JP6648076B2 - Resin precursor, resin composition containing the same, resin film and method for producing the same, and laminate and method for producing the same - Google Patents

Description

  The present invention relates to, for example, a resin precursor used for a substrate for a flexible device, a resin composition containing the same, a resin film and a method for producing the same, and a laminate and a method for producing the same.

  Generally, for applications requiring high heat resistance, a polyimide (PI) resin film is used as the resin film. A general polyimide resin is obtained by solution polymerization of an aromatic dianhydride and an aromatic diamine to produce a polyimide precursor, followed by ring closure dehydration at a high temperature, thermal imidization, or chemical imidization using a catalyst. It is a high heat resistant resin to be manufactured.

  Polyimide resin is an insoluble and infusible super heat-resistant resin, and has excellent properties such as heat-resistant oxidation resistance, heat resistance, radiation resistance, low-temperature resistance, and chemical resistance. For this reason, polyimide resins are used in a wide range of fields including electronic materials such as insulating coatings, insulating films, semiconductors, and electrode protection films for TFT-LCDs, and recently, in the field of display materials such as liquid crystal alignment films. Instead of a glass substrate that has been conventionally used, adoption of a colorless and transparent flexible substrate utilizing its lightness and flexibility is also being studied.

  However, a general polyimide resin is colored brown or yellow due to a high aromatic ring density, has a low transmittance in a visible light region, and is difficult to use in a field where transparency is required.

  In order to solve the problem of improving the transparency of such a polyimide, for example, Non-Patent Document 1 discloses the use of an acid dianhydride having a specific structure and a diamine having a specific structure to improve transmittance and transparency of hue. Are described. Further, Patent Documents 1 to 4 disclose 4,4-bis (diaminodiphenyl) sulfone (hereinafter, also referred to as 4,4-DAS) and 3,3-bis (diaminodiphenyl) sulfone (hereinafter, 3,3-DAS). Also described is a polyimide having improved transmittance and hue transparency by using an acid dianhydride having a specific structure.

Further, in Examples 9 and 10 of Patent Document 6 described below, a specific aromatic tetracarboxylic dianhydride, an alicyclic diamine, and a silicon-containing diamine are copolymerized to obtain high Tg, transparency, and high adhesion. A polyimide precursor capable of producing a polyimide exhibiting properties and low warpage is described.
Further, in Example 3 of Patent Document 7 and Example 3 of Patent Document 8 described below, a polyimide precursor obtained by copolymerizing aromatic tetracarboxylic dianhydride, bis (diaminodiphenyl) sulfone and silicon-containing diamine was used. It is described that it is used as a resin for semiconductor protection and a photosensitive resin composition.

JP-A-61-141732 JP 06-271670 A JP-A-09-040774 JP 2000-313804 A International Publication No. 2012/118020 pamphlet International Publication No. 2011/122198 pamphlet International Publication No. 1991/010699 Pamphlet JP-A-4-224823

Latest Polyimide (Basic and Application), Japan Polyimide Study Group, P152

  However, the physical properties of known transparent polyimides are not sufficient to be used as, for example, semiconductor insulating films, TFT-LCD insulating films, electrode protective films, ITO electrode substrates for touch panels, and heat-resistant colorless transparent substrates for flexible displays.

  For example, when a polyimide resin is used for a colorless transparent substrate for a flexible display, a polyimide film is formed on a support glass (hereinafter, also referred to as a support), and a TFT element is usually formed on the polyimide film. And an inorganic film may be formed. When the coefficient of linear expansion of polyimide (hereinafter also referred to as CTE) is high, residual stress is generated between the polyimide film and the inorganic film due to the CTE mismatch between the inorganic film or the support glass and the polyimide film. There is a problem that the glass is warped or the performance of the TFT element is reduced. Therefore, there is a problem that the residual stress of the polyimide is reduced in order to improve the warpage of the support glass. The polyimides described in Patent Documents 1 to 4 have a high residual stress, and have a problem that the support glass is warped when applied to a colorless transparent substrate for a flexible display.

  In order to form a polyimide film, for example, a polyimide precursor is applied on a glass substrate, and the glass substrate on which the polyimide precursor is applied is placed in an oven furnace into which nitrogen gas is introduced, and heated at 250 ° C. It is generally necessary to heat to 400 ° C. (hereinafter also referred to as a curing step). In polyimides with improved transparency and transmittance and hue described in Patent Documents 1 to 4 and Non-Patent Document 1, when the oxygen concentration in the oven furnace during curing is high, specifically, the oxygen concentration is 100 ppm. In the case of the above, there is a problem of oxygen concentration dependency, such as an increase in the YI value and a decrease in the total light transmittance.

  Further, when a polyimide resin is used for the colorless transparent substrate for a flexible display, a TFT element is usually formed on the polyimide film by a photolithography process using a photoresist. A polyimide film used for a colorless transparent substrate for a flexible display (hereinafter, also referred to as a polyimide substrate) is used in a step of removing a photoresist included in this step, because it is exposed to a chemical such as a photoresist stripping solution, These agents need to be chemically resistant. As described in Patent Document 1, in a polyimide composed of 4,4-DAS or 3,3-DAS and an acid dianhydride having a specific structure, minute cracks are formed on the polyimide substrate during a photoresist stripping step. There is a problem in terms of chemical resistance, such as a phenomenon in which the polyimide substrate becomes cloudy due to the entry and a phenomenon that the total light transmittance decreases.

  Patent Document 5 describes that a flexible silicon-containing diamine is introduced by block copolymerization for the purpose of reducing residual stress while maintaining the glass transition temperature and Young's modulus of polyimide. However, as described in Comparative Example 4 of Patent Document 5, when a silicon-containing diamine is copolymerized in a block, the phase separation of the silicone portion proceeds unless the polyimide precursor is dissolved using a combination of special solvents, In a sea-island structure having different refractive indices, the structure of the island portion becomes large, the film becomes cloudy, and the total light transmittance decreases. Also, when using a combination of special solvents having a low boiling point, after applying the polyimide precursor solution to the substrate, if left at room temperature for several hours, haze occurs, the coating film may become cloudy, leaving time Had to be managed. Thus, in order to produce a transparent thermosetting film using a polyimide obtained by block copolymerizing a silicon-containing diamine, a precursor is dissolved using a combination of special solvents, and then the precursor solution is applied. There was a problem that it was necessary to control the leaving time.

  In Examples 9 and 10 of Patent Document 6, a polyimide precursor obtained by copolymerizing an aromatic tetracarboxylic dianhydride, an alicyclic diamine and a silicone diamine, and a polyimide obtained therefrom are described. I have. However, the present inventors have confirmed that this polyamide has a problem that the yellowness is high, the total light transmittance is low, and the yellowness and the transmittance are easily affected by the oxygen concentration at the time of curing the polyimide ( See Comparative Example 25 of the present specification).

  Patent Documents 7 and 8 describe polyimide precursors obtained by copolymerizing (diaminodiphenyl) sulfone, aromatic tetracarboxylic dianhydride, and silicone diamine, and polyimides obtained therefrom. However, the present inventors have confirmed that the mass ratio of the silicon-containing monomer relative to the total mass of the silicon-containing monomer, the polyvalent carboxylic derivative, and the diamine compound used when synthesizing the polyimide precursor is disclosed in Patent Document 7. Is small, the resulting polyimide has a large residual stress, which is unsuitable for the display process. On the other hand, the patent document 8 is large, so that the obtained polyimide becomes cloudy and is unsuitable for use in a transparent display. There was a problem (see Comparative Examples 23 and 24 in the specification of the present application).

  The present invention has been made in view of the above-described problems, and can provide a transparent resin cured product without requiring a special combination of solvents, and is generated between the resin and an inorganic film. It is an object of the present invention to provide a resin precursor which has a low residual stress, has excellent chemical resistance, and can give a cured resin having a small influence on the YI value and the total light transmittance due to the oxygen concentration during the curing step. . Another object of the present invention is to provide a resin composition containing the resin precursor, a resin film obtained by curing the resin composition, a method for producing the same, and a laminate and a method for producing the same.

  The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, a heat-resistant resin precursor having a specific structure can form a transparent cured resin without requiring a combination of special solvents, Such a cured resin has a low residual stress generated between the inorganic film and the resin, has excellent chemical resistance, and has a small influence on the YI value and the total light transmittance due to the oxygen concentration during the curing step. And found the present invention based on this finding. That is, the present invention is as follows.

で表されるジアミンを含み、
該樹脂前駆体が、下記一般式（２）：

｛式中、複数存在するＲ₃及びＲ₄は、それぞれ独立に、炭素数１〜２０の一価の有機基であり、そしてｈは、３〜２００の整数である。｝で表される構造を有し、
該ケイ素基含有化合物の量が該多価化合物の総質量基準で６質量％〜２５質量％である、
該樹脂前駆体。
［２］ 該アミノ基反応性基が、カルボキシル基、置換カルボキシル基及び酸無水物基からなる群から選択される１つ以上を含む、［１］に記載の樹脂前駆体。
［３］ 該ケイ素基含有化合物が、下記一般式（３）：

｛式中、複数存在するＲ₂は、それぞれ独立に、単結合又は炭素数１〜２０の二価の有機基であり、Ｒ₃及びＲ₄は、それぞれ独立に、炭素数１〜２０の一価の有機基であり、複数存在してもよいＲ₅は、それぞれ独立に、炭素数１〜２０の一価の有機基であり、Ｌ₁、Ｌ₂、及びＬ₃は、それぞれ独立に、アミノ基、イソシアネート基、カルボキシル基、酸無水物基、酸エステル基、酸ハライド基、ヒドロキシ基、エポキシ基、又はメルカプト基であり、ｊは、３〜２００の整数であり、ｋは、０〜１９７の整数である。｝で表されるシリコーン化合物を含む、［１］又は［２］に記載の樹脂前駆体。
［４］ 該一般式（３）において、Ｌ₁及びＬ₂が、それぞれ独立に、アミノ基又は酸無水物基であり、そしてｋが０である、［３］に記載の樹脂前駆体。
［５］ 該一般式（３）において、Ｌ₁及びＬ₂が共にアミノ基である、［４］に記載の樹脂前駆体。
［６］ 該樹脂前駆体が、ユニット１及びユニット２を含有し、
該ユニット１が、少なくとも下記一般式（４）；

｛式中、複数存在するＲ₁は、それぞれ独立に、水素原子、炭素数１〜２０の一価の脂肪族炭化水素、又は一価の芳香族基であり、複数存在してもよいＸ₁は、それぞれ独立に、炭素数４〜３２の四価の有機基であり、そしてｎは、１〜１００の整数である。｝
で表される構造を有し、
該ユニット２が、下記一般式（５）：

｛式中、複数存在するＲ₁は、それぞれ独立に、水素原子、炭素数１〜２０の一価の脂肪族炭化水素、又は一価の芳香族基であり、複数存在するＲ₂は、それぞれ独立に、炭素数３〜２０の二価の脂肪族炭化水素、又は二価の芳香族基であり、Ｒ₃及びＲ₄は、それぞれ独立に、炭素数１〜２０の一価の有機基であり、複数存在してもよいＸ₂は、それぞれ独立に、炭素数４〜３２の四価の有機基であり、ｌは、３〜５０の整数であり、そしてｍは、１〜１００の整数である。｝で表される構造、又は、下記一般式（６）：

｛式中、複数存在するＲ₁は、それぞれ独立に、水素原子、炭素数１〜２０の一価の脂肪族炭化水素、又は一価の芳香族基であり、複数存在するＲ₃及びＲ₄は、それぞれ独立に、炭素数１〜２０の一価の有機基であり、複数存在するＲ₈は、それぞれ独立に、炭素数３〜２０の三価の脂肪族炭化水素、又は三価の芳香族基であり、ｐは、１〜１００の整数であり、そしてｑは３〜５０の整数である。｝で表される構造、又は上記一般式（５）で表される構造と上記一般式（６）で表される構造の両者、を有する、［１］〜［５］のいずれか１項に記載の樹脂前駆体。
［７］ 該ユニット１及び該ユニット２の合計量が、該樹脂前駆体の総質量基準で３０質量％以上である、［６］に記載の樹脂前駆体。
［８］ 該樹脂前駆体が、下記一般式（７）：

｛式中、複数存在するＲ₁は、それぞれ独立に、水素原子、炭素数１〜２０の一価の脂肪族炭化水素、又は一価の芳香族基であり、複数存在してもよいＸ₃は、それぞれ独立に、炭素数４〜３２の二価の有機基であり、複数存在してもよいＸ₄は、それぞれ独立に、炭素数４〜３２の四価の有機基であり、そしてｔは１〜１００の整数である。｝で表される構造を有するユニット３を更に含有する、［６］又は［７］に記載の樹脂前駆体。
［９］ 該一般式（７）において、Ｘ₃が、２，２’−ビス（トリフルオロメチル）ベンジジンからアミノ基を除いた構造である残基である、［８］に記載の樹脂前駆体。
［１０］ 該ユニット１及び該ユニット２が、
ピロメリット酸二無水物（ＰＭＤＡ）及びビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）からなる群より選ばれる１つ以上に由来する部位と、
４，４’−オキシジフタル酸二無水物（ＯＤＰＡ）、４，４’−（ヘキサフルオロイソプロピリデン）ジフタル酸無水物（６ＦＤＡ）、シクロヘキサン−１，２，４，５−テトラカルボン酸二無水物（ＣＨＤＡ）、３，３’，４，４’−ジフェニルスルホンテトラカルボン酸二無水物（ＤＳＤＡ）、４，４’−ビフェニルビス（トリメリット酸モノエステル酸無水物）（ＴＡＨＱ）、及び９，９’−ビス（３，４−ジカルボキシフェニル）フルオレン二無水物（ＢＰＡＦ）からなる群より選ばれる１つ以上に由来する部位と
の組み合わせである部位を、該ユニット１及び該ユニット２の酸二無水物由来部位の総量基準で６０モル％以上の量で含む、［６］〜［９］のいずれか１項に記載の樹脂前駆体。
［１１］ 該Ｒ₃及び該Ｒ₄が、それぞれ独立に、炭素数１〜３の一価の脂肪族炭化水素基、又は炭素数６〜１０の一価の芳香族炭化水素基である、［１］〜［１０］のいずれか１項に記載の樹脂前駆体。
［１２］ 該Ｒ₃及び該Ｒ₄の少なくとも一部がフェニル基である、［１］〜［１１］のいずれか１項に記載の樹脂前駆体。
［１３］ 該樹脂前駆体を不活性雰囲気下３００〜５００℃の条件で加熱硬化させて得られる樹脂が、−１５０℃〜０℃の領域の少なくとも１つのガラス転移温度及び１５０℃〜３８０℃の領域の少なくとも１つのガラス転移温度を有し、かつ０℃より大きく１５０℃より小さい領域においてガラス転移温度を有さない、［１］〜［１２］のいずれか１項に記載の樹脂前駆体。
［１４］ ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）由来の部位を、該樹脂前駆体の酸二無水物由来部位の総量基準で２０モル％以上含む、［１］〜［１３］のいずれか１項に記載の樹脂前駆体。
［１５］ 一部がイミド化されている、［１］〜［１４］のいずれか１項に記載の樹脂前駆体。
［１６］ ［１］〜［１５］のいずれか１項に記載の樹脂前駆体と、下記一般式（８）：

