JP2006089492A - New diamine and new polyimide composition using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new diamine having a photosensitive group and to provide a polyimide composition using the diamine as a raw material. <P>SOLUTION: This new photosensitive group-having diamine of general formula (1) (X and Y are each a divalent group; Z is a photosensitive group), and a polyimide composition is characterized by containing ≥1 wt.% of a photosensitive group-having polyimide obtained by reacting the diamine with an acid anhydride in an organic polar solvent and then thermally or chemically imidizing the obtained polyamic acid. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel diamine, a production method thereof, a novel polyimide composition using the novel diamine as a raw material, and a production method thereof. Specifically, the present invention relates to a novel diamine which is a raw material for a polymer having a photosensitive group in the structure of the diamine and having both photoreactivity and thermal reactivity specific to the photosensitive group, and a polyimide composition using the same.

  A well-known polymer having a cinnamic acid skeleton is polyvinyl cinnamate (polyvinyl having a cinnamic acid skeleton) (Jpn. J. Appl. Phys., 31 (1992), 2155 and J. Photopolymer Sci. and Tech. 8 (1995), 257). Polyvinyl cinnamate is a useful photosensitive resin that utilizes a reaction in which a cinnamic acid skeleton dimerizes with light (J. Appl Polymer Sci., 2, 302 (1995)). This polyvinyl cinnamate is used as a negative photosensitive resin. It is speculated that introduction of a photosensitive group into a polymer can provide a useful photosensitive resin, but at present, no raw material for a polymer, that is, a reactive monomer is provided.

  In particular, polyimide or polyamide is excellent in heat resistance among various organic polymers, so that cinnamon can be used in spite of being an excellent resin widely used in the fields of space and aviation to electronic communication. Few monomers having a photosensitive group such as an acid skeleton are known.

  It aims at providing the novel diamine which has a photosensitive group, its manufacturing method, the polyimide composition which uses the diamine as a raw material, and its manufacturing method.

（但し、Ｘ、Ｙは、２価の結合鎖、Ｚは化６

から選ばれる１種以上の感光基を、ＡはＨ，ＣＨ₃，Ｆ，Ｃｌ，Ｂｒ，ＣＨ₃Ｏ−を示す。）で表される新規ジアミンを、
特には、上記一般式（１）中、Ｘは、−，−ＣＨ₂−，−ＣＯＯ−，−ＮＨ−，−Ｏ−から選択される２価の結合鎖、Ｙは、−，−ＣＯＯ−，−ＯＯＣ−，−（ＣＨ₂）_mＯ−，−（ＣＨ₂）_mＣＯＯ−，−（ＣＨ₂）_mＯＯＣ−，−（ＣＨ₂）_m−から選択される２価の結合鎖（ｍは１〜１５の整数を示す。）である新規ジアミンを、
本発明の第二は、構造が下記一般式（２）化７

（但し、Ｘは、−，−ＣＨ₂−，−ＣＯＯ−，−ＮＨ−，−Ｏ−から選択される２価の結合鎖、Ｙは、−ＣＯＯ−，−ＯＯＣ−，−（ＣＨ₂）_mＯ−，−（ＣＨ₂）_mＣＯＯ−，−（ＣＨ₂）_mＯＯＣ−，−（ＣＨ₂）_m−から選択される２価の結合鎖、ｍは１〜１５の整数を、Ｚは化８

から選ばれる１種以上の感光基を、ＡはＨ，ＣＨ₃，Ｆ，Ｃｌ，Ｂｒ，ＣＨ₃Ｏ−を、ＢとＤは４価の結合鎖を、Ｅは２価の結合鎖を、ｐは１〜１００、ｑは０〜９９を示す。）を１重量％以上含むことを特徴とする新規ポリイミド組成物である。 As a result of intensive studies, the present inventors have found that a predetermined object can be achieved by a novel diamine having a specific structure, and have completed the present invention. The first of the present invention is the following general formula (1)

(Where X and Y are divalent linking chains, Z is

A represents one or more photosensitive groups selected from: A, H, CH ₃ , F, Cl, Br, CH ₃ O—. ) A new diamine represented by
In particular, in the general formula (1), X is a divalent linking chain selected from —, —CH ₂ —, —COO—, —NH—, and —O—, and Y is —, —COO—. _{, -OOC -, - (CH 2} ) m O -, - (CH 2) m COO -, - (CH 2) m OOC -, - (CH 2) m - 2 divalent linking chain selected from (m Represents an integer of 1 to 15.)
In the second aspect of the present invention, the structure is represented by the following general formula (2).

Wherein X is a divalent linking chain selected from —, —CH ₂ —, —COO—, —NH—, —O—, and Y is —COO—, —OOC—, — (CH ₂ ). _{m O -, - (CH 2} ) m COO -, - (CH 2) m OOC -, - (CH 2) m - 2 divalent linking chain selected from, m is an integer of 1 to 15, Z is 8

One or more photosensitive groups selected from: A is H, CH ₃ , F, Cl, Br, CH ₃ O—, B and D are tetravalent bond chains, E is a divalent bond chain, p represents 1 to 100, and q represents 0 to 99. ) In an amount of 1% by weight or more.

  The novel diamine according to the present invention can be a raw material for a polymer having both photoreactivity and thermal reactivity peculiar to a photosensitive group, and the novel polyimide composition according to the present invention can be a useful photosensitive resin.

（但し、Ｘは、−，−ＣＨ₂−，−ＣＯＯ−，−ＮＨ−，−Ｏ−から選択される２価の結合鎖、Ｙは、−，−ＣＯＯ−，−ＯＯＣ−，−（ＣＨ₂）_mＯ−，−（ＣＨ₂）_mＣＯＯ−，−（ＣＨ₂）_mＯＯＣ−，−（ＣＨ₂）_m−から選択される２価の結合鎖、ｍは１〜１５の整数を、Ｚは化１０

から選ばれる１種以上の感光基を、ＡはＨ，ＣＨ₃，Ｆ，Ｃｌ，Ｂｒ，ＣＨ₃Ｏ−を示す。）の構造を有することを特徴とする。 Hereinafter, embodiments of the novel diamine and novel polyimide composition according to the present invention will be described. The novel diamine according to the present invention is a novel diamine which has a photosensitive group and serves as a raw material for a polymer having both photoreactivity and thermal reactivity specific to the photosensitive group. Specifically, the diamine according to the present invention is represented by the general formula (1)

(Where X is a divalent linking chain selected from —, —CH ₂ —, —COO—, —NH—, —O—, Y is —, —COO—, —OOC—, — (CH _{2) m O -, - (} CH 2) m COO -, - (CH 2) m OOC -, - (CH 2) m - 2 divalent linking chain selected from, m is an integer of 1 to 15, Z is

A represents one or more photosensitive groups selected from: A, H, CH ₃ , F, Cl, Br, CH ₃ O—. ).

