JP2006342310A - New polyimide precursor and utilization of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyimide precursor imidizing at ≤200°C, usable as substrates for rigid and flexible printed circuits and to provide a photosensitive resin composition using the same. <P>SOLUTION: The invention relates to the polyimide precursor comprising an imide structure having a side chain of carbon-carbon double bond as a connecting group between imide groups, having already formed ring structure and a polyamic acid structure originating from a silicone diamine and relates to the photosensitive resin composition comprising the same and a (meth)acrylic compound having a carbon-carbon double bond and a photo reaction initiator. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a partially imidized polyimide precursor and use thereof.

Polyimide is excellent in heat resistance among various organic polymers, and thus is widely used in the fields of space and aviation to electronic communication and OA equipment. Particularly in recent years, electronic devices have been rapidly increasing in functionality, performance, and size, and accordingly, electronic components have been required to be smaller and lighter, and photosensitive polyimide has been used. ing.

  The photosensitive polyimide is an ion-bonded photosensitive polyimide obtained by mixing a polyamic acid with a compound having a tertiary amine and a (meth) acryloyl group to form a photosensitive polyimide (see Patent Document 1), and a carboxyl group of the polyamic acid. In addition, an ester bond type photosensitive polyimide having a methacryloyl group introduced through an ester bond (see Patent Documents 2 and 3) and an isocyanate compound having a methacryloyl group are introduced into the carboxyl group portion of the polyamic acid. Polyimide (see Patent Literature 4, Patent Literature 5, Patent Literature 6, and Patent Literature 7) and photosensitive polyimide (see Patent Literature 8) in which polyamic acid and (meth) acrylic compound are mixed have been developed.

However, these photosensitive polyimides can only be obtained by imidization after exposure / development in the state of polyamic acid, so it was necessary to apply a temperature of 250 ° C. or higher to FPC, and some photosensitive polyimides have an acroyl group. There is a problem that the film thickness must be removed by heat and the film thickness is greatly reduced. In addition, since heating at 250 ° C. or higher is necessary, it is impossible to use photosensitive polyimide for rigid and flexible printed circuit boards because other components are deteriorated.
JP 54-145794 A (published November 14, 1979) Japanese Patent Publication No.55-030207 (released on August 9, 1980) Japanese Patent Publication No. 55-041422 (released on October 24, 1980) JP 59-160140 (published September 10, 1984) JP 03-170547 A (published July 24, 1991) Japanese Patent Laid-Open No. 03-186847 (published on August 14, 1991) JP 61-118424 A (published June 5, 1986) JP 11-52569 A (published February 26, 1999)

  An object of the present invention is to provide a polyimide precursor that can be imidized at a low temperature of 200 ° C. or lower, and a photosensitive composition using the same, in which photosensitive polyimide can be used for rigid and flexible printed circuit boards.

  The present invention provides a partially imidized polyimide precursor having the following carbon-carbon double bond in the side chain and a photosensitive resin composition comprising the same and a (meth) acryl compound having a carbon-carbon double bond as essential components. Thus, the above-described problems can be solved.

  The first of the present invention is a polyimide precursor having at least the structure of formula (1) and the structure of formula (2) in one molecule.

（式中Ｒ^１は４価の有機基を示し、Ｒ^２は、少なくとも１つ以上の炭素−炭素二重結合を有する１価の有機基を側鎖に有する、２価の有機基、Ｒ^３は式（３）を示し、式（３）中、、Ｒ^４は、同一であっても異なっていても良く、メチル基・エチル基・フェニル基のいずれかを示し、ｘ＝２〜１０、ｙ＝４〜３０を示す。）

(Wherein R ¹ represents a tetravalent organic group, and R ² represents a divalent organic group having a monovalent organic group having at least one carbon-carbon double bond in the side chain, R ³ Represents Formula (3), and in Formula (3), R ⁴ may be the same or different, and represents any of a methyl group, an ethyl group, and a phenyl group, and x = 2 to 10, (y = 4-30)

本発明により、２００℃以下の低温でイミド化することが出来る。

According to the present invention, imidization can be performed at a low temperature of 200 ° C. or lower.

  2nd of this invention is a polyimide precursor which has the structure of Formula (4) in 1 molecule in addition to Formula (1) and Formula (2) as described in 1st invention.

（式中、Ｒ^５は２価の有機基を示す。）
本発明の第３は、前記ポリイミド前駆体中の全Ｒ_２、Ｒ_３、Ｒ_５中、前記式（１）のＲ_２のモル分率が１〜８０％であり、前記式（２）のＲ_３のモル分率が１０〜９０％であり、前記式（４）のＲ_５のモル分率が０〜７０％であることを特徴とする第２の発明に記載のポリイミド前駆体である。

(In the formula, R ⁵ represents a divalent organic group.)
The third of the present invention, the in all _{R 2,} R 3, _{R 5} of the polyimide precursor, the mole fraction of _{R 2} 1 to 80% of said formula (1), the formula (2) The polyimide precursor according to the second invention, wherein the mole fraction of R ₃ is 10 to 90%, and the mole fraction of R _{5 in} the formula (4) is 0 to 70%. .

The fourth of the present invention, in the formula (1), R ² is a polyimide precursor according to the first to third invention, characterized in that the formula (5).

（Ｒ^６は、同一であっても異なっていても良く、炭素−炭素二重結合を有する１価の有機基もしくは水素のいずれか一方を示し、Ｒ^７は、同一であっても異なっていても良く、−，−(Ｃ＝Ｏ)−，−Ｃ(ＣＨ_３)_２−，−ＣＨ_２−，−ＳＯ_２−，−Ｏ−，−Ｃ(ＣＦ_３)_２−，−ＣＨ(ＣＨ_３)−，−Ｃ(ＣＨ_３)(ＣＨ_２ＣＨ_３)−，シクロヘキシルのいずれかを示し、Ｒ^８は、同一であっても異なっていても良く、Ｈ，ＣＨ_３−，ＣＨ_３ＣＨ_２−，ＯＨ，ＣＯＯＨのいずれかを示し、ｍは０〜３を示す。但し、式（５）中には少なくとも１つ以上の、炭素−炭素二重結合を有する１価の有機基が存在するものとする。）
本発明の第５は、前記式（１）において、Ｒ^２が式（６）であることを特徴とする第１〜３の発明に記載のポリイミド前駆体である。

(R ⁶ may be the same or different, and represents either a monovalent organic group having a carbon-carbon double bond or hydrogen, and R ⁷ is the same or different. may, -, - (C = O ) -, - C (CH 3) 2 -, - CH 2 -, - SO 2 -, - O -, - C (CF 3) 2 -, - CH (CH 3 )-, -C (CH ₃ ) (CH ₂ CH ₃ )-, or cyclohexyl, R ⁸ may be the same or different, and H, CH _3- , CH ₃ CH _2- , OH, or COOH, and m represents 0 to 3. However, in formula (5), at least one monovalent organic group having a carbon-carbon double bond is present. And)
The fifth of the present invention, in the formula (1), R ² is a polyimide precursor according to the first to third invention, characterized in that the formula (6).

（Ｒ^６は、同一であっても異なっていても良く、炭素−炭素二重結合を有する１価の有機基もしくは水素のいずれか一方を示し、Ｒ^７は、同一であっても異なっていても良く、−，−(Ｃ＝Ｏ)−，−Ｃ(ＣＨ_３)_２−，−ＣＨ_２−，−ＳＯ_２−，−Ｏ−，−Ｃ(ＣＦ_３)_２−，−ＣＨ(ＣＨ_３)−，−Ｃ(ＣＨ_３)(ＣＨ_２ＣＨ_３)−，シクロヘキシルのいずれかを示し、Ｒ^８は、同一であっても異なっていても良く、Ｈ，ＣＨ_３−，ＣＨ_３ＣＨ_２−，ＯＨ，ＣＯＯＨのいずれかを示し、ｎは１〜４を示す。但し、式（６）中には少なくとも１つ以上の、炭素−炭素二重結合を有する１価の有機基が存在するものとする。）
本発明の第６は、第１〜５の発明に記載の（Ａ）ポリイミド前駆体１００重量部に加えて、（Ｂ）炭素−炭素二重結合を有する（メタ）アクリル化合物１〜４００重量部を必須成分とする感光性樹脂組成物である。本発明により、２００℃以下の低温でイミド化でき、リジット及びフレキシブルプリント基板用途等種々に用いる事が出来る。

(R ⁶ may be the same or different, and represents either a monovalent organic group having a carbon-carbon double bond or hydrogen, and R ⁷ is the same or different. may, -, - (C = O ) -, - C (CH 3) 2 -, - CH 2 -, - SO 2 -, - O -, - C (CF 3) 2 -, - CH (CH 3 )-, -C (CH ₃ ) (CH ₂ CH ₃ )-, or cyclohexyl, R ⁸ may be the same or different, and H, CH _3- , CH ₃ CH _2- , OH, or COOH, and n is 1 to 4. However, in formula (6), there is at least one monovalent organic group having a carbon-carbon double bond. And)
6th of this invention is 1-400 weight part of (B) (meth) acrylic compounds which have a carbon-carbon double bond in addition to 100 weight part of (A) polyimide precursor as described in 1st-5th invention. Is a photosensitive resin composition containing as an essential component. According to the present invention, it can be imidized at a low temperature of 200 ° C. or less, and can be used in various applications such as rigid and flexible printed circuit boards.

  7th of this invention is the photosensitive resin composition which uses 0.01-50 weight part of (C) photoreaction initiators as an essential component in addition to 6th invention.

  In addition to the seventh invention, the eighth of the present invention is (D) a compound having a carbon-carbon double bond and a tertiary amino group in the molecule or a compound having a carbon-carbon double bond and an amide group. It is a photosensitive resin composition having 01 to 30 parts by weight as an essential component.

  A ninth aspect of the present invention is a photosensitive dry film resist comprising the photosensitive resin composition according to any one of the sixth to eighth aspects of the invention.

  A tenth aspect of the present invention is a printed wiring board formed by forming the photosensitive dry film resist according to the ninth aspect as an insulating protective layer.

  The polyimide precursor of this invention contains the diamine of a specific structure as mentioned above, and has the organic group which has a carbon-carbon double bond in the site | part which carried out the partial imidation in the side chain. Therefore, the photosensitive resin composition containing the polyimide precursor and the (meth) acrylic compound having a carbon-carbon double bond is imidized at a temperature lower than that of the conventional imide-based photosensitive resin composition. Is possible. Therefore, when used for an electronic component such as a printed circuit board, there is an effect of preventing other constituent materials from being thermally deteriorated by heating during imidization.

  The polyimide precursor used in the present invention will be described. The present invention is not limited to this.

<(A) Polyimide precursor>
The present invention is a partially imidized polyimide precursor having the following carbon-carbon double bond in the side chain, and has the structures of the following formulas (1) and (2).

（式中Ｒ^１は４価の有機基を示し、Ｒ^２は、少なくとも１つ以上の炭素−炭素二重結合を有する１価の有機基を側鎖に有する、２価の有機基、Ｒ^３は式（３）を示し、式（３）中、、Ｒ^４は、同一であっても異なっていても良く、メチル基・エチル基・フェニル基のいずれかを示し、ｘ＝２〜１０、ｙ＝４〜３０を示す。）

(Wherein R ¹ represents a tetravalent organic group, and R ² represents a divalent organic group having a monovalent organic group having at least one carbon-carbon double bond in the side chain, R ³ Represents Formula (3), and in Formula (3), R ⁴ may be the same or different, and represents any of a methyl group, an ethyl group, and a phenyl group, and x = 2 to 10, (y = 4-30)

（ＯＨ基を有する酸二無水物末端のポリアミド酸のオリゴマー（Ｐ））
スキーム（１）のようにまず最初に、酸二無水物とＯＨ基を有するジアミン化合物とを有機極性溶媒中で反応させ、ＯＨ基を有する酸二無水物末端のポリアミド酸のオリゴマー（Ｐ）を合成する。この際の当量数は、酸二無水物＞ＯＨ基を有するジアミン化合物、とする。

(OH oligomer-containing polyamic acid oligomer (P))
As shown in scheme (1), first, an acid dianhydride and a diamine compound having an OH group are reacted in an organic polar solvent, and an acid dianhydride-terminated polyamic acid oligomer (P) having an OH group is obtained. Synthesize. The number of equivalents in this case is acid dianhydride> a diamine compound having an OH group.

（式中Ｒ^１は４価の有機基を示し、Ｒ^９はＯＨ基を有するジアミンからＯＨ基とアミノ基とを除いた有機基を示し、ｏは１〜４の整数を示す。）
具体的には、酸二無水物とＯＨ基を有するジアミン化合物とを有機溶媒中で８０℃以下、好ましくは５０℃以下の反応温度下に１〜１２時間付加重合反応させて、酸二無水物末端のポリアミド酸のオリゴマー（Ｐ）が得られる。この際の当量数は、酸二無水物＞ＯＨ基を有するジアミン化合物であり、酸二無水物÷ＯＨ基を有するジアミン化合物のモル比は、１より大きく１０以下であり、好ましくは１．１以上５以下であり、更に好ましくは１．３以上３以下である。

(In the formula, R ¹ represents a tetravalent organic group, R ⁹ represents an organic group obtained by removing an OH group and an amino group from a diamine having an OH group, and o represents an integer of 1 to 4.)
Specifically, an acid dianhydride and a diamine compound having an OH group are subjected to an addition polymerization reaction in an organic solvent at a reaction temperature of 80 ° C. or lower, preferably 50 ° C. or lower for 1 to 12 hours. A terminal polyamic acid oligomer (P) is obtained. The number of equivalents in this case is acid dianhydride> a diamine compound having an OH group, and a molar ratio of acid dianhydride ÷ OH group having a diamine group is greater than 1 and 10 or less, preferably 1.1. It is 5 or less and more preferably 1.3 or more and 3 or less.

  As an organic solvent in this polymerization reaction, for example, N, N-dimethylsulfoxide, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2- Examples include pyrrolidone and hexamethylenephosphoamide, and these can be used alone or in combination of two or more.

(Polyimide oligomer with acid dianhydride terminal having OH group (Q))
Next, a method for synthesizing an acid dianhydride-terminated polyimide oligomer (Q) having an OH group will be described.

  The acid dianhydride-terminated polyamic acid oligomer (P) obtained as described above is dehydrated and cyclized as shown in Scheme (2), and has an dianhydride-terminated polyimide oligomer (Q). It becomes. A known method can be used for the dehydration cyclization method. For example, a thermal cyclization method by refluxing with toluene, xylene or the like, or a chemical cyclization method with an aromatic tertiary amine such as acetic anhydride and pyridine can be used.

（式中Ｒ^１は４価の有機基を示し、Ｒ^９はＯＨ基を有するジアミンからＯＨ基とアミノ基とを除いた有機基を示し、ｏは１〜４の整数を示す。）
その他のポリアミド酸をポリイミドに脱水環化する方法として、ポリアミド酸溶液を減圧下で、加熱・脱水する方法がある。この方法は、イミド化により生成する水を加熱・減圧し、積極的に系外に除去するため、加水分解を抑えることができる。また、用いた原料の酸二無水物中に、加水分解により開環したテトラカルボン酸或いは、酸二無水物の片方が加水開環したもの等が混入することによってポリアミド酸の重合反応が停止した場合でも、イミド化の際に減圧・加熱することにより、開環した酸無水物が再び閉環することが期待できる。

(In the formula, R ¹ represents a tetravalent organic group, R ⁹ represents an organic group obtained by removing an OH group and an amino group from a diamine having an OH group, and o represents an integer of 1 to 4.)
As another method of dehydrating and cyclizing polyamic acid to polyimide, there is a method of heating and dehydrating a polyamic acid solution under reduced pressure. In this method, water generated by imidization is heated and decompressed and actively removed from the system, so that hydrolysis can be suppressed. Moreover, the polymerization reaction of the polyamic acid was stopped by mixing the raw acid dianhydride with a tetracarboxylic acid which was ring-opened by hydrolysis or one of the acid dianhydride hydrolyzed. Even in the case, it can be expected that the ring-opened acid anhydride is closed again by heating under reduced pressure during imidization.