｛式中、複数存在してもよいＸ₃は、それぞれ独立に、炭素数４〜３２の四価の有機基であり、複数存在するＲ₁は、それぞれ独立に、水素原子、炭素数１〜２０の一価の脂肪族炭化水素、又は一価の芳香族基であり、そしてｒは、１〜１００の整数である。｝で表される構造を有する樹脂前駆体とを含む、前駆体混合物。
［１７］ ［１］〜［１５］のいずれか１項に記載の樹脂前駆体、又は［１６］に記載の前駆体混合物を含む、フレキシブルデバイス材料。
［１８］ ［１］〜［１５］のいずれか１項に記載の樹脂前駆体の硬化物又は［１６］に記載の前駆体混合物の硬化物である、樹脂フィルム。
［１９］ ［１］〜［１５］のいずれか１項に記載の樹脂前駆体又は［１６］に記載の前駆体混合物と、溶媒と、を含有する、樹脂組成物。
［２０］ 該樹脂組成物を支持体の表面に展開した後、該樹脂組成物を窒素雰囲気下３００℃〜５００℃で加熱することによって該樹脂組成物に含まれる該樹脂前駆体をイミド化して得られる樹脂が示す２０μｍ膜厚での黄色度が７以下である、［１９］に記載の樹脂組成物。
［２１］ 該樹脂組成物を支持体の表面に展開した後、該樹脂組成物を窒素雰囲気下３００℃〜５００℃で加熱することによって該樹脂組成物に含まれる該樹脂前駆体をイミド化して得られる樹脂が示す１０μｍ膜厚での残留応力が２５ＭＰａ以下である、［１９］又は［２０］に記載の樹脂組成物。
［２２］ ［１９］〜［２１］のいずれか１項に記載の樹脂組成物の硬化物である、樹脂フィルム。
［２３］ ［１９］〜［２１］のいずれか１項に記載の樹脂組成物を支持体の表面上に展開する工程と、
該支持体及び該樹脂組成物を加熱して該樹脂組成物に含まれる該樹脂前駆体をイミド化して樹脂フィルムを形成する工程と、
該樹脂フィルムを該支持体から剥離する工程と、
を含む、樹脂フィルムの製造方法。
［２４］ 支持体と、該支持体の表面上に形成された、［１９］〜［２１］のいずれか１項に記載の樹脂組成物の硬化物である樹脂膜とを含む、積層体。
［２５］ 支持体の表面上に、［１９］〜［２１］のいずれか１項に記載の樹脂組成物を展開する工程と、
該支持体及び該樹脂組成物を加熱して該樹脂組成物に含まれる該樹脂前駆体をイミド化して樹脂膜を形成し、これにより該支持体及び該樹脂膜を含む積層体を得る工程と、
を含む、積層体の製造方法。
［２６］ ディスプレイ基板の製造に用いられるポリイミド樹脂膜であって、厚み２０μｍにおけるＲｔｈが２０〜９０ｎｍである、ポリイミド樹脂膜。
［２７］ 支持体の表面上にポリイミド前駆体を含む樹脂組成物を展開する工程と、
該支持体及び該樹脂組成物を加熱してポリイミド前駆体をイミド化して、［２６］に記載のポリイミド樹脂膜を形成する工程と、
該ポリイミド樹脂膜上に素子を形成する工程と、
該素子が形成された該ポリイミド樹脂膜を該支持体から剥離する工程と
を含む、ディスプレイ基板の製造方法。 [1] A resin precursor obtained by polymerizing a polymerization component containing an amino group and an amino group-reactive group,
The polymerization component includes a polyvalent compound having two or more groups selected from an amino group and an amino group-reactive group,
The polyvalent compound contains a silicon group-containing compound,
The polyvalent compound has the following formula (1):

Including a diamine represented by
The resin precursor has the following general formula (2):

In the formula, a plurality of R ₃ and R ₄ are each independently a monovalent organic group having 1 to 20 carbon atoms, and h is an integer of 3 to 200. Has a structure represented by｝,
The amount of the silicon group-containing compound is 6% by mass to 25% by mass based on the total mass of the polyvalent compound;
The resin precursor.
[2] The resin precursor according to [1], wherein the amino group-reactive group includes at least one selected from the group consisting of a carboxyl group, a substituted carboxyl group, and an acid anhydride group.
[3] The silicon group-containing compound is represented by the following general formula (3):

In the formula, a plurality of R ₂ are each independently a single bond or a divalent organic group having 1 to 20 carbon atoms, and R ₃ and R ₄ are each independently a 1 to 20 carbon atom. Is a valent organic group, and a plurality of R _{5 s} which may be present are each independently a monovalent organic group having 1 to 20 carbon atoms, and L ₁ , L ₂ , and L ₃ are each independently An amino group, an isocyanate group, a carboxyl group, an acid anhydride group, an acid ester group, an acid halide group, a hydroxy group, an epoxy group, or a mercapto group; j is an integer of 3 to 200; It is an integer of 197. The resin precursor according to [1] or [2], comprising the silicone compound represented by｝.
[4] The resin precursor according to [3], wherein in the general formula (3), L ₁ and L ₂ are each independently an amino group or an acid anhydride group, and k is 0.
[5] The resin precursor according to [4], wherein in the general formula (3), L ₁ and L ₂ are both amino groups.
[6] The resin precursor contains a unit 1 and a unit 2,
The unit 1 has at least the following general formula (4);

In the formula, a plurality of R ₁ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or a monovalent aromatic group, and a plurality of X ₁ may be present. Are each independently a tetravalent organic group having 4 to 32 carbon atoms, and n is an integer of 1 to 100. ｝
Having a structure represented by
The unit 2 has the following general formula (5):

In the formula, a plurality of R ₁ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or a monovalent aromatic group, and a plurality of R ₂ are each independently Independently a divalent aliphatic hydrocarbon having 3 to 20 carbon atoms or a divalent aromatic group, and R ₃ and R ₄ are each independently a monovalent organic group having 1 to 20 carbon atoms. X ₂ , which may be present plurally, is each independently a tetravalent organic group having 4 to 32 carbon atoms, 1 is an integer of 3 to 50, and m is an integer of 1 to 100 It is.構造 or the following general formula (6):

｛In the formula, a plurality of R ₁ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or a monovalent aromatic group, and a plurality of R ₃ and R ₄ Are each independently a monovalent organic group having 1 to 20 carbon atoms, and a plurality of R ₈ are each independently a trivalent aliphatic hydrocarbon having 3 to 20 carbon atoms or a trivalent aromatic group. Group, p is an integer from 1 to 100, and q is an integer from 3 to 50.に, or any one of [1] to [5], having a structure represented by the general formula (5) and a structure represented by the general formula (6). The resin precursor described in the above.
[7] The resin precursor according to [6], wherein the total amount of the unit 1 and the unit 2 is 30% by mass or more based on the total mass of the resin precursor.
[8] The resin precursor has the following general formula (7):

In the formula, a plurality of R ₁ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or a monovalent aromatic group, and a plurality of X ₃ may be present. Are each independently a divalent organic group having 4 to 32 carbon atoms, and a plurality of X _{4 s} which may be present are each independently a tetravalent organic group having 4 to 32 carbon atoms, and t Is an integer of 1 to 100. The resin precursor according to [6] or [7], further comprising a unit 3 having a structure represented by｝.
[9] The resin precursor according to [8], wherein in the general formula (7), X ₃ is a residue having a structure obtained by removing an amino group from 2,2′-bis (trifluoromethyl) benzidine. .
[10] The unit 1 and the unit 2
A site derived from one or more selected from the group consisting of pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic dianhydride (BPDA);
4,4'-oxydiphthalic dianhydride (ODPA), 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), cyclohexane-1,2,4,5-tetracarboxylic dianhydride ( CHDA), 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4'-biphenylbis (trimellitic acid monoester anhydride) (TAHQ), and 9,9 '-Bis (3,4-dicarboxyphenyl) fluorene dianhydride (BPAF) is combined with a site derived from one or more selected from the group consisting of The resin precursor according to any one of [6] to [9], which contains 60 mol% or more based on the total amount of the anhydride-derived sites.
[11] The R ₃ and the R ₄ are each independently a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, [ 1] The resin precursor according to any one of [10].
[12] The resin precursor according to any one of [1] to [11], wherein at least a part of R ₃ and R ₄ is a phenyl group.
[13] A resin obtained by heating and curing the resin precursor under the condition of 300 to 500 ° C. in an inert atmosphere has a glass transition temperature of at least one in a region of −150 ° C. to 0 ° C. and a temperature of 150 ° C. to 380 ° C. The resin precursor according to any one of [1] to [12], which has at least one glass transition temperature in a region and does not have a glass transition temperature in a region greater than 0 ° C and smaller than 150 ° C.
[14] Any one of [1] to [13], wherein a site derived from biphenyltetracarboxylic dianhydride (BPDA) is contained in an amount of 20 mol% or more based on the total amount of sites derived from acid dianhydride of the resin precursor. The resin precursor according to item.
[15] The resin precursor according to any one of [1] to [14], wherein a part is imidized.
[16] The resin precursor according to any one of [1] to [15], and the following general formula (8):

{Wherein, optionally X ₃ also there are a plurality, each independently, a tetravalent organic group 4 to 32 carbon atoms, R ₁ existing in plural, each independently, a hydrogen atom, 1 to carbon atoms 20 monovalent aliphatic hydrocarbons or monovalent aromatic groups, and r is an integer from 1 to 100. And a resin precursor having a structure represented by｝.
[17] A flexible device material comprising the resin precursor according to any one of [1] to [15] or the precursor mixture according to [16].
[18] A resin film which is a cured product of the resin precursor according to any one of [1] to [15] or a cured product of the precursor mixture according to [16].
[19] A resin composition comprising the resin precursor according to any one of [1] to [15] or the precursor mixture according to [16], and a solvent.
[20] After the resin composition is spread on the surface of a support, the resin precursor contained in the resin composition is imidized by heating the resin composition at 300 ° C. to 500 ° C. in a nitrogen atmosphere. The resin composition according to [19], wherein the obtained resin has a yellowness of 7 or less at a film thickness of 20 μm.
[21] After the resin composition is spread on the surface of a support, the resin precursor contained in the resin composition is imidized by heating the resin composition at 300 ° C. to 500 ° C. in a nitrogen atmosphere. The resin composition according to [19] or [20], wherein the obtained resin has a residual stress at a film thickness of 10 μm of 25 MPa or less.
[22] A resin film, which is a cured product of the resin composition according to any one of [19] to [21].
[23] a step of spreading the resin composition according to any one of [19] to [21] on a surface of a support;
Heating the support and the resin composition to imidize the resin precursor contained in the resin composition to form a resin film,
Peeling the resin film from the support,
A method for producing a resin film, comprising:
[24] A laminate comprising a support and a resin film formed on the surface of the support, which is a cured product of the resin composition according to any one of [19] to [21].
[25] a step of spreading the resin composition according to any one of [19] to [21] on a surface of a support;
Heating the support and the resin composition to imidize the resin precursor contained in the resin composition to form a resin film, thereby obtaining a laminate including the support and the resin film; and ,
A method for producing a laminate, comprising:
[26] A polyimide resin film used for manufacturing a display substrate, wherein the Rth at a thickness of 20 µm is 20 to 90 nm.
[27] a step of spreading a resin composition containing a polyimide precursor on the surface of the support;
Heating the support and the resin composition to imidize the polyimide precursor to form a polyimide resin film according to [26];
Forming an element on the polyimide resin film,
Removing the polyimide resin film on which the element is formed from the support.

  According to the present invention, a transparent resin cured product can be provided without requiring a special solvent combination, and a low residual stress is generated between the resin and the inorganic film, the chemical resistance is excellent, and the curing is performed. There is provided a resin precursor capable of giving a cured resin having a small influence on a YI value and a total light transmittance by an oxygen concentration in a process.

  Hereinafter, exemplary embodiments of the present invention (hereinafter, abbreviated as “embodiments”) will be described in detail. It should be noted that the present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist. The number of repeating structural units in the formula of the present disclosure is only intended to include the number of the structural units in the entire resin precursor unless otherwise specified, and therefore, a specific bonding mode such as a block structure. It should be noted that this is not intended. Unless otherwise specified, the characteristic values described in the present disclosure are values measured by a method described in the section of [Examples] or a method understood by those skilled in the art to be equivalent thereto. Intend.

で表されるジアミンを含み、
該樹脂前駆体が、下記一般式（２）：

｛式中、複数存在するＲ₃及びＲ₄は、それぞれ独立に、炭素数１〜２０の一価の有機基であり、そしてｈは、３〜２００の整数である。｝で表される構造を有し、
該ケイ素基含有化合物の量が該多価化合物の総質量基準で６質量％〜２５質量％である、
該樹脂前駆体を提供する。 <Resin precursor>
The resin precursor according to the embodiment of the present invention,
A resin precursor obtained by polymerizing a polymerization component containing an amino group and an amino group reactive group,
The polymerization component includes a polyvalent compound having two or more groups selected from an amino group and an amino group-reactive group,
The polyvalent compound contains a silicon group-containing compound,
The polyvalent compound has the following formula (1):

Including a diamine represented by
The resin precursor has the following general formula (2):

In the formula, a plurality of R ₃ and R ₄ are each independently a monovalent organic group having 1 to 20 carbon atoms, and h is an integer of 3 to 200. Has a structure represented by｝,
The amount of the silicon group-containing compound is 6% by mass to 25% by mass based on the total mass of the polyvalent compound;
The resin precursor is provided.