  Moreover, the polyimide composition concerning this invention is a novel polyimide composition which used the novel diamine which has the said photosensitive group as a diamine component.

  Below, the manufacturing method of the novel diamine which concerns on this invention, and the manufacturing method of a polyimide composition are described in detail. This novel diamine is obtained by synthesizing the corresponding dinitrate and reducing the nitrate.

から選ばれる感光基を表す。）を反応することにより一般式（１）中のＸ＝ＣＯＯ、Ｙ＝−に相当するジニトロ化物を得ることができる。 For example, in the presence of an esterification catalyst such as dinitrobenzoic acid chloride or toluenesulfonic acid chloride, dinitrobenzoic acid and Z-OH (Z is

Represents a photosensitive group selected from: ) Can be reacted to obtain a dinitrated product corresponding to X = COO and Y =-in the general formula (1).

By reacting with dinitrobenzyl alcohol and Z—COOH in the presence of an esterification catalyst such as Z—COCl or toluenesulfonic acid chloride, X = —CH ₂ —, Y = —OOC— in the general formula (1) The corresponding dinitrate can be obtained.

  By reacting dinitroaniline with Z-COCl, a dinitrated product corresponding to X = —NH— and Y = —OC— in the general formula (1) can be obtained.

  By reacting with dinitrophenol and Z-COOH in the presence of an esterification catalyst such as Z-COCl or toluenesulfonic acid chloride, the dinitrated compound corresponding to X = -OOC-, Y =-in general formula (1) Can be obtained.

And dinitrobenzoic acid chloride _{HO- (CH 2) m OH (} m = 1~15) or dinitrobenzoic acid and HO- (CH ₂₎ in the presence of an esterification catalyst such as toluene sulfonic acid chloride _m OH _(m = 1 ˜15) is reacted to synthesize (NO ₂ ) ₂ —C ₆ H ₃ COO (CH ₂ ) _m OH (m = 1 to 15) and then esterify Z-COCl or toluenesulfonic acid chloride. by reaction with Z-COOH in the presence of a catalyst, the general formula (1) X = -OOC- _{in, Y = - (CH 2)} m corresponding dinitro compound to OOC- can be obtained.

Alternatively, dinitrobenzoic acid chloride is reacted with a halogenated alkyl alcohol (m = 1 to 15) such as HO— (CH ₂ ) _m —Br to give (NO ₂ ) ₂ —C ₆ H ₃ —COO— (CH ₂ ) When _m -Br is reacted with Z-COOK or Z-COOCs in a polar aprotic solvent such as N-methyl-2-pyrrolidone or dimethylformamide, X = COO, Y = (CH ₂ ) A dinitrated product corresponding to _m- OOC can also be obtained.

  By reacting dinitrophenol with Z-COCl, a dinitrated product corresponding to X = O, Y =-can be obtained.

Dinitrophenol and a bishalogenated alkyl such as Br— (CH ₂ ) _m —Br (m = 1 to 15) are reacted in the presence of alkali to give (NO ₂ ) ₂ —C ₆ H ₃ —O— (CH ₂ ) X = O, Y = (CH ₂ ) _m by reacting Z-COOK or Z-COOCs in a polar aprotic solvent such as N-methyl-2-pyrrolidone or dimethylformamide as _m -Br. A dinitrated product corresponding to -OOC can be obtained.

Br— (CH ₂ ) _m —COCl (m = 1 to 15) and Z—OH are reacted to form Br— (CH ₂ ) _m —COO—Z, and an alkali such as cesium dinitrobenzoate or potassium dinitrobenzoate. By reacting a metal salt in a polar aprotic solvent such as N-methyl-2-pyrrolidone or dimethylformamide, a dinitrated product corresponding to X═COO, Y═ (CH ₂ ) _m —COO— can be obtained. .

  The diamine of the present invention can be obtained by Bechamp reduction of these dinitrates or hydrogenation using a special catalyst.

  The “special catalyst” in the present invention is a catalyst in which platinum is supported on carbon black (Pt-carbon black), or a catalyst in which platinum mixed with sodium or iron is supported on activated carbon (Pt-activated carbon). ) Etc. These catalysts usually use activated carbon loaded with a noble metal, but when loaded on activated carbon, the ratio of reducing the double bond of the photosensitive group is lower than that of the catalyst loaded on carbon black. Become more. Therefore, it is desirable to use a catalyst supported on carbon black. However, when using a catalyst supported on activated carbon, it is possible to selectively reduce the nitro group by suppressing the reduction of the photosensitive group to a double bond by mixing iron or sodium into the platinum. It becomes.

  In addition, when using a palladium-based catalyst, poisoning substances such as sulfur are mixed to reduce the activity of the catalyst, thereby suppressing the reduction of the photosensitive group to a double bond and selectively reducing the nitro group. It becomes possible to do.

  The reduction conditions for this dinitrate will be described. Since this dinitro compound has a double bond of a photosensitive group, the double bond may be reduced if a severe reduction condition is selected, and decomposition may occur if performed under strong acidity. Furthermore, under alkaline conditions, Michael addition may occur, so it is necessary to optimize the reducing conditions.

  Suitable for the reduction of this dinitro compound is a catalyst in which platinum is supported on carbon black (Pt-carbon black) or a catalyst in which platinum mixed with sodium or iron is supported on activated carbon (Fe-Pt-). Hydrogenation performed in an organic solvent using activated carbon or Na-Pt-activated carbon). In general, a catalyst in which palladium is supported on activated carbon used for hydrogenation (Pd-activated carbon) has a strong reaction activity and reduces the double bond of the photosensitive group. Pd-activated carbon catalyst must be used. Also, Pt-carbon black or a catalyst in which platinum mixed with sodium or iron is supported on activated carbon (Fe-Pt-activated carbon or Na-Pt-activated carbon) is reduced to a double bond in this reduction system. In this manner, the nitro group is selectively reduced, so that the desired diamine can be obtained in a high yield.

