JP2018009063A - Polyimide precursor composition, polyimide composition, and polyimide film and polyimide laminate obtained from these compositions - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a material that achieve both a high elastic modulus and a high elongation.SOLUTION: A composition contains a polyimide precursor. The polyimide precursor has a repeating unit containing a structure represented by the following structural formula (1), and a repeating unit containing a structure forming a non-covalent bond, with a molecular terminal of the polyimide precursor sealed. There are also provided a polyimide film obtained from the composition, and a polyimide laminate having a resin layer obtained from the composition (where Ris a tetracarboxylic acid residue, and Ris a diamine residue).SELECTED DRAWING: None

Description

  The present invention relates to a composition containing a polyimide precursor that exhibits excellent mechanical properties over a wide range of firing conditions, a composition containing polyimide, a polyimide film and a polyimide laminate excellent in mechanical properties obtained from these compositions.

  Conventionally, polyimides having excellent heat resistance, electrical insulation properties, wear resistance, chemical resistance, mechanical properties, and the like have been widely used in the fields of electricity, electronic parts, transportation equipment, space, aircraft, and the like.

  Polyimide is usually supplied as a precursor polyamic acid solution, and the polyamic acid solution is heated at a temperature of about 300 ° C. to 350 ° C. to remove the solvent and dehydrate and ring-close the polyimide. However, this process (hereinafter referred to as “imidization”) requires heating for a long time, and usually requires heating for several hours, which has caused low production efficiency. In general, a film that can be formed by heating in a short time, and a highly heat-resistant polyimide has a rigid skeleton, making it a material with extremely high elastic modulus and low elongation characteristics, and for applications that require flexibility. Could not be applied. On the other hand, when a flexible skeleton is introduced with emphasis on elongation characteristics, mechanical properties such as heat resistance and elastic modulus are remarkably lowered, and it cannot be applied to applications requiring mechanical strength.

In order to shorten the heating time, Patent Document 1 discloses a soluble polyimide that has previously completed the imidization reaction.
Patent Document 2 discloses a polyimide precursor using a solvent having a low volatility temperature.
Patent Document 3 discloses a polyimide having a skeleton having an amide bond in a polyimide skeleton like an amideimide material.

JP2015-134842A JP 2008-308553 A JP 2013-028688 A

However, when the imidization reaction is completed in advance as in Patent Document 1, the solvent resistance of the resulting polyimide is low, causing problems such as polymer precipitation. In addition, although it is effective to increase the heating temperature, at a heating temperature of 400 ° C. or more, the mechanical properties of the polyimide are remarkably deteriorated and sometimes weakened.
In addition, when a solvent having a low volatility temperature is used as in Patent Document 2, it is necessary to make polyimide a skeleton having high solubility in various organic solvents, so that the resulting polyimide has insufficient heat resistance and mechanical properties. was there.
In Patent Document 3, when an amide bond is present as in the case of an amide-imide material, the production efficiency is increased because there are few imide sites, but the amide bond has high water absorption and solvent affinity, so that the resulting polyimide has high hydrolyzability. There was a problem that.

The present invention has been accomplished in view of the above problems, and introduces a sealing structure at the end of a polyimide precursor molecule or a polyimide molecule, and introduces a structure that forms a non-covalent bond, thereby achieving a high elastic modulus. The present invention provides a material that is compatible with high elongation.
The present invention has the following configuration.
[1] A composition containing a polyimide precursor, wherein the polyimide precursor has a repeating unit containing a structure represented by the following structural formula (1) and a repeating unit containing a structure that forms a non-covalent bond. And the molecular terminal is sealed, The composition characterized by the above-mentioned.

（式中、Ｒ¹はテトラカルボン酸残基、Ｒ²はジアミン残基を表す。）
［２］前記非共有結合が水素結合である［１］に記載のポリイミド前駆体組成物。
［３］前記ポリイミド前駆体の非共有結合を形成する構造の含有量が、ポリイミド前駆体中の全ての繰り返し単位が前記構造を１つずつ含む場合を１００％とすると、２％以上、かつ７５％以下である［１］または［２］に記載のポリイミド前駆体組成物。
［４］前記ポリイミド前駆体の末端封止率が３０％以上である［１］〜［３］の何れかに記載のポリイミド前駆体組成物。
［５］［１］〜［４］のいずれかに記載のポリイミド前駆体組成物より得られるポリイミドフィルム。
［６］［１］〜［４］のいずれかに記載のポリイミド前駆体組成物より得られる樹脂層を有するポリイミド積層体。
［７］ポリイミドを含む組成物であって、前記ポリイミドが、下記構造式（２）で表される構造を含む繰り返し単位及び非共有結合を形成する構造を含む繰り返し単位を有し、且つ分子末端が封止されていることを特徴とするポリイミド組成物。

(In the formula, R ¹ represents a tetracarboxylic acid residue, and R ² represents a diamine residue.)
[2] The polyimide precursor composition according to [1], wherein the non-covalent bond is a hydrogen bond.
[3] When the content of the structure forming a non-covalent bond of the polyimide precursor is 100% when all the repeating units in the polyimide precursor include the structure one by one, 2% or more and 75 % Of the polyimide precursor composition according to [1] or [2].
[4] The polyimide precursor composition according to any one of [1] to [3], wherein a terminal blocking rate of the polyimide precursor is 30% or more.
[5] A polyimide film obtained from the polyimide precursor composition according to any one of [1] to [4].
[6] A polyimide laminate having a resin layer obtained from the polyimide precursor composition according to any one of [1] to [4].
[7] A composition containing polyimide, wherein the polyimide has a repeating unit containing a structure represented by the following structural formula (2) and a repeating unit containing a structure forming a non-covalent bond, and a molecular terminal Is a polyimide composition characterized by being sealed.

（式中、Ｒ³はテトラカルボン酸残基、Ｒ⁴はジアミン残基を表す。）
［８］前記非共有結合が水素結合である［７］に記載のポリイミド組成物。
［９］前記ポリイミドの非共有結合を形成する構造の含有量が、ポリイミド中の全ての繰り返し単位が前記構造を１つずつ含む場合を１００％とすると、２％以上、かつ７５％以下である［７］または［８］に記載のポリイミド組成物。
［１０］前記ポリイミドの末端封止率が３０％以上である［７］〜［９］の何れかに記載のポリイミド組成物。
［１１］［７］〜［１０］のいずれかに記載のポリイミド組成物より得られるポリイミドフィルム。
［１２］［７］〜［１０］のいずれかに記載のポリイミド組成物より得られる樹脂層を有するポリイミド積層体。

(In the formula, R ³ represents a tetracarboxylic acid residue, and R ⁴ represents a diamine residue.)
[8] The polyimide composition according to [7], wherein the non-covalent bond is a hydrogen bond.
[9] The content of the structure forming the non-covalent bond of the polyimide is 2% or more and 75% or less, assuming that 100% is the case where all the repeating units in the polyimide contain one structure. [7] or the polyimide composition according to [8].
[10] The polyimide composition according to any one of [7] to [9], wherein the end-capping rate of the polyimide is 30% or more.
[11] A polyimide film obtained from the polyimide composition according to any one of [7] to [10].
[12] A polyimide laminate having a resin layer obtained from the polyimide composition according to any one of [7] to [10].

  According to the present invention, a material having both a high elastic modulus and a high elongation can be provided.

  Embodiments of the present invention will be described in detail below, but the objects and methods exemplified below are examples (representative examples) of embodiments of the present invention, and the present invention is not deviated from the gist thereof. It is not limited to these contents.

[Polyimide precursor]
The polyimide precursor of the composition of the present invention has a repeating unit containing a structure represented by the following structural formula (1) and a repeating unit containing a structure forming a non-covalent bond, and the molecular terminal is sealed. It is what.
The repeating unit including the structure represented by the following structural formula (1) and the repeating unit including a structure forming a non-covalent bond may be the same, that is, the polyamic precursor is represented by the following structural formula (1). And a structure that forms a non-covalent bond with the structure represented by

Examples of the polyimide precursor include polyamic acid, polyamic acid ester, and a mixture thereof.
Moreover, the main part of the polyimide precursor includes a polyimide precursor structure and a part thereof has a polyimide structure.

（式中、Ｒ¹はテトラカルボン酸残基、Ｒ²はジアミン残基を表す。）
本発明のポリイミド前駆体は、ランダム重合体でもブロック共重合体でもよい。
また、本発明のポリイミド前駆体は、１種でもよく、複数種の混合物でもよい。各ポリイミド前駆体は、同じ反応条件で合成されたもの、同じイミド化率、溶媒に対する溶解性が同じもののみである必要はなく、異なる条件で製造され、物性が異なっていてもよい。なお、イミド化率は、組成物に含まれるポリイミド前駆体の平均値を表す。

(In the formula, R ¹ represents a tetracarboxylic acid residue, and R ² represents a diamine residue.)
The polyimide precursor of the present invention may be a random polymer or a block copolymer.
Further, the polyimide precursor of the present invention may be one kind or a mixture of plural kinds. Each polyimide precursor does not have to be synthesized under the same reaction conditions, the same imidization rate, and the same solubility in a solvent, but may be produced under different conditions and may have different physical properties. In addition, an imidation rate represents the average value of the polyimide precursor contained in a composition.