The polymerization component contains an amino group and an amino group-reactive group. The polymerization component includes a polyvalent compound having two or more groups selected from an amino group and an amino group-reactive group. For example, the polymerization component may be a mixture of a polyvalent compound having an amino group and a polyvalent compound having an amino group-reactive group, or a polyvalent compound containing both an amino group and an amino group-reactive group. May be included, or a combination thereof.
In the present disclosure, an amino group-reactive group intends a group having reactivity to an amino group. Examples of the amino group-reactive group include an acid group (eg, a carboxyl group, an acid anhydride group, and a substituted carboxyl group (eg, an acid ester group, an acid halide group, etc.)), a hydroxy group, an epoxy group, and a mercapto group. No. Examples of the compound containing an acid group include dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, and acid dianhydrides, acid esters, and acid chlorides of these carboxylic acids. Therefore, the resin precursor of the present embodiment can be a polyimide precursor. In a typical embodiment, the amino group-reactive group comprises one or more selected from the group consisting of a carboxyl group, a substituted carboxyl group, and an anhydride group. In a preferred embodiment, the amino group-reactive group is one or more selected from the group consisting of a carboxyl group, a substituted carboxyl group, and an acid anhydride group.

  The polyvalent compound contains at least a diamine represented by the general formula (1). The compound represented by the general formula (1) includes, for example, 4,4- (diaminodiphenyl) sulfone (hereinafter, also referred to as 4,4-DAS), 3,4- (diaminodiphenyl) sulfone (hereinafter, 3,4 -DAS), and one or more selected from the group consisting of 3,3- (diaminodiphenyl) sulfone (hereinafter also referred to as 3,3-DAS).

  At least one of the polyvalent compounds is a silicon group-containing compound. The structure represented by the general formula (2) is derived from a silicon-containing compound. The amount of the silicon group-containing compound is 6% by mass to 25% by mass (hereinafter, this mass fraction is also referred to as the silicon group-containing monomer concentration) based on the mass of the polyvalent compound. The silicon group-containing monomer concentration of 6% by mass or more is advantageous from the viewpoint of sufficiently obtaining the effect of reducing the stress generated between the resin film and the inorganic film and the effect of reducing the yellowness, and is preferably 7% by mass. It is preferably at least 8 mass%, more preferably at least 8 mass%, further preferably at least 10 mass%. On the other hand, the silicon group-containing monomer concentration of 25% by mass or less is advantageous from the viewpoint of improving transparency, lowering yellowness, and obtaining good heat resistance without clouding the resulting polyimide. %, More preferably 20% by mass or less. From the viewpoint of improving the chemical resistance, the YI value, the total light transmittance, the birefringence, the residual stress, and the oxygen dependency of the optical characteristics, the concentration of the silicon-containing monomer should be 10% by mass or more and 20% by mass or less. Is particularly preferred.

In the general formula (2), a plurality of R ₃ and R ₄ are each independently a monovalent organic group having 1 to 20 carbon atoms. Examples of the monovalent organic group having 1 to 20 carbon atoms include a monovalent hydrocarbon group having 1 to 20 carbon atoms, an amino group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an epoxy group. be able to.

  Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. As the alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms is preferable from the viewpoint of heat resistance and residual stress, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group , An isobutyl group, a t-butyl group, a pentyl group, a hexyl group and the like. As the cycloalkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms is preferable from the above viewpoint, and specific examples include a cyclopentyl group and a cyclohexyl group. The aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms from the above viewpoint, and specific examples include a phenyl group, a tolyl group, and a naphthyl group.

  Examples of the amino group having 1 to 20 carbon atoms include an amino group and a substituted amino group (for example, a bis (trialkylsilyl) amino group).

  Examples of the monovalent alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, a phenoxy group, a propenyloxy group, and a cyclohexyloxy group.

In the general formula (2), a plurality of R ₃ and R ₄ are each independently a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. It is preferable that the base is a group from the viewpoint that the obtained polyimide film has both high heat resistance and low residual stress. In this respect, the monovalent aliphatic hydrocarbon having 1 to 3 carbon atoms is preferably a methyl group, and the aromatic group having 6 to 10 carbon atoms is preferably a phenyl group.

  H in the general formula (2) is an integer of 3 to 200, preferably an integer of 10 to 200, more preferably an integer of 20 to 150, further preferably an integer of 30 to 100, and particularly preferably 35 to 80. Is an integer. When h is 2 or less, the residual stress of the polyimide obtained from the resin precursor of the present disclosure may be deteriorated (that is, increased). When h exceeds 200, the varnish containing the resin precursor and the solvent may be used. When the varnish is prepared, problems such as clouding of the varnish and reduction of the mechanical strength of the polyimide may occur.

  In the resin precursor of the present embodiment, the silicon group-containing compound has the following general formula (3):

｛式中、複数存在するＲ₂は、それぞれ独立に、単結合又は炭素数１〜２０の二価の有機基であり、Ｒ₃及びＲ₄は、それぞれ独立に、炭素数１〜２０の一価の有機基であり、複数存在してもよいＲ₅は、それぞれ独立に、炭素数１〜２０の一価の有機基であり、Ｌ₁、Ｌ₂、及びＬ₃は、それぞれ独立に、アミノ基、イソシアネート基、カルボキシル基、酸無水物基、酸エステル基、酸ハライド基、ヒドロキシ基、エポキシ基、又はメルカプト基であり、ｊは、３〜２００の整数であり、ｋは、０〜１９７の整数である。｝で表されるシリコーン化合物を含むことが好ましい。好ましい態様において、ケイ素基含有化合物は、一般式（３）で表されるシリコーン化合物である。

In the formula, a plurality of R ₂ are each independently a single bond or a divalent organic group having 1 to 20 carbon atoms, and R ₃ and R ₄ are each independently a 1 to 20 carbon atom. Is a valent organic group, and a plurality of R _{5 s} which may be present are each independently a monovalent organic group having 1 to 20 carbon atoms, and L ₁ , L ₂ , and L ₃ are each independently An amino group, an isocyanate group, a carboxyl group, an acid anhydride group, an acid ester group, an acid halide group, a hydroxy group, an epoxy group, or a mercapto group; j is an integer of 3 to 200; It is an integer of 197. It preferably contains a silicone compound represented by｝. In a preferred embodiment, the silicon group-containing compound is a silicone compound represented by the general formula (3).

Examples of the divalent organic group having 1 to 20 carbon atoms in R ₂ include a methylene group, an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, and an arylene group having 6 to 20 carbon atoms. Can be As the alkylene group having 2 to 20 carbon atoms, an alkylene group having 2 to 10 carbon atoms is preferable from the viewpoint of heat resistance, residual stress and cost, and dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene and the like. And the like. The cycloalkylene group having 3 to 20 carbon atoms is preferably a cycloalkylene group having 3 to 10 carbon atoms from the above viewpoint, and examples thereof include a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, and a cycloheptylene group. Among them, a divalent aliphatic hydrocarbon having 3 to 20 carbon atoms is preferable from the above viewpoint. As the arylene group having 6 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms is preferable from the above viewpoint, and examples thereof include a phenylene group and a naphthylene group.

In general formula (3), R ₃ and R ₄ are the general formula (2) have the same meanings as R ₃ and R _4, preferred embodiments are as described above for the general formula (2). R ₅ has the same meaning as a monovalent organic group having 1 to 20 carbon atoms, that is, R ₃ and R ₄ , and preferred embodiments are the same as R ₃ and R ₄ .

In the general formula (3), L ₁ , L ₂ , and L ₃ each independently represent an amino group, an isocyanate group, a carboxyl group, an acid anhydride group, an acid ester group, an acid halide group, a hydroxy group, an epoxy group, Or a mercapto group.

The amino group may be substituted, and examples thereof include a bis (trialkylsilyl) amino group. Specific examples of the compound represented by the general formula (3) in which L ₁ , L ₂ , and L ₃ are amino groups include amino-modified methylphenylsilicon at both ends (for example, X22-1660B- manufactured by Shin-Etsu Chemical Co., Ltd.). 3 (number average molecular weight 4,400) and X22-9409 (number average molecular weight 1,300)), amino-modified dimethyl silicone at both ends (for example, X22-161A (number average molecular weight 1,600) manufactured by Shin-Etsu Chemical Co., Ltd.), X22 -161B (number average molecular weight 3,000) and KF8012 (number average molecular weight 4,400); BY16-835U (number average molecular weight 900) manufactured by Toray Dow Corning; and Silaplane FM3311 (number average molecular weight 1000) manufactured by Chisso. ) And the like.
Specific examples of the compound in which L ₁ , L ₂ and L ₃ are isocyanate groups include the above-mentioned isocyanate-modified silicone obtained by reacting the amino-modified silicone with a phosgene compound at both ends.

Specific examples of the compound in which L ₁ , L ₂ , and L ₃ are carboxyl groups include, for example, X22-162C (number average molecular weight 4,600) of Shin-Etsu Chemical Co., Ltd., and BY16-880 (number average of Toray Dow Corning). Molecular weight 6,600).

Specific examples of the compound in which L ₁ , L ₂ and L ₃ are an acid anhydride group include the following formula groups:

で表される基の少なくとも１つを有するアシル化合物等が挙げられる。

And an acyl compound having at least one of the groups represented by

Specific examples of compounds in which L ₁ , L ₂ , and L ₃ are acid anhydride groups include X22-168AS (manufactured by Shin-Etsu Chemical, number average molecular weight 1,000) and X22-168A (manufactured by Shin-Etsu Chemical, number average molecular weight, X22-168B (Shin-Etsu Chemical, number average molecular weight 3,200), X22-168-P5-8 (Shin-Etsu Chemical, number average molecular weight 4,200), DMS-Z21 (Gerest, Average molecular weight of 600 to 800).

As a specific example of the compound in which L ₁ , L ₂ and L ₃ are an acid ester group, the compound in which L ₁ , L ₂ and L ₃ are a carboxyl group or an acid anhydride group is reacted with an alcohol. And the resulting compounds.

Specific examples of the compound in which L ₁ , L ₂ , and L ₃ are an acid halide group include carboxylic acid chloride, carboxylic acid fluoride, carboxylic acid bromide, and carboxylic acid iodide.

Specific examples of the compound in which L ₁ , L ₂ , and L ₃ are hydroxy groups include KF-6000 (manufactured by Shin-Etsu Chemical, number average molecular weight 900) and KF-6001 (manufactured by Shin-Etsu Chemical, number average molecular weight 1,800) , KF-6002 (manufactured by Shin-Etsu Chemical, number average molecular weight 3,200), KF-6003 (manufactured by Shin-Etsu Chemical, number average molecular weight 5,000) and the like. A compound having a hydroxy group is considered to react with a compound having a carboxyl group or an acid anhydride group.

Specific examples of the compound in which L ₁ , L ₂ , and L ₃ are epoxy groups include X22-163 (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 400) and KF-105 (manufactured by Shin-Etsu Chemical Co., Ltd.) Number average molecular weight 980), X22-163A (manufactured by Shin-Etsu Chemical, number average molecular weight 2,000), X22-163B (manufactured by Shin-Etsu Chemical, number average molecular weight 3,500), X22-163C (manufactured by Shin-Etsu Chemical, number average molecular weight 5) X22-169AS (Shin-Etsu Chemical, number average molecular weight 1,000), X22-169B (Shin-Etsu Chemical, number average molecular weight 3,400), both terminal alicyclic epoxy type; X22-9002 (made by Shin-Etsu Chemical, functional group equivalent: 5,000 g / mol), which is an epoxy type; Compounds having an epoxy group are believed to react with the diamine.

Specific examples of the compound in which L ₁ , L ₂ , and L ₃ are mercapto groups include X22-167B (manufactured by Shin-Etsu Chemical, number average molecular weight 3,400) and X22-167C (manufactured by Shin-Etsu Chemical, number average molecular weight 4, 600) and the like. It is considered that the compound having a mercapto group reacts with the compound having a carboxyl group or an acid anhydride group.

L ₁ , L ₂ , and L ₃ are each independently preferably an amino group or an acid anhydride group, from the viewpoint of improving the molecular weight of the resin precursor, or from the viewpoint of heat resistance of the obtained polyimide, and furthermore, From the viewpoint of avoiding cloudiness of the varnish containing the precursor and the solvent, or from the viewpoint of cost, it is more preferable that the varnish is independently an amino group.
Or, from the viewpoint of avoiding cloudiness of the varnish containing the resin precursor and the solvent, or from the viewpoint of cost, L ₁ and L ₂ are each independently an amino group or an acid anhydride group, and k is 0. Is preferred. In this case, it is more preferable that both L ₁ and L ₂ are amino groups.

  In formula (3), preferred embodiments of j are the same as those described above for h in formula (2). In the general formula (3), k is an integer of 0 to 197, preferably 0 to 100, more preferably 0 to 50, and particularly preferably 0 to 25. When k exceeds 197, when a varnish containing a resin precursor and a solvent is prepared, problems such as the varnish becoming cloudy may occur. When k is 0, it is preferable from the viewpoint of improving the molecular weight of the resin precursor or from the viewpoint of the heat resistance of the obtained polyimide. When k is 0, it is advantageous that j is 3 to 200 from the viewpoint of improving the molecular weight of the resin precursor or the viewpoint of heat resistance of the obtained polyimide.

In a preferred embodiment, in each formula of the present disclosure, R ₃ and R ₄ are each independently a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms or 6 to 6 carbon atoms from the viewpoint of residual stress and cost. And 10 monovalent aromatic hydrocarbon groups. Alternatively, in each formula of the present disclosure, a part of R ₃ and R ₄ is preferably a phenyl group from the viewpoint of heat resistance and residual stress.

  In a preferred embodiment, the polyvalent compound contains a tetracarboxylic dianhydride and a diamine. In a preferred embodiment, the polyvalent compound includes a tetracarboxylic dianhydride, a dicarboxylic acid, and a diamine.

<Tetracarboxylic dianhydride>
As the tetracarboxylic dianhydride as an example of the polyvalent compound contained in the polymerization raw material, specifically, an aromatic tetracarboxylic dianhydride having 8 to 36 carbon atoms and a 6 to 36 carbon atoms Compounds selected from the alicyclic tetracarboxylic dianhydrides are preferred from the viewpoint of reducing the YI value and the total light transmittance.