  In the Pt-carbon black system, Fe-Pt-activated carbon system or Na-Pt-activated carbon system, the platinum concentration in the catalyst is about 0.1 to 40% by weight, and 0.1% or more is contained. The effect of the catalyst is manifested. The higher the platinum concentration, the more the reaction rate tends to improve. However, since it is a noble metal, it is preferable to use a catalyst having a platinum concentration of about 1 to 20%.

  Similarly, in the Pd-activated carbon system, the palladium concentration in the catalyst is about 0.1 to 40% by weight, and the effect of the catalyst is manifested if it is contained by 0.1% or more. The higher the palladium concentration, the better the reaction rate. However, since it is a noble metal, it is preferable to use a catalyst having a palladium concentration of about 1 to 30%. In the Fe-Pt-activated carbon system or Na-Pt-activated carbon system, the iron or sodium content is about 0.1 to 40% by weight, preferably 0.1 to 20%, particularly preferably 0. It is about 1 to 10%. These catalysts have the same effect whether they are used in a dry state or in a state containing water after adding water. Use in a water-containing state is desirable industrially because dust does not rise and handling properties are good.

  Solvents used for the reduction include alcohols, dioxane, aromatic solvents such as toluene and xylene, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, and formamide systems such as N, N-dimethylformamide and N, N-diethylformamide. Solvent, acetamide solvent such as N, N-dimethylacetamide, N, N-diethylacetamide, pyrrolidone solvent such as N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, phenol, o-, m-, Alternatively, it is not limited as long as it does not inhibit the reaction and dissolves the diamine or dinitrate, such as phenol solvents such as p-cresol, xylenol, halogenated phenol, catechol, or hexamethylphosphoramide, γ-butyrolactone.

  As conditions for Bechamp reduction, dinitrate is reduced by adding Fe powder in a solvent and heating at a temperature of 130 ° C. or lower. As the solvent, the solvents described above can be used, and acetic acid, alcohols, dioxane and the like are particularly preferable.

  Next, a method for synthesizing the polyimide of the present invention represented by the general formula (2) using the diamine according to the present invention produced above will be described.

  A polyimide composition having a photosensitive group can be obtained by reacting the diamine and acid dianhydride in an organic polar solvent to form polyamic acid and imidizing it thermally or chemically. Here, the method of thermally imidizing is a method of dehydrating imidization by adding a tertiary amine and an azeotropic solvent to the polyamic acid copolymer already described. In general, in the method of thermally imidizing, an imidization reaction occurs when heated to 150 ° C. or higher, but at a temperature condition of 180 ° C. or higher, a double bond contained in the photosensitive group reacts, which is not desirable. . Therefore, it is desirable to thermally imidize by adding the above-mentioned tertiary amine at a temperature of 180 ° C. or lower, or chemically imidize at a temperature of 180 ° C. or lower.

  The method of chemically imidizing is a method of imidizing a polyamic acid polymer or a solution thereof by adding a stoichiometric or higher amount of dehydrating agent and a catalytic amount of a tertiary amine and heating.

  Examples of the dehydrating agent here include aliphatic acid anhydrides such as acetic anhydride, aromatic acid anhydrides, and the like. Examples of the catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as pyridine, picoline, and isoquinoline.

  The average molecular weight of the obtained polyamic acid is desirably 5,000 to 1,000,000. If the average molecular weight is less than 5000, the molecular weight of the produced polyimide composition becomes small, and if the polyimide composition is used as it is as a photoreactive resin, the resin becomes brittle, which is not preferable. On the other hand, if it exceeds 1,000,000, the viscosity of the polyamic acid varnish becomes too high, which makes it difficult to handle.

  Moreover, it is also possible to combine various organic additives, inorganic fillers, or various reinforcing agents with this polyimide composition.

  Examples of the organic polar solvent used in the above polyamic acid production reaction include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, Acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o-, m-, or p -Phenolic solvents such as cresol, xylenol, halogenated phenol, catechol, hexamethylphosphoramide, γ-butyrolactone, and the like. These can be used singly or as a mixture, and further, some aromatic hydrocarbons such as xylene and toluene can be used.

ブタンテトラカルボン酸二無水物、１，２，３，４−シクロブタンテトラカルボン酸二無水物、１，３−ジメチル−１，２，３，４−シクロブタンテトラカルボン酸、１，２，３，４−シクロペンタンテトラカルボン酸二無水物、２，３，５−トリカルボキシシクロペンチル酢酸二無水物、３，５，６−トリカルボキシノルボナン−２−酢酸二無水物、２，３，４，５−テトラヒドロフランテトラカルボン酸二無水物、５−（２，５−ジオキソテトラヒドロフラル）−３−メチル−３−シクロヘキセン−１，２−ジカルボン酸二無水物、ビシクロ［２，２，２］−オクト−７−エン−２，３，５，６−テトラカルボン酸二無水物等の脂肪族または脂環式テトラカルボン酸二無水物；１，４，５，８−ナフタレンテトラカルボン酸二無水物、２，３，６，７−ナフタレンテトラカルボン酸二無水物、３，３’，４，４'−ジメチルジフェニルシランテトラカルボン酸二無水物、３，３’，４，４'−テトラフェニルシランテトラカルボン酸二無水物、１，２，３，４−フランテトラカルボン酸二無水物、４，４’−ビス（３，４−ジカルボキシフェノキシ）ジフェニルスルフィド二無水物、４，４’−ビス（３，４−ジカルボキシフェノキシ）ジフェニルスルホン二無水物、４，４’−ビス（３，４−ジカルボキシフェノキシ）ジフェニルプロパン二無水物、３，３'，４，４’−パーフルオロイソプロピリデンジフタル酸二無水物、ビス（フタル酸）フェニルホスフィンオキサイド二無水物、ｐ−フェニレン−ビス（トリフェニルフタル酸）二無水物、ｍ−フェニレン−ビス（トリフェニルフタル酸）二無水物、ビス（トリフェニルフタル酸）−４，４'
−ジフェニルエーテル二無水物、ビス（トリフェニルフタル酸）−４，４'−ジフェニルメタン二無水物等の芳香族テトラカルボン酸二無水物；１，３，３ａ，４，５，９ｂ−ヘキサヒドロ−２，５−ジオキソ−３−フラニル）−ナフト［１，２−ｃ］フラン−１，３−ジオン、１，３，３ａ，４，５，９ｂ−ヘキサヒドロ−５−メチル−５−（テトラヒドロ−２，５−ジオキソ−３−フラニル）−ナフト［１，２−ｃ］フラン−１，３−ジオン、１，３，３ａ，４，５，９ｂ−ヘキサヒドロ−８−メチル−５−（テトラヒドロ−２，５−ジオキソ−３−フラニル）−ナフト［１，２−ｃ］フラン−１，３−ジオン、下記一般式（３）化１３