(Acid dianhydride)
Any acid dianhydride can be used in the present invention. Although it will not specifically limit if it is an acid dianhydride, For example, 2,2'- hexafluoro propylidene diphthalic dianhydride, 2,2-bis (4-hydroxyphenyl) propane dibenzoate-3,3 ', 4 , 4′-tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane Tetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbonane-2-acetic acid dianhydride Anhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-di Aliphatic or alicyclic tetracarboxylic dianhydrides such as carboxylic dianhydrides, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydrides; Pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride 4,4'-bis (3,4-dicar Xylphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride P-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, Examples thereof include aromatic tetracarboxylic dianhydrides such as bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride. These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

  In order to obtain a polyimide having high solubility in an organic solvent, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 2,2′-hexafluoropropylidenediphthalic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 4,4- (4,4′-isopropylidenediphenoxy) bisphthalic anhydride, 2,2-bis (4-hydroxyphenyl) propane Dibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-tetra It is desirable to partially use phenylsilane tetracarboxylic dianhydride, 1,2-ethanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride.

(Diamine compound having an OH group)
In the present invention, any diamine compound having an OH group can be used. Although not particularly limited, preferred structures can be represented by general formula (7) and general formula (8).

（Ｒ^７は、同一であっても異なってもよく、−，−(Ｃ＝Ｏ)−，−Ｃ(ＣＨ_３)_２−，−ＣＨ_２−，−ＳＯ_２−，−Ｏ−，−Ｃ(ＣＦ_３)_２−，−ＣＨ(ＣＨ_３)−，−Ｃ(ＣＨ_３)(ＣＨ_２ＣＨ_３)−，シクロヘキシルを、Ｒ^１０は、同一であっても異なってもよく、Ｈ，ＣＨ_３−，ＣＨ_３ＣＨ_２−を、ｍは０〜３を示す。）

^{(R 7} may be the same or different, -, - (C = O ) -, - C (CH 3) 2 -, - CH 2 -, - SO 2 -, - O -, - C (CF ₃ ) ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) (CH ₂ CH ₃ ) —, cyclohexyl, R ¹⁰ may be the same or different, and H, CH ₃ -, _CH 3 _{CH 2} - a, m denotes 0 to 3).

（Ｒ^７は、同一であっても異なってもよく、−，−(Ｃ＝Ｏ)−，−Ｃ(ＣＨ_３)_２−，−ＣＨ_２−，−ＳＯ_２−，−Ｏ−，−Ｃ(ＣＦ_３)_２−，−ＣＨ(ＣＨ_３)−，−Ｃ(ＣＨ_３)(ＣＨ_２ＣＨ_３)−，シクロヘキシルを、Ｒ^１０は、同一であっても異なっても良く、Ｈ，ＣＨ_３−，ＣＨ_３ＣＨ_２−を、ｎは１〜４を示す。）
式（７）の具体的な、化合物名として、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、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、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ヒドロキシジフェニルメタン等のヒドロキシジフェニルアルカン類、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化合物、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フェニルスルフォン化合物、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等を例示することが出来る。

^{(R 7} may be the same or different, -, - (C = O ) -, - C (CH 3) 2 -, - CH 2 -, - SO 2 -, - O -, - C (CF ₃ ) ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) (CH ₂ CH ₃ ) —, cyclohexyl, R ¹⁰ may be the same or different, and H, CH ₃ -, _CH 3 _{CH 2} - a, n represents shows 1-4).
Specific compound names of formula (7) include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, 4,4′-diamino- Hydroxybiphenyl compounds such as 2,2′-dihydroxybiphenyl, 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxybiphenyl, 3,3′-diamino-4,4′-dihydroxydiphenylmethane, 2,2-bis [3-amino-4-hydroxyphenyl] propane, 2,2-bis [4-amino-3-hydroxyphenyl] propane, 2,2-bis [3-amino-4-hydroxyphenyl] hexa Hydroxydiphenylalkanes such as hydroxydiphenylmethane such as fluoropropane, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 4,4′-dia -3,3'-dihydroxydiphenyl ether, hydroxydiphenyl ether compounds such as 4,4'-diamino-2,2'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4 '-Diamino-3,3'-dihydroxydiphenylsulfone, diphenylsulfone compounds such as 4,4'-diamino-2,2'-dihydroxydiphenylsulfone, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4, Examples include 4'-diamino-3,3'-dihydroxydiphenylmethane, 4,4'-diamino-2,2'-dihydroxydiphenylmethane, and the like.

    As a specific compound name of the formula (8), 2,2′-methylenebis {4-methyl-6- (3,5-dimethyl-4-aminobenzyl) phenol}, 2,6-bis (3,5 -Dimethyl-4-aminobenzyl) -4-methylphenol, 2,2'-bis {4-methyl-6- (3,5-dimethyl-4-aminobenzyl) phenol} -2,6- (4-methyl Phenol) and the like.

  Other diamine compounds having an OH group that can be used include 4,6-diaminoresorcinol, 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxydiphenylmethane, 4,4′-diamino- 2,2 ′, 5,5′-tetrahydroxydiphenyl ether, 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxydiphenyl sulfone, 2,2-bis [4- (4-amino-3) Bis [(hydroxyphenyl) phenyl] alkane compounds such as -hydroxyphenoxy) phenyl] propane, bis [(hydroxyphenoxy) such as 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] sulfone Phenyl] sulfone compounds, diaminophenols such as 2,4-diaminophenol, 4,4′-bis (4-a Bruno 3 hydrate carboxymethyl) bis biphenyl, and the like (hydrate carboxymethyl phenoxy) biphenyl compounds, and the like can be exemplified.

(Acid dianhydride terminal imide oligomer having carbon-carbon double bond (R))
Next, as shown in Scheme (3), a method for introducing a monovalent organic group having a carbon-carbon double bond into an acid dianhydride-terminated polyimide oligomer (Q) having an OH group will be described.

（式中Ｒ^１は４価の有機基を示し、Ｒ^９はＯＨ基を有するジアミンからＯＨ基とアミノ基とを除いた有機基を示し、Ｒ^１１は炭素−炭素二重結合を有する１価の有機基を、ｏは１〜４の整数を示し、ｐは１〜５０の整数を示す。）
炭素−炭素二重結合を有する酸二無水物末端イミドオリゴマー（Ｒ）は、ＯＨ基を有する酸二無水物末端のポリイミドオリゴマー（Ｑ）と、無水メタクリル酸、無水クロトン酸、無水アンゲリル酸、無水４−メチル−２−ペンテン酸、無水２−メチル−４−ペンテン酸、無水２−メチル−２−ペンテン酸、無水２−ヘプテン酸、無水３−ヘプテン酸、無水２−オクテン酸、無水３−オクテン酸等の炭素−炭素二重結合を有する酸無水物、とを反応させることにより容易に合成することが出来る。酸無水物を反応溶媒として用いても良いし、ジメチルスルホキシド、ジエチルスルホキシドなどのスルホキシド系溶媒、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジエチルホルムアミドなどのホルムアミド系溶媒、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジエチルアセトアミドなどのアセトアミド系溶媒、Ｎ−メチル−２−ピロリドン、Ｎ−ビニル−２−ピロリドンなどのピロリドン系溶媒、テトラヒドロフラン、ジオキサン、ジオキソラン等のエーテル系溶媒、ブチルセロソルブ等のセロソルブ系あるいはヘキサメチルホスホルアミド、γ−ブチロラクトン等、更にはキシレン、トルエンのような芳香族炭化水素等を溶媒として用いてもよい。反応温度は、３０〜１５０℃程度で、反応時間は１〜１０時間程度である。また、触媒として、トリエチルアミン、ピリジン等の３級アミンを加えると反応時間が短くなる傾向にある。

(Wherein R ¹ represents a tetravalent organic group, R ⁹ represents an organic group obtained by removing an OH group and an amino group from a diamine having an OH group, and R ¹¹ represents a monovalent group having a carbon-carbon double bond. And o represents an integer of 1 to 4, and p represents an integer of 1 to 50.)
The acid dianhydride terminal imide oligomer (R) having a carbon-carbon double bond is composed of an acid dianhydride terminal polyimide oligomer (Q) having an OH group, methacrylic anhydride, crotonic acid anhydride, angelic anhydride, anhydrous 4-methyl-2-pentenoic acid, 2-methyl-4-pentenoic anhydride, 2-methyl-2-pentenoic anhydride, 2-heptenoic anhydride, 3-heptenoic anhydride, 2-octenoic anhydride, 3- It can be easily synthesized by reacting with an acid anhydride having a carbon-carbon double bond such as octene acid. An acid anhydride may be used as a reaction solvent, a sulfoxide solvent such as dimethyl sulfoxide and diethyl sulfoxide, a formamide solvent such as N, N-dimethylformamide and N, N-diethylformamide, N, N-dimethylacetamide, Acetamide solvents such as N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, ether solvents such as tetrahydrofuran, dioxane and dioxolane, cellosolve such as butyl cellosolve, or Hexamethylphosphoramide, γ-butyrolactone and the like, and aromatic hydrocarbons such as xylene and toluene may be used as the solvent. The reaction temperature is about 30 to 150 ° C., and the reaction time is about 1 to 10 hours. Further, when a tertiary amine such as triethylamine or pyridine is added as a catalyst, the reaction time tends to be shortened.

  As another method, an acid dianhydride-terminated imide oligomer (R) having a carbon-carbon double bond, an acid dianhydride-terminated polyimide oligomer having an OH group, methacrylic acid, methacrylic acid, crotonic acid, Angelic acid, 4-methyl-2-pentenoic acid, 2-methyl-4-pentenoic acid, 2-methyl-2-pentenoic acid, 2-heptenoic acid, 3-heptenoic acid, 2-octenoic acid, 3-octenoic acid, etc. The acid having a carbon-carbon double bond can be easily synthesized by dehydration esterification with a dehydrating agent such as dicyclocarbodiimide in the presence of a tertiary amine such as triethylamine or pyridine. Reaction solvents such as dimethyl sulfoxide, diethyl sulfoxide and other sulfoxide solvents, N, N-dimethylformamide, formamide solvents such as N, N-diethylformamide, acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide Solvents, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, ether solvents such as tetrahydrofuran, dioxane and dioxolane, hexamethylphosphoramide, γ-butyrolactone and the like, further xylene, An aromatic hydrocarbon such as toluene can be used. The reaction temperature is about room temperature to about 150 ° C., and the reaction time is about 1 to 10 hours.

  Furthermore, as another method for obtaining the acid dianhydride-terminated imide oligomer (R) having a carbon-carbon double bond, there is the following method.

（式中Ｒ^１は４価の有機基を示し、Ｒ^９はＯＨ基を有するジアミンからＯＨ基とアミノ基とを除いた有機基を、ｏは１〜４の整数を示し、ｐは１〜５０の整数を示す。）
すなわち、スキーム（４）のように、酸二無水物とＯＨ基を有するジアミン化合物を反応させて得られるＯＨ基を有する酸二無水物末端のポリアミド酸オリゴマー（Ｐ）を合成した後で、イソキノリン類、βピコリン等のピコリン類、ピリジン類等の３級アミンの存在下で、無水メタクリル酸・無水メタクリル酸、無水クロトン酸、無水アンゲリル酸、無水４−メチル−２−ペンテン酸、無水２−メチル−４−ペンテン酸、無水２−メチル−２−ペンテン酸、無水２−ヘプテン酸、無水３−ヘプテン酸、無水２−オクテン酸、無水３−オクテン酸等の炭素−炭素二重結合を有する酸無水物等の２重結合を有する無水物とを反応させることで、イミド化と炭素−炭素二重結合の導入を同時に行うことができる。

(Wherein R ¹ represents a tetravalent organic group, R ⁹ represents an organic group obtained by removing an OH group and an amino group from a diamine having an OH group, o represents an integer of 1 to 4, and p represents 1 to Indicates an integer of 50.)
That is, after synthesizing an acid dianhydride-terminated polyamic acid oligomer (P) having an OH group obtained by reacting an acid dianhydride with a diamine compound having an OH group as shown in Scheme (4), isoquinoline is synthesized. , Methacrylic anhydride / methacrylic anhydride, crotonic anhydride, angelic anhydride, 4-methyl-2-pentenoic anhydride, 2-hydroxy anhydride in the presence of tertiary amines such as picolins such as β-picoline and pyridines It has a carbon-carbon double bond such as methyl-4-pentenoic acid, 2-methyl-2-pentenoic anhydride, 2-heptenoic anhydride, 3-heptenoic anhydride, 2-octenoic anhydride, and 3-octenoic anhydride. By reacting with an anhydride having a double bond such as an acid anhydride, imidization and introduction of a carbon-carbon double bond can be performed simultaneously.

(Polyimide precursor)
The acid dianhydride terminal imide oligomer (R) having a carbon-carbon double bond thus obtained and the silicon diamine represented by the formula (9) in an organic solvent are 100 ° C. or lower, preferably 50 ° C. The polyimide precursor of the present invention can be synthesized by an addition polymerization reaction at the following reaction temperature for 0.5 to 12 hours.

（式中、Ｒ^４は、同一であっても異なっていても良く、メチル基・エチル基・フェニル基のいずれかを示し、ｘ＝２〜１０、ｙ＝４〜３０を示す。）
発明のポリイミド前駆体は、０．５ｇ／Ｎ−メチル−２−ピロリドン１００ｍｌの濃度溶液として、３０℃における対数粘度が ０．２〜４．０の範囲になるように分子量をコントロールすることがこのましく、より好ましくは０．３〜 ２．０の範囲である。

(Wherein, ^{R 4} may be the same or different and indicates one of a methyl group, an ethyl group, a phenyl group, x = 2 to 10, indicating the y = 4 to 30.)
The molecular weight of the polyimide precursor of the invention is controlled so that the logarithmic viscosity at 30 ° C. is in the range of 0.2 to 4.0 as a solution of 0.5 g / N-methyl-2-pyrrolidone 100 ml. More preferably, it is in the range of 0.3 to 2.0.

  As an organic solvent in this polymerization reaction, for example, N, N-dimethylsulfoxide, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2- Pyrrolidone, hexamethylenephosphoamide, dioxolane, tetrahydrofuran, dioxolane and the like can be mentioned, and these can be used alone or in admixture of two or more.

  Usually, when a polyamic acid derived from an aromatic diamine is closed and imidized, it is necessary to shorten the molecular chain length as shown in Scheme (5). Therefore, in order to imidize, it is necessary to heat at a temperature higher than the temperature at which the entire molecular chain can move, and it is necessary to raise the temperature to 250 ° C or higher.