  More specifically, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride (hereinafter also referred to as 6FDA), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-cyclohexene -1,2 dicarboxylic anhydride, pyromellitic dianhydride (hereinafter also referred to as PMDA), 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone Tetracarboxylic dianhydride (hereinafter also referred to as BTDA), 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride ( Hereinafter, also referred to as BPDA), 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride (hereinafter, also referred to as DSDA), 2,2 ′, 3,3′-biphenyltet Carboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylidene-4,4'-diphthalic dianhydride, 2,2-propylidene-4,4'-diphthalic dianhydride Anhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic Acid dianhydride, 1,5-pentamethylene-4,4′-diphthalic dianhydride, 4,4′-oxydiphthalic dianhydride (hereinafter also referred to as ODPA), thio-4,4′-diphthalic acid Dianhydride, sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis (3,4-dicarboxyphenyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) Benzene dianhydride, 1,4-bis (3,4-dical Xyphenoxy) benzene dianhydride, 1,3-bis [2- (3,4-dicarboxyphenyl) -2-propyl] benzene dianhydride, 1,4-bis [2- (3,4-dicarboxy) Phenyl) -2-propyl] benzene dianhydride, bis [3- (3,4-dicarboxyphenoxy) phenyl] methane dianhydride, bis [4- (3,4-dicarboxyphenoxy) phenyl] methane dianhydride 2,2-bis [3- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride ( Hereinafter also referred to as BPADA), bis (3,4-dicarboxyphenoxy) dimethylsilane dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyl Disiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid Dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride , Ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride (hereinafter also referred to as CBDA), Pentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride (hereinafter referred to as C DA), 3,3 ′, 4,4′-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4, 4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene- 4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylidene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4, 4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis (cyclohexane − , 2-dicarboxylic acid) dianhydride, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, rel- [1S, 5R, 6R] -3 -Oxabicyclo [3,2,1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 4- (2,5-dioxotetrahydrofuran-3- Yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, ethylene glycol-bis- (3,4-dicarboxylic anhydride phenyl) ether, 4,4′-biphenylbis (tri Meric acid monoester acid anhydride (hereinafter also referred to as TAHQ), 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride (hereinafter also referred to as BPAF). ) And the like.

  Among them, BTDA and PMDA are preferred from the viewpoint of reducing CTE, improving chemical resistance, improving glass transition temperature (Tg), and improving mechanical elongation. Further, 6FDA, ODPA and BPADA are preferred from the viewpoints of a decrease in yellowness, a decrease in birefringence and an improvement in mechanical elongation. Further, BPDA is preferable from the viewpoints of reduction of residual stress, reduction of yellowness, reduction of birefringence, improvement of chemical resistance, improvement of Tg and improvement of mechanical elongation. Further, CHDA is preferred from the viewpoint of reducing residual stress and reducing yellowness. Among them, BPDA having a tonic structure exhibiting high chemical resistance, high Tg and low CTE, and tetracarboxylic dianhydride selected from the group consisting of 6FDA, ODPA, and CHDA having low yellowness and low birefringence. It is preferable to use a combination of and from the viewpoints of high chemical resistance, low residual stress, low yellowness, low birefringence, and improvement in total light transmittance.

  Among them, from the viewpoint of high elongation, improvement in chemical resistance, and high Young's modulus, in addition to the above effects, the site derived from BPDA is at least 20 mol% of the site derived from all acid dianhydrides. Preferably, it is more preferably 50 mol% or more, further preferably 80 mol% or more, and may be 100%.

<Dicarboxylic acid>
In addition, the resin precursor in the present embodiment, in addition to the above-mentioned tetracarboxylic dianhydride, as long as the performance is not impaired, improves the mechanical elongation, improves the glass transition temperature, and reduces the yellowness. The thermosetting film can be made into a polyamideimide by introducing a polyamide component by copolymerizing a dicarboxylic acid for the purpose of adjusting the temperature. Examples of such a dicarboxylic acid include a dicarboxylic acid having an aromatic ring and an alicyclic dicarboxylic acid, particularly, an aromatic dicarboxylic acid having 8 to 36 carbon atoms, from the viewpoint of reduction in YI value and total light transmittance. And at least one compound selected from the group consisting of alicyclic dicarboxylic acids having 6 to 34 carbon atoms. Specifically, isophthalic acid, terephthalic acid, 4,4′-biphenyldicarboxylic acid, 3,4′-biphenyldicarboxylic acid, 3,3′-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,3- Naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-sulfonylbisbenzoic acid, 3,4′-sulfonylbisbenzoic acid, 3,3′-sulfonylbisbenzoic acid, 4,4'-oxybisbenzoic acid, 3,4'-oxybisbenzoic acid, 3,3'-oxybisbenzoic acid, 2,2-bis (4-carboxyphenyl) propane, 2,2-bis (3-carboxyphenyl ) Propane, 2,2′-dimethyl-4,4′-biphenyldicarboxylic acid, 3,3′-dimethyl-4,4′-biphenyldicarboxylic acid, 2,2′-dimethyl 3,3′-biphenyldicarboxylic acid, 9,9-bis (4- (4-carboxyphenoxy) phenyl) fluorene, 9,9-bis (4- (3-carboxyphenoxy) phenyl) fluorene, 4,4′- Bis (4-carboxyphenoxy) biphenyl, 4,4'-bis (3-carboxyphenoxy) biphenyl, 3,4'-bis (4-carboxyphenoxy) biphenyl, 3,4'-bis (3-carboxyphenoxy) biphenyl 3,3′-bis (4-carboxyphenoxy) biphenyl, 3,3′-bis (3-carboxyphenoxy) biphenyl, 4,4′-bis (4-carboxyphenoxy) -p-terphenyl, 4,4 '-Bis (4-carboxyphenoxy) -m-terphenyl, 3,4'-bis (4-carboxyphenoxy) -p-terphenyl 3,3'-bis (4-carboxyphenoxy) -p-terphenyl, 3,4'-bis (4-carboxyphenoxy) -m-terphenyl, 3,3'-bis (4-carboxyphenoxy) -m -Terphenyl, 4,4'-bis (3-carboxyphenoxy) -p-terphenyl, 4,4'-bis (3-carboxyphenoxy) -m-terphenyl, 3,4'-bis (3-carboxy) Phenoxy) -p-terphenyl, 3,3′-bis (3-carboxyphenoxy) -p-terphenyl, 3,4′-bis (3-carboxyphenoxy) -m-terphenyl, 3,3′-bis (3-carboxyphenoxy) -m-terphenyl, 1,1-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4,4′-ben Phenol Nji carboxylic acid, 1,3-phenylene diacetic acid, 1,4-phenylene diacetic acid, and include 5-aminoisophthalic acid derivatives such as described in WO 2005/068535 pamphlet. When these dicarboxylic acids are actually copolymerized into a polymer, they may be used in the form of an acid chloride derivative or an active ester derivative derived from thionyl chloride or the like.

  Of these, terephthalic acid is particularly preferred from the viewpoint of reducing the YI value and improving Tg. When a dicarboxylic acid is used instead of a tetracarboxylic acid, the dicarboxylic acid content is preferably 50 mol% or less based on the total number of moles of the dicarboxylic acid and the tetracarboxylic acid, from the viewpoint of chemical resistance. preferable.

<Diamine>
The diamine contained in the polymerization component includes the diamine represented by the general formula (1). The diamine represented by the general formula (1) can constitute, for example, a diamine-derived site of unit 1 described below. In the resin precursor, the site derived from the diamine represented by the general formula (1) is suitable for the yellowness of the polyimide film, low birefringence, improvement of the total light transmittance, and residual stress generated between the polyimide film and the inorganic film. From the viewpoints of reduction, high Tg, and high breaking strength, it is preferably at least 20 mol%, more preferably at least 50 mol%, even more preferably at least 80 mol% of all diamine-derived sites.

  Further, the diamine can include a diamine having a divalent silicon-containing group having 2 to 100 silicon atoms (hereinafter, also simply referred to as silicon-containing diamine). As the silicon-containing diamine, for example, the following general formula (9):

｛式中、複数存在するＲ₂は、それぞれ独立に、炭素数３〜２０の二価の脂肪族炭化水素、又は二価の芳香族基であり、Ｒ₃及びＲ₄は、それぞれ独立に、炭素数１〜２０の一価の有機基であり、ｌは、３〜５０の整数である。｝で表されるジアミノ（ポリ）シロキサンが好適である。このようなジアミンは例えば後述のユニット２を構成できる。

｛In the formula, a plurality of R ₂ are each independently a divalent aliphatic hydrocarbon having 3 to 20 carbon atoms or a divalent aromatic group, and R ₃ and R ₄ are each independently It is a monovalent organic group having 1 to 20 carbon atoms, and 1 is an integer of 3 to 50. Diamino (poly) siloxane represented by｝ is preferred. Such a diamine can constitute, for example, a unit 2 described below.

Preferred structures of R _{2 in} the general formula (9) include a methylene group, an ethylene group, a propylene group, a butylene group and a phenylene group. Preferable examples of R ₃ and R ₄ in the general formula (9) include a methyl group, an ethyl group, a propyl group, a butyl group and a phenyl group. Particularly preferred is a group.

  Specific examples of the compound represented by the general formula (9) include amine-modified methylphenylsilicone oil at both ends (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400), X22-9409 (number Average molecular weight 1300)), amino-modified dimethyl silicone at both terminals (Shin-Etsu Chemical Co., Ltd .: X22-161A (number average molecular weight 1600), X22-161B (number average molecular weight 3000), KF8021 (number average molecular weight 4400), manufactured by Toray Dow Corning : BY16-835U (number average molecular weight 900) manufactured by Chisso Corporation: Thyraplane FM3311 (number average molecular weight 1000). Among these, a methylphenyl silicone oil modified at both ends with amines is particularly preferable from the viewpoint of improving chemical resistance and Tg.

  In addition, diamines include 2,2'-bis (trifluoromethyl) benzidine (hereinafter, also referred to as TFMB), 4,4'- (or 3,4'-, 3,3'-, 2,4'-). ) Diaminodiphenyl ether, 4,4 ′-(or 3,3 ′-) diaminodiphenylsulfone, 4,4 ′-(or 3,3 ′-) diaminodiphenylsulfide, 4,4′-benzophenonediamine, 3,3 ′ -Benzophenonediamine, 4,4'-di (4-aminophenoxy) phenylsulfone, 4,4'-di (3-aminophenoxy) phenylsulfone, 4,4'-bis (4-aminophenoxy) biphenyl, 1, 4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis {4- (4-aminophenoxy) phenyl} Bread, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,2'-bis (4-aminophenyl) propane, 2,2', 6,6'-tetramethyl- 4,4′-diaminobiphenyl, 2,2 ′, 6,6′-tetratrifluoromethyl-4,4′-diaminobiphenyl, bis {(4-aminophenyl) -2-propyl} 1,4-benzene, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-aminophenoxyphenyl) fluorene, 3,3′-dimethylbenzidine, 3,3′-dimethoxybenzidine and 3,5-diamino 2,6-diaminopyridine, 2,4-diaminopyridine, bis (4-aminophenyl-2-propyl) -1,4-benzene, 3,3′-bis (trifluoromethyl -4,4'-diaminobiphenyl (3,3'-TFDB), 2,2'-bis [3 (3-aminophenoxy) phenyl] hexafluoropropane (3-BDAF), 2,2'-bis [4 (4-aminophenoxy) phenyl] hexafluoropropane (4-BDAF), 2,2′-bis (3-aminophenyl) hexafluoropropane (3,3′-6F), and 2,2′-bis ( It may contain one or more members selected from the group consisting of 4-aminophenyl) hexafluoropropane (4,4′-6F). These diamines can constitute a diamine-derived site of the unit 3 described later. Among these, 1,4-cyclohexanediamine and TFMB are the most preferable from the viewpoint of a decrease in yellowness, a decrease in CTE, and a decrease in YI value.

｛式中、複数存在するＲ₁は、それぞれ独立に、水素原子、炭素数１〜２０の一価の脂肪族炭化水素、又は一価の芳香族基であり、複数存在してもよいＸ₁は、それぞれ独立に、炭素数４〜３２の四価の有機基であり、そしてｎは、１〜１００の整数である。｝
で表される構造を有し、
該ユニット２は、下記一般式（５）：

｛式中、複数存在するＲ₁は、それぞれ独立に、水素原子、炭素数１〜２０の一価の脂肪族炭化水素、又は一価の芳香族基であり、複数存在するＲ₂は、それぞれ独立に、炭素数３〜２０の二価の脂肪族炭化水素、又は二価の芳香族基であり、Ｒ₃及びＲ₄は、それぞれ独立に、炭素数１〜２０の一価の有機基であり、複数存在してもよいＸ₂は、それぞれ独立に、炭素数４〜３２の四価の有機基であり、ｌは、３〜５０の整数であり、そしてｍは、１〜１００の整数である。｝で表される構造、又は、下記一般式（６）：

｛式中、複数存在するＲ₁は、それぞれ独立に、水素原子、炭素数１〜２０の一価の脂肪族炭化水素、又は一価の芳香族基であり、複数存在するＲ₃及びＲ₄は、それぞれ独立に、炭素数１〜２０の一価の有機基であり、複数存在するＲ₈は、それぞれ独立に、炭素数３〜２０の三価の脂肪族炭化水素、又は三価の芳香族基であり、ｐは、１〜１００の整数であり、そしてｑは３〜５０の整数である。｝で表される構造、又は上記一般式（５）で表される構造と上記一般式（６）で表される構造の両者、を有する。 The resin precursor more preferably includes the following units 1 and 2.
Unit 1 has at least the following general formula (4);

In the formula, a plurality of R ₁ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or a monovalent aromatic group, and a plurality of X ₁ may be present. Are each independently a tetravalent organic group having 4 to 32 carbon atoms, and n is an integer of 1 to 100. ｝
Having a structure represented by
The unit 2 has the following general formula (5):

In the formula, a plurality of R ₁ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or a monovalent aromatic group, and a plurality of R ₂ are each independently Independently a divalent aliphatic hydrocarbon having 3 to 20 carbon atoms or a divalent aromatic group, and R ₃ and R ₄ are each independently a monovalent organic group having 1 to 20 carbon atoms. X ₂ , which may be present plurally, is each independently a tetravalent organic group having 4 to 32 carbon atoms, 1 is an integer of 3 to 50, and m is an integer of 1 to 100 It is.構造 or the following general formula (6):

｛In the formula, a plurality of R ₁ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or a monovalent aromatic group, and a plurality of R ₃ and R ₄ Are each independently a monovalent organic group having 1 to 20 carbon atoms, and a plurality of R ₈ are each independently a trivalent aliphatic hydrocarbon having 3 to 20 carbon atoms or a trivalent aromatic group. Group, p is an integer from 1 to 100, and q is an integer from 3 to 50. ｝, Or both the structure represented by the general formula (5) and the structure represented by the general formula (6).