（式中Ｒ₁は芳香環を有する２価の結合鎖を示し、Ｒ₂およびＲ₃はそれぞれ水素原子またはアルキル基を示す。）
下記一般式（４）化１４

（式中Ｒ₄は芳香環を有する２価の結合鎖を示し、Ｒ₅およびＲ₆はそれぞれ水素原子またはアルキル基を示す。）で表わされる化合物等の芳香環を有する脂肪族テトラカルボン酸二無水物等を挙げることができる。これらのテトラカルボン酸二無水物は、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。 The acid dianhydride used in this polyimide composition, that is, the acid dianhydride corresponding to B or D in the general formula (2) is not particularly limited as long as it is an acid dianhydride.

Butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4 -Cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbonane-2-acetic acid dianhydride, 2,3,4,5- Tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct- Aliphatic or alicyclic tetracarboxylic dianhydrides such as 7-ene-2,3,5,6-tetracarboxylic dianhydride; 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2 3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic acid Dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3 4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic acid Dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) Acid) dianhydride, bis (triphenyl phthalic acid) -4,4 '
-Aromatic tetracarboxylic dianhydrides such as diphenyl ether dianhydride and bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride; 1,3,3a, 4,5,9b-hexahydro-2, 5-Dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5- (tetrahydro-2, 5-Dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2, 5-Dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, the following general formula (3)

(Wherein R ₁ represents a divalent linking chain having an aromatic ring, and R ₂ and R ₃ each represent a hydrogen atom or an alkyl group.)
The following general formula (4)

(Wherein R ₄ represents a divalent linking chain having an aromatic ring, and R ₅ and R ₆ each represent a hydrogen atom or an alkyl group). An aliphatic tetracarboxylic acid having an aromatic ring such as a compound represented by An anhydride etc. can be mentioned. These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

（ＴはＨ，ＣＨ₃，Ｆ，Ｃｌ，Ｂｒ，ＣＨ₃Ｏ−を表す。）
から選ばれる２価の結合鎖）や、
４，４'−ジアミノフェニルエタン、４，４’−ジジアミノフェニルスルフィド、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、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、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、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；
下記一般式（６）化１６

（式中Ｒ₇は、−Ｏ−，−ＣＯＯ−，−ＯＣＯ−，−ＣＯＮＨ−及び−ＣＯ−から選ばれる２価の結合鎖を示し、
Ｒ₈はステロイド骨格を有する１価の結合鎖を示す。）で表わされるモノ置換フェニレンジアミン類；
下記化学式 化１７

（Ｒ₉は炭素数１〜１２の炭化水素基を示し、ｙは１〜３の整数であり、ｚは１〜２０の整数である。）で表わされる化合物等を挙げることができる。 Various diamines can be used as the diamine used in the polyimide composition, that is, the diamine corresponding to E in the general formula (2). Although it will not specifically limit if it is diamine, For example, General formula (5)
H ₂ N-G-NH ₂
(G is

(T represents H, CH ₃ , F, Cl, Br, CH ₃ O—.)
A divalent linking chain selected from
4,4′-diaminophenylethane, 4,4′-didiaminophenyl sulfide, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4′-diaminobiphenyl, 5-amino-1- (4′- Aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 3,5-diamino-3′-trifluoromethylbenzanilide 3,5-diamino-4′-trifluoromethylbenzanilide, 3,4′-diaminodiphenyl ether, 2,7-diaminofluorene, 4,4′-methylene-bis (2-chloroaniline), 2,2 ′ , 5,5′-tetrachloro-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, 9,9-bis (4-aminophenyl) fluorene, 4,4 ′-(p-phenyleneisopropyl Ridene) bisaniline, 4,4 ′-(m-phenyleneisopropylidene) bisaniline, 2,2′-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4′- Aromatic diamines such as 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, 4,4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadiene cyclopentadienylide diamine, hexahydro-4,7-meth Noin mite range diamine, tricyclo [6,2,1,0 ^2.7] - undecylenate range methyl diamine, 4,4'-methylenebis (cyclohexylamine) Aliphatic diamines and cycloaliphatic diamines;
The following general formula (6)

(Wherein R ₇ represents a divalent linking chain selected from —O—, —COO—, —OCO—, —CONH—, and —CO—;
R ₈ represents a monovalent linking chain having a steroid skeleton. Monosubstituted phenylenediamines represented by:
The following chemical formula

(R ₉ represents a hydrocarbon group having 1 to 12 carbon atoms, y is an integer of 1 to 3, and z is an integer of 1 to 20).

  Next, the polymerization method will be specifically described.

（但し、Ｘは、−，−ＣＨ₂−，−ＣＯＯ−，−ＮＨ−，−Ｏ−から選択される２価の結合鎖、Ｙは、−，−ＣＯ−，−ＯＯＣ−，−（ＣＨ₂）_mＯ−，−（ＣＨ₂）_mＣＯＯ−，−（ＣＨ₂）_mＯＯＣ−，−（ＣＨ₂）_m−から選択される２価の結合鎖、ｍは１〜１５の整数を、Ｚは化１９

から選ばれる１種以上の感光基を、ＡはＨ，ＣＨ₃，Ｆ，Ｃｌ，Ｂｒ，ＣＨ₃Ｏ−を示す。）
で表されるジアミンと、一般式（７）化２０

（式中Ｂは、１種または２種以上の４価の結合鎖である。）で表される酸二無水物を前記有機溶媒中に溶解または拡散させて反応させる。 First, in an inert atmosphere such as argon or nitrogen, the general formula (1)

(Where X is a divalent linking chain selected from —, —CH ₂ —, —COO—, —NH—, —O—, Y is —, —CO—, —OOC—, — (CH _{2) m O -, - (} CH 2) m COO -, - (CH 2) m OOC -, - (CH 2) m - 2 divalent linking chain selected from, m is an integer of 1 to 15, Z is

A represents one or more photosensitive groups selected from: A, H, CH ₃ , F, Cl, Br, CH ₃ O—. )
And a diamine represented by the general formula (7)

(In the formula, B is one or two or more tetravalent linking chains.) The acid dianhydride represented by the formula is dissolved or diffused in the organic solvent and reacted.

（式中Ｄは、１種又は２種以上の４価の結合鎖である。）
で表される１種以上の酸二無水物を有機溶媒中に添加し、ポリアミド酸共重合体溶液を得る。これらの酸二無水物成分及びジアミン成分のモル比を調整して一般式（２）のｐとｑの関係がｍ＝１〜１００、ｎ＝０〜９９かつｍ＋ｎ＝１００である範囲であるポリアミド酸共重合体を任意に得ることができる。 In this case, when the diamine and the acid dianhydride are substantially equimolar, a polyamic acid solution of p = 100 represented by the general formula (2) is obtained. When the molar ratio of the diamine and the acid dianhydride is different, the polyamic acid solution further contains the general formula (8)
H ₂ N-E-NH ₂
(Wherein E represents one or more divalent linking chains) is added in an organic solvent dissolved in a slurry state or in a solid state. . In this solution, the general formula (9)

(In the formula, D is one or more tetravalent linking chains.)
One or more kinds of acid dianhydrides represented by the following are added to an organic solvent to obtain a polyamic acid copolymer solution. A polyamide in which the molar ratio of these acid dianhydride components and diamine components is adjusted so that the relationship between p and q in the general formula (2) is in a range where m = 1 to 100, n = 0 to 99, and m + n = 100. An acid copolymer can be arbitrarily obtained.

  As the addition order of each monomer, the diamine component represented by the general formula (1) and the general formula (8) is first added to an organic polar solvent, and then the general formula (7) which is an acid dianhydride component. The acid dianhydride component represented by formula (9) is added, and then the acid dianhydride component represented by formula (9) may be added to form a polyamic acid copolymer solution. In addition, the diamine component represented by the general formula (8) is previously added to the organic polar solvent, the general formula (7) which is an acid dianhydride component is added, and then represented by the general formula (1). It is good also as a solution of a polyamic acid copolymer by adding a diamine component and then adding an acid dianhydride component represented by the general formula (9). In addition, the general formula (1) and the general formula (8), which are diamine components, are first added to an organic polar solvent, and then the general formula (7) and the general formula (9), which are acid dianhydride components, are added. At the same time, it may be a polyamic acid copolymer solution, and is not particularly limited.

  If the above addition method is reversed and the acid dianhydride is added first and the diamine component is added later, the same is true.

It is also possible to synthesize polyamide using the novel diamine according to the present invention. Specifically, the diamine of the present invention and any dicarboxylic acid are heated in a homogeneous solution using an amide solvent such as N, N-dimethylacetamide or N-methyl-2-pyrrolidone in the presence of a condensing agent. Done. Examples of the condensing agent include (PhO) ₃ P, (PhO) PCl ₂ , PhPOCl ₂ , and Me ₂ SiCl _2, and can be used in combination with pyridine in an amide solvent.

  Furthermore, polyamide can also be synthesized by reacting the diamine of the present invention with dicarboxylic acid chloride. The reaction between the dicarboxylic acid chloride and the diamine may be carried out at a low temperature in an amide solvent, or it is a two-phase system of an organic solvent that is not mixed with water and water, and the dicarboxylic acid chloride is dissolved in the organic phase as a diamine. And sodium hydroxide or sodium carbonate, which are acid acceptors, may be dissolved and polymerized at the interface between the organic phase and the aqueous phase. As a method for synthesizing polyamide, a general method in which diamine and dicarboxylic acid are heated and melted at a high temperature is not desirable because a double bond of a photosensitive group is decomposed.

  The novel diamine and novel polyimide composition according to the present invention obtained as described above have good reactivity to light and heat, and can be used for various applications such as printing and semiconductor production.

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

(Example)
In the examples, ESDA is 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride, and 6FDA is 4,4 ′-(hexafluoro). Isopropylidene) diphthalic anhydride, DMAc represents N, N-dimethylacetamide, and DMF represents N, N-dimethylformamide.

  The weight average molecular weight was measured under the following conditions using GPC manufactured by Waters. (Column: KD-806M 2 manufactured by Shodex, temperature 60 ° C., detector: RI, flow rate: 1 ml / min, developing solution: DMF (lithium bromide 0.03 M, phosphoric acid 0.03 M), data concentration: 0.00. (2 wt%, injection amount: 20 μl, reference material: polyethylene oxide)

Example 1
Synthesis of 3,5-dinitrobenzoic acid chloride Take 3,5-dinitrobenzoic acid and ethyl acetate in a reaction vessel and add thionyl chloride (a few moles to dinitrobenzoic acid) to which a few drops of DMF are added. Stir at reflux until no hydrogen gas is generated. The reaction solution was concentrated until a solid started to precipitate, and poured into hexane, and the precipitate was separated by filtration and dried to obtain 3,5-dinitrobenzoic acid chloride in a yield of 97%.

Synthesis of 2 ′-(3,5-dinitrobenzoate) -chalcone 115.3 g (0.5 mol) of 3,5-dinitrobenzoic acid chloride and 700 ml of methyl ethyl ketone were placed in a reaction vessel and heated to 60 ° C. with stirring in a nitrogen stream. 112.1 g (0.5 mol) of 2′-hydroxychalcone, 800 ml of methyl ethyl ketone, and 80 g of pyridine were added dropwise. After completion of dropping, the mixture was stirred at reflux for about 2 hours. After completion of the reaction, the mixture was filtered off, the solution was concentrated, washed with water and dried to obtain 193 g of 2 ′-(3,5-dinitrobenzoate) -chalcone.

Synthesis of synthesis of 2 ′-(3,5-diaminobenzoate) -chalcone 41.8 g (100 mmol) of 2 ′-(3,5-dinitrobenzoate) -chalcone, 10 g of activated carbon powder containing 5% Pt-2% iron, 500 ml of 1,4-dioxane was taken in a reaction vessel (hydrogenation apparatus), and heated and stirred at 60 ° C. in a hydrogen atmosphere. Since 14.4 liters of hydrogen was absorbed and the absorption of hydrogen ceased, the reaction was stopped, the reaction solution was filtered off, the catalyst was removed, and then concentrated to 2 ′-(3,5-diaminobenzoate)- 35.8 g of chalcone was obtained.

Synthesis of polyimide In a 2000 ml separable flask equipped with a stirrer, 35.8 g (0.1 mol) of 2 ′-(3,5-diaminobenzoate) -chalcone and 250 g of DMAc were taken, and 57.65 g (0.1 mol) of ESDA was added. The mixture was added with vigorous stirring at once, and stirring was continued for 30 minutes.

  β-picoline 18.61 g (0.2 mol), acetic anhydride 50 g, and DMAc 100 g were added to the above reaction solution, and heated to about 120 ° C. to imidize. These reactions were performed under a nitrogen stream.

  After completion of the reaction, it was added to methanol, stirred vigorously with a mixer, filtered and dried to obtain 88 g of yellow polyimide powder. The weight average molecular weight of this polyimide powder was 100,000.

(Example 2)
Synthesis of 7 '-(3,5-dinitrobenzoate) -coumarin Take 115.3 g (0.5 mol) of 3,5-dinitrobenzoic acid chloride and 700 ml of methyl ethyl ketone in a reaction vessel, and heat and stir at 60 ° C under a nitrogen stream. 7-hydroxycoumarin 81.1 g (0.5 mol), methyl ethyl ketone 800 ml, and pyridine 50 g were added dropwise. After completion of dropping, the mixture was stirred at reflux for about 2 hours. After completion of the reaction, the solution was filtered off, the solution was concentrated, washed with water and dried.
177 g of-(3,5-dinitrobenzoate) -coumarin was obtained.

Synthesis of synthesis of 7 ′-(3,5-diaminobenzoate) -coumarin 7 ′-(3,5-dinitrobenzoate) -coumarin 35.6 (100 mmol), 10 g of activated carbon powder containing 5% Pt-2% iron, 500 ml of 1,4-dioxane was taken in a reaction vessel (hydrogenation apparatus), and heated and stirred at 60 ° C. in a hydrogen atmosphere. Since 14.4 liters of hydrogen was absorbed and the absorption of hydrogen ceased, the reaction was stopped, the reaction solution was filtered off, the catalyst was removed, and then concentrated to 2 ′-(3,5-diaminobenzoate)- 29.6 g of coumarin was obtained.

Synthesis of polyimide In a 2000 ml separable flask equipped with a stirrer, 29.6 g (0.1 mol) of 2 ′-(3,5-diaminobenzoate) -coumarin and 250 g of DMAc were taken, and 28.8 g (0.05 mol) of ESDAg was added. The mixture was added with vigorous stirring at once, and stirring was continued for 30 minutes. Next, 22.2 g (0.05 mol) of 6FDA was added with vigorous stirring at once, and stirring was continued for 30 minutes. β-picoline 18.61 g (0.2 mol), acetic anhydride 50 g, and DMAc 100 g were added to the above reaction solution, and heated to about 120 ° C. to imidize. These reactions were performed under a nitrogen stream.

  After completion of the reaction, it was added to methanol, stirred vigorously with a mixer, filtered and dried to obtain 75 g of a pale yellow polyimide powder. The weight average molecular weight of this polyimide powder was 120,000.

(Example 3)
Synthesis of Coumarin-3-Carboxylic Chloride Take Coumarin-3-Carboxylic Acid and Ethyl Acetate in a reaction vessel and add thionyl chloride (a few moles of dinitrobenzoic acid) with a few drops of DMF to add hydrogen chloride. Stir at reflux until no more gas is generated. The reaction solution was concentrated until a solid began to precipitate, and poured into hexane, and the precipitate was separated by filtration and dried to obtain coumarin-3-carboxylic chloride in a yield of 87%.

Synthesis of coumarin-3-carboxylate- (3,5-dinitrobenzyl) 104.3 g (0.5 mol) of coumarin-3-carboxyl chloride and 700 ml of methyl ethyl ketone were placed in a reaction vessel, and heated and stirred at 60 ° C. in a nitrogen stream. Then, 99.1 g (0.5 mol) of 3,5-dinitrobenzyl alcohol, 800 ml of methyl ethyl ketone, and 80 g of pyridine were added dropwise. After completion of dropping, the mixture was stirred at reflux for about 2 hours. After completion of the reaction, the mixture was filtered off, and the solution was concentrated, washed with water and dried to obtain 183.3 g of coumarin-3-carboxylate- (3,5-dinitrobenzyl).

Synthesis of coumarin-3-carboxylate- (3,5-diaminobenzyl) 37.03 g (100 mmol) of coumarin-3-carboxylate- (3,5-dinitrobenzyl) 10 g of carbon graphite containing 5% Pt, 1, 4-Dioxane (500 ml) was placed in a reaction vessel (hydrogenation apparatus), and heated and stirred at 60 ° C. in a hydrogen atmosphere. Since 14.4 liters of hydrogen was absorbed and the absorption of hydrogen ceased, the reaction was stopped, the reaction solution was filtered off, the catalyst was removed, and then concentrated to coumarin-3-carboxylate- (3,5- 31 g of diaminobenzyl) was obtained.

Synthesis of polyimide In a 2000 ml separable flask equipped with a stirrer, 31 g (0.1 mol) of coumarin-3-carboxylate- (3,5-diaminobenzyl) and 250 g of DMAc were taken, and 28.8 g (0.05 mol) of ESDA was added. The mixture was added with vigorous stirring at once, and stirring was continued for 30 minutes. Next, 22.2 g (0.05 mol) of 6FDA was added with vigorous stirring at once, and stirring was continued for 30 minutes.

  β-picoline 18.61 g (0.2 mol), acetic anhydride 50 g, and DMAc 100 g were added to the above reaction solution, and heated to about 120 ° C. to imidize. These reactions were performed under a nitrogen stream.

  After completion of the reaction, the reaction mixture was poured into methanol, stirred vigorously with a mixer, filtered and dried to obtain 78 g of yellow polyimide powder. The weight average molecular weight of this polyimide powder was 120,000.

Example 4
Synthesis of coumarin-3-carboxylate-1- (3,5-dinitrophenyl ester) 104.3 g (0.5 mol) of coumarin-3-carboxyl chloride and 700 ml of methyl ethyl ketone were placed in a reaction vessel, and 60 ° C. under a nitrogen stream. Then, 78.05 g (0.5 mol) of 3,5-dinitrophenol, 800 ml of methyl ethyl ketone, and 80 g of pyridine were added dropwise. After completion of dropping, the mixture was stirred at reflux for about 2 hours. After completion of the reaction, the reaction mixture was filtered off, and the solution was concentrated, washed with water and dried to obtain 155.9 g of coumarin-3-carboxylate-1- (3,5-dinitrophenyl ester).

Synthesis of coumarin-3-carboxylate-1- (3,5-diaminophenyl ester) 32.8 g (100 mmol) of coumarin-3-carboxylate-1- (3,5-dinitrophenyl ester) containing 5% Pt 10 g of carbon graphite and 500 ml of 1,4-dioxane were placed in a reaction vessel (hydrogenation apparatus), and the mixture was heated and stirred at 60 ° C. in a hydrogen atmosphere. Since 14.4 liters of hydrogen was absorbed and the absorption of hydrogen ceased, the reaction was stopped, the reaction solution was filtered off, the catalyst was removed, and then concentrated to coumarin-3-carboxylate-1- (3, 26.8 g of 5-diaminophenyl ester) was obtained.

Synthesis of polyimide In a 2000 ml separable flask equipped with a stirrer, 26.8 g (0.1 mol) of coumarin-3-carboxylate-1- (3,5-diaminophenyl ester) and 250 g of DMAc were taken, and 28.8 g of ESDA (0 .05 mol) was added with vigorous stirring at once, and stirring was continued for 30 minutes. Next, 22.2 g (0.05 mol) of 6FDA was added with vigorous stirring at once, and stirring was continued for 30 minutes.

  β-picoline 18.61 g (0.2 mol), acetic anhydride 50 g, and DMAc 100 g were added to the above reaction solution, and heated to about 120 ° C. to imidize. These reactions were performed under a nitrogen stream.

  After completion of the reaction, it was added to methanol, stirred vigorously with a mixer, filtered and dried to obtain 80 g of pale yellow polyimide powder. The weight average molecular weight of this polyimide powder was 130,000.

(Example 5)
Synthesis of 1- (3,5-dinitrophenoxy) -2-bromoethane 187.9 g (1 mol) of 1,2-dibromoethane, 18.4 g (0.1 mol) of 3,5-dinitrophenol, 138. potassium carbonate. 2 (1 mol) and 400 ml of dimethylformamide were placed in a reaction vessel and stirred under reflux for 24 hours under a nitrogen flow. The reaction solution was poured into water, and the precipitate was purified by column to obtain 20 g of 1- (3,5-dinitrophenoxy) -2-bromoethane.

Synthesis of cesium coumarin-3-carboxylate 95 g (0.5 mol) of coumarin-3-carboxylic acid and 81.5 g (0.25 mol) of cesium carbonate were placed in a reaction vessel, and acetone: water = 1: 1 (volume ratio). ) 600 ml of the mixed solution was added and stirred. When the solution became uniform, it was concentrated and dried to obtain 161.5 g (0.5 mol) of cesium coumarin-3-carboxylate.

Synthesis of 1- (3,5-dinitrophenoxy) -2- (coumarin-3-carboxylate) ethane 19.44 g (0.08 mol) of 1- (3,5-dinitrophenoxy) -2-bromoethane, coumarin- Cesium 3-carboxylate (32.3 g, 0.1 mol) and dimethylformamide (200 ml) were taken up in the reaction solution, and 100 ° C.
The reaction was carried out for 8 hours under a nitrogen flow.
After completion of the reaction, the reaction solution was poured into water. The precipitate was purified by column to obtain 26.5 g of 1- (3,5-dinitrophenoxy) -2- (coumarin-3-carboxylate) ethane.

Synthesis of 1- (3,5-diaminophenoxy) -2- (coumarin-3-carboxylate) ethane Synthesis was performed in the same manner as in Example 4.

Synthesis of polyimide In a 2000 ml separable flask equipped with a stirrer, 20.5 g (0.07 mol) of 1- (3,5-diaminophenoxy) -2- (coumarin-3-carboxylate) ethane and 250 g of DMAc were taken, and 6FDA15 0.5 g (0.035 mol) was added with rapid stirring, and stirring was continued for 30 minutes. Next, 15.5 g (0.035 mol) of 6FDA was added with vigorous stirring at once, and stirring was continued for 30 minutes.

  β-picoline 18.61 g (0.2 mol), acetic anhydride 50 g, and DMAc 100 g were added to the above reaction solution, and heated to about 120 ° C. to imidize. These reactions were performed under a nitrogen stream. After completion of the reaction, it was added to methanol, stirred vigorously with a mixer, filtered and dried to obtain 50 g of a white solid.

(Example 6)
Synthesis of cesium α-pyrone-5-carboxylate 70 g (0.5 mol) of α-pyrone-5-carboxylic acid and 81.5 g (0.25 mol) of cesium carbonate were placed in a reaction vessel, and acetone: water = 1: 600 ml of 1 (volume ratio) mixture was added and stirred. When the solution became uniform, it was concentrated and dried to obtain 151.5 g (0.5 mol) of α-pyrone-5-carboxylic acid.

Synthesis of 1- (3,5-dinitrophenoxy) -2- (α-pyrone-5-carboxylate) ethane 19.44 g (0.08 mol) of 1- (3,5-dinitrophenoxy) -2-bromoethane, 30.5 g (0.1 mol) of cesium α-pyrone-5-carboxylate and 200 ml of dimethylformamide were taken into the reaction solution, and 100 ° C
The reaction was carried out for 8 hours under a nitrogen flow.

  After completion of the reaction, the reaction solution was poured into water. The precipitate was purified by column to obtain 26.0 g of 1- (3,5-ditrophenoxy) -2- (α-pyrone-5-carboxylate) ethane.

Synthesis of 1- (3,5-diaminophenoxy) -2- (α-pyrone-5-carboxylate) ethane Synthesis was performed in the same manner as in Example 4.

Synthesis of polyimide 1- (3,5-diaminophenoxy) -2- (coumarin-3-carboxylate) ethane was converted to 1- (3,5-diaminophenoxy) -2- (α-pyrone-5-carboxylate) ethane The compound was synthesized in the same manner as in Example 5 except that the method was replaced. The obtained polyimide was 45 g of a white solid and had a molecular weight of 150,000.

(Example 7)
Synthesis of 3-bromopropionate- (2-chalcone) 67.3 g (mol) of 2-hydroxychalcone, 32 g of pyridine, and 500 ml of methyl ethyl ketone were placed in a reaction vessel, and 51.4 g (0.3 mol) of 3-bromopropionic acid chloride. ) Was dissolved in 300 ml of methyl ethyl ketone and slowly dropped. After completion of the dropwise addition, the mixture was stirred under reflux for 2 hours under a nitrogen flow. The reaction solution was concentrated, washed with water, dried and purified by column to obtain 100 g of 3-bromopropionate- (2-chalcone).

Synthesis of 3- (3,5-dinitrobenzoate) -propionate- (2-chalcone) 71.8 g (0.2 mol) of 3-bromopropionate- (2-chalcone), cesium 3,5-dinitrobenzoate 68.8 g (0.2 mol) and 600 ml of dimethylformamide were placed in a reaction vessel and reacted for 8 hours in a 100 ° C. nitrogen atmosphere. After completion of the reaction, the reaction solution was poured into water. The precipitate was purified by column to obtain 73.6 g (0.15 mol) of 3- (3,5-dinitrobenzoate) -propionate- (2-chalcone).

Synthesis of 3- (3,5-diaminobenzoate) -propionate- (2-chalcone) Synthesis was performed in the same manner as in Example 1.

Synthesis of polyimide Synthesis was performed in the same manner as in Example 1 except that the diamine component 3- (3,5-diaminobenzoate) -propionate- (2-chalcone) was used, and 95 g of a yellow solid was obtained. The molecular weight was 120,000.

(Example 8)
Synthesis of 3,5-dinitrobenzoate-2-bromoethane 134.8 g (0.5 mol) of 3,5-dinitrobenzoic acid chloride and 700 ml of acetone are placed in a reaction vessel and heated and stirred at 60 ° C. under a nitrogen stream. Bromoethanol 75 g (0.6 mol), acetone 200 ml, and pyridine 80 g were added dropwise. After completion of dropping, the mixture was stirred at reflux for about 2 hours. After completion of the reaction, the mixture was filtered, and the solution was concentrated, washed with water and dried to obtain 144 g of 3,5-dinitrobenzoate-2-bromoethane.

Synthesis of 1- (3,5-dinitrobenzoate) -2- (coumarin-3-carboxylate) -ethane 96.6 g (mol) of cesium coumarin-3-carboxylate, 3,5-dinitrobenzoate-2-bromoethane 95 0.7 g (0.3 mol) and 1000 ml of dimethylformamide were placed in a reaction vessel and reacted at 100 ° C. for 8 hours under a nitrogen flow. After completion of the reaction, the reaction solution was poured into water, and the precipitate was purified by column to obtain 107 g of 1- (3,5-dinitrobenzoate) -2- (coumarin-3-carboxylate) -ethane.

Synthesis of 1- (3,5-diaminobenzoate) -2- (coumarin-3-carboxylate) -ethane Synthesis was performed in the same manner as in Example 1.

Synthesis of polyimide 90 g of a yellow solid was synthesized in the same manner as in Example 1 except that 1- (3,5-diaminobenzoate) -2- (coumarin-3-carboxylate) -ethane was used as the diamine component. Got. The molecular weight was 140,000.

Example 9
Synthesis of 1- (3,5-dinitrophenyl) -coumarin-3-carboxamide 91.6 g (0.5 mol) of 3,5-dinitroaniline, 600 ml of pyridine, 1,8-diazabicyclo- [5,4,0 ] 76 g (0.5 mol) of 7-undecene was placed in a reaction vessel, 104.3 g (0.5 mol) of coumarin-3-carboxylic chloride was added, and the mixture was refluxed and stirred for 3 hours under a nitrogen gas stream. After completion of the reaction, the mixture was concentrated, washed with water, dried and purified by recrystallization to obtain 142 g of 1- (3,5-dinitrophenyl) -coumarin-3-carboxamide.

Synthesis of 1- (3,5-diaminophenyl) -coumarin-3-carboxamide Synthesis was performed in the same manner as in Example 1.

Synthesis of polyimide Synthesis was performed in the same manner as in Example 1 except that 1- (3,5-diaminophenyl) -coumarin-3-carboxamide was used as the diamine component, to obtain 80 g of a yellow solid. The molecular weight was 160,000.

Claims (4)

The following general formula (1)

(Where X and Y are divalent linking chains, Z is

A represents one or more photosensitive groups selected from: A, H, CH ₃ , F, Cl, Br, CH ₃ O—. ) A new diamine. X in the general formula (1) _{is, -, - CH 2 -,} - COO -, - NH -, - novel diamine according to claim 1 wherein the divalent linking chain selected from O-. Y is of the general formula (1) -, - COO - , - OOC -, - (CH 2) m O -, - (CH 2) m COO -, - (CH 2) m OOC -, - (CH 2 2. The novel diamine according to claim 1, which is a divalent linking chain selected from _m- . (However, m represents an integer of 1 to 15.) The structure is represented by the following general formula (2)

(However, the divalent linking chain Y in which X is selected from —, —CH ₂ —, —COO—, —NH—, —O— is —, —COO—, —OOC—, — (CH ₂ ). _{m O -, - (CH 2} ) m COO -, - (CH 2) m OOC -, - (CH 2) m -, a divalent linking chain selected from (1 to 15 m in the formula) , Z is the chemical formula 4

One or more photosensitive groups selected from
(In the formula, A represents H, CH ₃ , F, Cl, Br, CH ₃ O—)
B and D are tetravalent linking chains,
E is a divalent linking chain,
p represents an integer of 1 to 100, and q represents an integer of 0 to 99. ) In an amount of 1% by weight or more.