それに反して、スキーム（６）に表されるようにシリコンジアミン由来のポリアミド酸は、シロキサン部位が低温で自由に振動できるため、分子鎖全体が運動できる温度以下の温度でも、イミド化することができる。よって、本発明のポリイミド前駆体は、シリコンジアミン由来のポリアミド酸以外の部位を既にイミド化しているため、２００℃以下の低温でイミド化を行うことが出来るのである。また、シリコンジアミン由来ポリアミド酸のカルボン酸の影響で、感光性樹脂として用いた際には、現像液のアルカリ性溶液により現像可能となる。
言い換えると本発明のポリイミド前駆体は、シリコンジアミン由来のポリアミド酸を残し、それ以外のジアミン由来のポリアミド酸はすべてイミド化したものである。

On the other hand, as shown in scheme (6), the polyamic acid derived from silicon diamine can be imidized even at a temperature below the temperature at which the entire molecular chain can move because the siloxane moiety can freely vibrate at a low temperature. it can. Therefore, since the polyimide precursor of this invention has already imidized parts other than the polyamic acid derived from silicon diamine, it can imidize at the low temperature of 200 degrees C or less. Further, due to the influence of the carboxylic acid of the silicon diamine-derived polyamic acid, it can be developed with an alkaline solution of a developer when used as a photosensitive resin.
In other words, the polyimide precursor of the present invention is a polyamic acid derived from silicon diamine, and all other polyamic acids derived from diamine are imidized.

（式（４）の構造を有するポリイミド前駆体）
本発明には、式（１）、式（２）以外に式（４）の構造を有しても良い。式（４）の構造を導入するために用いられる酸二無水物末端のポリイミドオリゴマーの合成法について説明する。
最初に、酸二無水物とジアミン化合物とを有機極性溶媒中で反応させ、酸二無水物末端のポリアミド酸のオリゴマーを合成する。この際の当量数は、酸二無水物＞ジアミン化合物とする。ついで、酸二無水物末端オリゴマーのポリアミド酸を、脱水環化して酸二無水物末端オリゴマーとする。酸二無水物末端のポリアミド酸のオリゴマーの合成方法や脱水環化して酸二無水物末端ポリイミドオリゴマーとするイミド化方法は、既述のＯＨ基を有する酸二無水物末端ポリイミドオリゴマー（Ｑ）と同様である。用いることのできるジアミン化合物は、アミノ基を２個有するジアミン化合物であればすべて用いる事が出来る。ジアミン化合物であれば特に限定されないが、例えば、ｐ−フェニレンジアミン、ｍ−フェニレンジアミン、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノフェニルエタン、４，４’−ジアミノフェニルエーテル、４，４’−ジジアミノフェニルスルフィド、４，４’−ジジアミノフェニルスルフォン、１，５−ジアミノナフタレン、３，３−ジメチル−４，４’−ジアミノビフェニル、５−アミノ−１−（４’−アミノフェニル）−１，３，３−トリメチルインダン、６−アミノ−１−（４’−アミノフェニル）−１，３，３−トリメチルインダン、４，４’−ジアミノベンズアニリド、３，５−ジアミノ−３‘−トリフルオロメチルベンズアニリド、３，５−ジアミノ−４’−トリフルオロメチルベンズアニリド、３，４’−ジアミノジフェニルエーテル、２，７−ジアミノフルオレン、２，２−ビス（４−アミノフェニル）ヘキサフルオロプロパン、４，４’−メチレン−ビス（２−クロロアニリン）、２，２’，５，５’−テトラクロロ−４，４’−ジアミノビフェニル、２，２’−ジクロロ−４，４’−ジアミノ−５，５’−ジメトキシビフェニル、３，３’−ジメトキシ−４，４’−ジアミノビフェニル、４，４’−ジアミノ−２，２’−ビス（トリフルオロメチル）ビフェニル、２，２−ビス［４−（４−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］ヘキサフルオロプロパン、１，４−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、１，３’−ビス（４−アミノフェノキシ）ベンゼン、９，９−ビス（４−アミノフェニル）フルオレン、４，４’−（ｐ−フェニレンイソプロピリデン）ビスアニリン、４，４’−（ｍ−フェニレンイソプロピリデン）ビスアニリン、２，２’−ビス［４−（４−アミノ−２−トリフルオロメチルフェノキシ）フェニル］ヘキサフルオロプロパン、４，４’−ビス［４−（４−アミノ−２−トリフルオロメチル）フェノキシ］−オクタフルオロビフェニル等の芳香族ジアミン；ジアミノテトラフェニルチオフェン等の芳香環に結合された２個のアミノ基と当該アミノ基の窒素原子以外のヘテロ原子を有する芳香族ジアミン；１，１−メタキシリレンジアミン、１，３−プロパンジアミン、テトラメチレンジアミン、ペンタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、４，４−ジアミノヘプタメチレンジアミン、１，４−ジアミノシクロヘキサン、イソフォロンジアミン、テトラヒドロジシクロペンタジエニレンジアミン、ヘキサヒドロ−４，７−メタノインダニレンジメチレンジアミン、トリシクロ［６，２，１，０^２．７］−ウンデシレンジメチルジアミン、４，４’−メチレンビス（シクロヘキシルアミン）等の脂肪族ジアミンおよび脂環式ジアミン、４，６−ジアミノレゾルシノール、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、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、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、４，４’−ジアミノ−２，２’，５，５’−テトラヒドロキシジフェニルメタン等のヒドロキシジフェニルメタン等のヒドロキシジフェニルアルカン類、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、４，４’−ジアミノ−２，２’，５，５’−テトラ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化合物、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、４，４’−ジアミノ−２，２’，５，５’−テトラヒドロキシジフェニルスルフォン等のジフェニルスルフォン化合物、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、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、２，４−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、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、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−ヒドロキシフェニル]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等、２，５−ジアミノテレフタル酸等のジアミノフタル酸類、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、４，４’−ジアミノ−２，２’，５，５’−テトラカルボキシビフェニル等のカルボキシビフェニル化合物類、３，３’−ジアミノ−４，４’−ジカルボ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、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、４，４’−ジアミノ−２，２’，５，５’−テトラカルボキシジフェニルメタン等のカルボキシジフェニルアルカン類、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、４，４’−ジアミノ−２，２’，５，５’−テトラカルボキシジフェニルエーテル等のカルボキシジフェニルエーテル化合物、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、４，４’−ジアミノ−２，２’，５，５’−テトラカルボキシジフェニルスルフォン等のジフェニルスルフォン化合物、２，２−ビス［４−（４−アミノ−３−カルボキシフェノキシ）フェニル］プロパン等のビス［（カルボキシフェノキシ）フェニル］アルカン化合物類、２，２−ビス［４−（４−アミノ−３−カルボキシフェノキシ）フェニル］スルフォン等のビス［（カルボキシフェノキシ）フェニル］スルフォン化合物、３，５−ジアミノ安息香酸等のジアミノ安息香酸類をあげることができる。これらのジアミン化合物は単独でまたは２種以上組み合わせて用いることができる。これらのジアミン化合物を導入すれば、本発明のポリイミド前駆体を感光性樹脂として用いた場合、現像液に用いられるアルカリ水溶液への溶解性が向上するため好ましい。特にこれらのジアミンの中でも、式（７）、式（８）、式（１０）に示される化合物を少なくとも一部用いる事が好ましく、更に好ましくはシリコンジアミン以外のジアミン成分中の５％モル以上、特に好ましくは１０モル％以上用いる事が好ましい。

(Polyimide precursor having the structure of formula (4))
The present invention may have the structure of the formula (4) in addition to the formulas (1) and (2). A method for synthesizing the acid dianhydride-terminated polyimide oligomer used to introduce the structure of the formula (4) will be described.
First, an acid dianhydride and a diamine compound are reacted in an organic polar solvent to synthesize an acid dianhydride terminal polyamic acid oligomer. The number of equivalents in this case is acid dianhydride> diamine compound. Subsequently, the polyamic acid of the acid dianhydride terminal oligomer is subjected to dehydration cyclization to form an acid dianhydride terminal oligomer. The acid dianhydride-terminated polyamic acid oligomer synthesis method and dehydration cyclization to make an acid dianhydride-terminated polyimide oligomer include the above-described acid dianhydride-terminated polyimide oligomer (Q) having an OH group. It is the same. As the diamine compound that can be used, any diamine compound having two amino groups can be used. Although it will not specifically limit if it is a diamine compound, For example, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminophenylethane, 4,4'-diaminophenyl ether, 4, 4'-didiaminophenyl sulfide, 4,4'-didiaminophenyl sulfone, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'-amino Phenyl) -1,3,3-trimethylindane, 6-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 4,4′-diaminobenzanilide, 3,5-diamino- 3'-trifluoromethylbenzanilide, 3,5-diamino-4'-trifluoromethylbenzanilide, 3,4'-diaminodiphe Ether, 2,7-diaminofluorene, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetra Chloro-4,4′-diaminobiphenyl, 2,2′-dichloro-4,4′-diamino-5,5′-dimethoxybiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 4,4 '-Diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl ] Hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) -biphenyl, 1,3'-bis (4-aminophenoxy) benze 9,9-bis (4-aminophenyl) fluorene, 4,4 ′-(p-phenyleneisopropylidene) bisaniline, 4,4 ′-(m-phenyleneisopropylidene) bisaniline, 2,2′-bis [4 Aromatic diamines such as-(4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-bis [4- (4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl An aromatic diamine having two amino groups bonded to an aromatic ring such as diaminotetraphenylthiophene and a hetero atom other than the nitrogen atom of the amino group; 1,1-metaxylylenediamine, 1,3-propanediamine , Tetramethylenediamine, pentamethylenediamine, octamethylenediamine, nonamethylenediamine, 4, - diamino heptamethylene diamine, 1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadiene cyclopentadienylide diamine, hexahydro-4,7-meth Noin mite range diamine, tricyclo [6,2,1,0 ^{2. 7} ] -undecylenedimethyl diamine, aliphatic diamines such as 4,4′-methylenebis (cyclohexylamine) and alicyclic diamines, 4,6-diaminoresorcinol, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, 4,4′-diamino-2,2′-dihydroxybiphenyl, 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxybiphenyl Hydroxybiphenyl compounds such as 3,3′-diamino-4,4′-dihydroxy Sidiphenylmethane, 2,2-bis [3-amino-4-hydroxyphenyl] propane, 2,2-bis [4-amino-3-hydroxyphenyl] propane, 2,2-bis [3-amino-4-hydroxy Phenyl] hexafluoropropane, hydroxydiphenylalkanes such as hydroxydiphenylmethane such as 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxydiphenylmethane, 3,3′-diamino-4,4′-dihydroxy Diphenyl ether, 4,4′-diamino-3,3′-dihydroxydiphenyl ether, 4,4′-diamino-2,2′-dihydroxydiphenyl ether, 4,4′-diamino-2,2 ′, 5,5′-tetra Hydroxydiphenyl ether compounds such as hydroxydiphenyl ether, 3,3′-diamino-4,4′-dihydroxy Diphenyl sulfone, 4,4′-diamino-3,3′-dihydroxydiphenyl sulfone, 4,4′-diamino-2,2′-dihydroxydiphenyl sulfone, 4,4′-diamino-2,2 ′, 5,5 Diphenylsulfone compounds such as' -tetrahydroxydiphenylsulfone, bis [(hydroxyphenyl) phenyl] alkane compounds such as 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] propane, 2,2 -Bis [(hydroxyphenoxy) phenyl] sulfone compounds such as bis [4- (4-amino-3-hydroxyphenoxy) phenyl] sulfone, diaminophenols such as 2,4-diaminophenol, 3,3′-diamino- 4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxydiph Bis (hydroxyphenoxy) biphenyl compounds such as nilmethane, 4,4′-diamino-2,2′-dihydroxydiphenylmethane, 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl, 4'-diamino-3,3'-dihydroxydiphenylmethane, 4,4'-diamino-2,2'-dihydroxydiphenylmethane, 2,2-bis [3-amino-4-hydroxyphenyl] propane, 4,4 Bis (hydroxyphenoxy) biphenyl compounds such as' -bis (4-amino-3-hydroxyphenoxy) biphenyl, diaminophthalic acids such as 2,5-diaminoterephthalic acid, 3,3'-diamino-4, 4'-dicarboxybiphenyl, 4,4'-diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-2,2'-dicarboxy Carboxyphenyl compounds such as phenyl, 4,4′-diamino-2,2 ′, 5,5′-tetracarboxybiphenyl, 3,3′-diamino-4,4′-dicarboxydiphenylmethane, 2,2-bis [3-amino-4-carboxyphenyl] propane, 2,2-bis [4-amino-3-carboxyphenyl] propane, 2,2-bis [3-amino-4-carboxyphenyl] hexafluoropropane, 4, Carboxydiphenylalkanes such as 4′-diamino-2,2 ′, 5,5′-tetracarboxydiphenylmethane, 3,3′-diamino-4,4′-dicarboxydiphenyl ether, 4,4′-diamino-3, 3'-dicarboxydiphenyl ether, 4,4'-diamino-2,2'-dicarboxydiphenyl ether, 4,4'-diamino-2,2 ' Carboxydiphenyl ether compounds such as 5,5′-tetracarboxydiphenyl ether, 3,3′-diamino-4,4′-dicarboxydiphenyl sulfone, 4,4′-diamino-3,3′-dicarboxydiphenyl sulfone, 4, Diphenyl sulfone compounds such as 4′-diamino-2,2′-dicarboxydiphenyl sulfone, 4,4′-diamino-2,2 ′, 5,5′-tetracarboxydiphenyl sulfone, 2,2-bis [4- Bis [(carboxyphenoxy) phenyl] alkane compounds such as (4-amino-3-carboxyphenoxy) phenyl] propane, 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] sulfone, etc. Bis [(carboxyphenoxy) phenyl] sulfone compound, 3,5-diamino It is possible to increase the diamino benzoic acids Ikikosanto. These diamine compounds can be used alone or in combination of two or more. When these diamine compounds are introduced, when the polyimide precursor of the present invention is used as a photosensitive resin, the solubility in an alkaline aqueous solution used for a developer is improved. In particular, among these diamines, it is preferable to use at least a part of the compounds represented by formula (7), formula (8), and formula (10), more preferably 5% mol or more in the diamine component other than silicon diamine, It is particularly preferable to use 10 mol% or more.

（Ｒ^７は、同一であっても異なってもよく、−，−(Ｃ＝Ｏ)−，−Ｃ(ＣＨ_３)_２−，−ＣＨ_２−，−ＳＯ_２−，−Ｏ−，−Ｃ(ＣＦ_３)_２−，−ＣＨ(ＣＨ_３)−，−Ｃ(ＣＨ_３)(ＣＨ_２ＣＨ_３)−，シクロヘキシルを、Ｒ^１０は、同一であっても異なってもよく、Ｈ，ＣＨ_３−，ＣＨ_３ＣＨ_２−を、ｍは０〜３を示す。）

^{(R 7} may be the same or different, -, - (C = O ) -, - C (CH 3) 2 -, - CH 2 -, - SO 2 -, - O -, - C (CF ₃ ) ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) (CH ₂ CH ₃ ) —, cyclohexyl, R ¹⁰ may be the same or different, and H, CH ₃ -, _CH 3 _{CH 2} - a, m denotes 0 to 3).

（Ｒ^７は、同一であっても異なってもよく、−，−(Ｃ＝Ｏ)−，−Ｃ(ＣＨ_３)_２−，−ＣＨ_２−，−ＳＯ_２−，−Ｏ−，−Ｃ(ＣＦ_３)_２−，−ＣＨ(ＣＨ_３)−，−Ｃ(ＣＨ_３)(ＣＨ_２ＣＨ_３)−，シクロヘキシルを、Ｒ^１０は、同一であっても異なっても良く、Ｈ，ＣＨ_３−，ＣＨ_３ＣＨ_２−を、ｎは１〜４を示す。）

^{(R 7} may be the same or different, -, - (C = O ) -, - C (CH 3) 2 -, - CH 2 -, - SO 2 -, - O -, - C (CF ₃ ) ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) (CH ₂ CH ₃ ) —, cyclohexyl, R ¹⁰ may be the same or different, and H, CH ₃ -, _CH 3 _{CH 2} - a, n represents shows 1-4).