  The weight average molecular weight (Mw) of the polyimide precursor is not particularly limited. The weight average molecular weight in terms of polystyrene is usually 1000 or more, preferably 3000 or more, more preferably 5000 or more. Moreover, it is 200000 or less normally, Preferably it is 180000 or less, More preferably, it is 150,000 or less. By being in this range, the solubility in a solvent, the composition viscosity and the like tend to be easily handled with ordinary production equipment, which is preferable. The polystyrene-reduced weight average molecular weight can be determined by gel permeation chromatography (GPC).

  The number average molecular weight (Mn) of the polyimide precursor is not particularly limited. The number average molecular weight in terms of polystyrene is usually 500 or more, preferably 1000 or more, more preferably 2500 or more. Further, it is usually 100,000 or less, preferably 90000 or less, more preferably 80000 or less. By being in this range, the solubility in a solvent, the composition viscosity, and the like tend to be easily handled by ordinary production equipment, which is preferable. The number average molecular weight in terms of polystyrene can be determined by the same method as the weight average molecular weight.

The molecular weight distribution (PDI: weight average molecular weight / number average molecular weight (Mw / Mn)) of the polyimide precursor is usually 1 or more, preferably 1.1 or more, more preferably 1.2 or more. Moreover, it is 10 or less normally, Preferably it is 9 or less, More preferably, it is 8 or less. By being in this range, a film excellent in uniformity and smoothness of components in the film tends to be obtained.
In this invention, molecular weight represents the average value of the polyimide precursor contained in a composition.
The polyimide precursor of the present invention is preferably soluble in a solvent. In the present invention, “soluble in a solvent” means that when a polyimide precursor is dissolved at 0.5% by mass at room temperature (25 ° C.) in a solvent constituting the composition, it is completely dissolved. That means.

[Polyimide]
The polyimide of the composition of the present invention has a repeating unit containing a structure represented by the following structural formula (2) and a repeating unit containing a structure forming a non-covalent bond, and the molecular terminal is sealed. It is.

（式中、Ｒ³はテトラカルボン酸残基、Ｒ⁴はジアミン残基を表す。）
ポリイミドとしては、ポリイミドの主となる部分がポリイミド構造で、一部がポリイミド前駆体構造となっているものも含む。

(In the formula, R ³ represents a tetracarboxylic acid residue, and R ⁴ represents a diamine residue.)
Examples of the polyimide include those in which the main part of the polyimide has a polyimide structure and a part thereof has a polyimide precursor structure.

The polyimide of the present invention may be a random polymer or a block copolymer.
Further, the polyimide of the present invention may be one kind or a mixture of plural kinds. Each polyimide does not have to be synthesized under the same reaction conditions, the same imidization rate, and the same solubility in a solvent, but may be adjusted under different conditions and may have different physical properties. In addition, an imidation rate represents the average value of the polyimide contained in a composition.

  The weight average molecular weight (Mw) of the polyimide is not particularly limited. The weight average molecular weight in terms of polystyrene is usually 1000 or more, preferably 3000 or more, more preferably 5000 or more. Moreover, it is 200000 or less normally, Preferably it is 180000 or less, More preferably, it is 150,000 or less. By being in this range, the solubility in a solvent, the composition viscosity and the like tend to be easily handled with ordinary production equipment, which is preferable. The polystyrene-reduced weight average molecular weight can be determined by gel permeation chromatography (GPC).

  The number average molecular weight (Mn) of the polyimide is not particularly limited. The number average molecular weight in terms of polystyrene is usually 500 or more, preferably 1000 or more, more preferably 2500 or more. Further, it is usually 100,000 or less, preferably 90000 or less, more preferably 80000 or less. By being in this range, the solubility in a solvent, the composition viscosity, and the like tend to be easily handled by ordinary production equipment, which is preferable. The number average molecular weight in terms of polystyrene can be determined by the same method as the weight average molecular weight.

The molecular weight distribution (PDI: weight average molecular weight / number average molecular weight (Mw / Mn)) of polyimide is usually 1 or more, preferably 1.1 or more, more preferably 1.2 or more. Moreover, it is 10 or less normally, Preferably it is 9 or less, More preferably, it is 8 or less. By being in this range, a film excellent in uniformity and smoothness of components in the film tends to be obtained.
In this invention, molecular weight represents the average value of the polyimide contained in a composition.
The polyimide of the present invention is preferably soluble in a solvent. In the present invention, “soluble in a solvent” means that when a polyimide is dissolved at 0.5 mass% at room temperature (25 ° C.) in a solvent constituting the composition, it is completely dissolved. Say.

[Tetracarboxylic acid residue and diamine residue]
The tetracarboxylic acid residue and the diamine residue that the polyimide precursor and polyimide of the present invention have are structures derived from raw material compounds.
Examples of the compound that generates a tetracarboxylic acid residue include tetracarboxylic dianhydride, and examples of the compound that generates a diamine residue include a diamine compound.
<Tetracarboxylic dianhydride>
Examples of the tetracarboxylic dianhydride include an aromatic ring-containing tetracarboxylic dianhydride, an aliphatic tetracarboxylic dianhydride, and a silicone-based tetracarboxylic dianhydride.
As tetracarboxylic dianhydride having an aromatic ring, tetracarboxylic dianhydride having one aromatic ring in one molecule, tetracarboxylic dianhydride having two or more independent aromatic rings in one molecule And tetracarboxylic dianhydrides having a condensed aromatic ring in one molecule.
Among these, since the viscosity at the time of production is easy to control, tetracarboxylic dianhydride having one aromatic ring in one molecule or two or more independent aromatic rings in one molecule. The tetracarboxylic dianhydride having two or more independent aromatic rings in one molecule is particularly preferable.
Examples of the tetracarboxylic dianhydride having one aromatic ring in one molecule include pyromellitic dianhydride and 1,2,3,4-benzenetetracarboxylic dianhydride. .

  Examples of tetracarboxylic dianhydrides having two or more independent aromatic rings in one molecule include 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3- Dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2-bis (3 4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3 -Dicarboxyphenyl) ether dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2', 3,3'-benzophenone tetracarboxylic dianhydride, 4,4 ' − Xydiphthalic dianhydride, 4,4- (p-phenylenedioxy) diphthalic dianhydride, 4,4- (m-phenylenedioxy) diphthalic dianhydride, 2,2 ', 6,6'- Biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2, 3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2′-bis (trifluoromethyl) -4,4 ′, 5,5′-biphenyltetra Carboxylic dianhydride, 4,4 '-(hexafluorotrimethylene) -diphthalic dianhydride, 4,4'-(octafluorotetramethylene) -diphthalic dianhydride, 2,2'-bis (tri Fluoromethyl) -4,4 ', 5 '-Biphenyltetracarboxylic dianhydride, 4,4'-(hexafluorotrimethylene) -diphthalic dianhydride, 4,4 '-(octafluorotetramethylene) -diphthalic dianhydride, 2,2- Bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1 , 3,3,3-hexafluoropropane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride and 2, Examples include 2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride dianhydride.

  Examples of tetracarboxylic dianhydrides having a condensed aromatic ring in one molecule include 1,2,5,6-naphthalenedicarboxylic dianhydride, 1,4,5,8-naphthalenedicarboxylic dianhydride, 2, 3,6,7-naphthalenedicarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride and 1,2,7 , 8-phenanthrenetetracarboxylic dianhydride and the like.

  Examples of the aliphatic tetracarboxylic dianhydride include alicyclic tetracarboxylic dianhydrides and chain aliphatic tetracarboxylic dianhydrides.

  Examples of the alicyclic tetracarboxylic dianhydride include 3,3 ′, 4,4′-biscyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1 , 2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4 -Cyclobutanetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, tricyclo [6.4.0.0 (2 7)] dodecane-1,8: 2,7-tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 4- (2,5-dioxotetrahydrofuran-3 Yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride and 1,1′-bicyclohexane-3,3 ′, 4,4′-tetracarboxylic dianhydride It is done.

  Examples of chain aliphatic tetracarboxylic dianhydrides include ethylene tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, etc. Is mentioned.

  Examples of the silicon-based tetracarboxylic dianhydride include those represented by the following structural formula (3).

