino compound uses the aromatic diamine shown by following General formula (4) as a raw material, The photosensitive resin composition of any one of Claims 1-3 characterized by the above-mentioned.

(In the formula, R ₆ is a divalent organic group.)   The photosensitive resin composition according to any one of claims 1 to 4, 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 2-5 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 6.   The (A) component, the (B) component, the (C) component, and the (D) component in the photosensitive resin composition are based on 100 parts by weight of the total solid content of the (A) component and the (B) component. The component (C) is blended so as to be 10 to 100 parts by weight, and the component (D) is blended so as to be 0.1 to 50 parts by weight. The photosensitive resin composition as described.   The blending ratio of the (E) thermosetting resin is 0.5 to 100 weights with respect to 100 parts by weight of the solid content of the sum of the components (A), (B), (C) and (D). It mix | blends so that it may become a part, The photosensitive resin composition of Claim 8 characterized by the above-mentioned.   The photosensitive resin composition solution obtained by melt | dissolving the photosensitive resin composition of any one of Claims 1-9 in the organic solvent.   The cured film obtained by hardening the photosensitive resin composition of any one of Claims 1-9.   The insulating film obtained from the photosensitive resin composition of any one of Claims 1-9.   The printed wiring board with an insulating film which coat | covered the photosensitive resin composition of any one of Claims 1-9 on the printed wiring board.

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