（Ｒ^７は、同一であっても異なってもよく、−，−(Ｃ＝Ｏ)−，−Ｃ(ＣＨ_３)_２−，−ＣＨ_２−，−ＳＯ_２−，−Ｏ−，−Ｃ(ＣＦ_３)_２−，−ＣＨ(ＣＨ_３)−，−Ｃ(ＣＨ_３)(ＣＨ_２ＣＨ_３)−，シクロヘキシルを、Ｒ^１０は、同一であっても異なってもよく、Ｈ，ＣＨ_３−，ＣＨ_３ＣＨ_２−を、ｒは０〜４を示す。）
式（４）の構造を本発明のポリイミド前駆体中に導入するために用いられる、酸二無水物末端のポリイミドオリゴマーは、ジイソシアネートと酸二無水物とを反応しても合成することが出来る。ジイソシアネートと酸二無水物による酸二無水物末端オリゴマーの合成法について説明する。

^{(R 7} may be the same or different, -, - (C = O ) -, - C (CH 3) 2 -, - CH 2 -, - SO 2 -, - O -, - C (CF ₃ ) ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) (CH ₂ CH ₃ ) —, cyclohexyl, R ¹⁰ may be the same or different, and H, CH ₃ -, _CH 3 _{CH 2} - a, r is shown a 0-4).
The acid dianhydride-terminated polyimide oligomer used for introducing the structure of the formula (4) into the polyimide precursor of the present invention can also be synthesized by reacting diisocyanate and acid dianhydride. A method for synthesizing an acid dianhydride-terminated oligomer using diisocyanate and acid dianhydride will be described.

  The acid dianhydride and the diisocyanate compound are subjected to a polycondensation reaction in an organic solvent for 1 to 12 hours to decarboxylate to obtain an oligomer of an acid dianhydride terminal oligomer. The number of equivalents in this case is acid dianhydride> diisocyanate compound, and the ratio of acid dianhydride ÷ diisocyanate compound is more than 1 and 10 or less, preferably 1.1 or more and 5 or less, more preferably 1.3 or more and 3 or less.

  The conditions for the polycondensation reaction of acid dianhydride and diisocyanate compound in an organic solvent include, for example, N, N-dimethylsulfoxide, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, After heating at room temperature to 80 ° C in a polar solvent such as N, N-diethylacetamide, N-methyl-2-pyrrolidone or hexamethylenephosphoamide, the reaction is further heated to about 150 to 200 ° C to promote the reaction. At this time, it is more preferable to reduce the pressure because the decarboxylation reaction is promoted.

  The acid dianhydride used for the polyimide precursor of the present invention is the same acid dianhydride as that used in the method of synthesizing the acid dianhydride-terminated polyimide oligomer obtained by reacting the acid dianhydride and the diamine compound. Anhydrides can be used.

  Although the diisocyanate used for the polyimide precursor of this invention will not be specifically limited if it is a diisocyanate, The following diisocyanate can be illustrated. For example, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6- Hexamethylene diisocyanate, lysine diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 1,3-bis (isocyanate) -Tomethyl) -cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate Carbodiimidized diphenylmethane polyisocyanate, tolidine diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, tetramethyloxy Range isocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, dimer acid diisocyanate, norbornene diisocyanate and the like can be raised. The acid dianhydride-terminated polyimide oligomer having a monovalent organic group having a carbon-carbon double bond synthesized as shown in the above-mentioned scheme (3) and the acid dianhydride-terminated polyimide oligomer thus obtained. Can be synthesized with the above-described silicon diamine of formula (9) in a solvent to synthesize the polyimide precursor of the present invention. The synthesis conditions are the same as the reaction conditions for the above-mentioned acid dianhydride-terminated polyimide oligomer (Q) having an OH group and the silicon diamine represented by the formula (9).

The constituent mole fractions of the formula (1), formula (2) and formula (4) in the preferred polyimide precursor, that is, each R ₂ , R in all R ₂ , R ₃ , R ₅ in the polyimide precursor ₃ , the molar fraction of R ₅ is 1 to 80% of the molar fraction of R ₂ of the formula (1), and the molar fraction of R ₃ of the formula (2) is 10 to 90%, The molar fraction of R _{5 in} the formula (4) is 0 to 70%. More preferably, the mole fraction of R _{2 in} the formula (1) is 3 to 70%, the mole fraction of R _{3 in} the formula (2) is 20 to 80%, and the formula (4) mole fraction of R ₅ is 0-60%. If it deviates from this range, good photosensitivity may not be obtained or heat resistance may be impaired.

(Polyamide acid oligomer with acid dianhydride having COOH group)
In the present invention, in addition to the method for synthesizing the polyimide precursor (A) using the above-described diamine group-containing diamine compound, the following diamine compound having a COOH group may be used. Can be synthesized.

(Diamine compound having a COOH group)
Any diamine compound having a COOH group can be used in the present invention, and although not particularly limited, a preferred structure can be represented by the general formula (10).

（Ｒ^７は、同一であっても異なってもよく、−，−(Ｃ＝Ｏ)−，−Ｃ(ＣＨ_３)_２−，−ＣＨ_２−，−ＳＯ_２−，−Ｏ−，−Ｃ(ＣＦ_３)_２−，−ＣＨ(ＣＨ_３)−，−Ｃ(ＣＨ_３)(ＣＨ_２ＣＨ_３)−，シクロヘキシルを、Ｒ^１０は、同一であっても異なってもよく、Ｈ，ＣＨ_３−，ＣＨ_３ＣＨ_２−を、ｒは０〜４を示す。）
（ＣＯＯＨ基を有するジアミン化合物を用いた（Ａ）ポリイミド前駆体）
上記で説明した、ＯＨ基を有するジアミン化合物を用いた、（Ａ）ポリイミド前駆体の合成方法において、ＯＨ基を有するジアミン化合物を用いる代わりに、上述したＣＯＯＨ基を有するジアミン化合物を用い、その他は同様の合成方法により、（Ａ）ポリイミド前駆体を合成することが出来る。

^{(R 7} may be the same or different, -, - (C = O ) -, - C (CH 3) 2 -, - CH 2 -, - SO 2 -, - O -, - C (CF ₃ ) ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) (CH ₂ CH ₃ ) —, cyclohexyl, R ¹⁰ may be the same or different, and H, CH ₃ -, _CH 3 _{CH 2} - a, r is shown a 0-4).
((A) Polyimide precursor using a diamine compound having a COOH group)
In the method for synthesizing the polyimide precursor (A) using the diamine compound having an OH group described above, instead of using the diamine compound having an OH group, the above-described diamine compound having a COOH group is used. The polyimide precursor (A) can be synthesized by the same synthesis method.

  Thus, the obtained (A) polyimide precursor can be utilized for the photosensitive resin composition.

  Below, (B) component, (C) component, (D) component, and other components which are components of the photosensitive resin composition other than (A) polyimide precursor obtained above are demonstrated.

<(B) (Meth) acrylic compound having unsaturated double bond>
Next, the (meth) acrylic compound having an unsaturated double bond as the component (B) used in the present invention will be described.

  In addition to the polyimide composition of the present invention, (B) a (meth) acrylic compound having an unsaturated double bond is added to obtain a photosensitive resin composition. Although the (meth) acryl compound used for this invention will not be specifically limited if it has an unsaturated double bond, The following can be illustrated.

    For example, bisphenol F EO modified (n = 2 to 50) diacrylate, bisphenol A EO modified (n = 2 to 50) diacryl, sphenol S EO modified (n = 2 to 50) diacrylate, 1,6-hexane Diol 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 dimethyl ester Tacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexamethacrylate, tetramethylolpropane tetramethacrylate, tetraethylene glycol dimethacrylate, methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, β-methacryloyloxyethyl hydrogen phthalate, β-methacryloyloxyethyl hydrogen succinate, 3-chloro-2-hydroxypropyl methacrylate, stearyl methacrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy polyethylene glycol acrylate, β-acryloyloxyethyl hydrogensa Sinate, 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-bis [4- (methacryloxydiethoxy) phenyl] propane, 2 , 2-bis [4- (methacryloxy polyethoxy) phenyl] propane, polyethylene glycol diacrylate, tripropylene glycol diacrylate, poly Propylene glycol diacrylate, 2,2-bis [4- (acryloxydiethoxy) phenyl] propane, 2,2-bis [4- (acryloxypolyethoxy) phenyl] propane, 2-hydroxy 1-acryloxy-3-methacryloxypropane , Trimethylolpropane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetraacrylate, methoxydipropylene glycol methacrylate, methoxytriethylene glycol acrylate, nonylphenoxypolyethylene glycol acrylate, nonylphenoxypolypropylene glycol acrylate, 1-acryloyloxypropyl-2 -Phthalate, isostearyl acrylate, polyoxyethylene alkyl ether acrylate, Nylphenoxyethylene glycol acrylate, polypropylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 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 diacrylate, 2,2-hydrogenated bis [4 -(Acryloxy polyethoxy) phenyl] propane, 2,2-bis [4- (acryloxy polypropoxy) phenyl] propane, 2,4-diethyl-1,5-pentanediol diacrylate, ethoxylated totime Roll propane triacrylate, propoxylated tomethylol propane triacrylate, isocyanuric acid tri (ethane acrylate), pentathritol tetraacrylate, ethoxylated pentathritol tetraacrylate, propoxylated pentathritol tetraacrylate, ditrimethylolpropane tetreacrylate, di Pentaerythritol polyacrylate, triallyl isocyanurate, glycidyl methacrylate, glycidyl allyl ether, 1,3,5-triacryloylhexahydro-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′-isopropyl Dendiphenol diacrylate and the like can be exemplified. In order to improve the crosslink density, it is particularly desirable to use a bifunctional or higher monomer.

As other compounds having a carbon-carbon double bond, styrene, divinylbenzene, vinyl-4-t-butylbenzoate, vinyl n-butyl ether, vinyl isobutyl ether, vinyl n-butyrate, vinyl n-caprolate, vinyl n- Vinyl compounds such as caprylate and allyl compounds such as triallyl isocyanurate and diallyl phthalate may be used.
The compound having a carbon-carbon double bond is preferably blended in an amount of 1 to 400 parts by weight, more preferably 3 to 300 parts by weight, based on 100 parts by weight of the polyimide precursor of the present invention. If it deviates from the range of 1 to 400 parts by weight, the intended effect may not be obtained. In addition, as a compound which has a carbon-carbon double bond, one type of compound may be used and several types may be mixed and used.

<(C) Photoreaction initiator>
The photoreaction initiator that is the component (C) used in the present invention will be described.

  The photoinitiator of this invention is a general term for the compound which generate | occur | produces a radical by light irradiation. Although it will not specifically limit if a radical is generate | occur | produced by light irradiation of 250-450 nm, The following can be illustrated.

  For example, acylphosphine oxide compounds represented by the following formulas (11) and (12) may be mentioned. The radicals generated thereby react with a reactive group having a double bond (vinyl, acroyl, methacryloyl, allyl, etc.) to promote crosslinking.

（式中、Ｒ^１３，Ｒ^１４，Ｒ^１５，Ｒ^１６，Ｒ^１７，Ｒ^１８は、Ｃ_６Ｈ_５−，Ｃ_６Ｈ_４（ＣＨ_３）−，Ｃ_６Ｈ_２（ＣＨ_３）_３−，（ＣＨ_３）_３Ｃ−，Ｃ_６Ｈ_３Ｃｌ_２−，メトキシ基，エトキシ基のいずれかを表す。）
特に式（１２）で表されるアシルフォスフィンオキシドは、光硬化性が高く好ましい。

(Wherein R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ are C ₆ H ₅ —, C ₆ H ₄ (CH ₃ ) —, C ₆ H ₂ (CH ₃ ) ₃ —, (CH ₃ ) ₃ C—, C ₆ H ₃ Cl ₂ —, a methoxy group, or an ethoxy group is represented.)
In particular, the acylphosphine oxide represented by the formula (12) is preferable because of high photocurability.

  Moreover, various peroxides and the following sensitizers can be used in combination as the photoreaction initiator. Particularly preferred is a combination of 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone and a sensitizer.

  The photosensitive resin composition used in the present invention can contain a sensitizer in order to achieve photosensitive sensitivity that can be practically used. Preferred examples of the sensitizer include mihiraketone, bis-4,4′-diethylaminobenzophenone, benzophenone, camphorquinone, benzyl, 4,4′-dimethylaminobenzyl, 3,5-bis (diethylaminobenzylidene) -N-methyl. -4-piperidone, 3,5-bis (dimethylaminobenzylidene) -N-methyl-4-piperidone, 3,5-bis (diethylaminobenzylidene) -N-ethyl-4-piperidone, 3,3′-carbonylbis ( 7-diethylamino) coumarin, riboflavin tetrabutyrate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 3,5-dimethyl Thioxanthone, 3,5-diisopropylthioxanthone, 1-phenyl-2- (ethoxycarbonyl) oxyiminopropan-1-one, benzoin ether, benzoin isopropyl ether, benzanthrone, 5-nitroacenaphthene, 2-nitrofluorene, anthrone, 1,2-benzanthraquinone, 1-phenyl-5-mercapto-1H-tetrazole, thioxanthen-9-one, 10-thioxanthenone, 3-acetylindole, 2,6-di (p-dimethylaminobenzal) -4 -Carboxycyclohexanone, 2,6-di (p-dimethylaminobenzal) -4-hydroxycyclohexanone, 2,6-di (p-diethylaminobenzal) -4-carboxycyclohexanone, 2,6-di (p-diethylamino) Benza ) -4-hydroxycyclohexanone, 4,6-dimethyl-7-ethylaminocoumarin, 7-diethylamino-4-methylcoumarin, 7-diethylamino-3- (1-methylbenzimidazolyl) coumarin, 3- (2-benzimidazolyl) -7-diethylaminocoumarin, 3- (2-benzothiazolyl) -7-diethylaminocoumarin, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) quinoline, 4- (p-dimethylaminostyryl) ) Quinoline, 2- (p-dimethylaminostyryl) zenzothiazole, 2- (p-dimethylaminostyryl) -3,3-dimethyl-3H-indole and the like, but are not limited thereto.

  The sensitizer is preferably blended in an amount of 0.01 to 50 parts by weight, more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the polyimide precursor of the present invention. When the amount is outside the range of 0.01 to 50 parts by weight, the sensitizing effect may not be obtained or the developability may be adversely affected. As the sensitizer, one kind of compound may be used, or several kinds may be mixed and used.