（式中、Ｘは酸無水物構造を含む有機基であり、Ｒ⁵及びＲ⁶はそれぞれ独立に２価の有機基であり、Ｒ⁷及びＲ⁸は、それぞれ独立に置換基を有していてもよい、アルキル基又はフェニル基であり、ｎ¹は３〜２００の整数である。
＜ジアミン化合物＞
ジアミン化合物としては、芳香族ジアミン化合物、脂肪族ジアミン化合物及びシリコーン系ジアミン化合物等が挙げられる。これらの化合物は、１種を単独で用いても、２種以上を任意の比率及び組合せで用いてもよい。
芳香族ジアミン化合物としては、１分子内に芳香環が１つであるジアミン化合物、１分子内に独立した２つ以上の芳香環を有するジアミン化合物、１分子内に縮合芳香環を有するジアミン化合物等が挙げられる。これらの中でも、製造時の粘度制御が容易になる点で、１分子内の芳香環が１つであるジアミン化合物又は独立した２つ以上の芳香環を有するジアミン化合物が好ましく、独立した２つ以上の芳香環を有するジアミン化合物が特に好ましい。
１分子内に芳香環が１つであるジアミン化合物としては、例えば、１，４−フェニレンジアミン、１，２−フェニレンジアミン及び１，３−フェニレンジアミン等が挙げられる。
１分子内に独立した２つ以上の芳香環を有するジアミン化合物としては、例えば、４，４’−（ビフェニル−２，５−ジイルビスオキシ）ビスアニリン、４，４’−ジアミノジフェニルエーテル、３，４’−ジアミノジフェニルエーテル、１，４−ビス（４−アミノフェノキシ）ベンゼン、１，３−ビス（４−アミノフェノキシ）ベンゼン、ビス（４−（４−アミノフェノキシ）フェニル）スルホン、２，２−ビス（４−（４−アミノフェノキシ）フェニル）プロパン、ビス（４−（３−アミノフェノキシ）フェニル）スルホン、１，３−ビス（４−アミノフェノキシ）ネオペンタン、４，４’−ジアミノ−３，３’−ジメチルビフェニル、４，４’−ジアミノ−２，２’−ジメチルビフェニル、４，４’−ビス（４−アミノフェノキシ）ビフェニル、４，４’−ジアミノジフェニルスルホン、３，３’−ジアミノジフェニルスルホン、４，４’−ジアミノジフェニルスルフィド、Ｎ−（４−アミノフェノキシ）−４−アミノベンズアミン、２，２’−ビス（トリフルオロメチル）−４，４’−ジアミノビフェニル、ビス（３−アミノフェニル）スルホン、ノルボルナンジアミン、４，４’−ジアミノ−２−（トリフルオロメチル）ジフェニルエーテル、５−トリフルオロメチル−１，３−ベンゼンジアミン、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、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−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、２−トリフルオロメチル−ｐ−フェニレンジアミン及び２，２−ビス（３−アミノ−４−メチルフェニル）ヘキサフルオロプロパン等が挙げられる。中でも溶解性の点から、４，４’−ジアミノジフェニルエーテル、３，４’−ジアミノジフェニルエーテル、（４−（４−アミノフェノキシ）フェニル）スルホン、４，４’−ジアミノジフェニルスルホン、３，３’−ジアミノジフェニルスルホン、２，２’−ビス（トリフルオロメチル）−４，４’−ジアミノビフェニル及び２，２−ビス（４−（４−アミノフェノキシ）フェニル）プロパン等が好ましい。

(In the formula, X is an organic group containing an acid anhydride structure, R ⁵ and R ⁶ are each independently a divalent organic group, and R ⁷ and R ⁸ are each independently having a substituent. It may be an alkyl group or a phenyl group, and n ¹ is an integer of 3 to 200.
<Diamine compound>
Examples of the diamine compound include aromatic diamine compounds, aliphatic diamine compounds, and silicone-based diamine compounds. These compounds may be used individually by 1 type, or may be used 2 or more types by arbitrary ratios and combinations.
As an aromatic diamine compound, a diamine compound having one aromatic ring in one molecule, a diamine compound having two or more independent aromatic rings in one molecule, a diamine compound having a condensed aromatic ring in one molecule, etc. Is mentioned. Among these, a diamine compound having one aromatic ring in one molecule or a diamine compound having two or more independent aromatic rings is preferable in terms of facilitating viscosity control during production. Particularly preferred are diamine compounds having the following aromatic rings.
Examples of the diamine compound having one aromatic ring in one molecule include 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, and the like.
Examples of the diamine compound having two or more independent aromatic rings in one molecule include 4,4 ′-(biphenyl-2,5-diylbisoxy) bisaniline, 4,4′-diaminodiphenyl ether, 3,4 '-Diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, bis (4- (4-aminophenoxy) phenyl) sulfone, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, bis (4- (3-aminophenoxy) phenyl) sulfone, 1,3-bis (4-aminophenoxy) neopentane, 4,4′-diamino-3,3 '-Dimethylbiphenyl, 4,4'-diamino-2,2'-dimethylbiphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, , 4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfide, N- (4-aminophenoxy) -4-aminobenzamine, 2,2′-bis (trifluoro) Methyl) -4,4′-diaminobiphenyl, bis (3-aminophenyl) sulfone, norbornanediamine, 4,4′-diamino-2- (trifluoromethyl) diphenyl ether, 5-trifluoromethyl-1,3-benzene Diamine, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 2,2-bis [4- {4-amino-2- (trifluoromethyl) phenoxy} phenyl] hexafluoropropane, 2-trifluorome Le -p- phenylenediamine and 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane, and the like. Among them, from the viewpoint of solubility, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, (4- (4-aminophenoxy) phenyl) sulfone, 4,4′-diaminodiphenylsulfone, 3,3′- Diaminodiphenyl sulfone, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2,2-bis (4- (4-aminophenoxy) phenyl) propane and the like are preferable.

  Examples of the diamine compound having a condensed aromatic ring in one molecule include 4,4 ′-(9-fluorenylidene) dianiline, 2,7-diaminofluorene, 1,5-diaminonaphthalene and 3,7-diamino-2,8-. Examples include dimethyldibenzothiophene 5,5-dioxide.

  Examples of the aliphatic diamine compound include alicyclic diamine compounds and chain aliphatic diamine compounds. Among these, from the viewpoint of solubility, alicyclic diamine compounds are preferable, and 1,4-diaminocyclohexane or 1,3-bis (aminomethyl) cyclohexane is particularly preferable.

  Examples of the alicyclic diamine compound include 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 4,4′-methylenebis (2-methylcyclohexylamine) and the like.

Examples of chain aliphatic diamine compounds include (1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-hexamethylenediamine, 1, 5-diaminopentane, 1,10-diaminodecane, 1,2-diamino-2-methylpropane, 2,3-diamino-2,3-butanediamine, 2-methyl-1,5-diaminopentane) and the like. It is done.
Examples of the silicone-based diamine compound include those represented by the following structural formula (4).

（式中、Ｒ⁹及びＲ¹⁰はそれぞれ独立に２価の有機基であり、Ｒ¹¹及びＲ¹²はそれぞれ独立に置換基を有していてもよい、アルキル基又はフェニル基であり、ｎ²は３〜２００の整数である。）

(Wherein R ⁹ and R ¹⁰ are each independently a divalent organic group, R ¹¹ and R ¹² are each independently an alkyl group or a phenyl group which may have a substituent, and n ² Is an integer from 3 to 200.)

Among these compounds, a tetracarboxylic anhydride and / or an amine compound capable of introducing a tetracarboxylic acid residue and / or a diamine residue having a flexible skeleton are preferable for maintaining the mechanical properties of the polyimide precursor and polyimide. In the present invention, the flexible skeleton is a skeleton having a structure in which a bond axis in a molecule is likely to rotate and bend.
Either one or both of the tetracarboxylic anhydride and the amine compound may have the flexible skeleton. Further, a tetracarboxylic anhydride having a flexible skeleton or one amine compound may be used alone, or two or more may be used in any ratio and combination. Examples of such tetracarboxylic acid anhydrides include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, and 4 , 4'-oxydiphthalic dianhydride and the like. Examples of the diamine compound include 4,4′-diaminodiphenyl ether, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis (4- (4-aminophenoxy) phenyl) propane and bis (4- ( 4-aminophenoxy) phenyl) sulfone and the like.
Among these, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride or 4,4′-diaminodiphenyl ether is preferable from the viewpoint of achieving both mechanical properties and heat resistance.

[Structures that form non-covalent bonds]
The polyimide precursor and polyimide of this invention have a repeating unit containing the structure which forms a noncovalent bond.
It is known that elastic modulus increases when molecular chains are connected by chemical bonds. Chemical bonds include covalent bonds and non-covalent bonds. When molecular chains are linked by covalent bonds, the elastic modulus increases, but mechanical flexibility (elongation) decreases. Usually, when a polyimide precursor or polyimide is baked at a certain temperature or more, the terminal of the molecule reacts with another molecule or a specific site in the molecule to form a covalent bond, so that flexibility is lowered. The polyimide precursor and polyimide of the present invention have a repeating unit including a structure in which a molecular end is blocked to suppress formation of a covalent bond, flexibility is maintained, and a molecule forms a non-covalent bond. Thus, a non-covalent bond (hereinafter sometimes simply referred to as “non-covalent bond”) is formed between molecules and / or a specific site in the molecule, and has an appropriate elastic modulus due to the intermolecular interaction, It was possible to achieve both elastic modulus and flexibility.
The non-covalent bond is not particularly limited, and examples include ionic bond, π-π stacking, and hydrogen bond. Among them, hydrogen bond is preferable. When it has a hydrogen bond, the heat resistance of a polyimide precursor and a polyimide becomes high, and since it is excellent in a mechanical characteristic, it is preferable.
The content of the structure that forms a non-covalent bond in the molecule is not particularly limited, but in the case of a polyimide precursor, each repeating unit in the polyimide precursor forms a structure that forms a non-covalent bond one by one. When the content is 100%, it is usually larger than 0%, preferably 2% or more, more preferably 5% or more, usually less than 100%, preferably 75% or less, more preferably 50% or less. Also, in the case of polyimide, when 100% is a case where all repeating units include one structure forming a non-covalent bond, it is usually larger than 0%, preferably 2% or more, more preferably 5% or more, Usually, it is less than 100%, preferably 75% or less, more preferably 50% or less. When the introduction amount is within this range, it is easy to obtain the composition of the present invention having good mechanical properties such as tensile elastic modulus and elongation.
The content of the structure forming a non-covalent bond in the molecule can be usually determined by NMR, IR, Raman, titration, mass spectrometry or the like.

As a method for introducing a structure that forms a non-covalent bond into a repeating unit, a method of polymerizing a monomer having a structure that forms a non-covalent bond or a non-covalent bond by a polymerization reaction when producing a polyimide precursor or polyimide. A method for forming the structure to be formed is mentioned.
For example, as a structure for forming a hydrogen bond, a structure in which a hydrogen atom is bonded to an electrically negative atom such as halogen such as fluorine, sulfur, oxygen, or nitrogen can be given. A hydrogen atom in such a structure and an electronegative atom in the molecule or another molecule form a hydrogen bond, thereby increasing the mechanical strength such as the elastic modulus of the polyimide precursor or polyimide.
Specifically, as a structure for forming a hydrogen bond, —NH— (imino bond; sometimes referred to as imino group), ═NH (imino group), —CONH— (amide bond; amide group) -NHCOO- (urethane bond; sometimes referred to as urethane group), -NHCONH- (urea bond; sometimes referred to as urea group), -NHCSNH- (thiourea bond; sometimes referred to as thiourea group) -NH ₂ (amino group), - OH (hydroxyl), - COOH (carboxy group), - SH (thiol group), - CHON (OH) - like can be mentioned (hydroxy amide group) and -OCSH (thiocarboxy group) It is done. Among these, an amide bond, a urea bond, and a hydroxyl group are preferable.
Examples of a method for introducing a structure forming a hydrogen bond into a molecule include a method of polymerizing a monomer having one or more types of the structure when a polyimide precursor or a polyimide is produced.
Examples of the monomer having one or more structures that form hydrogen bonds include tetracarboxylic dianhydrides and diamine compounds having one or more structures that form hydrogen bonds.
Specifically, examples of the tetracarboxylic dianhydride include 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, and examples of the diamine compound include 4,4′-diamino. Benzanilide, 4,4′-bis (4-aminobenzamide) -3,3′-dihydroxybiphenyl, 2,2′-bis (3-amino-4-hydroxyphenyl) sulfone, 2,2′-bis (3 -Amino-4-hydroxyphenyl) propane, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (4-amino-3-carboxyphenyl) methane and the like.
These monomers may be used individually by 1 type, or may be used 2 or more types by arbitrary ratios and combinations.

  The amount of these monomers to be introduced is not particularly limited. However, in the case of a polyimide precursor, it is usually 0.5 mol% or more, preferably 5 mol in all repeating units in the polyimide precursor (in the polyimide precursor molecule). % Or more, more preferably 10 mol% or more, usually 50 mol% or less, preferably 40 mol% or less, more preferably 30 mol% or less. Also in the case of polyimide, in all repeating units in the precursor, usually 0.5 mol% or more, preferably 5 mol% or more, more preferably 10 mol% or more, usually 50 mol% or less, preferably 40 mol% or less, more preferably 30 mol% or less. When the amount of the monomer introduced is within this range, the composition of the present invention having both high elasticity and high elongation can be easily obtained.

  Next, as a method for terminal sealing of the polyimide precursor or polyimide of the present invention, there is a method of reacting a monofunctional compound as a terminal sealing agent when manufacturing a polyimide precursor or polyimide. Such end capping agents are not particularly limited, and examples thereof include acid anhydrides, amines, epoxies, isocyanates, and alcohols. In order to maintain the reaction efficiency and heat resistance, an acid anhydride or an amine is preferred.

Examples of acid anhydrides include aromatic acid anhydrides and aliphatic acid anhydrides. Examples of the aromatic acid anhydride include phthalic anhydride, 2,3-naphthalenedicarboxylic anhydride, 1,2-naphthalenedicarboxylic anhydride, 4-methylphthalic anhydride, 3-methylphthalic anhydride, 4- Examples include chlorophthalic anhydride, 4-tert-butylphthalic anhydride, and 4-fluorophthalic anhydride.
The aliphatic acid anhydride has a linear structure and a cyclic structure, and the aliphatic acid anhydride having a linear structure includes butyl succinic anhydride, decyl succinic anhydride, n-octyl succinic anhydride, dodecyl succinic acid. Anhydrides, (2-methyl-2-propyl) -succinic anhydride, 2-octyl succinic anhydride and the like.
Examples of the aliphatic acid anhydride having a cyclic structure include cis-1,2-cyclohexylcarboxylic acid anhydride, tras-1,2-cyclohexyldicarboxylic acid anhydride, and 4-methylcyclohexane-1,2-dicarboxylic acid anhydride. Such as things.
In particular, phthalic anhydride, 2,3-naphthalenedicarboxylic acid anhydride, 1,2-naphthalenedicarboxylic acid anhydride, 4-methylphthalic acid anhydride or 3-methylphthalic acid anhydride are used to maintain mechanical properties and heat resistance. preferable.

Examples of amines include aromatic amines and aliphatic amines.
Examples of the aromatic acid amine include aniline, 1-naphthylamine, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene, N, N-dimethyl-1,4-phenylenediamine, 2-chloroaniline, 4- Chloroaniline, 4-aminopyridine, cytosine, p-toluidine, 4-butylaniline, 4- (2-aminoethyl) pyridine, 4-amino-4-ethylpyridine, 4-amino-3-ethylpyridine and isonicotinamide Etc.
The aliphatic amine has a linear structure and a cyclic structure, and examples of the aliphatic amine having a linear structure include ethylamine, tert-butylamine, isopropylamine, isobutylamine, neopentylamine, and propylamine.
Examples of the aliphatic amine having a cyclic structure include cyclohexylamine, 4-methylcyclohexylamine, 3-methylcyclohexylamine, aminomethylcyclohexane, 4- (2-aminoethyl) cyclohexylamine, and 4-butylcyclohexylamine.
In order to maintain mechanical properties and heat resistance, phthalic anhydride, aniline, 4-aminopyridine and 1-naphthylamine are preferred.

  Epoxy includes phenyl glycidyl ether, methylphenyl glycidyl ether, dimethylphenyl glycidyl ether, trimethylphenyl glycidyl ether, tetramethylphenyl glycidyl ether, ethylphenyl glycidyl ether, diethylphenyl glycidyl ether, triethylphenyl glycidyl ether, tetraethylphenyl glycidyl ether, isopropyl Phenyl glycidyl ether, diisopropyl phenyl glycidyl ether, triisopropyl phenyl glycidyl ether, tetraisopropyl phenyl glycidyl ether, orthophenyl phenyl glycidyl ether, m-phenyl phenyl glycidyl ether, p-phenyl phenyl glycidyl ether, p-tertiary butyl phenyl Luglycidyl ether, o-tert-butylphenyl glycidyl ether, m-tert-butylphenyl glycidyl ether, chlorophenyl glycidyl ether, dichlorophenyl glycidyl ether, trichlorophenyl glycidyl ether, tetrachlorophenyl glycidyl ether, bromophenyl glycidyl ether, dibromophenyl glycidyl ether, Examples include tribromophenyl glycidyl ether and tetrabromophenyl glycidyl ether.

Isocyanates include monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, benzyl isocyanate, (meth) acryloyl isocyanate, 2- (meth) acryloyloxyethyl isocyanate, 3- (meth) acryloyloxypropyl. Examples include (meth) acryloyloxyalkyl isocyanates such as isocyanate, 2- (meth) acryloyloxy-1-methylethyl isocyanate, and 2- (meth) acryloyloxy-2-methylethyl isocyanate.
Examples of the alcohol include methanol, ethanol, 3 carbon atoms, 1-propanol and 2-propanol, 4 carbon atoms, 1-butanol, 2-butanol, isobutanol, and t-butanol; -Pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-ethyl-1-propanol, etc .; 1-hexanol having 6 carbon atoms, 2 -Hexanol, 3-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 2-methyl-3-pentanol, 2-ethyl-1-butanol 3-ethyl-2-butanol, 2,3-dimethyl-1-butanol, cyclohexanol and the like; Tanol, 2-heptanol, 3-heptanol, 4-heptanol, 2-methyl-1-hexanol, 2-methyl-3-hexanol, 2-methyl-4-hexanol, 3-methyl-1-hexanol, 3-methyl- 2-hexanol, 3-methyl-4-hexanol, 2-ethyl-1-pentanol, 2-ethyl-3-pentanol, 2,2-dimethyl-1-pentanol, 2,3-dimethyl-1-pen Tanol, 2,4-dimethyl-1-pentanol, etc .; those having 8 carbon atoms, 1-octanol, 2-octanol, 3-octanol, 4-octanol, 2-methyl-1-heptanol, 2-methyl-3- Heptanol, 2-methyl-4-heptanol, 2-ethyl-1-hexanol, 2-ethyl-3-hexanol, 2-ethyl 4-hexanol, 2-propyl-1-pentanol, 2-propyl-3-pentanol, 2-propyl-4-pentanol, 2,3-dimethyl-1-hexanol and 2,4-dimethyl-1-hexanol And the like: 9 carbon atoms, 1-nonanol, 2-nonanol, 3-nonanol, 4-nonanol, 5-nonanol, 2-methyl-1-octanol, 2-methyl-3-octanol, 2-methyl-4- Octanol, 2-methyl-5-octanol, 2-methyl-6-octanol, 2-ethyl-1-heptanol, 2-ethyl-3-heptanol, 2-ethyl-4-heptanol, 2-ethyl-5-heptanol, 2,6-dimethyl-1-heptanol, 2,6-dimethyl-4-heptanol, 3,5,5-trimethyl-1-hexanol , 3,5,5-trimethyl-2-hexanol, 2,2,4-trimethyl-1-hexanol and the like; 10 carbon atoms, 1-decanol, 2-decanol, 3-decanol, 4-decanol, 5 -Decanol, 2-methyl-1-nonanol, 2-methyl-3-nonanol, 2-methyl-4-nonanol, 2-methyl-5-nonanol, 2-ethyl-1-octanol, 2-ethyl-3-octanol 2-ethyl-4-octanol, 2-ethyl-5-octanol and the like; 11 carbon atoms, 1-dodecanol, 2-dodecanol, 3-dodecanol, 4-dodecanol, 2-methyl-1-undecanol, 2-ethyl -1-decanol, 2-propyl-1-nonanol and the like; 12 carbon atoms, 1-dodecanol, 2-dodecanol, 3 Dodecanol, 1-ethyl-1-decanol, 2-ethyl-1-decanol, 3-ethyl-1-decanol, 2-butyl-1-octanol and the like; 13 carbon atoms, 1-tridecanol, 2-tridecanol, 3 -Tridecanol, 1-ethyl-1-undecanol, 2-ethyl-1-undecanol, 3-ethyl-1-undecanol, 2-butyl-1-nonanol, etc .; carbon 14, 1-tetradecanol, 2-tetradecane Diol, 3-tetradecanol, 2-methyl-1-tridecanol, 2-ethyl-1-dodecanol, 2-propyl-1-undecanol, etc .; carbon 15, 1-pentadecanol, 2-pentadecanol, 3-pentadecanol, 2-methyl-1-tetradecanol, 2-ethyl-1-tridecano 1-hexadecanol, 2-hexadecanol, 3-hexadecanol, 2-methyl-1-pentadecanol, 2-ethyl-1-tetra, which is carbon 16; Decanol, 2-propyl-1-tridecanol, etc .; carbon 17 such as 1-heptadecanol, 2-heptadecanol, 3-heptadecanol, 2-methyl-1-hexadecanol, 2-ethyl-1 -Pentadecanol, 2-propyl-1-tetradecanol, etc .; carbon 18, 1-octadecanol, 2-octadecanol, 3-octadecanol, 2-methyl-1-heptadecanol, 2 -Ethyl-1-hexadecanol, 2-propyl-1-pentadecanol, etc .; carbon 19, 1-nonadecanol, 2-nonadecanol, 3-no Nadecanol, 2-methyl-1-octadecanol, 2-ethyl-1-heptadecanol, 2-propyl-1-hexadecanol and the like; carbon 20, 1-eicosanol, 2-eicosanol, 3-eicosanol, Examples thereof include monohydric alcohols such as 2-methyl-1-nonadecanol, 2-ethyl-1-octadecanol and 2-propyl-1-heptadecanol.

In general, the lower limit of the terminal blocking rate is preferably 30% or more, more preferably 50% or more, still more preferably 80% or more, and particularly preferably 90% or more. The upper limit is 100% or less.
The end capping rate is preferably 80% or more and 100% or less.
The end-capping rate can be usually determined by NMR, IR, Raman, titration, mass spectrometry or the like.

[Production method of polyimide precursor]
The polyimide precursor of the present invention includes a tetracarboxylic dianhydride, a diamine compound, a monomer having a structure that forms a non-covalent bond, other monomers and a sealing agent as necessary (hereinafter referred to as “raw material” together) Obtained by reacting in a solvent. The method for reacting the raw materials is not particularly limited, and the addition order and the addition method of the respective raw materials are not particularly limited. For example, a tetracarboxylic dianhydride and a diamine compound, a monomer having a structure that forms a non-covalent bond, another monomer and a sealing agent as necessary are sequentially added to a solvent, and stirred at an appropriate temperature to obtain a polyimide. A precursor can be obtained.
Examples of other monomers used as needed include diisocyanate compounds. Examples of the diisocyanate compound include an aromatic skeleton having an aliphatic skeleton, such as hexamethylene diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, dicyclohexylmethane 4,4′-diisocyanate, and 1,3-bis (isocyanatomethyl) cyclohexane. 3,3′-dichloro-4,4′-diisocyanate biphenyl, 3,3′-dimethyl-4,4′-diisocyanate biphenyl, 1,5-diisocyanate naphthalene, methylenediphenyl 4,4-diisocyanate, 1,3 -Phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, m-xylylene diisocyanate, etc.

  The amount of the diamine compound is usually 0.7 mol or more, preferably 0.8 mol or more, and usually 1.3 mol or less, preferably 1.2 mol or less, relative to 1 mol of tetracarboxylic dianhydride. is there. By making a diamine compound into this range, it exists in the tendency for the yield of the polyimide precursor obtained to improve.

The concentration of the tetracarboxylic dianhydride and the diamine compound in the solvent can be appropriately set according to the reaction conditions and the viscosity of the obtained polyimide precursor.
The total mass of the tetracarboxylic dianhydride and the diamine compound is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, based on the total amount of the solution containing the tetracarboxylic dianhydride, the diamine compound and the solvent. It is usually 70% by mass or less, preferably 50% by mass or less. Since the concentrations of the tetracarboxylic dianhydride and the diamine compound are not too low, the molecular weight tends to increase. In addition, by not being too high, the viscosity does not become too high and the solution tends to be easily stirred.
In addition, when the monomer having a structure forming a non-covalent bond is a tetracarboxylic dianhydride and / or a diamine compound, the amount and concentration of the tetracarboxylic dianhydride and diamine compound include these amounts. Value.

The temperature at which the raw materials are reacted is not particularly limited as long as the reaction proceeds, but is usually 0 ° C. or higher, preferably 20 ° C. or higher, and usually 120 ° C. or lower, preferably 100 ° C. or lower.
The reaction time is usually 1 hour or longer, preferably 2 hours or longer, usually 100 hours or shorter, preferably 42 hours or shorter. By carrying out under such conditions, the polyimide precursor tends to be obtained at a low cost and in a high yield.
The pressure during the reaction may be normal pressure, pressurization, or reduced pressure. The atmosphere may be air or an inert atmosphere.

  The solvent used in the reaction is not particularly limited. For example, hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene, xylene, mesitylene and anisole; halogenation such as carbon tetrachloride, methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, dichlorobenzene and fluorobenzene Hydrocarbon solvents; ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane and methoxybenzene; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol solvents such as glycol dimethyl ether, diethylene glycol dimethyl ether and propylene glycol monomethyl ether acetate Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; sulfone solvents such as dimethyl sulfoxide; heterocyclic systems such as pyridine, picoline, lutidine, quinoline and isoquinoline; Solvents; phenolic solvents such as phenol and cresol; lactone solvents such as γ-butyrolactone, γ-valerolactone and δ-valerolactone. These solvents may be used alone or in combination of two or more in any ratio and combination.

  The obtained polyimide precursor may be used as it is, or may be added to a poor solvent to precipitate as a solid, and then re-dissolved in another solvent to obtain a composition containing the polyimide precursor. .

  The poor solvent to be used is not particularly limited and may be appropriately selected depending on the type of the polyimide precursor, but ether solvents such as diethyl ether and diisopropyl ether; ketone solvents such as acetone, methyl ethyl ketone, isobutyl ketone and methyl isobutyl ketone; methanol, Examples include alcohol solvents such as ethanol and isopropyl alcohol. Among these, alcohol solvents are preferable because precipitates can be obtained efficiently, the boiling point is low, and drying tends to be easy. These solvents may be used alone or in combination of two or more in any ratio and combination.

[Production method of polyimide]
There is no restriction | limiting in particular in the manufacturing method of the polyimide of this invention. For example, a method for producing polyimide from the aforementioned polyimide precursor, a tetracarboxylic dianhydride, a diamine compound, a monomer having a structure forming a non-covalent bond, and if necessary, producing a polyimide directly from other monomers and a sealing agent Or the like can be used.
Examples of other monomers used as necessary include the compounds mentioned in the above-described method for producing a polyimide precursor.

<Method of manufacturing from polyimide precursor>
A polyimide can be obtained by dehydrating and cyclizing (imidizing) the polyimide precursor obtained by the above-described method or the like in the presence of a solvent. Although imidation can be performed using any conventionally known method, for example, thermal imidization for thermal cyclization, chemical imidization for chemical cyclization, and the like can be given. These imidation reactions may be performed alone or in combination.
Although there is no restriction | limiting in particular in the density | concentration of the polyimide precursor at the time of imidation reaction, Usually, 1 mass% or more, Preferably it is 5 mass% or more, and is 70 mass% or less normally, Preferably it is 40 mass% or less. By setting it within this range, the imidation rate can be controlled, production efficiency tends to be high, and the solution viscosity tends to be easy to manufacture.

(Heat imidization)
Examples of the solvent for imidizing the polyimide precursor include the same solvents as those used in the reaction for obtaining the polyimide precursor described above (hereinafter sometimes referred to as “polyimide precursor production”). The solvent at the time of manufacturing the polyimide precursor and the solvent at the time of manufacturing the polyimide may be the same or different.
In this case, water generated by imidization may be discharged out of the system in order to inhibit the ring closure reaction. The concentration of the polyimide precursor during the imidation reaction is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, and usually 70% by mass or less, preferably 40% by mass or less. By carrying out in this range, the production efficiency tends to be high and the solution viscosity tends to be easy to produce.

The reaction temperature for heat imidation is not particularly limited, but is usually 50 ° C. or higher, preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and usually 300 ° C. or lower, preferably 280 ° C. or lower, more preferably 250 ° C. or lower. is there. Performing in this range is preferable because the imidization reaction proceeds efficiently and reactions other than the imidization reaction tend to be suppressed.
The pressure during the reaction may be normal pressure, increased pressure, or reduced pressure. The atmosphere may be air or an inert atmosphere.

  Further, as an imidization accelerator for promoting imidization, a compound having a function of enhancing nucleophilicity and electrophilicity can be added. Specifically, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, triethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, triethylenediamine, N-methylpyrrolidine, N-ethylpyrrolidine , Tertiary amine compounds such as N-methylpiperidine, N-ethylpiperidine, imidazole, pyridine, quinoline and isoquinoline; carboxylic acids such as 4-hydroxyphenylacetic acid, 3-hydroxybenzoic acid, N-acetylglycine and N-benzoylglycine Compound; Polyhydric phenol compound such as methyl 3,5-dihydroxyacetophenone, methyl 3,5-dihydroxybenzoate, pyrogallol, methyl gallate, ethyl gallate and naphthalene-1,6-diol; 2-hydride Xipyridine, 3-hydroxypyridine, 4-hydroxypyridine, 4-pyridinemethanol, N, N-dimethylaminopyridine, nicotine aldehyde, isonicotialdehyde, picolinaldehyde, picolinaldehyde oxime, nicotinaldehyde oxime, isonicotialdehyde oxime, picolinic acid Ethyl, ethyl nicotinate, ethyl isonicotinate, nicotinamide, isonicotinamide, 2-hydroxynicotinic acid, 2,2′-dipyridyl, 4,4′-dipyridyl, 3-methylpyridazine, quinoline, isoquinoline, phenanthroline, 1 , 10-phenanthroline, imidazole, benzimidazole, and heterocyclic compounds such as 1,2,4-triazole.

  Among these, at least one selected from the group consisting of a tertiary amine compound, a carboxylic acid compound and a heterocyclic compound is preferable, and at least one selected from the group consisting of triethylamine, imidazole and pyridine controls the imidization rate. It is more preferable because it tends to be easy to do. These compounds may be used individually by 1 type, or may be used 2 or more types by arbitrary ratios and combinations.

The amount of the imidization accelerator used is usually 0.01 mol% or more, preferably 0.1 mol% or more, more preferably 1 mol% or more based on the carboxyl group or ester group. Moreover, it is preferable that it is 50 mol% or less, and it is more preferable that it is 10 mol% or less. When the amount of the imidization accelerator used is in the above range, the imidization reaction proceeds efficiently and a polyimide with a controlled imidation rate tends to be obtained.
Moreover, the timing which adds an imidation promoter can be adjusted suitably in order to make it a desired imidation rate, may be before a heating start, and may be during a heating. Moreover, you may add in multiple times.

(Chemical imidization)
Chemical imidation is a method in which a polyimide precursor is chemically imidized using a dehydrating condensing agent in the presence of a solvent.
Examples of the solvent used in the chemical imidization include the same solvents as those used in the reaction for obtaining the above polyimide precursor.

  Examples of the dehydrating condensing agent include N, N-2-substituted carbodiimides such as N, N-dicyclohexylcarbodiimide and N, N-diphenylcarbodiimide; acid anhydrides such as acetic anhydride and trifluoroacetic anhydride; thionyl chloride and tosyl chloride Chlorides of: acetyl chloride, acetyl bromide, propionyl iodide, acetyl fluoride, propionyl chloride, propionyl bromide, propionyl iodide, propionyl fluoride, isobutyryl chloride, isobutyryl bromide, isobutyryl iodide, isobuty Ryl fluoride, n-butyryl chloride, n-butyryl bromide, n-butyryl iodide, n-butyryl fluoride, mono-, di-, tri-chloroacetyl chloride, mono-, di- Tri-bromoacetyl chloride, mono-, di-, tri-iodo acetyl chloride, mono-, di-, tri-fluoroacetyl chloride, chloroacetic anhydride, phenylphosphonic dichloride, thionyl chloride, thionyl bromide, thionyl iodide and Halogenated compounds such as thionyl fluoride; phosphorus compounds such as phosphorus trichloride, triphenyl phosphite, and diethyl phosphate cyanide.

  Among these, acid anhydrides and halogenated compounds are preferable, and in particular, acid anhydrides tend to allow the imidization reaction to proceed efficiently and to obtain a polyimide with a controlled imidization rate. preferable. These compounds may be used individually by 1 type, or may be used 2 or more types by arbitrary ratios and combinations.

  The amount of these dehydrating condensing agents used is usually 0.1 mol or more, preferably 0.2 mol or more, and usually 1.0 mol or less, preferably 0.9 mol or less, relative to 1 mol of the polyimide precursor. By setting the dehydration condensing agent within this range, the imidization rate can be controlled.

The chemical imidation reaction temperature is not particularly limited, but is usually 0 ° C or higher, preferably 10 ° C or higher, more preferably 20 ° C or higher. Moreover, it is 150 degrees C or less normally, Preferably it is 130 degrees C or less, More preferably, it is 100 degrees C or less. It is preferable to carry out in this range since the imidization reaction proceeds efficiently and a polyimide having a controlled imidization rate tends to be obtained. Furthermore, it is preferable because side reactions other than the imidization reaction are suppressed.
The pressure during the reaction may be normal pressure, increased pressure, or reduced pressure. The atmosphere may be air or an inert atmosphere.

  Further, as the catalyst for promoting imidization, the above-mentioned tertiary amines and the like can be added in the same manner as in the heating imidization.

<Method of manufacturing polyimide directly from tetracarboxylic dianhydride, diamine compound, monomer having a structure forming a non-covalent bond, and other monomer and sealing agent as required>
The polyimide of the present invention can be obtained directly from a tetracarboxylic dianhydride, a diamine compound, a monomer having a structure forming a non-covalent bond, and if necessary, other monomers and a sealing agent using a conventionally known method. Can do. In this method, synthesis from a polyimide precursor to imidization is performed without stopping the reaction or isolating the precursor.