In the general formulas (4) and (6), the diamine-derived site is, for example, a group consisting of 4,4- (diaminodiphenyl) sulfone, 3,4- (diaminodiphenyl) sulfone, and 3,3- (diaminodiphenyl) sulfone. From one or more diamines selected from In the general formulas (4) and (5), the acid anhydride-derived sites are respectively an acid dianhydride having a tetravalent organic group X ₁ (X ₁ is as defined above) and a tetravalent organic group X ₂ (X ₂ is as defined above). The diamine-derived site in the structure represented by the general formula (5) is derived from diamino (poly) siloxane represented by the general formula (9).

Unit 1 and Unit 2 are heat-resistant, from the viewpoint of reduction of YI value and total light transmittance,
A site derived from one or more selected from the group consisting of pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic dianhydride (BPDA);
4,4'-oxydiphthalic dianhydride (ODPA), 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), cyclohexane-1,2,4,5-tetracarboxylic dianhydride ( CHDA), 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4'-biphenylbis (trimellitic acid monoester anhydride) (TAHQ), and 9,9 A site which is a combination with a site derived from one or more selected from the group consisting of '-bis (3,4-dicarboxyphenyl) fluorene dianhydride (BPAF), It is preferably contained in an amount of 60 mol% or more, more preferably 65 mol% or more, and still more preferably 70 mol% or more, based on the total amount of the origin site.

  In the resin precursor according to the present embodiment, the total mass of the units 1 and 2 is 30% by mass or more based on the total mass of the resin precursor, which reduces the YI value and the birefringence. , And Tg, and more preferably 70% by mass or more from the viewpoint of reducing the birefringence. Most preferably, it is 100% by mass.

｛式中、複数存在するＲ₁は、それぞれ独立に、水素原子、炭素数１〜２０の一価の脂肪族炭化水素、又は一価の芳香族基であり、複数存在してもよいＸ₃は、それぞれ独立に、炭素数４〜３２の二価の有機基であり、複数存在してもよいＸ₄は、それぞれ独立に、炭素数４〜３２の四価の有機基であり、そしてｔは１〜１００の整数である。｝で表される構造を有するユニット３を更に含有してもよい。 Further, the resin precursor according to the present embodiment may have the following general formula (7) as needed, as long as the performance is not impaired.

In the formula, a plurality of R ₁ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or a monovalent aromatic group, and a plurality of X ₃ may be present. Are each independently a divalent organic group having 4 to 32 carbon atoms, and a plurality of X _{4 s} which may be present are each independently a tetravalent organic group having 4 to 32 carbon atoms, and t Is an integer of 1 to 100. A unit 3 having a structure represented by｝ may be further included.

  Unit 3 has a structure in which the diamine-derived site is a site derived from a diamine other than a compound selected from the group consisting of 4,4-DAS, 3,4-DAS, 3,3-DAS, and a silicon-containing diamine. It is.

In the unit 3, R ₁ is preferably a hydrogen atom. X ₃ is preferably a divalent aromatic group or an alicyclic group from the viewpoints of heat resistance, reduction of YI value and total light transmittance. X ₄ is preferably a divalent aromatic group or an alicyclic group from the viewpoints of heat resistance, reduction of YI value and total light transmittance. Among them, X ₃ is preferably a residue having a structure obtained by removing an amino group from 2,2′-bis (trifluoromethyl) benzidine. The organic groups X ₁ , X ₂ and X ₄ may be the same or different from each other.

  The mass ratio of the unit 3 in the resin precursor according to the present embodiment is not more than 80% by mass, preferably not more than 70% by mass in the total resin structure, and is dependent on the oxygen dependence of the YI value and the total light transmittance. It is preferable from the viewpoint of reduction.

  The resin precursor according to the present embodiment is obtained by heating and curing the resin precursor at 300 to 500 ° C. under an inert atmosphere (for example, under an atmosphere of nitrogen or argon) or an inert resin. A resin obtained by heating and curing at 350 ° C. in an atmosphere has at least one glass transition temperature in a region of −150 ° C. to 0 ° C. and at least one glass transition temperature in a region of 150 ° C. to 380 ° C .; It is preferable not to have a glass transition temperature in a region larger than 0 ° C. and smaller than 150 ° C. It is preferable that the glass transition temperature exists between the region of −150 ° C. to 0 ° C. and the region of 150 ° C. to 380 ° C. from the viewpoint of improving the balance between the residual stress and the total light transmittance. From the viewpoint of heat resistance, the glass transition temperature in the range of 150 to 380 ° C is more preferably in the range of 200 to 380 ° C, and still more preferably in the range of 250 to 380 ° C. The fact that the resin precursor has blocks 1 and 2 described below is advantageous in forming such a resin precursor.

  The resin precursor according to the present embodiment is preferably composed of a block 1 mainly composed of the unit 1 and a block 2 mainly composed of the unit 2 from the viewpoint of improving heat resistance. Further, the resin precursor may include the unit 3 described above in the block 1. These blocks may be connected alternately or in a permutation in the polymer chain.

  The above-described block 1 contributes to the development of Tg in the range of 150 to 380 ° C in the polyimide obtained by heating and curing the resin precursor of the present embodiment. Therefore, it is preferable that the block 1 is a block consisting only of the repetition of the above-described unit 1. However, it does not exclude the inclusion of the unit 3 other than the unit 1 as long as the target Tg can be expressed.

  Similarly, the above-mentioned block 2 contributes to expressing Tg in the range of −150 to 0 ° C. in the polyimide obtained by heating and curing the resin precursor of the present embodiment. Therefore, it is preferable that the block 2 is a block consisting only of the repetition of the above-described unit 2, but it does not exclude the inclusion of a unit other than the unit 2 as long as the target Tg can be expressed.

  In the resin precursor having block 1 and block 2, the sum of the number of repetitions of units 1 and 3 in block 1 is preferably 2 to 500, more preferably 5 to 300, and most preferably 10 to 200 on average. The number of repetitions of the unit 2 in the block 2 is preferably 1.1 to 300, more preferably 1.1 to 200, and most preferably 1.2 to 100, per molecule. When the sum of the number of repetitions of the units 1 and 3 in the block 1 is 500 or less and the number of repetitions of the unit 2 in the block 2 is 300 or less, the solubility of the resin precursor in the solvent is good, which is preferable.

  The ratio defined by the sum of the number of repetitions of units 1 and 3 in block 1 divided by the number of repetitions of unit 2 in block 2 (hereinafter also referred to as unit ratio) depends on the type and molecular weight of the raw materials used. However, it is preferably 0.5 to 100, and more preferably 10 to 50. As described above, the polyimide which is a cured product of the resin precursor having the blocks 1 and 2 has the glass transition temperature derived from the block 1 in the region A of 150 ° C. to 380 ° C., and the glass derived from the block 2 It may have the advantage that it has a transition temperature in the region B from -150 ° C to 0 ° C, and the region C between the region A and the region B does not have a glass transition temperature. When the value of the unit ratio is 0.5 or more, the heat resistance of the cured polyimide resin is sufficient, which is preferable. When the ratio is 100 or less, the residual stress can be reduced, which is preferable.

  On the other hand, when a high molecular weight silicone compound (specifically, a silicone compound having an average molecular weight of 3000 or more) is used as the silicon group-containing compound in the polymerization component, it can be obtained without forming a block copolymer as described above. Polyimide can develop a low residual stress with the inorganic film while maintaining a high glass transition temperature. This is because, according to the high molecular weight silicone compound, the silicone unit itself has a long-chain siloxane structure and is considered to have the same function as the block structure. Here, when the silicone compound has a high molecular weight, the functional group concentration is reduced, so that even if the number of moles charged is small, the above high glass transition temperature and low residual stress can be exhibited.

  For example, when the high-molecular-weight silicone compound is a diamine, the resin precursor is formed by the combination of a unit 1 of the general formula (4) derived from (diaminodiphenyl) sulfone and a unit 2 of the general formula (5) derived from silicone diamine. A polyimide precursor mixture, ie, a blend, is formed in which there is a single (i.e., unit 2 is not copolymerized) polyimide precursor of unit 1 in addition to the polymer.

  Accordingly, the present disclosure also includes a precursor mixture including the resin precursor of the present embodiment described above and an additional resin precursor (for example, the polyimide precursor of the unit 1 alone). Here, as a specific example of the polyimide precursor of the unit 1 alone, the following general formula (8):

｛式中、複数存在してもよいＸ₃は、それぞれ独立に、炭素数４〜３２の四価の有機基であり、複数存在するＲ₁は、それぞれ独立に、水素原子、炭素数１〜２０の一価の脂肪族炭化水素基、又は一価の芳香族基であり、そしてｒは、１〜１００の整数である。｝で表される構造を有する樹脂前駆体が挙げられる。

{Wherein, optionally X ₃ also there are a plurality, each independently, a tetravalent organic group 4 to 32 carbon atoms, R ₁ existing in plural, each independently, a hydrogen atom, 1 to carbon atoms 20 is a monovalent aliphatic hydrocarbon group or a monovalent aromatic group, and r is an integer of 1 to 100. And a resin precursor having a structure represented by｝.

On the other hand, when the high molecular weight silicone compound is other than a diamine, for example, L ₁ , L ₂ , and L ₃ in the general formula (3) each independently represent an acid anhydride group, a carboxyl group, or an acid ester group. , An acid halide group, a hydroxy group, an epoxy group, or a mercapto group.

  When the polymer component in the resin precursor according to the present embodiment contains a high-molecular-weight silicone compound, the polyimide, which is a cured product of the resin precursor, maintains a high glass transition temperature in the region of 150 ° C to 380 ° C. In addition, the unique characteristic that the residual stress between the inorganic film and the inorganic film can be significantly reduced can be achieved.

  The number average molecular weight of the resin precursor according to the present embodiment is preferably 3,000 to 1,000,000, more preferably 5,000 to 500,000, further preferably 7000 to 300,000, and particularly preferably 10,000 to 250,000. It is preferable that the molecular weight is 3,000 or more from the viewpoint of obtaining good heat resistance and strength (for example, high elongation), and it is preferable that the molecular weight be 1,000,000 or less, from the viewpoint of obtaining good solubility in a solvent, coating and the like. It is preferable from the viewpoint that a desired film thickness can be applied without bleeding during processing. From the viewpoint of obtaining high mechanical elongation, the molecular weight is preferably 50,000 or more. In the present disclosure, the number average molecular weight is a value determined by gel permeation chromatography in terms of standard polystyrene.

  In a preferred embodiment, the resin precursor may be partially imidized.

  The resin precursor of this embodiment has a glass transition temperature on the high temperature side of 150 ° C. to 380 ° C. as heat resistance that can withstand a display manufacturing process including a TFT element device on a colorless and transparent polyimide substrate, and has an inorganic property. It is possible to form a polyimide resin having a residual stress between the film and a film having a thickness of 10 μm and 25 MPa or less. In a more preferred embodiment, the resin precursor can form a polyimide resin having a glass transition temperature of 240 ° C. to 380 ° C. and a residual stress between the inorganic film and the inorganic film of 10 μm and 20 MPa or less. If the polyimide resin has a glass transition temperature between -150 and 0 ° C., since this temperature is below room temperature, it does not affect the heat resistance required in the actual display manufacturing process.

In a preferred embodiment, the resin precursor has the following characteristics.
After a solution obtained by dissolving the resin precursor in a solvent (eg, N-methyl-2-pyrrolidone) is developed on the surface of the support, the solution is heated at 300 to 500 ° C. (eg, 350 ° C.) in a nitrogen atmosphere. (For example, for 1 hour), the resin obtained by imidizing the resin precursor has a yellowness of 7 or less at a thickness of 20 μm.
After a solution obtained by dissolving the resin precursor in a solvent (eg, N-methyl-2-pyrrolidone) is developed on the surface of the support, the solution is heated at 300 to 500 ° C. (eg, 350 ° C.) in a nitrogen atmosphere. (For example, 1 hour), the resin obtained by imidizing the resin precursor has a residual stress of 25 MPa or less at a film thickness of 10 μm.

<Production of resin precursor>
Next, a method for synthesizing the resin precursor according to the present embodiment will be described. For example, when the resin precursor according to the present embodiment is composed of two blocks such as the above-described block 1 and block 2, polyimide precursors corresponding to each block are separately prepared, and thereafter, By mixing them and subjecting them to a condensation reaction, the resin precursor according to the present embodiment can be obtained. Here, so that both blocks can be subjected to the condensation reaction, when the terminal group of the polyimide precursor of one block is a carboxylic acid, the terminal group of the polyimide precursor of the other block is an amino group. For example, the molar ratio of the raw materials, for example, the molar ratio of tetracarboxylic dianhydride and diamine is adjusted. According to this method, a more preferable polyimide precursor having complete blocking properties can be synthesized.

  On the other hand, the tetracarboxylic dianhydride as a polymerization raw material is common between the block 1 and the block 2, and an aromatic diamine is used as a raw material of the block 1, and a highly reactive silicon-containing diamine is used as a raw material of the block 2. When used, a synthesis method utilizing the difference in reactivity between the two diamines may be possible. For example, an aromatic diamine and a silicon-containing diamine are simultaneously added to a tetracarboxylic dianhydride prepared in advance and subjected to a condensation reaction to produce a polyimide precursor having a certain degree of blockability. In this method, a blockable polyimide precursor having complete blockability cannot be synthesized, but a blockable polyimide precursor can be synthesized. Here, having the block property means that a glass transition temperature corresponding to each block is observed in the polyimide resin after heat curing. For example, the polyimide resin has 4,4 in each of the above-described regions A and B. Block 1 derived from a polycondensate of one or more selected from the group consisting of-(diaminodiphenyl) sulfone, 3,4- (diaminodiphenyl) sulfone, and 3,3- (diaminodiphenyl) sulfone and tetracarboxylic anhydride And the glass transition temperature of the block 2 derived from the polycondensate of the silicon-containing diamine and the tetracarboxylic anhydride.

  As described above, in the resin precursor according to the present embodiment, the polyimide resin obtained by heating and curing the resin precursor has glass transition temperatures in the high-temperature region A and the low-temperature region B, respectively. It is advantageous to have a certain degree of blocking, but this advantage can be obtained even if the polyimide resin does not have complete blocking. The above-mentioned advantage of the resin precursor having the blocks 1 and 2 is that if a glass transition temperature is not observed in the region C between the region A and the region B, a unit other than the blocks 1 and 2 is contained. It is possible to get it even if you do.