    In addition, the photosensitive resin composition used in the present invention can contain a photopolymerization auxiliary agent in order to achieve practical photosensitivity. Examples of the photopolymerization assistant include 4-diethylaminoethylbenzoate, 4-dimethylaminoethylbenzoate, 4-diethylaminopropylbenzoate, 4-dimethylaminopropylbenzoate, 4-dimethylaminoisoamylbenzoate, N-phenylglycine, N- Methyl-N-phenylglycine, N- (4-cyanophenyl) glycine, 4-dimethylaminobenzonitrile, ethylene glycol dithioglycolate, ethylene glycol di (3-mercaptopropionate), trimethylolpropane thioglycolate, Trimethylolpropane tri (3-mercaptopropionate), pentaerythritol tetrathioglycolate, pentaerythritol tetra (3-mercaptopropionate), trimethylolethane trithio Licolate, trimethylolpropane trithioglycolate, trimethylolethanetri (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), thioglycolic acid, α-mercaptopropionic acid, t-butylperoxy Benzoate, t-butylperoxymethoxybenzoate, t-butylperoxynitrobenzoate, t-butylperoxyethylbenzoate, phenylisopropylperoxybenzoate, di-t-butyldiperoxyisophthalate, tri-t-butyltriperoxy trimellitate, tri t-butyl triperoxy trimesitate, tetra t-butyltetraperoxypyromellitate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 3,3 ′, 4,4 -Tetra (t-butylperoxycarbonyl) benzophenone, 3,3,4,4'-tetra (t-amylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (t-hexylperoxycarbonyl) benzophenone, 2,6-di (p-azidobenzal) -4-hydroxycyclohexanone, 2,6-di (p-azidobenzal) -4-carboxycyclohexanone, 2,6-di (p-azidobenzal) -4-methoxycyclohexanone, 2, 6-di (p-azidobenzal) -4-hydroxymethylcyclohexanone, 3,5-di (p-azidobenzal) -1-methyl-4-piperidone, 3,5-di (p-azidobenzal) -4-piperidone, 3, , 5-Di (p-azibenzal) -N-acetyl-4-piperidone, 3,5-di (p-azidobenzal)- N-methoxycarbonyl-4-piperidone, 2,6-di (p-azidobenzal) -4-hydroxycyclohexanone, 2,6-di (m-azidobenzal) -4-carboxycyclohexanone, 2,6-di (m-azidobenzal) ) -4-methoxycyclohexanone, 2,6-di (m-azidobenzal) -4-hydroxymethylcyclohexanone, 3,5-di (m-azidobenzal) -N-methyl-4-piperidone, 3,5-di (M-azidobenzal) -4-piperidone, 3,5-di (m-azidobenzal) -N-acetyl-4-piperidone, 3,5-di (m-azidobenzal) -N-methoxycarbonyl-4-piperidone, 2, 6-di (p-azidocinnamylidene) -4-hydroxycyclohexanone, 2,6-di (p-azidocinnamylidene) -4-carboxycyclohexanone 2,6-di (p-azidocinnamylidene) -4-cyclohexanone, 3,5-di (p-azidocinnamylidene) -N-methyl-4-piperidone, 4,4′-diazidochalcone, 3,3′-diazidochalcone, 3,4′-diazidochalcone, 4,3′-diazidochalcone, 1,3-diphenyl-1,2,3-propanetrione-2- (o-acetyl) oxime 1,3-diphenyl-1,2,3-propanetrione-2- (on-propylcarbonyl) oxime, 1,3-diphenyl-1,2,3-propanetrione-2- (o-methoxycarbonyl) ) Oxime, 1,3-diphenyl-1,2,3-propanetrione-2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-1,2,3-propanetrione-2- (o-benzoyl) Oh Xime, 1,3-diphenyl-1,2,3-propanetrione-2- (o-phenyloxycarbonyl) oxime, 1,3-bis (p-methylphenyl) -1,2,3-propanetrione-2 -(O-benzoyl) oxime, 1,3-bis (p-methoxyphenyl) -1,2,3-propanetrione-2- (o-ethoxycarbonyl) oxime, 1- (p-methoxyphenyl) -3- (P-Nitrophenyl) -1,2,3-propanetrione-2- (o-phenyloxycarbonyl) oxime and the like can be used, but are not limited thereto. Further, as another auxiliary agent, trialkylamines such as triethylamine, tributylamine, and triethanolamine can be mixed.

  The photopolymerization assistant is preferably blended in an amount of 0.01 to 50 parts by weight, more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the polyimide precursor of the present invention. If the content falls outside the range of 0.01 to 50 parts by weight, the intended sensitization effect may not be obtained, or the developability may be adversely affected. In addition, one type of compound may be used as a photopolymerization assistant, and several types may be mixed.

<(D) Compound having carbon-carbon double bond and tertiary amino group in the molecule or compound having carbon-carbon double bond and amide group>
The compound having a carbon-carbon double bond and a tertiary amino group in the molecule and a compound having a carbon-carbon double bond and an amide group as the component (D) used in the present invention will be described. This compound will not be specifically limited if it is a compound which has a carbon-carbon double bond and an amino group in a molecule | numerator, or has a carbon-carbon double bond and an amide group.

  Preferable specific examples of the compound having a carbon-carbon double bond and an amino group include dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, N, N-dimethylaminoethyl methacrylamide, N, N -Dimethylaminopropyl methacrylamide, N, N-diethylaminoethyl methacrylamide, N, N-diethylaminopropyl methacrylamide, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl acrylate, N, N-dimethylaminoethylacrylamide , N, N-dimethylaminopropylacrylamide, N, N-diethylaminoethylacrylamide, N, N-diethylaminopropylacrylamide, etc. But it is not limited.

  Preferred specific examples of the compound having a carbon-carbon double bond and an amide group include acrylamide, methacrylamide, N-methyl methacrylamide, N-methyl acrylamide, N-ethyl methacrylamide, N-ethyl acrylamide, N-isopropyl. Methacrylamide, N-isopropylacrylamide, N-butylmethacrylamide, N-butylacrylamide, diacetoneacrylamide, diacetonemethacrylamide, N-cyclohexylmethacrylamide, N-cyclohexylacrylamide, N-methylolacrylamide, acryloylmorpholine, methacryloyl Morpholine, acryloylpiperidine, methacryloylpiperidine, crotonamide, N-methylcrotonamide, N-isopropylcrotonamide, N Butyl crotonate amide, acetate allyl amide, the like allyl amide propionic acid without limitation. In particular, aminoacrylate derivatives and acrylamide derivatives are preferred in terms of sensitivity.

<Other components contained in the photosensitive resin composition>
The photosensitive resin composition of the present invention may contain an epoxy compound in addition to the polyimide precursor, the (meth) acryl compound, and the photoinitiator.

  The epoxy compound is not particularly limited as long as it has an epoxy group in the molecule, and can be exemplified as follows.

  For example, bisphenol resin such as Epicoat 828 (manufactured by Yuka Shell), orthocresol novolak resin such as 180S65 (manufactured by Yuka Shell), bisphenol A novolak resin such as 157S70 (manufactured by Yuka Shell), 1032H60 (oiled Trishydroxyphenylmethane novolak resin such as ESN375, Naphthalene aralkyl novolac resin such as ESN375, Tetraphenylolethane 1031S (Yukaka Shell), YGD414S (Tohto Kasei), Trishydroxyphenylmethane EPPN502H (Nippon Kayaku) And glycidylamine type resins such as special bisphenol VG3101L (Mitsui Chemicals), special naphthol NC7000 (Nippon Kayaku), TETRAD-X, TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the like.

  Moreover, the compound which has an epoxy group and a double bond and a triple bond in a molecule | numerator can also be mixed. Examples thereof include allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, glycidyl vinyl ether, propargyl glycidyl ether, glycidyl propionate, ethynyl glycidyl ether, and the like.

  In particular, among epoxy compounds, use of an epoxy compound having one epoxy group in the molecule is particularly desirable because it can suppress curing shrinkage during curing. As monofunctional epoxy compounds, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, alkyl monoglycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, allyl glycidyl ether, pt-butylphenyl glycidyl ether, nonylphenyl glycidyl ether, p -Sec-butylphenyl glycidyl ether, alkylphenol monoglycidyl ether, versatic acid monoglycidyl ester, linear alcohol monoglycidyl ether, glycerol monoglycidyl ether, polyglycol glycidyl ether, glycidyl methacrylate, etc. It is not a thing.

  Further preferred examples include pt-butylphenyl glycidyl ether, nonylphenyl glycidyl ether, p-sec-butylphenyl glycidyl ether, alkylphenol monoglycidyl ether, versatic acid monoglycidyl ester, linear alcohol monoglycidyl ether, glycerol monoglycidyl Ether, polyglycol glycidyl ether, 2-methylhexyl glycidyl ether, 3- (2-biphenyloxy) -1,2-epoxypropane, glycidyl 4-methoxyglycidyl ether, glycidyl mesityl ether, N- (2,3-epoxypropyl) ) Phthalimide, glycidyl hexadecyl ether, glycidyl nonyl phenyl ether, glycidyl lauryl ether, 3-dodecafluoroheproxy , 2-propoxide, Nippon Kayaku Co., Ltd. BR-250H, Nippon Kayaku Co., Ltd. BROC-Y, Nippon Kayaku Co., Ltd. BROC-C, Nippon Kayaku Co., Ltd. BROC, etc. can be illustrated. .

  The photosensitive resin composition of the present invention may contain a flame retardant in addition to the polyimide precursor, the (meth) acryl compound, and the photoinitiator.

Next, the flame retardant used in the present invention will be described.
When the flame retardant is a compound containing phosphorus, the phosphorus content is preferably 5.0% or more, more preferably 7.0% or more from the viewpoint that flame retardancy can be effectively imparted. When the flame retardant is a halogen-containing compound, the halogen content is preferably 15% or more, more preferably 20% or more from the viewpoint that flame retardancy can be effectively imparted. As halogen, those using chlorine or bromine are generally used. When the flame retardant is a compound containing a siloxane moiety, an organopolysiloxane compound containing an aromatic ring in a high ratio is preferable from the viewpoint of effectively imparting heat resistance and flame retardancy.

When a phosphorus compound is used as a flame retardant, examples of the phosphorus compound include phosphazenes, phosphines, phosphine oxides, phosphoric acid esters (including condensed phosphoric acid esters), and phosphorous compounds such as phosphorous acid esters. From the aspect of compatibility with the polyimide composition, phosphazene, phosphine oxide, or phosphate ester (including condensed phosphate ester) is preferable. The phosphorus content of the phosphorus compound used as a flame retardant is preferably 5.0% by weight, more preferably 7.0% by weight or more.
Furthermore, for example, SPE-100 (phosphazene compound manufactured by Otsuka Chemical Co., Ltd.), SPH-100 (phosphazene compound manufactured by Otsuka Chemical Co., Ltd.), TPP (triphenyl phosphate) can be provided from the viewpoint of imparting flame retardancy and resistance to hydrolysis. , TCP (tricresyl phosphate), TXP (trixylenyl phosphate), CDP (cresyl diphenyl phosphate), PX-110 (cresyl 2,6-xylenyl phosphate) (all manufactured by Daihachi Chemical) Non-halogen condensed phosphates such as acid esters, CR-733S (resinol diphosphate), CR-741, CR-747, PX-200) (all manufactured by Daihachi Chemical), Biscoat V3PA (Osaka Organic Chemical Industry) ), MR-260 (manufactured by Daihachi Chemical), etc., phosphoric acid (meth) acrylate, Such as phosphorous acid esters such as acid triphenyl ester.

When a halogen-containing compound is used as the flame retardant, the halogen content is preferably 30% by weight or more, more preferably 40% by weight or more, and most preferably 50% by weight or more. From the viewpoint of improving flame retardancy, the higher the halogen content, the better.
Examples of the halogen-containing compound include chlorine-containing organic compounds and bromine-containing organic compounds. From the viewpoint of imparting flame retardancy, bromine-containing compounds are preferred, and the following can be exemplified.
For example, brominated monomers such as New Frontier BR-30, BR-30M, BR-31, BR-42M (Daiichi Kogyo Seiyaku), brominated aromatic triazines such as Piroguard SR-245 (Daiichi Kogyo Seiyaku), Examples thereof include brominated aromatic polymers such as Pyroguard SR-250 and SR-400A (Daiichi Kogyo Seiyaku), and brominated aromatic compounds such as Piroguard SR-990A (Daiichi Kogyo Seiyaku).

The flame retardant may be a phosphorus compound having a halogen atom in one molecule. Examples of such a compound include CLP (tris (2-chloroethyl) phosphate), TMCPP (tris (chloropropyl) phosphate), And halogen-containing phosphates such as CRP (tris (dichloropropyl) phosphate) and CR-900 (tris (tribromoneopentyl) phosphate) (both manufactured by Daihachi Chemical).
Furthermore, when a compound having a siloxane moiety is used as a flame retardant, it is preferably an organopolysiloxane compound containing a high proportion of aromatic rings because it imparts flame retardancy, and the phenyl group is selected from all organic substituents. An organopolysiloxane compound containing 10 mol% or more, more preferably 20 mol% or more, and more preferably 25 mol% or more is preferable. The smaller the phenyl group content, the smaller the flame retardant effect, and the higher the phenyl group content, the higher the flame retardant effect.
When an organopolysiloxane compound having a low phenyl group content is used as a flame retardant, the dispersibility and compatibility with a new polyimide composition or a compound having a carbon-carbon double bond tend to be poor. When it is formed into a film, there is a tendency that only a low-transparency film in which a plurality of components having different refractive indexes are phase-separated or an opaque film is obtained. In addition, when such an organopolysiloxane compound having a low phenyl group content is used, it is difficult to obtain a sufficient flame retardant effect unless the amount added is increased, but the heat resistant resin composition produced when the amount added is increased. There is a tendency that physical properties such as mechanical strength of the material are significantly lowered.

Furthermore, when an organopolysiloxane compound is used, flame retarding of the resin can be realized without generating harmful gases during combustion. In the case of a resin composition containing a halogen-containing compound, although flame retardancy can be realized, there is a drawback that harmful halogen-based gas is generated during combustion.
The structure of the organopolysiloxane compound is generally composed of a combination of a trifunctional siloxane unit (T unit), a bifunctional siloxane unit (D unit), and a tetrafunctional siloxane unit (Q unit). A good combination in the present invention is a system containing a D unit such as a T / D system, a T / D / Q system, a D / Q system, and the like, and thereby provides good flame retardancy. In any combination, the D unit needs to be contained in an amount of 10 to 80 mol%. When the D unit is less than 10 mol%, the flexibility imparted to the organopolysiloxane compound is poor, and as a result, sufficient flame retardancy cannot be obtained. Moreover, when it exceeds 80 mol%, the dispersibility and solubility with (A) component: soluble polyimide will fall, and the external appearance and optical transparency and intensity | strength of a heat resistant resin composition will worsen. More preferably, the content of the D unit is in the range of 10 to 70 mol%. Therefore, according to the good D unit content, in the case of the T / D system, the content of the T unit is in the range of 30 to 90 mol%, and in the case of the T / D / Q system or the D / Q system, The content of T units is 0 to 89.99 mol%, preferably 10 to 79.99 mol%, and the content of Q units is 0.01 to 50 mol%. As long as the degree of freedom of space is secured, it is more advantageous to contain a larger amount of highly oxidized Q units in order to reproduce the flame retardancy. However, Q units in the organopolysiloxane compound are more advantageous. When the content exceeds 60 mol%, the inorganic fine particle property becomes too strong, and the dispersibility in the soluble polyimide becomes poor. Therefore, the blending amount needs to be kept below this. From the above siloxane unit content range, in consideration of the balance of flame retardancy, workability, molded product performance, etc., select a region where T units account for 40-80% by weight of the total weight of phenylsiloxane. It is further desirable to do so.
Here, exemplifying preferable constituent siloxane units, the trifunctional siloxane units (T units) are C ₆ H ₅ SiO _3/2 and CH ₃ SiO _3/2 , and the bifunctional siloxane units are (C ₆ H _{5 2} SiO _2/2 , (CH ₃ ) C ₆ H ₅ SiO _2/2 , (CH ₃ ) ₂ SiO _2/2 .
In this case, the dimethylsiloxane unit ((CH ₃ ) ₂ SiO _2/2 ) as the D unit for imparting flexibility has the greatest effect of imparting flexibility to the silicone resin. If the amount is too high, the flame retardancy tends to decrease, so that it is difficult to improve the flame retardancy, and it is not desirable to contain a large amount. Accordingly, the dimethylsiloxane unit is preferably suppressed to 60 mol% or less in the D unit. Methylphenylsiloxane units ((CH ₃ ) C ₆ H ₅ SiO _2/2 ) are most preferred because they can provide flexibility and at the same time increase the phenyl group content. In addition, the diphenylsiloxane unit ((C ₆ H ₅ ) ₂ SiO _2/2 ) is excellent in maintaining a high phenyl group content, but it has a structure in which bulky phenyl groups are concentrated on a single Si. Incorporating into the polysiloxane brings a structure having a large steric hindrance to the organopolysiloxane molecule, so that the spatial freedom of the siloxane skeleton is reduced, and the aromatic rings required for the flame retardant mechanism by the mutual coupling of the aromatic rings to act. Overlap may be difficult and may reduce the flame retardant effect. Therefore, the D unit may be used by blending these three raw materials so as to satisfy the above-mentioned range, but it is preferable to mainly use a methylphenylsiloxane unit.
The weight average molecular weight of the flame retardant phenylsiloxane is preferably in the range of 300 to 50,000. A weight average molecular weight of less than 300 is not preferable because the heat resistant resin composition may ooze out in the B-stage state. If it exceeds 50,000, the solubility in the developer is lowered, the development time is prolonged, and the workability may be lowered. More preferably, it is the range of 400-30,000.