  There are no particular limitations on the order and method of addition of the raw materials, for example, tetracarboxylic dianhydride, diamine compound, monomer having a structure that forms a non-covalent bond in the solvent, and other monomers and sealing agents as necessary. Are put in order, and a polyimide is obtained by stirring at a temperature at which the reaction until imidization proceeds.

  The amount of the diamine compound is usually 0.7 mol or more, preferably 0.8 mol or more, and usually 1.3 mol or less, preferably 1.2 mol or less, relative to 1 mol of tetracarboxylic dianhydride. By setting the amount of the diamine compound in such a range, it is possible to obtain a polyimide with a controlled imidization rate, and the yield of the resulting polyimide tends to be improved.

The concentration of the tetracarboxylic dianhydride and the diamine compound in the solvent can be appropriately set for each condition and the viscosity during polymerization. The total mass of the tetracarboxylic dianhydride and the diamine compound is not particularly set, but is usually 1% by mass or more, preferably 5% by mass or more, and usually 70% by mass or less, preferably with respect to the total liquid amount. It is 40 mass% or less. When the concentration in the solvent is in an appropriate range, the molecular weight tends to elongate, and stirring tends to be easy.
In addition, when the monomer having a structure forming a non-covalent bond is a tetracarboxylic dianhydride and / or a diamine compound, the amount and concentration of the tetracarboxylic dianhydride and diamine compound include these amounts. Value.

Examples of the solvent used in this reaction include the same solvents as those used in the reaction for obtaining the polyimide precursor.
Moreover, also when obtaining a polyimide from a raw material, heating imidation and / or chemical imidation can be used similarly to the case where a polyimide is obtained from a polyimide precursor. The reaction conditions for heating imidization and chemical imidization in this case are the same as described above.

  The obtained polyimide may be used as it is, or may be added to a poor solvent so that the polyimide is precipitated in a solid state and then re-dissolved in another solvent.

  There is no restriction | limiting in particular in the poor solvent to be used, Although it can select suitably according to the kind of polyimide, the solvent used when depositing the above-mentioned polyimide precursor can be used. Among them, alcohol solvents such as isopropyl alcohol are preferable because precipitates can be obtained efficiently and the boiling point is low and the drying tends to be easy. These solvents may be used alone or in combination of two or more in any ratio and combination.

[Composition Containing Polyimide Precursor and Composition Containing Polyimide]
The composition containing the polyimide precursor of the present invention (hereinafter sometimes simply referred to as “polyimide precursor composition”) is usually obtained by dissolving the polyimide precursor in a solvent. In addition, a composition containing polyimide (hereinafter, sometimes simply referred to as “polyimide composition”) is usually obtained by dissolving polyimide in a solvent.
The solvent used in these compositions of the present invention is not particularly limited. For example, hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene, xylene, mesitylene and anisole; carbon tetrachloride, methylene chloride, Halogenated hydrocarbon solvents such as chloroform, 1,2-dichloroethane, chlorobenzene, dichlorobenzene and fluorobenzene; ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane and methoxybenzene; acetone, methyl ethyl ketone, cyclohexanone and methyl Ketone solvents such as isobutyl ketone; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and Glycol solvents such as propylene glycol monomethyl ether acetate; amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; aprotic polar solvents such as dimethyl sulfoxide; pyridine, Heterocyclic solvents such as picoline, lutidine, quinoline and isoquinoline; phenolic solvents such as phenol and cresol; lactone solvents such as γ-butyrolactone, γ-valerolactone and δ-valerolactone; isopropyl alcohol, butanol, hexanol, 2 -Alcohol solvents such as ethyl-1-hexanol, heptanol and benzyl alcohol. These solvents may be used alone or in combination of two or more in any ratio and combination.

<Other components of the composition>
In the polyimide precursor composition and the polyimide composition of the present invention, as other components, for example, other resins, surfactants, antioxidants, lubricants, colorants, stabilizers, ultraviolet absorbers, charging You may contain an inhibitor, a flame retardant, a plasticizer, a mold release agent, a leveling agent, an antifoamer, etc. Moreover, you may mix | blend an inorganic type filler or an organic type filler in the range which does not impair the objective of this invention as needed.

  Examples of inorganic fillers include inorganic oxides such as silica, diatomaceous earth, barium ferrite, beryllium oxide, pumice and pumice balloons; hydroxides such as aluminum hydroxide and magnesium hydroxide; calcium carbonate, magnesium carbonate, base Metal carbonates such as basic magnesium carbonate, dolomite and dosonite; metal sulfates and sulfites such as calcium sulfate, barium sulfate, ammonium sulfate and calcium sulfite; talc, clay, mica, asbestos, glass fiber, glass balloon, glass beads, silica Silicates such as calcium oxide, montmorillonite and bentonite; carbons such as carbon fiber, carbon black, graphite and carbon hollow sphere; molybdenum sulfide, zinc borate, barium metaborate, calcium borate, sodium borate and boron Powdered, granular, plate-like or fibrous inorganic fillers such as fibers; powdery, granular, fibrous or whisker-like metal fillers such as metals, metal compounds and alloys; silicon carbide, silicon nitride, zirconia, nitriding Examples thereof include powder fillers such as aluminum, titanium carbide, and potassium titanate, granular fillers, fiber fillers, and whisker ceramic fillers.

Examples of organic fillers include shell fibers such as fir shells, carbon nanotubes, fullerenes, wood flour, cotton, jute, paper strips, cellophane pieces, aromatic polyamide fibers, cellulose fibers, nylon fibers, polyester fibers, polypropylene fibers And thermosetting resin powder and rubber.
As a filler, what processed into flat form, such as a nonwoven fabric, may be used, and several materials may be mixed and used. These various fillers and additive components may be added at any stage of any process for producing each composition.

  Among other components, it is preferable to include a leveling agent because the smoothness of the polyimide film tends to be improved. Examples of the leveling agent include silicone compounds. The silicone compound is not particularly limited. For example, polyether-modified siloxane, polyether-modified polydimethylsiloxane, polyether-modified hydroxyl group-containing polydimethylsiloxane, polyether-modified polymethylalkylsiloxane, polyester-modified polydimethylsiloxane, polyester-modified hydroxyl group Examples thereof include polydimethylsiloxane, polyester-modified polymethylalkylsiloxane, aralkyl-modified polymethylalkylsiloxane, highly polymerized silicone, amino-modified silicone, amino-derivative silicone, phenyl-modified silicone, and polyether-modified silicone.

  The concentration of the polyimide precursor contained in the polyimide precursor composition of the present invention and the concentration of the polyimide contained in the polyimide composition are not particularly limited, but are usually 3% by mass or more, preferably 5% by mass or more, more preferably 7%. It is at least mass%. Moreover, it is 60 mass% or less normally, Preferably it is 50 mass% or less, More preferably, it is 45 mass% or less. When the concentration is within this range, the composition can be easily produced, and the thickness and surface of the film tend to be uniform.

  The concentration of the polyimide precursor and the polyimide in the composition can be appropriately confirmed using a conventionally known method. For example, the solvent of the composition and other components can be distilled off using a method such as drying under reduced pressure, and the mass ratio before and after the distillation can be obtained.

Although there is no restriction | limiting in particular in the viscosity of the composition of this invention, it is a viscosity of the density | concentration 20% in 25 degreeC, and is 100 cP or more normally, Preferably it is 200 cP or more, More preferably, it is 500 cP or more. Moreover, it is 200000 cP or less normally, Preferably it is 100000 cP or less, More preferably, it is 80000 cP or less. When the viscosity of the composition is within this range, handling during production becomes easy, and handling during coating becomes easy.
The viscosity of the composition can be measured by a conventionally known method. For example, it can be measured using a vibration viscometer, an E-type viscometer or the like.
[Polyimide film and laminate obtained from polyimide precursor composition and polyimide resin composition]
A method for forming a film using the composition of the present invention is sometimes not limited, but examples thereof include a method of applying to a substrate.
Examples of the coating method include die coating, spin coating, dip coating, screen printing, spraying, casting method, coating method, spraying coating method, dipping method, calendar method, and fluency method. These methods can be appropriately selected according to the application area and the shape of the surface to be applied.

  The method for volatilizing the solvent contained in the film formed by coating or the like is not particularly limited. Usually, the solvent is volatilized by heating the carrier substrate coated with the composition. The heating method is not particularly limited, and examples thereof include hot air heating, vacuum heating, infrared heating, microwave heating, and heating by contact using a hot plate / hot roll.

  As the heating temperature in the above case, a suitable temperature can be used according to the kind of the solvent. The heating temperature is usually 40 ° C or higher, preferably 100 ° C or higher, more preferably 200 ° C or higher, particularly preferably 300 ° C or higher, usually 1000 ° C or lower, preferably 700 ° C or lower, more preferably 600 ° C or lower, particularly preferably. It is 500 degrees C or less. When heating temperature is 40 degreeC or more, it is preferable at the point from which a solvent is fully volatilized. Moreover, when heating temperature is 300 degreeC or more, since progress of an imidation reaction is quick, baking for a short time is attained. The heating atmosphere may be either air or an inert atmosphere, and is not particularly limited. However, when the polyimide is required to be colorless and transparent, it is preferable to heat in an inert atmosphere such as nitrogen to suppress coloring. .

<Polyimide film>
The thickness of the polyimide film of the present invention is usually 1 μm or more, preferably 2 μm or more, while usually 300 μm or less, preferably 200 μm or less. When the thickness is 1 μm or more, the polyimide film has sufficient strength and is obtained as an autonomous film, and the handling property tends to be improved. Moreover, it exists in the tendency which is easy to ensure the uniformity of a film by making thickness into 300 micrometers or less.

  The glass transition temperature (Tg) of the polyimide film of the present invention is not particularly limited, but is preferably 150 ° C or higher, more preferably 180 ° C or higher, and further preferably 200 ° C or higher. Due to the high glass transition temperature, it tends to be applicable to processing steps for various uses.

The required performance of the polyimide film depends on the application, but preferably has the following mechanical strength.
The tensile strength of the polyimide film of the present invention is not particularly limited, but is usually 50 MPa or more, preferably 70 MPa or more, and is usually 400 MPa or less, preferably 300 MPa or less. The tensile elastic modulus is not particularly limited, but is usually 1000 MPa or more, preferably 2000 MPa or more, more preferably 2500 MPa or more, still more preferably 3000 MPa or more, and usually 20 GPa or less, preferably 10 GPa or less, more preferably 5 GPa. It is as follows.
The tensile elongation at break is not particularly limited, but is usually 10% GL or more, preferably 20% GL or more, more preferably 30% GL or more, further preferably 50% GL or more, and usually 300% GL or less. , Preferably 200% GL or less.
When the polyimide film has such mechanical strength, it tends to be a film that can withstand various types of processing.
In particular, when the tensile elastic modulus of the polyimide film is 3000 MPa or more and 5000 MPa or less and the tensile fracture elongation is 50% GL or more and 200% GL or less, the high elastic modulus and the high elongation are compatible, and the surface protective layer is used for a device. It is suitably used for various applications such as a substrate, an insulating film or a wiring film.

The polyimide film of the present invention can be obtained, for example, by applying the polyimide composition of the present invention to a support, and then heating and peeling the film from the support, as described above.
The method for peeling the polyimide film from the support is not particularly limited, but a physical peeling method or a laser peeling method is preferable in that the film can be peeled without impairing the performance of the film.

The method of physically peeling is, for example, a method of obtaining a polyimide film by separating the periphery of a laminate comprising a polyimide film / support, a method of obtaining a polyimide film by sucking the periphery, and a support substrate with a fixed periphery And a method of obtaining a polyimide film by moving.
<Polyimide laminate>
The laminate of the present invention can be obtained, for example, by heating after applying the polyimide composition of the present invention to a substrate as described above.
The substrate is preferably hard and heat resistant. That is, it is preferable to use a material that does not deform under the temperature conditions required in the manufacturing process. Specifically, it is preferable that the base material is made of a material having a glass transition temperature of usually 200 ° C. or higher, preferably 250 ° C. or higher. For example, glass, ceramic, metal, a silicon wafer, etc. are mentioned.

When glass is used as the substrate, the glass used is not particularly limited. For example, blue plate glass (alkali glass), high silicate glass, soda lime glass, lead glass, aluminoborosilicate glass, non-alkali Examples thereof include glass (borosilicate glass, Corning Eagle XG, etc.) and aluminosilicate glass.
When a metal is used as the substrate, the metal used is not particularly limited, and examples thereof include gold, silver, copper, aluminum, and iron. These various alloys may be used.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, the following examples are shown in order to describe the present invention in detail, and the present invention is not limited to the following examples unless it is contrary to the gist thereof.

[Example 1]
A four-necked flask equipped with a thermocouple, a condenser and a stirrer was charged with 5.41 g (0.027 mol) of 4,4′-diaminodiphenyl ether (ODA) and 0.68 g of 4,4′-diaminobenzanilide (DABA) ( 0.003 mol), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) 8.83 g (0.03 mol), phthalic anhydride 0.089 g (0.0006 mol) and N, N ′ -60 g of dimethylacetamide (DMAc) was added, and the mixture was stirred and reacted at 80 ° C for 6 hours under nitrogen to obtain Composition 1 containing a polyimide precursor.

(Making polyimide film)
The obtained composition 1 is applied onto a glass substrate by a spin coating method, heated to 500 ° C. over 6 minutes in air using a hot plate, and then cooled to 300 ° C. or lower over 3 minutes. (High temperature baking) and a polyimide film 1 having a film thickness of 20 μm was obtained.

(Heat resistance evaluation)
The polyimide film 1 was punched out with a super straight cutter to a width of 6 mm and a length of 50 mm, and tan δ was measured using a DMS6100 manufactured by SII Nano Technology, using the obtained strip-shaped test piece. The peak value of tan δ was defined as Tg, and the results are shown in Table 2.
It was evaluated that the higher the Tg, the better the heat resistance.

(Mechanical property evaluation)
A test piece was prepared by cutting a polyimide film 1 conditioned in a constant temperature and humidity chamber at room temperature of 25 ° C. and a humidity of 50% overnight into a strip shape having a width of 10 mm. Using this test piece, using a tensile tester (STA-1225 manufactured by Orientec Co., Ltd.), a tensile test is performed under the conditions of a distance between chucks of 30 mm and a tensile speed of 10 mm / min, and a stress-strain curve is created. Elastic modulus (MPa) and tensile elongation at break (% GL) were determined.

[Example 2]
Experimental Example 1 except that the amount of 4,4′-diaminodiphenyl ether was changed to 4.51 g (0.023 mol) and the amount of 4,4′-diaminobenzanilide was changed to 0.68 g (0.008 mol). The composition 2 containing the polyimide precursor and the polyimide film 2 were obtained by the method. In the same manner as in Example 1, the Tg, tensile modulus, and tensile breaking elongation of the polyimide film 2 were determined.

[Comparative Example 1]
3,4′-Diaminodiphenyl ether 36.0 g (0.18 mol), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride 51.4 g (0.0.17 mol) and N, N′-dimethyl A composition 3 and a polyimide film 3 containing a polyimide precursor were obtained in the same manner as in Experimental Example 1 using 350 g of acetamide. In the same manner as in Example 1, the Tg, tensile modulus, and tensile breaking elongation of the polyimide film 3 were determined.

  As shown in Table 2, it can be seen that the polyimide precursor composition of the present invention and the polyimide film obtained from the composition are compatible with both high elastic modulus and high elongation even after high-temperature firing.

  The polyimide precursor composition and the polyimide composition of the present invention can be used for coating materials, surface protective layers, adhesives, device substrates, insulating films, wiring films, and the like. Moreover, the film and laminated body obtained from these compositions can be used for a surface protective layer, a device substrate, an insulating film, a wiring film, or the like.

Claims (12)

A composition containing a polyimide precursor, wherein the polyimide precursor has a repeating unit containing a structure represented by the following structural formula (1) and a repeating unit containing a structure forming a non-covalent bond, and a molecule The polyimide precursor composition characterized by the terminal being sealed.

(In the formula, R ¹ represents a tetracarboxylic acid residue, and R ² represents a diamine residue.)   The polyimide precursor composition according to claim 1, wherein the non-covalent bond is a hydrogen bond.   When the content of the structure forming the non-covalent bond of the polyimide precursor is 100% when all the repeating units in the polyimide precursor include the structure one by one, it is 2% or more and 75% or less. The polyimide precursor composition according to claim 1 or 2.   The polyimide precursor composition according to any one of claims 1 to 3, wherein a terminal blocking rate of the polyimide precursor is 30% or more.   The polyimide film obtained from the polyimide precursor composition of any one of Claims 1-4.   The polyimide laminated body which has a resin layer obtained from the polyimide precursor composition of any one of Claims 1-4. A composition containing polyimide, wherein the polyimide has a repeating unit containing a structure represented by the following structural formula (2) and a repeating unit containing a structure forming a non-covalent bond, and a molecular terminal is sealed. The polyimide composition characterized by the above-mentioned.

(In the formula, R ³ represents a tetracarboxylic acid residue, and R ⁴ represents a diamine residue.)   The polyimide composition according to claim 7, wherein the non-covalent bond is a hydrogen bond.   The content of the structure forming a non-covalent bond of the polyimide is 2% or more and 75% or less, assuming that 100% is a case where all the repeating units in the polyimide include one structure. Or the polyimide composition of 8.   The polyimide composition according to any one of claims 7 to 9, wherein a terminal sealing ratio of the polyimide is 30% or more.   The polyimide film obtained from the polyimide composition of any one of Claims 7-10.   The polyimide laminated body which has a resin layer obtained from the polyimide composition of any one of Claims 7-10.