  Further, by adding N, N-dimethylformamide dimethyl acetal or N, N-dimethylformamide diethyl acetal to the above-mentioned polyamic acid and heating, a part or all of the carboxylic acid is esterified, The viscosity stability of the solution containing the resin precursor and the solvent when stored at room temperature can also be improved. These ester-modified polyamic acids are prepared by reacting the above-mentioned tetracarboxylic anhydride with one equivalent of a monohydric alcohol based on an acid anhydride group in advance, and then reacting with a dehydrating condensing agent such as thionyl chloride or dicyclohexylcarbodiimide. After the reaction, it can also be obtained by a condensation reaction with a diamine.

<Resin composition>
Another embodiment of the present invention provides a resin composition containing the above-described resin precursor or precursor mixture, and a solvent. The resin composition is typically a varnish.

  As a more preferred embodiment, the resin composition is prepared by dissolving a carboxylic acid component and a diamine component in a solvent, for example, an organic solvent, and reacting the solution to obtain a polyamic acid solution containing a polyamic acid which is one embodiment of a resin precursor and a solvent. Can be manufactured. Here, the conditions during the reaction are not particularly limited. For example, the reaction temperature is −20 to 150 ° C., and the reaction time is 2 to 48 hours. In order to sufficiently promote the reaction of the silicon group-containing compound, heating at 120 ° C. for about 30 minutes is preferable. During the reaction, it is preferable to use an inert atmosphere such as argon or nitrogen.

  The solvent is not particularly limited as long as the solvent dissolves the polyamic acid. Known reaction solvents include dimethylene glycol dimethyl ether (DMDG), m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), acetone, diethyl One or more polar solvents selected from acetate, equamid M100 (trade name: manufactured by Idemitsu Kosan Co., Ltd.) and equamid B100 (trade name: manufactured by Idemitsu Kosan Co., Ltd.) are useful. Of these, NMP, DMAc, equamid M100 and equamid B100 are preferred. In addition, a low-boiling solution such as tetrahydrofuran (THF) or chloroform, or a low-absorbing solvent such as γ-butyrolactone may be used.

  Further, in the resin composition of the present invention, when the obtained polyimide forms an element such as a TFT, the alkoxysilane compound is used with respect to 100% by mass of the resin precursor in order to give sufficient adhesion to a support. Is preferably a composition containing from 0.01 to 2% by mass.

  When the content of the alkoxysilane compound is 0.01% by mass or more based on 100% by mass of the resin precursor, good adhesion to the support can be obtained, and the content of the alkoxysilane compound can be reduced. It is preferable that the content is 2% by mass or less from the viewpoint of storage stability of the resin composition. The content of the alkoxysilane compound is more preferably from 0.02 to 2% by mass, still more preferably from 0.05 to 1% by mass, and more preferably from 0.05 to 0.5% by mass, based on the resin precursor. %, More preferably 0.1 to 0.5% by mass.

  Examples of the alkoxysilane compound include 3-ureidopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, phenyltrimethoxysilane, and γ-aminopropyltriethoxysilane. Ethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltripropoxysilane, γ-aminopropyltributoxysilane, γ-aminoethyltriethoxysilane, γ-aminoethyltrimethoxysilane, γ-aminoethyltripropoxysilane , Γ-aminoethyltributoxysilane, γ-aminobutyltriethoxysilane, γ-aminobutyltrimethoxysilane, γ-aminobutyltripropoxysilane, γ-aminobutyltributoxysilane, and the like. These may be used in combination of two or more.

  After preparing the varnish described above, the solution may be heated at 130 to 200 ° C. for 5 minutes to 2 hours to partially dehydrate and imidize the polymer to such an extent that the polymer does not precipitate. By controlling the temperature and time, the imidization ratio can be controlled. By performing partial imidization, the viscosity stability of the resin precursor solution during storage at room temperature can be improved. As the range of the imidation ratio, 5% to 70% is preferable from the viewpoint of the solubility of the resin precursor in the solution and the storage stability of the solution.

In a preferred embodiment, the resin composition has the following characteristics.
After the resin composition is spread on the surface of the support, the resin composition is included in the resin composition by heating at 300 ° C. to 500 ° C. under a nitrogen atmosphere (or by heating at 350 ° C. under a nitrogen atmosphere). The resin obtained by imidizing the resin precursor has a yellowness of 7 or less at a film thickness of 20 μm.
After the resin composition is spread on the surface of the support, the resin composition is included in the resin composition by heating at 300 ° C. to 500 ° C. under a nitrogen atmosphere (or by heating at 350 ° C. under a nitrogen atmosphere). Residual stress at a film thickness of 10 μm of a resin obtained by imidizing a resin precursor is 25 MPa or less.

<Resin film>
Another embodiment of the present invention provides a resin film that is a cured product of the above-described resin precursor, a cured product of the above-described precursor mixture, or a cured product of the above-described resin composition.
Further, another aspect of the present invention is a step of developing the resin composition on the surface of the support,
Heating the support and the resin composition to imidize the resin precursor contained in the resin composition to form a resin film,
Peeling the resin film from the support,
And a method for producing a resin film.

  In a preferred embodiment of the method for producing a resin film, a polyamic acid solution obtained by dissolving and reacting an acid dianhydride component and a diamine component in an organic solvent can be used as the resin composition.

  Here, the support is an inorganic substrate such as a glass substrate such as a non-alkali glass substrate, but is not particularly limited.

  More specifically, the resin composition described above is spread and dried on an adhesive layer formed on the main surface of the inorganic substrate, and cured at a temperature of 300 to 500 ° C. under an inert atmosphere to obtain a resin. A film can be formed. Finally, the resin film is peeled from the support.

  Here, examples of the spreading method include known coating methods such as spin coating, slit coating, and blade coating. After the polyamic acid solution is spread on the adhesive layer, the heat treatment is performed at a temperature of 300 ° C. or less for 1 minute to 300 minutes mainly for the purpose of removing the solvent, and further, at 300 ° C. to 550 in an inert atmosphere such as nitrogen. A heat treatment is performed at a temperature of 1 ° C. for 1 minute to 300 minutes to polyimide the resin precursor. When producing a conventional colorless and transparent polyimide film, it is necessary to control the oxygen concentration in the oven to 100 ppm or less from the viewpoint of reducing the YI value and the total light transmittance. According to the body, management of 500 ppm or less is sufficient. From the viewpoint of reducing the YI value and improving the total light transmittance, the oxygen concentration is desirably 1000 ppm or less.

  Further, the thickness of the resin film according to the present embodiment is not particularly limited, and is preferably in the range of 10 to 200 μm, and more preferably 10 to 50 μm.

  The resin film according to the present embodiment preferably has a yellowness of 7 or less at a thickness of 20 μm. Further, it is preferable that the residual stress is 25 MPa or less at a film thickness of 10 μm. In particular, it is more preferable that the yellowness at a film thickness of 20 μm is 7 or less and the residual stress at a film thickness of 10 μm is 25 MPa or less. Such characteristics can be favorably realized, for example, by imidizing the resin precursor of the present disclosure at 300 ° C. to 500 ° C., more particularly 350 ° C. in a nitrogen atmosphere.

<Laminate>
Another embodiment of the present invention provides a laminate including a support and a resin film formed on the surface of the support, which is a cured product of the above-described resin composition.
Further, another aspect of the present invention, a step of spreading the resin composition on the surface of the support,
Heating the support and the resin composition to imidize the resin precursor contained in the resin composition to form a resin film, thereby obtaining a laminate including the support and the resin film; and ,
And a method for producing a laminate.
Such a laminate can be manufactured, for example, by not peeling a resin film formed in the same manner as the above-described method for manufacturing a resin film from a support.

This laminate is used, for example, for manufacturing a flexible device. More specifically, a semiconductor device is formed on a polyimide film, and then the support is peeled off to obtain a flexible device including a flexible transparent substrate made of the polyimide film.
Accordingly, another aspect of the present invention provides a flexible device material comprising the aforementioned resin precursor, or the aforementioned precursor mixture.

  As described above, the resin precursor according to the present embodiment has a specific structure, so that a resin film that does not become cloudy can be formed without requiring a special combination of solvents. Further, the yellowness (YI value) and the total light transmittance of the obtained resin film hardly depend on the oxygen concentration at the time of curing. In addition, the residual stress generated between the resin film and the inorganic film is low, has a practical glass transition temperature that can withstand the TFT manufacturing process, has excellent mechanical properties, and has chemical resistance that can withstand the photolithography process. . Therefore, the resin precursor is suitable for use in a transparent substrate of a flexible display.

  More specifically, when a flexible display is formed, a flexible substrate is formed thereon using a glass substrate as a support, and a TFT or the like is formed thereon. The process of forming a TFT on a substrate is typically performed at a wide range of temperatures of 150 to 650 ° C., but for actual desired performance, mainly a temperature of about 250 to 350 ° C. Then, a TFT-IGZO (InGaZnO) oxide semiconductor or a TFT (a-Si-TFT, poly-Si-TFT) is formed using an inorganic material.

  At this time, if the residual stress generated in the flexible substrate and the polyimide film is high, the glass substrate expands in a high-temperature TFT process and then contracts when cooled at room temperature, causing warpage or breakage of the glass substrate, peeling of the flexible substrate from the glass substrate, or the like. Problems arise. Generally, since a glass substrate has a smaller coefficient of thermal expansion than a resin, a residual stress is generated between the glass substrate and the flexible substrate. In consideration of this point, the resin film according to the present embodiment preferably has a residual stress generated between the resin film and the glass of 25 MPa or less based on the thickness of the film of 10 μm.

  In addition, the resin film according to the present embodiment had a yellowness of 7 or less based on the film thickness of 20 μm, and the transmittance was measured with an ultraviolet spectrophotometer based on the film thickness of 20 μm. In this case, the transmittance at 550 nm is preferably 85% or more. In addition, it is advantageous to obtain a resin film having a low YI value stably when the oxygen concentration in the oven used for producing the thermosetting film is small, and the thermosetting film is hardened at an oxygen concentration of 500 ppm or less. It is preferable that the YI value of the film is stable.

  In addition, the resin film according to the present embodiment has a mechanical elongation of 30% or more based on a film thickness of 20 μm from the viewpoint of improving the yield by improving the breaking strength when handling a flexible substrate and improving the yield. Is more preferable.

  The glass transition temperature of the resin film according to the present embodiment is preferably 250 ° C. or higher so that the resin substrate does not soften at the temperature at which the TFT element is manufactured.

  In addition, the resin film according to this embodiment preferably has chemical resistance enough to withstand a photoresist stripping solution in a photolithography step used for manufacturing a TFT element.

  There are two types of light extraction methods for a flexible display, a top emission method for extracting light from the front side of the TFT element and a bottom emission method for extracting light from the back side. The top emission method has a feature that the aperture ratio is easily increased because the TFT element does not interfere, and the bottom emission method has a feature that alignment is easy and manufacturing is easy. If the TFT element is transparent, it is possible to improve the aperture ratio even in the bottom emission method, so it is expected that the bottom emission method that is easy to manufacture will be adopted for large organic EL flexible displays. I have. When a resin substrate is used as the colorless transparent resin substrate used for the bottom emission method, the resin substrate comes to the viewer's side, so that optical isotropicity, that is, retardation in the thickness direction derived from the birefringence (Rth ) Is required from the viewpoint of improving image quality. Further, when used in the top emission method, it is not required that the Rth is low, but from the viewpoint that it can be commonly used for both methods, it is considered that a material having a low Rth is preferable. Specifically, the thickness is preferably 200 nm or less, more preferably 90 nm or less, still more preferably 80 nm or less, and particularly preferably 50 nm or less, based on the film thickness of 20 μm. If Rth is 100 nm or less, and even 90 nm or less, it satisfies the performance to be applied to not only the top emission type flexible display transparent substrate but also the bottom emission type flexible display transparent substrate and the touch panel electrode substrate. ing.

Another embodiment of the present invention provides a polyimide resin film used for manufacturing a display substrate, wherein the Rth at a thickness of 20 μm is 20 to 90 nm.
Further, another embodiment of the present invention, a step of developing a resin composition containing a polyimide precursor on the surface of the support,
Heating the support and the resin composition to imidize the polyimide precursor to form the polyimide resin film,
Forming an element on the polyimide resin film,
Stripping the polyimide resin film on which the element is formed from the support.

  The resin film according to the present embodiment that satisfies the above-mentioned physical properties is suitably used for applications whose use is limited by the yellow color of existing polyimide films, particularly as a colorless transparent substrate for flexible displays. Further, for example, a light-scattering sheet and a coating film (for example, an interlayer of a TFT-LCD, a gate insulating film, and a liquid crystal alignment film) on a protective film or a TFT-LCD, an ITO substrate for a touch panel, and a cover glass substitute resin for a smartphone. It can also be used in fields where colorless transparency and low birefringence are required, such as substrates. When the polyimide according to the present embodiment is applied as a liquid crystal alignment film, it contributes to an increase in aperture ratio, and a TFT-LCD with a high contrast ratio can be manufactured.

  The resin film and the laminate manufactured using the resin precursor according to the present embodiment are, for example, preferably used as a substrate for manufacturing a semiconductor insulating film, a TFT-LCD insulating film, an electrode protection film, and a flexible device. Can be used for Here, the flexible device includes, for example, a flexible display, a flexible solar cell, a flexible touch panel electrode substrate, a flexible illumination, and a flexible battery.

Hereinafter, the present invention will be described in more detail with reference to Examples, but these are described for explanation, and the scope of the present invention is not limited to the following Examples.
Various evaluations in Examples and Comparative Examples were performed as follows.

(Measurement of weight average molecular weight)
The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) under the following conditions. As a solvent, N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatography) was used, and 24.8 mmol / L lithium bromide monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) before measurement. , Purity 99.5%) and 63.2 mmol / L phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd., for high-performance liquid chromatography). The calibration curve for calculating the weight average molecular weight was created using standard polystyrene (manufactured by Tosoh Corporation).