  Such an organopolysiloxane compound can be produced by a known method. For example, organochlorosilane and / or organoalkoxysilane that can form the above siloxane units by hydrolysis condensation reaction, or partially hydrolyzed condensate thereof, hydrolyze all hydrolyzable groups (chlor groups, alkoxy groups, etc.) For this purpose, excess water, the raw material silane compound and the resulting organopolysiloxane compound are mixed into a mixed solution of a dissolvable organic solvent and subjected to a hydrolysis condensation reaction. An organopolysiloxa compound having a desired weight average molecular weight can be obtained by adjusting the reaction temperature and time, the amount of water and an organic solvent. When using, unnecessary organic solvent may be removed and powdered for use.

  For example, KF50-100S, KF54, KF56, HIVAC F4, HIVAC F5, X-22-1824B, KR211 and KR311 manufactured by Shin-Etsu Silicone Co., Ltd. can be mentioned. Also good.

The flame retardant is preferably used in an amount of 5 to 50% by weight based on the total amount of the novel polyimide composition and the compound having a carbon-carbon double bond. If it is less than 5%, it tends to be difficult to impart flame retardancy to the coverlay film after curing, and if it exceeds 50%, the mechanical properties of the coverlay film after curing tend to be poor.
In addition, when a halogen-containing compound is used as a flame retardant, antimony trioxide and / or antimony pentoxide is added, and the antimony oxide extracts halogen atoms from the flame retardant in the thermal decomposition start temperature range of the halogenated product. Since antimony is generated, the flame retardancy can be increased synergistically. The addition amount is preferably 0.1 to 10% by weight, more preferably 1 to 6% by weight based on the total weight of the novel polyimide composition, the compound having a carbon-carbon double bond, and the flame retardant. Preferably there is.
Since the antimony trioxide and antimony pentoxide white powders are not dissolved in an organic solvent, if the powder has a particle size of 100 μm or more, it becomes cloudy when mixed in the heat-resistant resin composition, making the resulting heat-resistant resin composition difficult. Although flame retardancy can be imparted, the transparency and developability tend to decrease, and therefore it is preferably 100 μm or less. Furthermore, in order to increase the flame retardancy without losing the transparency of the heat resistant resin composition, it is preferable to use antimony trioxide and / or antimony pentoxide having a powder particle size of 50 μm or less. More preferred is a powder having a particle size of 10 μm or less, and most preferred is a powder having a particle size of 5 μm or less.
Examples of antimony pentoxide having a particle size of 50 μm or less include Sun Epoch NA-3181, NA-4800, NA-1030, NA-1070L (all manufactured by Nissan Chemical Industries).

  Antimony trioxide and / or antimony pentoxide may be mixed in the heat-resistant resin composition as a powder, or if the powder settles in the heat-resistant resin composition, the powder is dispersed in an organic solvent. Alternatively, it may be mixed after making into a sol form. As a specific method for forming a sol, a dispersant is added to an organic solvent together with an antimony trioxide and / or antimony pentoxide powder to form a network to prevent the powder from settling. As this dispersing agent, a mixture of vapor phase silica (silicon dioxide) and alumina (aluminum trioxide) can be used. The dispersant is preferably added in an amount of 2 to 5 times the weight of antimony trioxide and / or antimony pentoxide.

The photosensitive resin composition of this invention is obtained using each component demonstrated above. Below, the utilization method of the said photosensitive resin composition is demonstrated.
<Method for preparing photosensitive resin composition and method for preparing photosensitive dry film resist>
Then, the preparation method of the photosensitive resin composition and the preparation methods of the photosensitive dry film resist are demonstrated. The photosensitive dry film resist is produced by uniformly applying and drying an organic solvent solution of a photosensitive resin composition on a support film.
<Method for preparing photosensitive resin composition>
First, the preparation method of the photosensitive resin composition of this invention is demonstrated. The photosensitive resin composition of the present invention has (A) a polyimide precursor, (B) a (meth) acrylic compound having an unsaturated double bond, (C) a photoreaction initiator, and other components as necessary. A solution obtained by mixing them in a proportion and uniformly dissolving them in an organic solvent is called an organic solvent solution of the photosensitive resin composition. The organic solvent is not particularly limited as long as it is an organic solvent that can dissolve the components contained in the photosensitive resin composition. Examples of the organic solvent include ether solvents such as dioxolane, dioxane, and tetrahydrofuran, ketone solvents such as acetone and methyl ethyl ketone, and alcohol solvents such as methyl alcohol and ethyl alcohol. These organic solvents may be used alone or in combination of two or more. In addition, since the organic solvent is removed in a later step, it is advantageous in terms of the manufacturing process to dissolve the components contained in the photosensitive resin composition and select one having the lowest boiling point as much as possible. .
<Method for producing photosensitive dry film resist>
Then, after apply | coating the organic solvent solution of said photosensitive resin composition uniformly on a support body film, a heating and / or hot air spray are performed. Thereby, the said organic solvent is removed and the photosensitive dry film resist in which the photosensitive resin composition became a film form can be obtained. The photosensitive dry film resist formed in this way is obtained by keeping the photosensitive resin composition in a semi-cured state (B stage). Therefore, when performing thermocompression bonding such as heat laminating, it has appropriate fluidity and can be suitably embedded in the pattern circuit of the printed wiring board. Moreover, after embedding a pattern circuit, it can be hardened completely by performing an exposure process, a thermocompression bonding process, and a heating cure.

  The temperature at which the organic solvent solution of the photosensitive resin composition is dried by performing the heating and / or hot air blowing is a (meth) acrylic compound having an unsaturated double bond contained in the photosensitive resin composition. It is sufficient that the temperature is such that the curable group such as does not react. Specifically, it is preferably 150 ° C. or lower, and particularly preferably 130 ° C. or lower. The drying time is preferably shorter as long as the organic solvent can be removed.

  The material for the support film is not particularly limited, but various commercially available films such as a polyethylene terephthalate (PET) film, a polyphenylene sulfide film, and a polyimide film can be used. Of the above support films, a PET film is often used because it has a certain degree of heat resistance and is relatively inexpensive. In addition, about the joint surface with the photosensitive dry film resist of a support body film, you may use what is surface-treated in order to improve adhesiveness and peelability.

  Furthermore, it is preferable to laminate a protective film on a photosensitive dry film resist prepared by applying a photosensitive resin composition to a support film and drying it. It is possible to prevent dust and dust in the air from adhering and prevent deterioration of quality due to drying of the photosensitive dry film resist.

  The protective film is preferably laminated and laminated on the photosensitive dry film resist surface at a temperature of 10 ° C to 50 ° C. In addition, when the temperature at the time of lamination processing becomes higher than 50 degreeC, the thermal expansion of a protective film will be caused and a wrinkle and a curl may arise in the protective film after a lamination process. In addition, since the said protective film peels at the time of use, it is preferable that the joint surface of a protective film and a photosensitive dry film resist has moderate adhesiveness at the time of storage, and is excellent in peelability.

  Although it does not specifically limit as a material of the said protective film, For example, a polyethylene film (PE film), a polyethylene vinyl alcohol film (EVA film), "the copolymer film of polyethylene and ethylene vinyl alcohol" (following ( "PE + EVA) copolymer film", "PE film and (PE + EVA) copolymer film laminate", or "(PE + EVA) copolymer and polyethylene film by simultaneous extrusion" (one side is PE film) And the other surface is a (PE + EVA) copolymer film surface).

The PE film has the advantages of being inexpensive and having excellent surface slipperiness. Further, the (PE + EVA) copolymer film has appropriate adhesion to the photosensitive dry film resist and releasability. By using such a protective film, when a three-layer structure sheet having three layers of a protective film, a photosensitive dry film resist, and a support film is wound in a roll shape, the surface slipperiness is improved. Can do.
<Production of printed wiring board>
A method for producing a printed wiring board formed by forming the photosensitive dry film resist according to the present invention as an insulating protective layer will be described. The case where a CCL formed with a pattern circuit (hereinafter referred to as CCL with a circuit) is used as an example of the printed wiring board will be described as an example, but the same technique can be used when forming a multilayer printed wiring board. Thus, an interlayer insulating layer can be formed.

  First, the protective film is peeled from the three-layer structure sheet having the protective film, the photosensitive dry film resist, and the support film described above. Below, what peeled the protective film is described as the photosensitive dry film resist with a support film. Then, the CCL with a circuit is covered with the photosensitive dry film resist with a support film and bonded by thermocompression bonding so that the photosensitive dry film resist and the circuit portion of the CCL with circuit are opposed to each other. The bonding by thermocompression bonding may be performed by hot pressing, laminating (thermal laminating), hot roll laminating or the like, and is not particularly limited.

  When the bonding is performed by heat laminating or heat roll laminating (hereinafter referred to as laminating), the processing temperature may be equal to or higher than the lower limit temperature (hereinafter, pressure bonding possible) at which laminating is possible. . Specifically, the temperature at which the pressure bonding is possible is preferably within a range of 50 to 150 ° C., more preferably within a range of 60 to 120 ° C., and particularly preferably within a range of 80 to 120 ° C. preferable.

  When the said process temperature exceeds 150 degreeC, the crosslinking reaction of the photosensitive reactive group contained in the photosensitive dry film resist may arise at the time of a lamination process, and hardening of the photosensitive dry film resist may advance. On the other hand, when the processing temperature is lower than 50 ° C., the fluidity of the photosensitive dry film resist is low, and it becomes difficult to embed the pattern circuit. Furthermore, adhesiveness with the copper circuit of CCL with a copper circuit and the base film of CCL with a copper circuit may fall.

  By the above-described thermocompression treatment, a sample in which a photosensitive dry film resist is laminated on a CCL with a circuit and a support film is further laminated is obtained. Next, pattern exposure and development are performed on the bonded sample. In pattern exposure and development, a photomask pattern is placed on the support film of the bonded sample, and exposure processing is performed through the photomask. Thereafter, the support film is peeled off and development processing is performed, whereby holes (vias) corresponding to the photomask pattern are formed.

  In addition, although the said support body film is peeled off after exposure processing, even if it peels after the photosensitive dry film resist with support body film is bonded together on CCL with a circuit, ie, before performing an exposure process. Good. From the viewpoint of protecting the photosensitive dry film resist, it is preferable to peel off after the exposure process is completed.

  Here, the light source used for exposure is preferably a light source that effectively emits light of 300 to 430 nm. The reason for this is that the photoreaction initiator contained in the photosensitive dry film resist normally functions by absorbing light of 450 nm or less.

  Moreover, as a developing solution used for the development processing, a basic solution in which a basic compound is dissolved may be used. The solvent for dissolving the basic compound is not particularly limited as long as it is a solvent that can dissolve the basic compound, but water is particularly preferable from the viewpoint of environmental problems.

  Examples of the basic compound include hydroxides or carbonates of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium bicarbonate, and organic amines such as tetramethylammonium hydroxide. A compound etc. can be mentioned. 1 type may be used for the said basic compound and 2 or more types of compounds may be used for it.

  The concentration of the basic compound contained in the basic solution is preferably in the range of 0.1 to 10% by weight, but from the point of alkali resistance of the photosensitive dry film resist, 0.1 to 5% by weight. % Is more preferable.

  The development processing method is not particularly limited, and examples thereof include a method in which a development sample is placed in a basic solution and stirring, and a method in which a developer is sprayed onto the development sample.

  In the present invention, in particular, a developing process using a spray developing machine using a 1 wt% sodium hydroxide aqueous solution adjusted to a liquid temperature of 40 ° C. as a developer can be exemplified. Here, the spray developing machine is not particularly limited as long as it is an apparatus that sprays a developer on a sample.

  Here, the development time until the pattern of the photosensitive dry film resist can be drawn may be any time as long as the pattern can be drawn, but it is preferable that development is possible in a time of 180 seconds or less, and development is possible in a time of 90 seconds or less. It is most preferable that development can be performed in a time of 60 seconds or less. When the development time exceeds 180 seconds, productivity tends to be inferior.

  Here, as a measure of the development time, there is a method of measuring the dissolution time of the photosensitive dry film resist in the B stage (semi-cured) state. Specifically, a sample in which a photosensitive dry film resist is bonded to a glossy surface of a copper foil is unexposed and a 1 wt% sodium hydroxide aqueous solution (liquid temperature 40 ° C.) is used as a developer, spray pressure. In this method, spray development is performed at 0.85 MPa. By this spray development process, the photosensitive dry film resist is preferably dissolved and removed in a time of 180 seconds or less. When the time until the photosensitive dry film resist is dissolved and removed exceeds 180 seconds, workability tends to be lowered.

  After the exposure / development treatment is performed as described above, the photosensitive dry film resist is completely cured by heating and curing the photosensitive dry film resist. Thereby, the hardened photosensitive dry film resist becomes an insulating protective film of the printed wiring board.

  In addition, when forming a multilayer printed wiring board, the protective layer of the printed wiring board is used as an interlayer insulating layer, and after sputtering, plating, or bonding with a copper foil is further performed on the interlayer insulating layer Then, a pattern circuit may be formed and the photosensitive dry film resist may be laminated as described above. Thereby, a multilayer printed wiring board can be produced.

  In the present embodiment, the case where the photosensitive dry film resist is used as an insulating protective material or an interlayer insulating material for a printed wiring board has been described. However, the photosensitive dry film resist can be used for purposes other than the above.

  Examples are described below, but the present invention is not limited to these examples.

  1,2-ethanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride (hereinafter referred to as TMEG) (2,2′-bis (4-hydroxyphenyl) propane as a raw material for polyimide Dibenzoate) -3,3 ′, 4,4′-tetracarboxylic dianhydride (hereinafter referred to as ESDA), 4,4 ′-(4,4′-isopropylidenediphenoxy) bisphthalic anhydride (hereinafter referred to as “EDDA”) , BPADA), 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride (hereinafter referred to as DSDA), 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride (Hereinafter referred to as BTDA), 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride (hereinafter referred to as a-BPDA), bis [4- (3-aminophenoxy) phenyl] sulfone (hereinafter referred to as “a-BPDA”) , BAPS M), silicon diamine, diaminobenzoic acid, [bis (4-amino-3-carboxy) phenyl] methane (hereinafter referred to as MBAA), 2,2-bis (3-amino-4-hydroxyphenyl) hexa Fluoropropane (hereinafter referred to as 6FAP) and 2,2-bis (3-amino-4-hydroxyphenyl) propane (hereinafter referred to as DAM-1) were used. N, N'-dimethylformamide (DMF) and dioxolane were used as solvents.

Example 1
<Synthesis of acid dianhydride-terminated oligomer introduced with a monovalent organic group having a carbon-carbon double bond: 1>
In a 2000 ml separable flask equipped with a stirrer, 36.63 g (100 mmol) of 6FAP and 180 g of DMF were taken and cooled and stirred. 115.3 g (200 mmol) of ESDA and 50 g of DMF were further added, and stirring was continued for 1 hour.
The reaction solution was placed in a vat and heated in a vacuum oven at 200 ° C. for 1 hour to obtain 145 g of an acid dianhydride-terminated oligomer having an OH group.

Next, 74.16 g of acid dianhydride-terminated oligomer having an OH group (50 mmol as acid dianhydride), 30.83 g (200 mmol) of methacrylic anhydride, and 100 mg of Q-1301 manufactured by Wako Pure Chemical Industries, Ltd. are put in a container and heated at 100 ° C. for 6 hours. Stirring was performed. After completion of the reaction, 100 g of dioxolane is added, poured into hexane, the precipitated solid is filtered off, dried in a vacuum oven (45 ° C.), and the target monovalent organic group having a carbon-carbon double bond is introduced. 79 g of the acid dianhydride terminated oligomer was obtained. (Yield 97.5%)
The amount of double bonds introduced was measured by 1H-NMR. Using a Gemini300 Varian operating frequency of 300 Hz, it was dissolved in a solvent DMSO-d6 to a concentration of 1% and measured. The amount of double bond introduced was determined from the signal of δ6.8 to 8.6 derived from the aromatic ring and the signal ratio in the vicinity of δ6.1 derived from CH ₂ = C. The introduction rate was 100%, and the signal of OH group group derived from 6FAP disappeared.
<Synthesis of polyimide precursor>
48.58 g of acid dianhydride-terminated oligomer introduced with a monovalent organic group having a carbon-carbon double bond described above (corresponding to 30 mmol as acid dianhydride) and 17.30 g (30 mmol) of ESDA were dissolved in 150 g of dioxolane. .
Silicon diamine KF-8010 (manufactured by Shin-Etsu Silicone) 24.9 g (30 mmol), 1.46 g (30 mmol) of 1,3-bis (3-aminopropyl) tetramethylsiloxane and 32.36 g of dioxolane were added and stirred at room temperature for 2 hours. To obtain a polyimide precursor solution.

The molecular weight was measured using a high-speed GPC (trade name HLC-8220GPC, manufactured by Tosoh Corporation). Measurement conditions were DMF (0.036M LiBr, 0.019M phosphoric acid included) as a developing solvent, Shodex made by Shodex, product name: KD-805-M, column temperature of 40 ° C., detector PI (PEO standard) was used, and the flow rate was 0.6 ml / min. As a result, the weight average molecular weight was 40000, the number average molecular weight was 15000, and the weight average molecular weight / number average molecular weight was 2.67.
<Evaluation of polyimide precursor: migration resistance>
Line / space = 50/50 μm shown in FIG. 1 on Nippon Steel Chemical's flexible copper-clad laminate (single-sided copper-clad laminate having a copper foil on one side of a polyimide resin: SC18-25-00FR) A comb pattern was formed.

  The polymide precursor solution was applied to the comb pattern using a bar coater and heated at 90 ° C. for 10 minutes, 120 ° C. for 10 minutes, and 170 ° C. for 1 hour to remove the organic solvent to obtain a laminate.

  In an environmental tester at 85 ° C. and 85% RH, a DC voltage of 60 V was applied to both terminals of the coated comb pattern, and changes in resistance value and presence / absence of migration were observed.

Migration resistance showed a resistance value of 500 ⁻¹⁰ Ω or more for 500 hours or more, and no dendrite was observed. Therefore, it was confirmed that imidization was completely completed by imidization at 170 ° C.

(Comparative Example 1)
3.24 g (30 mmol) of m-phenylenediamine, 49.8 g (60 mmol) of KF-8010 (manufactured by Shin-Etsu Silicone) and 130 g of DMF were placed in a reaction vessel, and 51.89 g (90 mmol) of ESDA was added thereto, followed by stirring for 1 hour. Next, 0.6 g of triethylamine, 200 mg of Q-1301 manufactured by Wako Pure Chemical Industries, Ltd. and 17.06 g (120 mmol) of glycidyl methacrylate were added, followed by stirring at 60 ° C. for 1 hour. After completion of the reaction, the reaction solution was poured into isopropyl alcohol, and the precipitated resin was dried with a vacuum oven to obtain 98 g of a polyimide precursor.

  In the same manner as in Example 1, the amount of glycidyl methacrylate introduced was determined. It was found that the amount introduced was 22% of the total carboxylic acid of the amic acid.

When this polyamic acid solution was measured under the same conditions as in Example 1, the weight average molecular weight was 53,000, the number average molecular weight was 19,600, and the weight average molecular weight / number average molecular weight was 2.70.
<Evaluation of polyimide precursor: migration resistance>
When migration resistance was evaluated in the same manner as in Example 1, a short circuit occurred in 50 hours, and dendrites were formed. Therefore, it was confirmed that imidation was not completed in 170 ° C. imidization.

(Example 2)
<Adjustment of photosensitive resin composition>
The following components were mixed to prepare a dioxolane solution with a solid content concentration of 30% by weight.
(A) 49 parts by weight of polyimide precursor synthesized in Example 1 (B) (meth) acrylic compound having an unsaturated double bond 10 parts by weight of Osaka Organic Chemical Co., Ltd. V # 2308 Light acrylate NP by Kyoeisha Chemical Co., Ltd. -4EA 15 parts by weight, and Dai-ichi Kogyo Seiyaku Co., Ltd. BR-42M 15 parts by weight (C) Photoinitiator Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide 1 part by weight (E) Others: Otsuka Chemical Co., Ltd. Phosphazene Compound SPE-100 10 parts by weight (adhesiveness)
The heat-resistant resin composition solution was applied to a polyimide film Apical 25 NPI (manufactured by Kaneka Chemical Co., Ltd.) so that the thickness after drying was 25 microns, dried at 90 ° C. for 5 minutes, and electrolytic copper foil (Mitsui Metals 3EC-VLP 1 An ounce rough surface was aligned with the heat-resistant resin composition side, laminated under conditions of 110 ° C. and 20000 Pa · m, and heated at 160 ° C. for 2 hours to obtain a laminate. This laminate was made according to the peel strength (90 degrees) of JIS C 6481. However, the width was measured at a width of 3 mm and converted to 1 cm. The adhesive strength was 5.8 N / cm.
(Solder heat resistance) The heat resistant resin composition solution was applied to the bright surface of electrolytic copper foil (3EC-VLP, 1 ounce made by Mitsui Metals) so that the thickness after drying was 25 microns, dried at 90 ° C for 5 minutes, 160 The laminate was obtained by heating at 2 ° C. for 2 hours. This laminate was conditioned at 40 ° C. and 95% RH for 24 hours, then immersed in a solder bath for 10 seconds, and the presence or absence of surface swelling and discoloration was observed. The highest temperature that did not cause blistering or discoloration was defined as the solder heat resistance temperature. The solder heat resistance temperature was 280 ° C.
(Photosensitivity) The photosensitive resin composition solution prepared above was applied onto a PET film (thickness 25 μm) so that the thickness after drying was 25 μm, and dried at 90 ° C. for 2 minutes to remove the organic solvent. Thus, a photosensitive dry film resist was obtained.

  The photosensitive resin composition surface of the photosensitive dry film resist was laminated on the bright surface of an electrolytic copper foil (3EC-VLP made by Mitsui Metals) and laminated at 100 ° C. and 20000 Pa · m while being shielded from light. .

A mask pattern was placed on the laminate, and 400 nm light was exposed by 300 mJ / cm ² and developed with a 1 wt% aqueous sodium hydroxide solution (liquid temperature 40 ° C.). The photomask pattern is drawn with minute holes of 500 μmφ, 200 μmφ, and 100 μmφ and lines with a line / space of 500 μm / 500 μm, 200 μm / 200 μm, and 100 μm / 100 μm. The pattern formed by development was then washed with distilled water to remove the developer.

Fine holes and lines / spaces of 100 μmφ could be drawn up to 100 μm / 100 μm.
(Migration resistance of photosensitive resin)
Line / space = 50/50 μm shown in FIG. 1 on Nippon Steel Chemical's flexible copper-clad laminate (single-sided copper-clad laminate having a copper foil on one side of a polyimide resin: SC18-25-00FR) A comb pattern was formed.

On the comb pattern, the photosensitive dry film resist prepared above was laminated and laminated under conditions of 100 ° C. and 20000 Pa · m. 400 nm light was exposed by 400 mJ / cm ² and then heated at 180 ° C. for 2 hours for lamination.

In an environmental tester at 85 ° C. and 85% RH, a DC voltage of 60 V was applied to both terminals of the coated comb pattern, and changes in resistance value and presence / absence of migration were observed.
Migration resistance showed a resistance value of 500 ⁻¹⁰ Ω or more for 500 hours or more, and no dendrite was observed.

(Comparative Example 2)
<Adjustment of photosensitive resin composition>
The following components were mixed to prepare a solid content concentration of 30% by weight. (The mixing ratio is the same as in Example 2)
(A) 49 parts by weight of the polyimide precursor synthesized in Comparative Example 1 (B) (meth) acrylic compound having an unsaturated double bond 10 parts by weight of Osaka Organic Chemical Co., Ltd. V # 2308 Light acrylate NP by Kyoeisha Chemical Co., Ltd. -4EA 15 parts by weight, and Dai-ichi Kogyo Seiyaku Co., Ltd. BR-42M 15 parts by weight (C) Photoinitiator Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide 1 part by weight (E) Others: Otsuka Chemical Co., Ltd. phosphazene compound SPE-100 10 parts by weight Each part was evaluated in the same manner as in Example 2.
(Adhesiveness)
When the adhesive strength was measured in the same manner as in Example 2, the adhesive strength was 1.5 N / cm.
(Solder heat resistance)
When the solder heat resistance temperature was measured in the same manner as in Example 2, the solder heat resistance temperature was 230 ° C.
(Photosensitivity)
When the photosensitivity was evaluated in the same manner as in Example 2, the pattern flowed with the developer, and the pattern could not be drawn.
(Migration resistance of photosensitive resin)
When migration resistance was evaluated in the same manner as in Example 2, the migration resistance was short-circuited in 40 hours, and dendrites were observed.

(Example 3)
<Synthesis of acid dianhydride terminal oligomer into which a monovalent organic group having a carbon-carbon double bond is introduced: 2>
To a 500 ml separable flask equipped with a stirrer, 41.64 g (80 mmol) of BPADA and 150 g of dioxolane were added and stirred. 14.65 g (40 mmol) of 6FAP was added to the vessel and stirring was continued for 1 hour. To this reaction solution, 7.45 g (80 mmol) of β-picoline, 61.66 g (400 mmol) of methacrylic anhydride and 200 mg of Q-1301 manufactured by Wako Pure Chemical Industries, Ltd. were added, and the mixture was heated and stirred at room temperature for 1 hour and at 100 ° C. for 3 hours. .

After completion of the reaction, 100 g of dioxolane is added, poured into hexane, the precipitated solid is filtered off, dried in a vacuum oven (45 ° C.), and the target monovalent organic group having a carbon-carbon double bond is introduced. As a result, 58 g of the acid dianhydride-terminated oligomer was obtained. (Yield 96.2%)
The amount of double bonds introduced was measured by 1H-NMR. Using a Gemini300 Varian operating frequency of 300 Hz, it was dissolved in a solvent DMSO-d6 to a concentration of 1% and measured. The amount of double bond introduced was determined from the signal of δ6.8 to 8.6 derived from the aromatic ring and the signal ratio in the vicinity of δ6.1 derived from CH ₂ = C. The introduction rate was 100%, and the signal of OH group derived from 6FAP disappeared.
<Synthesis of polyimide precursor>
45.21 g of the above acid dianhydride-terminated oligomer (corresponding to 30 mmol as acid dianhydride) was dissolved in 180 g of dimethylformamide. A mixed solution of 7.46 g (30 mmol) of 1,3-bis (3-aminopropyl) tetramethylsiloxane and 10 g of dimethylformamide was added and stirred at room temperature for 2 hours. After completion of the reaction, the reaction solution was poured into isopropyl alcohol, and the precipitated resin was dried with a vacuum oven to obtain 50 g of a polyimide precursor.

The polyimide precursor solution was measured under the same conditions as in Example 1. As a result, the weight average molecular weight was 45,000, the number average molecular weight was 17000, and the weight average molecular weight / number average molecular weight was 2.65.
<Evaluation of polyimide precursor: migration resistance>
When migration resistance was evaluated in the same manner as in Example 1, the migration resistance showed a resistance value of 500 ⁻¹⁰ Ω or more for 500 hours or more, and no dendrite was observed. Therefore, it was confirmed that imidization was completely completed by imidization at 170 ° C.
<Adjustment of photosensitive resin composition>
The following components were mixed to prepare a dioxolane solution with a solid content concentration of 30% by weight.
(A) 49 parts by weight of the polyimide precursor synthesized above (B) (meth) acrylic compound having an unsaturated double bond 10 parts by weight of Osaka Organic Chemical Co., Ltd. V # 2308 Light acrylate NP-4EA15 by Kyoeisha Chemical Co., Ltd. Parts by weight, and 15 parts by weight of BR-42M manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (C) Photoinitiator bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide 1 part by weight (E) Other: Otsuka Chemical Phosphazene compound SPE-100, manufactured by 10 parts by weight (adhesiveness)
The heat-resistant resin composition solution was applied to a polyimide film Apical 25 NPI (manufactured by Kaneka Chemical Co., Ltd.) so that the thickness after drying was 25 microns, dried at 90 ° C. for 5 minutes, and electrolytic copper foil (Mitsui Metals 3EC-VLP 1 An ounce rough surface was aligned with the heat-resistant resin composition side, laminated under conditions of 110 ° C. and 20000 Pa · m, and heated at 160 ° C. for 2 hours to obtain a laminate. This laminate was made according to the peel strength (90 degrees) of JIS C 6481. However, the width was measured at a width of 3 mm and converted to 1 cm. The adhesive strength was 5.8 N / cm.
(Solder heat resistance) The heat resistant resin composition solution was applied to the bright surface of electrolytic copper foil (3EC-VLP, 1 ounce made by Mitsui Metals) so that the thickness after drying was 25 microns, dried at 90 ° C for 5 minutes, 160 The laminate was obtained by heating at 2 ° C. for 2 hours. This laminate was conditioned at 40 ° C. and 95% RH for 24 hours, then immersed in a solder bath for 10 seconds, and the presence or absence of surface swelling and discoloration was observed. The highest temperature that did not cause blistering or discoloration was defined as the solder heat resistance temperature. The solder heat resistance temperature was 280 ° C.
(Photosensitivity) The photosensitive resin composition solution prepared above was applied onto a PET film (thickness 25 μm) so that the thickness after drying was 25 μm, and dried at 90 ° C. for 2 minutes to remove the organic solvent. Thus, a photosensitive dry film resist was obtained.

  The photosensitive resin composition surface of the photosensitive dry film resist was laminated on the bright surface of an electrolytic copper foil (3EC-VLP made by Mitsui Metals) and laminated at 100 ° C. and 20000 Pa · m while being shielded from light. .

A mask pattern was placed on the laminate, and 400 nm light was exposed by 300 mJ / cm ² and developed with a 1 wt% aqueous sodium hydroxide solution (liquid temperature 40 ° C.). The photomask pattern is drawn with minute holes of 500 μmφ, 200 μmφ, and 100 μmφ and lines with a line / space of 500 μm / 500 μm, 200 μm / 200 μm, and 100 μm / 100 μm. The pattern formed by development was then washed with distilled water to remove the developer.

Fine holes and lines / spaces of 100 μmφ could be drawn up to 100 μm / 100 μm.
(Migration resistance of photosensitive resin)
Line / space = 50/50 μm shown in FIG. 1 on Nippon Steel Chemical's flexible copper-clad laminate (single-sided copper-clad laminate having a copper foil on one side of a polyimide resin: SC18-25-00FR) A comb pattern was formed.