Column: Shodex KD-806M (Showa Denko KK)
Flow rate: 1.0 mL / min Column temperature: 40 ° C
Pump: PU-2080Plus (manufactured by JASCO)
Detector: RI-2031Plus (RI: differential refractometer, manufactured by JASCO)
UV-2075Plus (UV-VIS: UV-visible absorption spectrometer, manufactured by JASCO)

(Silicon group-containing monomer concentration)
The silicon group-containing monomer concentration was calculated from the following formula using the masses of the silicon group-containing monomer, the polyvalent carboxylic acid or its derivative, and the diamine compound used when synthesizing the resin precursor.
Silicon group-containing monomer concentration (%) = mass of silicon group-containing monomer /
(Mass of silicon group-containing monomer + mass of polycarboxylic acid or derivative thereof + mass of diamine compound) x 100

(Preparation of laminate and isolated film)
The resin composition is applied to a non-alkali glass substrate (thickness 0.7 mm) with a bar coater, leveled at room temperature for 5 minutes to 10 minutes, and a vertical cure oven (manufactured by Koyo Lindberg Co., model name VF-2000B) And heated at 350 ° C. for 60 minutes under a nitrogen atmosphere to produce a laminate. At this time, the oxygen concentration in the hot air oven was adjusted to 50 ppm, 100 ppm, and 500 ppm, respectively, and the oxygen concentration dependence of the YI value and the total light transmittance was examined. The thickness of the resin composition of the laminate was 20 μm. After curing (hardening treatment) at 350 ° C., the laminate was allowed to stand at room temperature for 24 hours, the resin film was peeled off from the glass, and the film was isolated. Evaluations other than the following yellowness and total light transmittance were performed by adjusting the oxygen concentration in a hot-air oven to 100 ppm and curing the resin film at 350 ° C. for 60 minutes as a sample.

(Evaluation of tensile elongation)
A resin film cured at 350 ° C. and having a sample length of 5 × 50 mm and a thickness of 20 μm was pulled at a speed of 100 mm / min using a tensile tester (RTG-1210 manufactured by A & D Corporation), and the tensile elongation was measured. .

(Yellowness, total light transmittance and its oxygen concentration dependence during curing)
The oxygen concentration in the oven was adjusted to 50 ppm, 100 ppm, and 500 ppm, respectively, and the resin film cured at 350 ° C. and having a thickness of 20 μm was manufactured by Nippon Denshoku Industries Co., Ltd. (Spectrophotometer: SE600) using a D65 light source. Yellowness (YI value) and total light transmittance were measured.

(Evaluation of thickness direction retardation (Rth))
The resin film cured at 350 ° C. and having a thickness of 20 μm was measured using a retardation birefringence measurement device (KOBRA-WR, manufactured by Oji Scientific Instruments). The wavelength of the measurement light was 589 nm.

(Evaluation of glass transition temperature and coefficient of linear expansion)
Regarding the measurement of the glass transition temperature (referred to as Tg (1)) and the linear expansion coefficient (CTE) in the room temperature region or higher, a resin film having a sample length of 5 × 50 mm and a thickness of 20 μm cured at 350 ° C. was manufactured by Shimadzu Corporation. Using a mechanical analyzer (TMA-50), a thermomechanical analysis was performed to determine the elongation of the test piece at a load of 5 g, a heating rate of 10 ° C./min, under a nitrogen atmosphere (flow rate 20 ml / min), and a temperature of 50 to 450 ° C. The measurement was performed, the inflection point was determined as the glass transition temperature, and the CTE of the heat-resistant resin film at 100 to 250 ° C was determined.

  Since it is impossible to measure the glass transition temperature (referred to as Tg (2)) below the room temperature region by the above-described method, the above resin film is subjected to a dynamic viscoelasticity measuring device (−150 ° C. to 400 ° C.) The inflection point of the E prime in a temperature range of room temperature or lower was measured by RHEOVIBRON MODEL RHEO-1021 manufactured by Orientec Co., Ltd., and the inflection point was determined as a glass transition temperature at a low temperature.

(Evaluation of residual stress)
Using a residual stress measuring device (manufactured by Tencor, model name FLX-2320), the resin composition was measured with a bar coater on a 6-inch silicon wafer having a thickness of 625 μm ± 25 μm in which the “warpage amount” was measured in advance. After applying and pre-baking at 140 ° C. for 60 minutes, heat curing treatment was performed at 350 ° C. for 1 hour under a nitrogen atmosphere using a vertical curing furnace (manufactured by Koyo Lindberg Co., model name: VF-2000B). A silicon wafer having a 10 μm-thick resin film was prepared. The amount of warpage of the wafer was measured using the above-described residual stress measuring device, and the residual stress generated between the silicon wafer and the resin film was evaluated.

(Evaluation of chemical resistance test)
A 20 μm-thick resin film piece cured at 350 ° C. was immersed in an NMP layer at room temperature, pulled up every 10 minutes, washed with ion-exchanged water, observed with a microscope, and cracked on the surface of the thermosetting film. The entry time was evaluated every 10 minutes up to 300 minutes.

[Example 1]
While introducing nitrogen gas, 1000 g of NMP was added to a 3 L separable flask with a stirring rod equipped with an oil bath, and 232.4 g of 3,3- (diaminodiphenyl) sulfone (defined as diamine 1) was added with stirring, Subsequently, 218.12 g of pyromellitic dianhydride (defined as tetracarboxylic anhydride 1) was added, and the mixture was stirred at room temperature for 30 minutes. This was heated to 50 ° C., stirred for 12 hours, and then amine-terminated methylphenylsilicone oil at both ends (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) (defined as a silicon-containing diamine). 105.6 g was dissolved in 298 g of NMP and added dropwise using a dropping funnel. After heating to 80 ° C. and stirring for 1 hour, the oil bath was removed and the temperature was returned to room temperature to obtain a transparent NMP solution of polyamic acid (hereinafter also referred to as varnish). Table 1 shows the composition and the weight average molecular weight (Mw) of the obtained polyamic acid. Table 4 shows the test results of the film cured at 350 ° C.

[Examples 2-33, 49-58]
In the same manner as in Example 1, the same operation as in Example 1 was performed, except that the types of diamine 1, tetracarboxylic anhydride 1, and silicon-containing diamine, and the added mass thereof were changed to those shown in Table 1, respectively. I went and got a varnish. Further, the amount of NMP added shown in Tables 1 and 2 indicates the total amount of NMP finally contained in the varnish, and is a mass containing 298 g of NMP for diluting the silicon group-containing diamine. The composition and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Tables 1, 2 and 7, respectively. The test results of the film cured at 350 ° C. are shown in Tables 4, 5, and 8, respectively. The formal compound names of the abbreviated compound names described in Tables 1 to 6 are described below.
3,3-DAS: 3,3- (diaminodiphenyl) sulfone 4,4-DAS: 4,4- (diaminodiphenyl) sulfone 3,4-DAS: 3,4- (diaminodiphenyl) sulfone PMDA: pyromellitic acid Dianhydride ODPA: 4,4'-oxydiphthalic dianhydride 6FDA: 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride BPDA: 3,3', 4,4'-biphenyltetracarboxylic dianhydride CHDA: cyclohexane-1,2,4,5-tetracarboxylic dianhydride DSDA: 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride BPADA: 2,2-bis [4- ( 3,4-Dicarboxyphenoxy) phenyl] propane dianhydride BPAF: 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride Things TAHQ: 4,4'- biphenyl-bis (trimellitic acid monoester acid anhydride)
BTDA: 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride TPE-R: 1,3-bis (4-aminophenoxy) benzene CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride Anhydride FM3311: Amine-modified dimethyl silicone oil at both ends (Silaplane FM3311 (number average molecular weight 1000, manufactured by Chisso))
TFMB: 2,2'-bis (trifluoromethyl) benzidine TACl: trimellitic anhydride chloride

[Example 34]
Nitrogen gas was introduced into a 3 L separable flask equipped with an oil bath and equipped with a stirring rod, 1274 g of NMP was added, and 4,4′-oxydiphthalic dianhydride (hereinafter referred to as ODPA) (defined as tetracarboxylic anhydride 1) Is added, and while stirring, 105.6 g of an amino-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight: 4400)) (defined as a silicon-containing diamine) is dissolved in 298 g of NMP. This was dropped using a dropping funnel. After stirring at room temperature for 1 hour, 149.9 g of 2,2′-bis (trifluoromethyl) benzidine (hereinafter referred to as TFMB) (defined as diamine 2) is added with stirring, and 3,3-DAS is subsequently added. 116.2 g was added with stirring, and the mixture was stirred at room temperature for 1 hour. Subsequently, the mixture was heated to 50 ° C., 147.1 g of BPDA (defined as tetracarboxylic anhydride 2) was added, and the mixture was stirred for 12 hours. After the temperature was raised to 80 ° C. and stirred for 4 hours, the oil bath was removed and the temperature was returned to room temperature to obtain a transparent NMP solution of polyamic acid (hereinafter also referred to as varnish). Table 2 shows the composition and the weight average molecular weight (Mw) of the obtained polyamic acid. Table 5 shows the test results of the film cured at 350 ° C.

[Examples 35, 39, 40, 44, 45]
Example 34 In the same manner as in Example 34, the types of diamine 1, diamine 2, tetracarboxylic anhydride 1, and tetracarboxylic anhydride 2 and the added mass thereof were changed to those shown in Table 2, respectively. A varnish was obtained by performing the same operation as described above. The amount of NMP added shown in Table 2 indicates the total amount of NMP finally contained in the varnish, and is a mass containing 298 g of NMP for diluting the silicon group-containing diamine. Table 2 shows the composition and the weight average molecular weight (Mw) of the obtained polyamic acid. Table 5 shows the test results of the films cured at 350 ° C.

[Example 36]
While introducing nitrogen gas, 1196 g of N-methylpyrrolidone (hereinafter referred to as NMP) was added to a 3 L separable flask equipped with a stir bar equipped with an oil bath, and 3,3- (diaminodiphenyl) sulfone (defined as diamine 1). Was added while stirring and heated to 50 ° C., and 147.1 g of BPDA (defined as tetracarboxylic anhydride 1) was added, followed by stirring for 30 minutes. Subsequently, 155.1 g of ODPA (defined as tetracarboxylic anhydride 2) was added, and the mixture was stirred for 8 hours, and then amine-modified methylphenylsilicone oil at both ends (Shin-Etsu Chemical: X22-1660B-3 (number average molecular weight 4400) )) 105.6 g (defined as silicon-containing diamine) was dissolved in 298 g of NMP and added dropwise using a dropping funnel. After heating to 80 ° C. and stirring for 1 hour, the oil bath was removed and the temperature was returned to room temperature to obtain a transparent NMP solution of polyamic acid (hereinafter also referred to as varnish). Table 2 shows the composition and the weight average molecular weight (Mw) of the obtained polyamic acid. Table 5 shows the test results of the film cured at 350 ° C.

[Examples 37, 42, 43, 46, 47]
In the same manner as in Example 36, the types of diamine 1, tetracarboxylic anhydride 1, and tetracarboxylic anhydride 2 and the added mass thereof were changed to those shown in Table 2, and the same as in Example 36 was performed. The operation was performed to obtain a varnish. The amount of NMP added shown in Table 2 indicates the total amount of NMP finally contained in the varnish, and is a mass containing 298 g of NMP for diluting the silicon group-containing diamine. Table 2 shows the composition and the weight average molecular weight (Mw) of the obtained polyamic acid. Table 5 shows the test results of the films cured at 350 ° C.

[Example 38]
While introducing nitrogen gas, 1200 g of NMP was added to a 3 L separable flask with a stirring rod equipped with an oil bath, and 232.4 g of 3,3- (diaminodiphenyl) sulfone (defined as diamine 1) was added with stirring, After heating to 50 ° C., 40.6 g of terephthalic acid chloride (defined as other monomer component) was dissolved in 200 g of γ-butyrolactone, added dropwise, and stirred for 30 minutes. Subsequently, 235.4 g of BPDA (defined as tetracarboxylic anhydride 1) was added, and the mixture was stirred for 8 hours. Then, both ends amine-modified methylphenylsilicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400) )) 105.6 g (defined as silicon-containing diamine) was dissolved in 298 g of NMP and added dropwise using a dropping funnel. After heating to 80 ° C. and stirring for 1 hour, the oil bath was removed and the temperature was returned to room temperature to obtain a transparent polyamic acid solution. After adding 1000 g of NMP and diluting the mixture, the mixture was added dropwise to 10 L of ion-exchanged water while depositing the powder of the polyamideimide precursor, and the powder was filtered off with a Buchner funnel. The powder was vacuum dried at 40 ° C. for 48 hours. 1403 g of NMP was added to the powder thus obtained to obtain an NMP solution of a polyamideimide precursor. Table 2 shows the composition and the weight average molecular weight (Mw) of the obtained polyamideimide precursor. Table 5 shows the test results of the film cured at 350 ° C.

[Examples 43 and 48]
In the same manner as in Example 38, the same operation as in Example 38 was performed, except that the types of diamine 1, tetracarboxylic anhydride 1, and other monomer components, and the added mass thereof were changed to those shown in Table 2, respectively. I got a varnish. The NMP addition amount shown in Table 2 indicates the total amount of NMP finally contained in the varnish. Table 2 shows the composition and the weight average molecular weight (Mw) of the obtained polyamideimide precursor. Table 5 shows the test results of the films cured at 350 ° C.

[Example 59]
To a 3 L separable flask with a stir bar equipped with an oil bath, while introducing nitrogen gas, 1000 g of NMP was added, and 248.30 g of 3,3- (diaminodiphenyl) sulfone (defined as diamine 1) was added with stirring. Subsequently, 275.13 g of BPDA (defined as tetracarboxylic anhydride 1) was added, and the mixture was stirred at room temperature for 30 minutes. This was heated to 50 ° C. and stirred for 12 hours, and then 104.58 g of an acid anhydride-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-168-P5-B (number average molecular weight 4200)) was NMP298 g. And added dropwise using a dropping funnel. After heating to 80 ° C. and stirring for 1 hour, the oil bath was removed and the temperature was returned to room temperature to obtain a transparent NMP solution of polyamic acid (hereinafter also referred to as varnish). Table 7 shows the composition and the weight average molecular weight (Mw) of the obtained polyamic acid. Table 8 shows the test results of the film cured at 350 ° C.

[Examples 60 to 66]
In the same manner as in Example 59, the same operation as in Example 1 was performed, except that the types of the diamine 1, the tetracarboxylic anhydride 1, and the silicon-containing diamine, and the added mass thereof were changed to those shown in Table 1, respectively. I went and got a varnish. Further, the amount of NMP added shown in Tables 1 and 2 indicates the total amount of NMP finally contained in the varnish, and is a mass containing 298 g of NMP for diluting the silicon group-containing diamine. Table 7 shows the composition and the weight average molecular weight (Mw) of the obtained polyamic acid. Table 8 shows the test results of the films cured at 350 ° C.

[Comparative Example 1]
To a 3 L separable flask equipped with a stirring rod equipped with an oil bath, while introducing nitrogen gas, 1065 g of NMP was added, and 248.3 g of 3,3- (diaminodiphenyl) sulfone (defined as diamine 1) was added with stirring. Subsequently, 218.12 g of pyromellitic dianhydride (defined as tetracarboxylic anhydride 1) was added, and the mixture was stirred at room temperature for 30 minutes. After the temperature was raised to 50 ° C. and stirred for 12 hours, the oil bath was removed and the temperature was returned to room temperature to obtain a transparent NMP solution of polyamic acid (hereinafter also referred to as varnish). Table 3 shows the composition and the weight average molecular weight (Mw) of the obtained polyamic acid. Table 6 shows the test results of the film cured at 350 ° C.