On the comb pattern, the photosensitive dry film resist prepared above was laminated and laminated under conditions of 100 ° C. and 20000 Pa · m. 400 nm light was exposed by 400 mJ / cm ² and then heated at 180 ° C. for 2 hours for lamination.

    In an environmental tester at 85 ° C. and 85% RH, a DC voltage of 60 V was applied to both terminals of the coated comb pattern, and changes in resistance value and presence / absence of migration were observed.

Migration resistance showed a resistance value of 500 ⁻¹⁰ Ω or more for 500 hours or more, and no dendrite was observed.

(Comparative Example 3)
6FAP 10.99 g (30 mmol), KF-8010 (manufactured by Shin-Etsu Silicone) 24.9 g (30 mmol) and dioxolane 124.7 g were placed in a reaction vessel, BPADA 31.23 g (60 mmol) was added, and the mixture was stirred for 1 hour to obtain a polyamic acid solution. When this polyamic acid solution was measured under the same conditions as in Example 1, the weight average molecular weight was 48,000, the number average molecular weight was 17000, and the weight average molecular weight / number average molecular weight was 2.82.
<Evaluation of polyimide precursor: migration resistance>
When migration resistance was evaluated in the same manner as in Example 1, a short circuit occurred in 50 hours, and dendrites were formed. Therefore, it was confirmed that imidation was not completed in 170 ° C. imidization.
<Adjustment of photosensitive resin composition>
The following components were mixed to prepare a solid content concentration of 30% by weight. (The mixing ratio is the same as in Example 2)
(A) 49 parts by weight of the polyimide precursor synthesized above (B) (meth) acrylic compound having an unsaturated double bond 10 parts by weight of Osaka Organic Chemical Co., Ltd. V # 2308 Light acrylate NP-4EA15 by Kyoeisha Chemical Co., Ltd. Parts by weight, and 15 parts by weight of BR-42M manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (C) Photoinitiator bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide 1 part by weight (E) Other: Otsuka Chemical Co., Ltd. Phosphazene Compound SPE-100 10 parts by weight Each part was evaluated in the same manner as in Example 2.
(Adhesiveness)
When the adhesive strength was measured in the same manner as in Example 2, the adhesive strength was 1.5 N / cm.
(Solder heat resistance)
When the solder heat resistance temperature was measured in the same manner as in Example 2, the solder heat resistance temperature was 230 ° C.
(Photosensitivity)
When the photosensitivity was evaluated in the same manner as in Example 2, the pattern flowed with the developer, and the pattern could not be drawn.
(Migration resistance of photosensitive resin)
When migration resistance was evaluated in the same manner as in Example 2, the migration resistance was short-circuited in 40 hours, and dendrites were observed.

Example 4
<Synthesis of acid dianhydride-terminated oligomer introduced with a monovalent organic group having a carbon-carbon double bond: 3>
To a 500 ml separable flask equipped with a stirrer, 41.64 g (80 mmol) of BPADA and 100 g of DMF were added and stirred while cooling with ice. Formula (13) 19.79 (40 mmol) was dissolved in 50 g of DMF, added to the vessel, and stirring was continued for 1 hour.
To this reaction solution, 7.45 g (80 mmol) of β-picoline, 61.66 g (400 mmol) of methacrylic anhydride and 200 mg of Q-1301 manufactured by Wako Pure Chemical Industries, Ltd. were added, and the mixture was heated and stirred at room temperature for 1 hour and at 100 ° C. for 3 hours. .

After completion of the reaction, 100 g of dioxolane is added, poured into hexane, the precipitated solid is filtered off, dried in a vacuum oven (45 ° C.), and the target monovalent organic group having a carbon-carbon double bond is introduced. 57 g of the acid dianhydride terminal oligomer thus obtained was obtained. (Yield 94.5%)
The amount of double bonds introduced was measured by 1H-NMR. Using a Gemini300 Varian operating frequency of 300 Hz, it was dissolved in a solvent DMSO-d6 to a concentration of 1% and measured. The amount of double bond introduced was determined from the signal of δ6.8 to 8.6 derived from the aromatic ring and the signal ratio in the vicinity of δ6.1 derived from CH ₂ = C. The introduction rate was 100%, and the signal of the OH group derived from the formula (13) disappeared.

＜ポリイミド前駆体の合成＞
上記の酸二無水物末端オリゴマー45.21ｇ（酸二無水物として30mmolに相当）とＥＳＤＡ17.30ｇ（30mmol)をジオキソラン135ｇに溶解した。シリコンジアミンKF-8010（信越シリコーン製）49.8 g (60mmol)とジオキソラン33.2ｇの混合溶液を加え、２時間室温で撹拌を行った。

<Synthesis of polyimide precursor>
45.21 g of the above acid dianhydride terminal oligomer (corresponding to 30 mmol as acid dianhydride) and 17.30 g (30 mmol) of ESDA were dissolved in 135 g of dioxolane. A mixed solution of 49.8 g (60 mmol) of silicon diamine KF-8010 (manufactured by Shin-Etsu Silicone) and 33.2 g of dioxolane was added and stirred at room temperature for 2 hours.

The polyimide precursor solution was measured under the same conditions as in Example 1. As a result, the weight average molecular weight was 55000, the number average molecular weight was 19000, and the weight average molecular weight / number average molecular weight was 2.89.
<Evaluation of polyimide precursor>
When migration resistance was evaluated in the same manner as in Example 1, the migration resistance showed a resistance value of 500 ⁻¹⁰ Ω or more for 500 hours or more, and no dendrite was observed. Therefore, it was confirmed that imidization was completely completed by imidization at 170 ° C.
<Adjustment of photosensitive resin composition>
The following components were mixed to prepare a dioxolane solution with a solid content concentration of 30% by weight.
(A) 49 parts by weight of the polyimide precursor synthesized above (B) (meth) acrylic compound having an unsaturated double bond 10 parts by weight of Osaka Organic Chemical Co., Ltd. V # 2308 Light acrylate NP-4EA15 by Kyoeisha Chemical Co., Ltd. Parts by weight, and 15 parts by weight of BR-42M manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (C) Photoinitiator bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide 1 part by weight (E) Other: Otsuka Chemical Phosphazene compound SPE-100, manufactured by 10 parts by weight (adhesiveness)
When the adhesive strength was measured in the same manner as in Example 2, the adhesive strength was 6.8 N / cm.
(Solder heat resistance)
When the solder heat resistance temperature was measured by the same method as in Example 2, the solder heat resistance temperature was 280 ° C.
(Photosensitivity)
When the photosensitivity was evaluated in the same manner as in Example 2, fine holes and lines / spaces of 100 μmφ could be drawn up to 100 μm / 100 μm.
(Migration resistance of photosensitive resin)
When the migration resistance was evaluated in the same manner as in Example 2, the migration resistance showed a resistance value of 500 ⁻¹⁰ Ω or more for 500 hours or more, and no dendrite was observed.

(Example 5)
<Synthesis of acid dianhydride terminal oligomer>
To a 500 ml separable flask equipped with a stirrer, 41.64 g (80 mmol) of BPADA and 100 g of DMF were added and stirred while cooling with ice. 4.56 g (40 mmol) of 3,5-diaminobenzoic acid was dissolved in 50 g of DMF, added to the vessel and stirred for 1 hour. The reaction solution was placed in a vat and heated in a vacuum oven at 190 ° C. for 1 hour to obtain 43.0 g of acid dianhydride-terminated oligomer.
<Synthesis of polyimide precursor>
33.57 g of the above acid dianhydride-terminated oligomer (corresponding to 30 mmol as acid dianhydride) was dissolved in 70 g of dioxolane. A mixed solution of 24.9 g (30 mmol) of silicon diamine KF-8010 (manufactured by Shin-Etsu Silicone) and 16.6 g of dioxolane was added, and the mixture was stirred at room temperature for 2 hours. Next, 0.6 g of triethylamine, 200 mg of Q-1301 manufactured by Wako Pure Chemical Industries, Ltd. and 11.37 g (80 mmol) of glycidyl methacrylate were added and stirred at 60 ° C. for 1 hour. After completion of the reaction, the reaction solution was poured into isopropyl alcohol, and the precipitated resin was dried with a vacuum oven to obtain 50 g of a polyimide precursor.

In the same manner as in Example 1, the amount of glycidyl methacrylate introduced was determined. It was found that the amount introduced was 20% of the total carboxylic acid. (However, it is unknown whether the carboxylic acid of amic acid or benzoic acid is introduced.)
The polyimide precursor solution was measured under the same conditions as in Example 1. As a result, the weight average molecular weight was 55000, the number average molecular weight was 19000, and the weight average molecular weight / number average molecular weight was 2.89.
<Evaluation of polyimide precursor>
When migration resistance was evaluated in the same manner as in Example 1, the migration resistance showed a resistance value of 500 ⁻¹⁰ Ω or more for 500 hours or more, and no dendrite was observed. Therefore, it was confirmed that imidization was completely completed by imidization at 170 ° C.
<Adjustment of photosensitive resin composition>
The following components were mixed to prepare a dioxolane solution with a solid content concentration of 30% by weight.
(A) 49 parts by weight of the polyimide precursor synthesized above (B) (meth) acrylic compound having an unsaturated double bond 10 parts by weight of Osaka Organic Chemical Co., Ltd. V # 2308 Light acrylate NP-4EA15 by Kyoeisha Chemical Co., Ltd. Parts by weight, and 15 parts by weight of BR-42M manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (C) Photoinitiator bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide 1 part by weight (E) Other: Otsuka Chemical Phosphazene compound SPE-100, manufactured by 10 parts by weight (adhesiveness)
When the adhesive strength was measured in the same manner as in Example 2, the adhesive strength was 6.8 N / cm.
(Solder heat resistance)
When the solder heat resistance temperature was measured by the same method as in Example 2, the solder heat resistance temperature was 280 ° C.
(Photosensitivity)
When the photosensitivity was evaluated in the same manner as in Example 2, fine holes and lines / spaces of 100 μmφ could be drawn up to 100 μm / 100 μm.
(Migration resistance of photosensitive resin)
When the migration resistance was evaluated in the same manner as in Example 2, the migration resistance showed a resistance value of 500 ⁻¹⁰ Ω or more for 500 hours or more, and no dendrite was observed.

(Example 6)
In the same manner as in Example 5, except that methacrylic acid-2-dimethylaminoethyl ester was added as component (D).
The following components were mixed to prepare a dioxolane solution with a solid content concentration of 30% by weight.
(A) 49 parts by weight of the polyimide precursor synthesized above (B) (meth) acrylic compound having an unsaturated double bond 10 parts by weight of Osaka Organic Chemical Co., Ltd. V # 2308 Light acrylate NP-4EA15 by Kyoeisha Chemical Co., Ltd. Parts by weight, and 15 parts by weight of BR-42M manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (C) Photoinitiator bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide 1 part by weight (D) methacrylic acid-2 -Dimethylaminoethyl ester 10 parts (E) Other: Otsuka Chemical Co., Ltd. Phosphazene Compound SPE-100 10 parts by weight (adhesiveness)
When the adhesive strength was measured in the same manner as in Example 2, the adhesive strength was 6.8 N / cm.
(Solder heat resistance)
When the solder heat resistance temperature was measured by the same method as in Example 2, the solder heat resistance temperature was 280 ° C.
(Photosensitivity)
When the photosensitivity was evaluated in the same manner as in Example 2, fine holes and lines / spaces of 100 μmφ could be drawn up to 70 μm / 70 μm.
(Migration resistance of photosensitive resin)
When the migration resistance was evaluated in the same manner as in Example 2, the migration resistance showed a resistance value of 500 ⁻¹⁰ Ω or more for 500 hours or more, and no dendrite was observed.

  As described above, the polyimide precursor according to the present invention is a partially imidized polyimide precursor having a specific structure. Therefore, the photosensitive resin composition containing the polyimide precursor and the (meth) acrylic compound having a carbon-carbon double bond can be imidized at 200 ° C. or lower.

  Therefore, the present invention can be used for manufacturing an electronic component having a low heat resistance of the substrate, such as a rigid or FPC substrate. In addition, the present invention can be used in the field of producing various resin molded products represented by films and laminates containing photosensitive polyimide. Furthermore, it can be widely applied to fields related to the manufacture of electronic components using such films and laminates.

It is a schematic diagram which shows the comb-shaped pattern (line / space = 50 micrometers / 50 micrometers) formed on a flexible copper bonding laminated board in the method of evaluating the migration resistance of the photosensitive resin of a present Example.

Claims (10)

A polyimide precursor having at least the structure of formula (1) and the structure of formula (2) in one molecule.

(Wherein R ¹ represents a tetravalent organic group, and R ² represents a divalent organic group having a monovalent organic group having at least one carbon-carbon double bond in the side chain, R ³ Represents formula (3), and in formula (3), R ⁴ may be the same or different, and represents any of a methyl group, an ethyl group, and a phenyl group, and x = 2 to 10, y = 4 to 30)

The polyimide precursor which has the structure of Formula (4) in 1 molecule in addition to Formula (1) and Formula (2) of Claim 1.

(In the formula, R ⁵ represents a divalent organic group having no carbon-carbon double bond in the molecule.) In all R ₂ , R ₃ and R ₅ in the polyimide precursor, the molar fraction of R _{2 in} the formula (1) is 1 to 80%, and the molar fraction of R _{3 in} the formula (2) is 3. The polyimide precursor according to claim 2, wherein the polyimide precursor has a molar fraction of R ₅ of the formula (4) of 0 to 70%. In the formula (1), a polyimide precursor of claim 1, wherein the R ² is Formula (5).

(R ⁶ may be the same or different, and represents either a monovalent organic group having a carbon-carbon double bond or hydrogen, and R ⁷ is the same or different. may, -, - (C = O ) -, - C (CH 3) 2 -, - CH 2 -, - SO 2 -, - O -, - C (CF 3) 2 -, - CH (CH 3 )-, -C (CH ₃ ) (CH ₂ CH ₃ )-, or cyclohexyl, R ⁸ may be the same or different, and H, CH _3- , CH ₃ CH _2- , OH, or COOH, and m represents 0 to 3. However, in formula (5), at least one monovalent organic group having a carbon-carbon double bond is present. And) In the formula (1), a polyimide precursor of claim 1, wherein the R ² is Formula (6).

(R ⁶ may be the same or different, and represents either a monovalent organic group having a carbon-carbon double bond or hydrogen, and R ⁷ is the same or different. may, -, - (C = O ) -, - C (CH 3) 2 -, - CH 2 -, - SO 2 -, - O -, - C (CF 3) 2 -, - CH (CH 3 )-, -C (CH ₃ ) (CH ₂ CH ₃ )-, or cyclohexyl, R ⁸ may be the same or different, and H, CH _3- , CH ₃ CH _2- , OH, or COOH, and n is 1 to 4. However, in formula (6), there is at least one monovalent organic group having a carbon-carbon double bond. And) In addition to 100 parts by weight of (A) polyimide precursor according to claims 1 to 5, a photosensitive resin composition comprising (B) 1 to 400 parts by weight of a (meth) acrylic compound having a carbon-carbon double bond as an essential component. object. In addition to Claim 6, (C) The photosensitive resin composition which uses 0.01-50 weight part of photoreaction initiators as an essential component. In addition to claim 7, (D) 0.01 to 30 parts by weight of a compound having a carbon-carbon double bond and a tertiary amino group in the molecule or a compound having a carbon-carbon double bond and an amide group in the molecule A photosensitive resin composition. A photosensitive dry film resist comprising the photosensitive resin composition according to claim 6. A printed wiring board comprising the photosensitive dry film resist according to claim 9 as an insulating protective layer.

Images