[Comparative Examples 2 to 21]
In the same manner as in Comparative Example 1, the varnish was obtained by performing the same operation as in Comparative Example 1 by changing the types of diamine 1 and tetracarboxylic anhydride 1 and the added mass thereof to those shown in Table 3, respectively. Was. Table 3 shows the composition and the weight average molecular weight (Mw) of the obtained polyamic acid. Table 6 shows the test results of the films cured at 350 ° C.

[Comparative Example 22]
Nitrogen gas was introduced into a 3 L separable flask equipped with a stir bar equipped with an oil bath, 1332 g of NMP was added, 299.8 g of TFMB (defined as diamine 2) was added with stirring, and 294.2 g of BPDA (tetracarboxylic anhydride) was added. 1), heated to 50 ° C. and stirred for 12 hours. A dropping funnel was prepared by dissolving 105.6 g of NMP-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight: 4400)) (defined as a silicon-containing diamine) in 298 g of NMP. Was added dropwise. After the completion of the dropwise addition, the temperature was raised to 80 ° C., and the mixture was stirred for 1 hour. Then, the oil bath was removed and the temperature was returned to room temperature to obtain a slightly turbid NMP solution of opaque polyamic acid (hereinafter also referred to as varnish). Table 3 shows the composition and the weight average molecular weight (Mw) of the obtained polyamic acid. Table 6 shows the test results of the film cured at 350 ° C.

[Comparative Example 23]
4.36 g (0.02 mol) of pyromellitic anhydride (PMDA) and 25.78 g of BTDA are dispersed in 240 g of N-methyl-2-pyrrolidone (NMP), and ω-ω'-bis- (3-aminopropyl) polydimethyl is dispersed. A solution obtained by dissolving 2.4 g of siloxane (average molecular weight: 480) in 50 g of diethylene glycol dimethyl ether (Dig) was added dropwise little by little, and the mixture was stirred and reacted for 1 hour. After reacting the diaminosiloxane and the tetracarboxylic dianhydride in this way, 14.62 g (0.05 mol) of 1,3-bis (4-aminophenoxy) benzene (TPE-R), and then further 3,3DAS11. 17 g were added little by little as a powder.

[Comparative Example 24]
A 1-liter flask equipped with a stirrer, a dropping funnel, a thermometer, a condenser, and a nitrogen purge device was fixed in cold water. After the atmosphere in the flask was replaced with nitrogen gas, 500 g of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) dehydrated and purified, and 3,3′4,4′-benzophenonetetracarboxylic dianhydride (BTDA) 25.11 g (0.0779 mol), 15.48 g (0.0623 mol) of 3,3′-diaminodiphenyl sulfone (3,3-DAS) and ω-ω′-bis- (3-aminopropyl) poly 14.96 g (0.0159 mol) of dimethylsiloxane (molecular weight: 960) was mixed to obtain a polyamic acid solution according to a conventional method.

[Comparative Example 25]
In a 300 mL four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, and cooling tube, 2.87 g (25.1 mmol) of 1,4-diaminocyclohexane as a diamine compound and amino-modified methylphenyl silicone at both ends (X22-1660B). -3) 3.42 g (0.8 mmol) were added. Next, after the inside of the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide was added and the mixture was stirred until it became uniform. 8.71 g (25.9 mmol) of diphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride (BPDA) as a polyvalent carboxylic acid derivative was added to the obtained solution at room temperature, and 24 hours at the same temperature. Stirring was continued for a time to obtain a composition (polyamic acid solution).

[Comparative Example 26]
As a component (B), 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl (hereinafter “TFMB”) is placed in a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube. 7.85 g (24.5 mmol) and 2.03 g (1.6 mmol) of amino-modified methyl phenyl silicone (X22-9409) at both ends were added. Next, after the inside of the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide was added and the mixture was stirred until it became uniform. 5.12 g (26.1 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (hereinafter also referred to as “CBDA”) as a component (A) is added to the obtained solution at room temperature, and the temperature is maintained as it is. For 24 hours to obtain a composition (polyamic acid solution).

  The YI values and total light transmittance shown in Tables 4 to 6 and Table 8 show the results (50 ppm / 100 ppm / 500 ppm) when the oxygen concentration in the oven was adjusted to 50 ppm, 100 ppm, and 500 ppm, respectively. .

  As shown in Tables 4, 5, and 8, it was confirmed that Examples 1 to 66 simultaneously satisfied the following conditions in film physical properties.

(1) Residual stress is 25 MPa or less. (2) Yellowness is 7 or less, little affected by oxygen concentration. (3) Glass transition temperature is 250 ° C or more in a temperature range of room temperature or more. (4) Total light transmittance is (5) Tensile elongation of 30% or more (6) NMP chemical resistance test of 30 minutes or more (7) Even if a varnish is made with NMP alone, the thermosetting film becomes cloudy High total light transmittance

  These satisfies the performance to be applied to a transparent substrate for a top emission type flexible display.

  In Examples 1 to 33, 36, 37, 41, 42, 46, 47, and 53 to 66, the retardation Rth in the film thickness direction derived from birefringence is 100 nm or less (20 to 90 nm), and the top emission type It satisfies the performance to be applied not only to transparent substrates for flexible displays, but also to bottom emission type transparent substrates for flexible displays and electrode substrates for touch panels. Further, the retardation Rth in the thickness direction is, as a copolymerization monomer, a polyimide not using a silicon group-containing monomer (Comparative Examples 1 to 22) and a polyimide using a silicon group-containing monomer (Examples 1 to 33). By comparison, it can be seen that the polyimide using the silicon group-containing monomer has a smaller Rth, and the silicon group-containing monomer contributes to the reduction of Rth of the polyimide.

  On the other hand, in Comparative Examples 1 to 26, the residual stress, the chemical resistance, and the tensile elongation are low, and the YI value and the total light transmittance are deteriorated by being affected by the oxygen concentration at the time of curing.

  From these results, the resin obtained from the resin precursor according to the present invention is colorless and transparent, has low residual stress generated between the resin and the inorganic film, is further excellent in chemical resistance, and has a YI value based on the oxygen concentration during curing. It was confirmed that the resin film had a small effect on the value and the total light transmittance.

  The present invention is not limited to the above embodiment, and can be implemented with various modifications.

  INDUSTRIAL APPLICABILITY The present invention can be suitably used, for example, as a substrate for a semiconductor insulating film, a TFT-LCD insulating film, an electrode protective film, a flexible display, a substrate for a touch panel ITO electrode, and the like.

Claims (24)

A polyimide resin precursor obtained by polymerizing a polymerization component containing an amino group and an amino group reactive group,
The polymerization component contains a polyvalent compound having two or more groups selected from an amino group and an amino group reactive group,
The polyvalent compound contains a silicon group-containing compound,
The polyvalent compound is pyromellitic dianhydride, 4,4′-oxydiphthalic dianhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, 3,3 ′, 4,4′- Biphenyltetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,2-bis [ 4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride and 4,4'-biphenylbis (trimellitic acid look-containing tetracarboxylic acid dianhydride is at least one compound selected from the group consisting of monoester acid anhydride),
The polyvalent compound contains 4,4′-diaminodiphenylsulfone, and the resin precursor is derived from the silicon-containing compound and has the following general formula (2):

｛In the formula, a plurality of R ₃ and R ₄ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, and at least a part of the R ₃ and R ₄ is a phenyl group; And h is an integer of 3 to 200. Has a structure represented by｝,
The resin precursor, wherein the amount of the silicon group-containing compound is 6% by mass to 25% by mass based on the total mass of the polyvalent compound. The silicon group-containing compound has the following general formula (3a):

In the formula, a plurality of R ₂ are each independently a single bond or a divalent organic group having 1 to 20 carbon atoms, and R ₃ and R ₄ are each independently a 1 to 20 carbon atom. L ₁ and L ₂ are each independently an amino group or an acid anhydride group, and j is an integer of 3 to 200. The resin precursor according to claim 1 , comprising a silicone compound represented by｝. The resin precursor according to claim 2 , wherein in the general formula (3a), L ₁ and L ₂ are both amino groups. The resin precursor contains a unit 1 and a unit 2,
The unit 1 has at least the following general formula (4);

In the formula, a plurality of R ₁ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or a monovalent aromatic group, and a plurality of X ₁ may be present. Are each independently a tetravalent organic group having 4 to 32 carbon atoms, and n is an integer of 1 to 100. Has a structure represented by｝,
The unit 2 has the following general formula (5):

In the formula, a plurality of R ₁ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or a monovalent aromatic group, and a plurality of R ₂ are each independently Each independently represents a divalent aliphatic hydrocarbon having 3 to 20 carbon atoms or a divalent aromatic group; R ₃ and R ₄ each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms; X ₂ , which may be plural, is independently a tetravalent organic group having 4 to 32 carbon atoms, 1 is an integer of 3 to 50, and m is 1 to 100 It is an integer.構造 or the following general formula (6):

｛In the formula, a plurality of R ₁ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or a monovalent aromatic group, and a plurality of R ₃ and R ₄ Are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a plurality of R ₈ are each independently a trivalent aliphatic hydrocarbon having 3 to 20 carbon atoms, or a trivalent aliphatic hydrocarbon group. An aromatic group, p is an integer from 1 to 100, and q is an integer from 3 to 50. Having a structure represented by｝ or both a structure represented by the general formula (5) and a structure represented by the general formula (6);
At least part of and / or diamines from sites in the general formula (6) of the diamine from the site in the general formula (4) is derived from 4,4 (diaminodiphenyl) sulfone, claim 1-3 The resin precursor according to any one of the above. The resin precursor according to claim 4 , wherein the total amount of the units 1 and 2 is 30% by mass or more based on the total mass of the resin precursor. The resin precursor has the following general formula (7):

In the formula, a plurality of R ₁ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or a monovalent aromatic group, and a plurality of X ₃ may be present. Are each independently a divalent organic group having 4 to 32 carbon atoms, and a plurality of X _{4 s} which may be present are each independently a tetravalent organic group having 4 to 32 carbon atoms, and t Is an integer of 1 to 100. Further comprising a unit 3 having the structure represented by}, resin precursor according to claim 4 or 5. In Formula (7), X ₃ is, 2,2'-bis residues a structure obtained by removing an amino group from (trifluoromethyl) benzidine, resin precursor according to claim 6. The unit 1 and the unit 2 are:
A site derived from one or more selected from the group consisting of pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic dianhydride (BPDA);
4,4'-oxydiphthalic dianhydride (ODPA), 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), cyclohexane-1,2,4,5-tetracarboxylic dianhydride ( CHDA), 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4'-biphenylbis (trimellitic acid monoester anhydride) (TAHQ), and 9,9 '-Bis (3,4-dicarboxyphenyl) fluorene dianhydride (BPAF) is combined with a site derived from one or more selected from the group consisting of The resin precursor according to any one of claims 4 to 7 , wherein the resin precursor is contained in an amount of 60 mol% or more based on the total amount of the anhydride-derived sites. Wherein the R ₃ and the R _4, each independently, an aliphatic hydrocarbon group, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in the monohydric 1 to 3 carbon atoms, wherein R ₃ and wherein at least a portion of R ₄ is a phenyl group, resin precursor according to any one of claims 1-8. The resin obtained by heating and curing the resin precursor under the condition of 300 to 500 ° C in an inert atmosphere has at least one glass transition temperature in a region of -150 ° C to 0 ° C and at least one of a region of 150 ° C to 380 ° C. The resin precursor according to any one of claims 1 to 9 , having one glass transition temperature and not having a glass transition temperature in a region greater than 0 ° C and smaller than 150 ° C. The resin according to any one of claims 1 to 10 , wherein a site derived from biphenyltetracarboxylic dianhydride (BPDA) is contained in an amount of 20 mol% or more based on the total amount of the site derived from acid dianhydride of the resin precursor. precursor. The resin precursor according to any one of claims 1 to 11, wherein a part of the resin precursor is imidized. The resin precursor according to any one of claims 1 to 12 , and the following general formula (8):

{Wherein, optionally X ₃ also there are a plurality, each independently, a tetravalent organic group 4 to 32 carbon atoms, R ₁ existing in plural, each independently, a hydrogen atom, 1 to carbon atoms 20 monovalent aliphatic hydrocarbons or monovalent aromatic groups, and r is an integer from 1 to 100. And a resin precursor having a structure represented by｝. A flexible device material comprising the resin precursor according to any one of claims 1 to 12 , or the precursor mixture according to claim 13 . A method for manufacturing a flexible device, comprising a step of forming a polyimide film from the resin precursor according to any one of claims 1 to 12 . The method for manufacturing a flexible device according to claim 15 , further comprising a step of providing a semiconductor device on the polyimide film. A resin film which is a cured product of the resin precursor according to any one of claims 1 to 12 or a cured product of the precursor mixture according to claim 13 . A resin composition comprising the resin precursor according to any one of claims 1 to 12 or the precursor mixture according to claim 13 , and a solvent. After the resin composition is spread on the surface of a support, a resin obtained by imidizing the resin precursor contained in the resin composition by heating the resin composition at 300 ° C. to 500 ° C. under a nitrogen atmosphere. 19. The resin composition according to claim 18 , wherein the yellowness at a film thickness of 20 μm is 7 or less. After the resin composition is spread on the surface of a support, a resin obtained by imidizing the resin precursor contained in the resin composition by heating the resin composition at 300 ° C. to 500 ° C. under a nitrogen atmosphere. residual stress at 10μm thickness indicated is less than 25 MPa, the resin composition according to claim 18 or 19. A resin film, which is a cured product of the resin composition according to any one of claims 18 to 20 . Spreading the resin composition according to any one of claims 18 to 20 on a surface of a support;
Heating the support and the resin composition to form a resin film by imidizing the resin precursor contained in the resin composition,
Peeling the resin film from the support,
A method for producing a resin film, comprising: A support, which is formed on a surface of said support, and a resin film which is a cured product of the resin composition according to any one of claims 18-20, laminate. Spreading the resin composition according to any one of claims 18 to 20 on the surface of a support;
Heating the support and the resin composition to imidize the resin precursor contained in the resin composition to form a resin film, thereby obtaining a laminate including the support and the resin film; and ,
A method for producing a laminate, comprising: