JP6435298B2 - RESIN PRECURSOR AND RESIN COMPOSITION CONTAINING THE SAME, RESIN FILM AND ITS MANUFACTURING METHOD, AND LAMINATE AND ITS MANUFACTURING METHOD - Google Patents

Description

  The present invention relates to, for example, a resin precursor and a resin composition containing the resin precursor, a resin film and a manufacturing method thereof, and a laminate and a manufacturing method thereof, which are used for a substrate for a flexible device.

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

  Polyimide resin is an insoluble and infusible super heat resistant resin, and has excellent characteristics such as heat oxidation resistance, heat resistance, radiation resistance, low temperature resistance, and chemical resistance. For this reason, polyimide resin is used in a wide range of fields including electronic materials such as insulating coating agents, 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 the conventionally used glass substrate, the adoption of a colorless and transparent flexible substrate utilizing its lightness and flexibility is also being studied.

  However, general polyimide resins are colored brown or yellow due to high aromatic ring density, have low transmittance in the visible light region, and have been difficult to use in fields where transparency is required.

  In response to the problem of improving the transparency of such polyimide, for example, Non-Patent Document 1 uses a dianhydride containing a specific structure and a diamine containing a specific structure, so that transparency and transparency of the hue are used. Polyimides with improved resistance are described. Furthermore, Patent Documents 1 to 4 include 4,4-bis (diaminodiphenyl) sulfone (hereinafter also referred to as 4,4-DAS) and 3,3-bis (diaminodiphenyl) sulfone (hereinafter 3,3-DAS). And polyimide having improved transmittance and hue transparency by using an acid dianhydride having a specific structure.

In Examples 9 and 10 of Patent Document 6 below, by copolymerizing a specific aromatic tetracarboxylic dianhydride, an alicyclic diamine, and a silicon-containing diamine, high Tg, transparency, and high adhesion are obtained. The polyimide precursor which can produce | generate the polyimide which expresses property and low warpage is described.
Further, in Example 3 of Patent Document 7 and Example 3 of Patent Document 8 below, a polyimide precursor obtained by copolymerizing an aromatic tetracarboxylic dianhydride, bis (diaminodiphenyl) sulfone and a silicon-containing diamine was prepared. And used as a semiconductor protective resin and a photosensitive resin composition.

Japanese Patent Laid-Open No. 61-141732 Japanese Patent Laid-Open No. 06-271670 Japanese Patent Laid-Open No. 09-040774 JP 2000-313804 A International Publication No. 2012/11820 Pamphlet International Publication No. 2011/122198 Pamphlet International Publication No. 1991/01699 Pamphlet JP-A-4-224823

The latest polyimide (basic and applied), Japan Polyimide Study Group, P152

  However, the physical properties of known transparent polyimides are not sufficient for use 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 flexible displays, 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. An inorganic film may be formed. When the linear expansion coefficient (hereinafter also referred to as CTE) of polyimide is high, residual stress is generated between the polyimide film and the inorganic film due to the mismatch of the inorganic film or the CTE between the support glass and the polyimide film. There is a problem that the glass is warped or the performance of the TFT element is deteriorated. For this reason, in order to improve the curvature of support glass, there exists a subject of making the residual stress of a polyimide low. The polyimides described in Patent Documents 1 to 4 have a high residual stress, and there is a problem that the support glass is warped when applied to a colorless and transparent substrate for a flexible display.

  In order to produce 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 has been introduced. It is generally necessary to heat to ˜400 ° C. (hereinafter also referred to as a curing step). In the polyimide which improved the transparency of the 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 above case, there is a problem of oxygen concentration dependency such that the YI value increases or the total light transmittance decreases.

  Further, when a polyimide resin is used for a colorless transparent substrate for flexible displays, a TFT element is usually formed on the polyimide film by a photolithography process using a photoresist. The polyimide film used for the colorless transparent substrate for flexible display (hereinafter also referred to as polyimide substrate) is exposed to chemicals such as a photoresist stripping solution used in the step of stripping the photoresist included in this step. These drugs must have chemical resistance. In polyimides composed of 4,4-DAS or 3,3-DAS and an acid dianhydride containing a specific structure, as described in Patent Document 1, fine cracks are formed on the polyimide substrate during the photoresist stripping process. There was a problem in terms of chemical resistance, such as the phenomenon that the polyimide substrate becomes clouded by entering and the phenomenon that the total light transmittance is reduced occurs.

  Patent Document 5 describes that a flexible silicon-containing diamine is introduced by block copolymerization in order to reduce 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 the silicon-containing diamine is copolymerized with a block, the phase separation of the silicone portion proceeds unless the polyimide precursor is dissolved using a special solvent combination, In the sea-island structure having different refractive indexes, the structure of the island portion becomes large, so that the film becomes clouded and the total light transmittance is lowered. Also, when using a special solvent combination with a low boiling point, if the polyimide precursor solution is applied to the substrate and then left at room temperature for several hours, haze may occur and the coating may become cloudy. Had to manage. Thus, in order to produce a transparent thermosetting film by polyimide block-copolymerized with a silicon-containing diamine, the 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 manage the standing time.

  Examples 9 and 10 of Patent Document 6 describe a polyimide precursor obtained by copolymerizing an aromatic tetracarboxylic dianhydride, an alicyclic diamine and a silicone diamine, and a polyimide obtained therefrom. Yes. 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 transmittance are easily affected by the oxygen concentration during polyimide curing ( (See Comparative Example 25 in the present specification).

  Patent Documents 7 and 8 describe a polyimide precursor obtained by copolymerizing (diaminodiphenyl) sulfone, aromatic tetracarboxylic dianhydride, and silicone diamine, and a polyimide obtained therefrom. However, as a result of confirmation by the present inventors, the mass ratio of the silicon group-containing monomer to the total mass of the silicon group-containing monomer, polyvalent carboxylic derivative, and diamine compound used when synthesizing the polyimide precursor is disclosed in Patent Document 7. The resulting polyimide has a large residual stress and is unsuitable for the display process. On the other hand, since it is large for Patent Document 8, the resulting polyimide is cloudy and unsuitable for use in a transparent display. There was a problem (see Comparative Examples 23 and 24 in the present specification).

  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 solvent combination, and is generated between the inorganic film and the inorganic film. An object of the present invention is to provide a resin precursor having a low residual stress, excellent chemical resistance, and capable of giving a cured resin having a small influence on the YI value and the total light transmittance due to the oxygen concentration during the curing process. . 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 production method thereof, a laminate, and a production method thereof.

  As a result of intensive studies to solve the above problems, the present inventors have been able to form a transparent resin cured product without requiring a combination of special solvents, the heat-resistant resin precursor having a specific structure, In addition, such cured resin is low in residual stress generated between the inorganic film, excellent in chemical resistance, and has little effect on the YI value and total light transmittance due to oxygen concentration during the curing process. Based on this finding, the present inventors have made the present invention. 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 comprises a silicon group-containing compound;
The polyvalent compound is represented by the following formula (1):

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 one or more 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 one having 1 to 20 carbon atoms. A plurality of R _{5 s} which may be present each independently is 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, and k is 0 to 0. It is an integer of 197. } The resin precursor as described in [1] or [2] containing the silicone compound represented by these.
[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 unit 1 and unit 2,
The unit 1 has at least the following general formula (4);

{In the formula, R ₁ existing in plural, each independently, a hydrogen atom, an aliphatic hydrocarbon, or a monovalent aromatic group having a monovalent C1-20, optionally X ₁ be a plurality of 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, R ₁ existing in plural, each independently, a hydrogen atom, an aliphatic hydrocarbon, or a monovalent aromatic group having a monovalent C1-20, R ₂ existing in plural, respectively Independently, it is 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. A plurality of X ₂ which may be present are 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. } 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 present.} 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. A group, p is an integer from 1 to 100, and q is an integer from 3 to 50. }, Or both of the structure represented by the general formula (5) and the structure represented by the general formula (6), according to any one of [1] to [5] The resin precursor as described.
[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 is represented by the following general formula (7):

{In the formula, R ₁ existing in plural, each independently, a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or an aromatic group of monovalent, optionally X ₃ be plurality of Are each independently a divalent organic group having 4 to 32 carbon atoms, and a plurality of X ₄ may be each independently a tetravalent organic group having 4 to 32 carbon atoms, and t Is an integer from 1 to 100. } The resin precursor as described in [6] or [7] which further contains the unit 3 which has a structure represented by these.
[9] The resin precursor according to [8], wherein in the general formula (7), X ₃ is a residue having a structure in which an amino group is removed from 2,2′-bis (trifluoromethyl) benzidine. .
[10] 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 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) is defined as the acid diacid of unit 1 and unit 2. The resin precursor according to any one of [6] to [9], which is contained in an amount of 60 mol% or more based on the total amount of 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 part of R ₃ and R ₄ is a phenyl group.
[13] A resin obtained by heat-curing the resin precursor under an inert atmosphere at 300 to 500 ° C has at least one glass transition temperature in the region of -150 ° C to 0 ° C and 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 larger than 0 ° C and smaller than 150 ° C.
[14] Any one of [1] to [13], wherein a portion derived from biphenyltetracarboxylic dianhydride (BPDA) is contained in an amount of 20 mol% or more based on the total amount of the acid dianhydride-derived portion of the resin precursor. The resin precursor according to item.
[15] The resin precursor according to any one of [1] to [14], which is partially imidized.
[16] The resin precursor according to any one of [1] to [15] and the following general formula (8):

{In the formula, X ₃ which may be present in plural are each independently a tetravalent organic group having 4 to 32 carbon atoms, and R _{1 which} is present in plural are each independently a hydrogen atom, 20 monovalent aliphatic hydrocarbons or monovalent aromatic groups, and r is an integer of 1 to 100. } The precursor mixture containing the resin precursor which has a structure represented by these.
[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 that 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 the 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. [19] The resin composition according to [19], wherein the obtained resin has a yellowness of 20 or less at a film thickness of 7 or less.
[21] After the resin composition is developed on the surface of the support, the resin precursor contained in the resin composition is imidized by heating the resin composition at 300 ° C to 500 ° C under a nitrogen atmosphere. Resin composition as described in [19] or [20] whose residual stress in 10 micrometers film thickness which the resin obtained shows is 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 developing the resin composition according to any one of [19] to [21] 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;
The manufacturing method of the resin film containing this.
[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 developing the resin composition according to any one of [19] to [21] 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; ,
The manufacturing method of a laminated body containing this.
[26] A polyimide resin film used for manufacturing a display substrate, wherein Rth is 20 to 90 nm at a thickness of 20 μm.
[27] developing a resin composition containing a polyimide precursor on the surface of the support;
Heating the support and the resin composition to imidize a polyimide precursor to form a polyimide resin film according to [26];
Forming an element on the polyimide resin film;
And a step of peeling 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 the need for a special solvent combination, the residual stress generated with the inorganic film is low, the chemical resistance is excellent, and the There is provided a resin precursor capable of providing a cured resin having a small influence on the YI value and the total light transmittance due to the oxygen concentration during the process.

  Hereinafter, exemplary embodiments of the present invention (hereinafter abbreviated as “embodiments”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary. Note that the number of repeating structural units in the formula of the present disclosure is only intended to be the number of structural units that can be included in the entire resin precursor, unless otherwise specified. It should be noted that is not intended. Further, unless otherwise specified, the characteristic values described in the present disclosure are values measured by a method described in the section of [Example] or a method understood by those skilled in the art to be equivalent thereto. Intended.

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 is:
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 comprises a silicon group-containing compound;
The polyvalent compound is represented by the following formula (1):

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 includes 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. It may be included or a combination thereof.
In the present disclosure, an amino group-reactive group intends a group having reactivity with an amino group. Examples of the amino group reactive group include an acid group (for example, a carboxyl group, an acid anhydride group, a substituted carboxyl group (for example, an acid ester group, an acid halide group, etc.)), a hydroxy group, an epoxy group, and a mercapto group. Can be mentioned. Examples of the compound containing an acid group include dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, and acid dianhydrides, acid esterified products, 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 includes one or more selected from the group consisting of a carboxyl group, a substituted carboxyl group, and an acid 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). Examples of the compound represented by the general formula (1) include 4,4- (diaminodiphenyl) sulfone (hereinafter, also referred to as 4,4-DAS), 3,4- (diaminodiphenyl) sulfone (hereinafter, 3,4). -DAS) and 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 group-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 concentration of the silicon group-containing monomer is preferably 6% by mass or more 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 7% by mass. Preferably, it is 8% by mass or more, more preferably 10% by mass or more. On the other hand, the silicon group-containing monomer concentration is 25% by mass or less, which is advantageous from the viewpoint of improving transparency, reducing yellowness, and obtaining good heat resistance without causing the resulting polyimide to become cloudy, and 22% by mass. % Or less, more preferably 20% by mass or less. From the standpoint of improving the chemical resistance, YI value, total light transmittance, birefringence, residual stress, and oxygen dependency of optical properties, the silicon group-containing monomer concentration is 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. The alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms from the viewpoint of heat resistance and residual stress, and specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group. , Isobutyl group, t-butyl group, pentyl group, hexyl group and the like. The cycloalkyl group having 3 to 20 carbon atoms is preferably a cycloalkyl group having 3 to 10 carbon atoms 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 methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group, phenoxy group, propenyloxy group, and cyclohexyloxy group.

In 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 it 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 General formula (2) is an integer of 3-200, Preferably it is an integer of 10-200, More preferably, it is an integer of 20-150, More preferably, it is an integer of 30-100, Especially preferably, it is 35-80 Is an integer. If h is 2 or less, the residual stress of the polyimide obtained from the resin precursor of the present disclosure may deteriorate (that is, increase). If h exceeds 200, a varnish containing a resin precursor and a solvent may be used. When prepared, the varnish may become cloudy or the mechanical strength of the polyimide may decrease.

  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 one having 1 to 20 carbon atoms. A plurality of R _{5 s} which may be present each independently is 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, and k is 0 to 0. It is an integer of 197. } Is preferably included. 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. It is done. The alkylene group having 2 to 20 carbon atoms is preferably an alkylene group having 2 to 10 carbon atoms from the viewpoint of heat resistance, residual stress, and cost, and is a dimethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group. Etc. 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 these, from the above viewpoint, a divalent aliphatic hydrocarbon having 3 to 20 carbon atoms is preferable. The arylene group having 6 to 20 carbon atoms is preferably an aromatic group having 3 to 20 carbon atoms 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 is synonymous with a monovalent organic group having 1 to 20 carbon atoms, that is, R ₃ and R ₄ , and a preferred embodiment is the same as R ₃ and R ₄ .

In the general formula (3), 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.

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 both-terminal amino-modified methyl phenyl silicone (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)), both-terminal amino-modified dimethyl silicone (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 manufactured by Chisso Corporation (number average molecular weight 1000) ) 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 silicones obtained by reacting both terminal amino-modified silicones with phosgene compounds.

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) manufactured by Shin-Etsu Chemical Co., Ltd. and BY16-880 (number average manufactured by Toray Dow Corning). Molecular weight 6,600) and the like.

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

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 acyl compounds having at least one of the groups represented by the formula:

Specific examples of the compound 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), X22-168A (manufactured by Shin-Etsu Chemical, number average molecular weight). 2,000), X22-168B (manufactured by Shin-Etsu Chemical, number average molecular weight 3,200), X22-168-P5-8 (manufactured by Shin-Etsu Chemical, number average molecular weight 4,200), DMS-Z21 (manufactured by Gerest, number Average molecular weight 600-800).

Specific examples of the compound in which L ₁ , L ₂ , and L ₃ are acid ester groups include reacting the compound in which L ₁ , L ₂ , and L ₃ are carboxyl groups or acid anhydride groups with an alcohol. And the resulting compound.

Specific examples of compounds in which L ₁ , L ₂ and L ₃ are acid halide groups include carboxylic acid chlorides, carboxylic acid fluorides, carboxylic acid bromides, carboxylic acid iodides, and the like.

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), KF-6001 (manufactured by Shin-Etsu Chemical, number average molecular weight 1,800). KF-6002 (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,200), KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd., 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 compounds in which L ₁ , L ₂ , and L ₃ are epoxy groups include X22-163 (manufactured by Shin-Etsu Chemical, number average molecular weight 400), KF-105 (manufactured by Shin-Etsu Chemical, 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) , 400); X22-169AS (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 1,000), X22-169B (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,400); X22-9002 (manufactured by Shin-Etsu Chemical Co., Ltd., functional group equivalent: 5,000 g / mol); The compound having an epoxy group is considered to react with 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), X22-167C (manufactured by Shin-Etsu Chemical, number average molecular weight 4, 600). A compound having a mercapto group is considered to react with a compound having a carboxyl group or an acid anhydride group.

L ₁ , L ₂ , and L ₃ are preferably each independently an amino group or an acid anhydride group from the viewpoint of improving the molecular weight of the resin precursor or the heat resistance of the resulting polyimide, From the viewpoint of avoiding white turbidity of a varnish containing a precursor and a solvent, or from the viewpoint of cost, it is more preferably an amino group independently.
Or, from the viewpoint of avoiding white turbidity of a varnish containing a resin precursor and a 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. It is preferable. In this case, it is more preferable that both L ₁ and L ₂ are amino groups.

  In general formula (3), a preferred embodiment of j is the same as that described above for h in general formula (2). In General formula (3), k is an integer of 0-197, Preferably it is 0-100, More preferably, it is 0-50, Most preferably, it is 0-25. When k exceeds 197, when a varnish containing a resin precursor and a solvent is prepared, the varnish may become cloudy. 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 resulting 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 heat resistance of the resulting 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. 10 monovalent aromatic hydrocarbon groups. Or, in the formulas of the present disclosure, some of the R ₃ and R _4, from the viewpoints of heat resistance, the residual stress is preferably a phenyl group.

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

<Tetracarboxylic dianhydride>
The tetracarboxylic dianhydride as an example of the polyvalent compound contained in the polymerization raw material is specifically an aromatic tetracarboxylic dianhydride having 8 to 36 carbon atoms and a carbon number of 6 to 36. A compound selected from alicyclic tetracarboxylic dianhydrides is preferable from the viewpoint of reduction in YI value and 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 acid Anhydride, 1,2-ethylene-4,4′-diphthalic dianhydride, 1,3-trimethylene-4,4′-diphthalic dianhydride, 1,4-tetramethylene-4,4′-diphthal 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-dicar Xylphenoxy) 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 ( Hereafter 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), cyclo 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 Merit acid monoester 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 preferable from the viewpoint of CTE reduction, chemical resistance improvement, glass transition temperature (Tg) improvement, and mechanical elongation improvement. Moreover, 6FDA, ODPA, and BPADA are preferable from the viewpoints of lowering the yellowness, lowering the birefringence, and improving the 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 preferable from the viewpoint of reduction of residual stress and reduction of yellowness. Among these, tetracarboxylic dianhydride selected from the group consisting of BPDA having a tough structure that exhibits high chemical resistance, high Tg, and low CTE, and 6FDA, ODPA, and CHDA having low yellowness and birefringence. Are preferably used in combination from the viewpoints of high chemical resistance, residual stress reduction, yellowness reduction, birefringence reduction, and total light transmittance improvement.

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

<Dicarboxylic acid>
Further, the resin precursor in the present embodiment has a performance such as improvement of mechanical elongation, improvement of glass transition temperature, reduction of yellowness in addition to the above-mentioned tetracarboxylic dianhydride within a range not impairing performance. For the purpose of adjusting the temperature, the thermosetting film can be made into polyamideimide by introducing a polyamide component by copolymerizing dicarboxylic acid. Examples of such dicarboxylic acids include dicarboxylic acids having an aromatic ring and alicyclic dicarboxylic acids, and in particular, aromatic dicarboxylic acids 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 is preferred. 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 with the polymer, they may be used in the form of acid chlorides or active esters derived from thionyl chloride or the like.

  Among these, terephthalic acid is particularly preferable from the viewpoint of reducing the YI value and improving Tg. When dicarboxylic acid is used instead of tetracarboxylic acid, it is from the viewpoint of chemical resistance that dicarboxylic acid is 50 mol% or less based on the total number of moles of dicarboxylic acid and tetracarboxylic acid combined. preferable.

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

  Further, the diamine can include a diamine having a divalent silicon-containing group having 2 to 100 silicon (hereinafter also simply referred to as a silicon-containing diamine). Examples of the silicon-containing diamine include 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 C1-C20 monovalent organic group, and l is an integer of 3-50. } The diamino (poly) siloxane represented by these is suitable. Such a diamine can constitute, for example, a unit 2 described later.

Preferred examples 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. In addition, 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, a phenyl group, and the like. Particularly preferred is a group.

  Specific examples of the compound represented by the general formula (9) include both-end amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400), X22-9409 (several Average molecular weight 1300)), both-end amino-modified dimethyl silicone (manufactured by 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: Silaplane FM3311 (number average molecular weight 1000)) and the like. Among these, both terminal amine-modified methyl phenyl silicone oils are particularly preferable from the viewpoints 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 ′-) diaminodiphenyl sulfone, 4,4 ′-(or 3,3 ′-) diaminodiphenyl sulfide, 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} propyl 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 Benzoic acid, 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 ( One or more selected from the group consisting of 4-aminophenyl) hexafluoropropane (4,4′-6F) may be included. These diamines can constitute diamine-derived sites of the unit 3 described later. Among these, 1,4-cyclohexanediamine and TFMB are most preferable from the viewpoints 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。 More preferably, the resin precursor includes the following unit 1 and unit 2.
Unit 1 has at least the following general formula (4);

{In the formula, R ₁ existing in plural, each independently, a hydrogen atom, an aliphatic hydrocarbon, or a monovalent aromatic group having a monovalent C1-20, optionally X ₁ be a plurality of 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, R ₁ existing in plural, each independently, a hydrogen atom, an aliphatic hydrocarbon, or a monovalent aromatic group having a monovalent C1-20, R ₂ existing in plural, respectively Independently, it is 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. A plurality of X ₂ which may be present are 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. } 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 present.} 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. A group, p is an integer from 1 to 100, and q is an integer from 3 to 50. }, Or a structure represented by the general formula (5) and a structure represented by the general formula (6).

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

Unit 1 and unit 2 are from the viewpoint of heat resistance, reduction in 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) is represented by unit 1 and unit 2 acid dianhydrides. 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 unit 1 and unit 2 is 30% by mass or more based on the total mass of the resin precursor, so that the YI value is reduced and the birefringence is reduced. From the viewpoint of improving Tg, 70% by mass or more is more preferable from the viewpoint of reducing the birefringence. Most preferably, it is 100 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。 Moreover, the resin precursor which concerns on this Embodiment is a range which does not impair performance as needed, following General formula (7):

{In the formula, R ₁ existing in plural, each independently, a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or an aromatic group of monovalent, optionally X ₃ be plurality of Are each independently a divalent organic group having 4 to 32 carbon atoms, and a plurality of X ₄ may be each independently a tetravalent organic group having 4 to 32 carbon atoms, and t Is an integer from 1 to 100. } May further contain a unit 3 having a structure represented by:

  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 silicon-containing diamine. It is.

In 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, YI value reduction, and total light transmittance. X ₄ is preferably a divalent aromatic group or alicyclic group from the viewpoints of heat resistance, YI value reduction, and total light transmittance. Among these, X ₃ is preferably a residue having a structure in which an amino group is removed 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 80% by mass or less, preferably 70% by mass or less in the total resin structure, and the oxygen dependency of the YI value and the total light transmittance is It is preferable from the viewpoint of reduction.

  The resin precursor according to the present embodiment is a resin obtained by heating and curing the resin precursor at 300 to 500 ° C. in an inert atmosphere (for example, in an atmosphere of nitrogen or argon), or the resin precursor is inert. A resin obtained by heat curing at 350 ° C. under an atmosphere has at least one glass transition temperature in the region of −150 ° C. to 0 ° C. and at least one glass transition temperature in the region of 150 ° C. to 380 ° C .; It is preferable not to have a glass transition temperature in a region greater than 0 ° C. and less than 150 ° C. The presence of a glass transition temperature in the −150 ° C. to 0 ° C. region and the 150 ° C. to 380 ° C. region is preferable 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 region of 150 ° C to 380 ° C is more preferably in the region of 200 to 380 ° C, and further preferably in the region of 250 to 380 ° C. It is advantageous in forming such a resin precursor that the resin precursor has blocks 1 and 2 described later.

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

  The block 1 described above contributes to developing Tg in the range of 150 to 380 ° C. in the polyimide obtained by heat curing the resin precursor of the present embodiment. Therefore, the block 1 is preferably a block consisting only of the repetition of the unit 1 described above, but 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 block 2 described above contributes to developing Tg in the range of −150 to 0 ° C. in the polyimide obtained by heat curing the resin precursor of the present embodiment. Therefore, the block 2 is preferably a block consisting only of the repetition of the unit 2 described above, but does not exclude the inclusion of units 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 repeating numbers of unit 1 and unit 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 repeating units 2 in block 2 is preferably 1.1 to 300, more preferably 1.1 to 200, and most preferably 1.2 to 100 on an average per molecule. It is preferable that the sum of the number of repeating units 1 and 3 in block 1 is 500 or less and the number of repeating units 2 in block 2 is 300 or less because the solubility of the resin precursor in the solvent is good.

  The ratio defined by the sum of the number of repetitions of unit 1 and unit 3 in block 1 divided by the number of repetitions of unit 2 in block 2 (hereinafter also referred to as the unit ratio) depends on the type of raw material used and the molecular weight. 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 block 1 and the block 2 has a glass transition temperature derived from the block 1 in the region A from 150 ° C. to 380 ° C., and the glass derived from the block 2 It can 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 above unit ratio is 0.5 or more, the heat resistance of the cured polyimide resin is sufficient, which is preferable. Moreover, when it is 100 or less, a residual stress can be made low and it 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 the block copolymer as described above. Polyimide can exhibit a low residual stress with an 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 lowered, so that the high glass transition temperature and the low residual stress can be exhibited even if the charged mole number is small.

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

  Therefore, 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 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。

{In the formula, X ₃ which may be present in plural are each independently a tetravalent organic group having 4 to 32 carbon atoms, and R _{1 which} is present in plural are each independently a hydrogen atom, 20 monovalent aliphatic hydrocarbon groups or monovalent aromatic groups, and r is an integer of 1 to 100. } The resin precursor which has a structure represented by this is mentioned.

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

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

  The number average molecular weight of the resin precursor according to the present embodiment is preferably 3000 to 1000000, more preferably 5000 to 500000, still more preferably 7000 to 300000, and particularly preferably 10000 to 250,000. The molecular weight is preferably 3000 or more from the viewpoint of obtaining good heat resistance and strength (for example, high elongation), and 1000000 or less is preferred from the viewpoint of obtaining good solubility in a solvent, coating and the like. It is preferable from the viewpoint that coating can be performed without bleeding at a desired film thickness 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 in terms of standard polystyrene using gel permeation chromatography.

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

  The resin precursor of the present 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 transparent polyimide substrate, and is inorganic. A polyimide resin having a residual stress between the films of 10 μm and a thickness of 25 MPa or less can be formed. 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 resin film of 10 μm and 20 MPa or less. In a polyimide resin, when a glass transition temperature is present at −150 to 0 ° C., this temperature is not higher than room temperature, and thus 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 (for example, N-methyl-2-pyrrolidone) is developed on the surface of the support, the solution is heated at 300 to 500 ° C. (for example, 350 ° C.) in a nitrogen atmosphere. In a resin obtained by imidizing the resin precursor by (for example, 1 hour), the yellowness at a film thickness of 20 μm is 7 or less.
After a solution obtained by dissolving the resin precursor in a solvent (for example, N-methyl-2-pyrrolidone) is developed on the surface of the support, the solution is heated at 300 to 500 ° C. (for example, 350 ° C.) in a nitrogen atmosphere. In the resin obtained by imidizing the resin precursor by (for example, 1 hour), the residual stress at a film thickness of 10 μm is 25 MPa or less.

<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 prepared separately, and then The resin precursor which concerns on this Embodiment can be obtained by mixing both and attaching | subjecting to a condensation reaction. Here, when the terminal group of the polyimide precursor of one block is a carboxylic acid so that both blocks can be subjected to a condensation reaction, the terminal group of the polyimide precursor of the other block becomes an amino group. The molar ratio of the raw materials, for example, the molar ratio of tetracarboxylic dianhydride and diamine is adjusted. In this method, a polyimide precursor having a more preferable complete block property can be synthesized.

  On the other hand, tetracarboxylic dianhydride which is a polymerization raw material is common between block 1 and block 2, aromatic diamine is used as the raw material for block 1, and silicon-containing diamine having high reactivity is used as the raw material for block 2. When used, a synthesis method utilizing the difference in reactivity between both diamines may be possible. For example, a polyimide precursor having a certain degree of blocking property can be produced by simultaneously adding an aromatic diamine and a silicon-containing diamine to a tetracarboxylic dianhydride prepared in advance and subjecting it to a condensation reaction. Although this method cannot synthesize a blocky polyimide precursor having complete blocking properties, it can synthesize a polyimide precursor having blocking properties. Here, having a block property means that the glass transition temperature corresponding to each block is observed in the polyimide resin after heat curing. For example, the polyimide resin is 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 a tetracarboxylic acid anhydride And the glass transition temperature of block 2 derived from a polycondensate of a silicon-containing diamine and a tetracarboxylic acid anhydride, respectively.

  As described above, in the resin precursor according to the present embodiment, the polyimide resin obtained by heat curing the resin precursor has a glass transition temperature in the high temperature region A and the low temperature region B, respectively. Although it is advantageous to have a block property of a certain degree, this advantage can be obtained even if the polyimide resin does not have a complete block property. Moreover, the above-mentioned advantage by the resin precursor which has the block 1 and 2 contains units other than the block 1 and the block 2 if the glass transition temperature is not recognized in the area | region C between this area | region A and this area | region B. You can get it even if you do.

  Further, by adding N, N-dimethylformamide dimethyl acetal or N, N-dimethylformamide diethyl acetal to the polyamic acid as described above and heating, by esterifying a part or all of the carboxylic acid, The viscosity stability of the solution containing the resin precursor and the solvent during storage at room temperature can also be improved. In addition to these ester-modified polyamic acids, the above-mentioned tetracarboxylic acid anhydride is previously reacted with one equivalent of monohydric alcohol with respect to the acid anhydride group, and then a dehydrating condensing agent such as thionyl chloride or dicyclohexylcarbodiimide After the reaction, it can also be obtained by a condensation reaction with diamine.

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

  As a more preferred embodiment, the resin composition is prepared by dissolving the carboxylic acid component and the diamine component in a solvent, for example, an organic solvent, and reacting them to form a polyamic acid solution containing the polyamic acid and the solvent which are one embodiment of the resin precursor. 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 advance the reaction of the silicon group-containing compound, heating at 120 ° C. for about 30 minutes is preferable. Moreover, it is preferable that it is inert atmosphere, such as argon and nitrogen, at the time of reaction.

  Moreover, if a solvent is a solvent which melt | dissolves a polyamic acid, it will not specifically limit. Known reaction solvents include dimethylene glycol dimethyl ether (DMDG), m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), acetone, diethyl One or more polar solvents selected from acetate, ecamide M100 (trade name: manufactured by Idemitsu Kosan Co., Ltd.) and ecamide B100 (trade name: manufactured by Idemitsu Kosan Co., Ltd.) are useful. Among these, NMP, DMAc, ecamide M100, and ecamide B100 are preferable. 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, an alkoxysilane compound is used with respect to 100% by mass of the resin precursor in order to give a support and sufficient adhesion. Is preferable to contain 0.01 to 2% by mass.

  When the content of the alkoxysilane compound is 0.01% by mass or more with respect to 100% by mass of the resin precursor, good adhesion to the support can be obtained, and the content of the alkoxysilane compound is It is preferable that it is 2 mass% or less from a viewpoint of the storage stability of a resin composition. As for content of an alkoxysilane compound, it is more preferable that it is 0.02-2 mass% with respect to a resin precursor, It is further more preferable that it is 0.05-1 mass%, 0.05-0.5 It is more preferable that it is mass%, and it is especially preferable that it is 0.1-0.5 mass%.

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

  After producing the above-mentioned varnish, a part of the polymer may be dehydrated and imidized to such an extent that the polymer does not precipitate by heating the solution at 130 to 200 ° C. for 5 minutes to 2 hours. The imidization rate can be controlled by controlling the temperature and time. By performing partial imidization, the viscosity stability of the resin precursor solution during storage at room temperature can be improved. As a range of the imidization rate, 5% to 70% is preferable from the viewpoints 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. in a nitrogen atmosphere (or by heating at 350 ° C. in a nitrogen atmosphere). The yellowness at a film thickness of 20 μm indicated by the resin obtained by imidizing the resin precursor is 7 or less.
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. in a nitrogen atmosphere (or by heating at 350 ° C. in a nitrogen atmosphere). Residual stress at a film thickness of 10 μm indicated by a resin obtained by imidizing the resin precursor is 25 MPa or less.

<Resin film>
Another aspect of the present invention provides a resin film that is a cured product of the aforementioned resin precursor, a cured product of the aforementioned precursor mixture, or a cured product of the aforementioned resin composition.
Further, another aspect of the present invention is a step of developing the above-mentioned resin composition on the surface of a support;
Heating the support and the resin composition to imidize a resin precursor contained in the resin composition to form a resin film;
Peeling the resin film from the support;
The manufacturing method of the resin film containing is provided.

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

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

  More specifically, the resin composition described above is spread and dried on the adhesive layer formed on the main surface of the inorganic substrate, and cured at a temperature of 300 to 500 ° C. in 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 developing method include known coating methods such as spin coating, slit coating, and blade coating. In addition, after the polyamic acid solution is spread on the adhesive layer, the heat treatment is performed at a temperature of 300 ° C. or lower for 1 to 300 minutes mainly for the purpose of solvent removal, and further at 300 ° C. to 550 under an inert atmosphere such as nitrogen. The resin precursor is polyimidized by heat treatment at a temperature of 1 ° C. for 1 minute to 300 minutes. 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 reduction in YI value and 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.

  Moreover, the thickness of the resin film which concerns on this Embodiment is not specifically limited, It is preferable that it is the range of 10-200 micrometers, More preferably, it is 10-50 micrometers.

  The resin film according to the present embodiment preferably has a yellowness of 7 or less at a film thickness of 20 μm. Moreover, it is preferable that a residual stress is 25 Mpa or less with 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 is 25 MPa or less at a film thickness of 10 μm. Such characteristics are satisfactorily realized, for example, by imidizing the resin precursor of the present disclosure at 300 ° C. to 500 ° C., more specifically 350 ° C., under a nitrogen atmosphere.

<Laminate>
Another aspect of the present invention provides a laminate comprising a support and a resin film formed on the surface of the support and being a cured product of the above-described resin composition.
Moreover, another aspect of the present invention is a step of developing the resin composition described above 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; ,
The manufacturing method of a laminated body containing is provided.
Such a laminate can be produced, for example, by not peeling a resin film formed in the same manner as in the method for producing a resin film from the support.

This laminated body is used for manufacturing a flexible device, for example. More specifically, a semiconductor device can be formed on a polyimide film, and then a support can be peeled off to obtain a flexible device including a flexible transparent substrate made of a 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, since the resin precursor according to the present embodiment has a specific structure, a resin film that does not become cloudy can be formed without requiring a special solvent combination. Further, the yellowness (YI value) and total light transmittance of the obtained resin film are less dependent on the oxygen concentration during 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 fabrication process, has excellent mechanical properties, and has chemical resistance that can withstand the photolithography process. . Therefore, the resin precursor is suitable for use on 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 the TFT on the substrate is typically performed at a wide range of temperatures of 150 to 650 ° C. However, in order to realize the actually desired performance, it is mainly at around 250 ° C. to 350 ° C. 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 warps or breaks, the flexible substrate peels off from the glass substrate, etc. Problems arise. In general, since the thermal expansion coefficient of a glass substrate is smaller than that of 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 on the basis of the film thickness of 10 μm.

  In addition, the resin film according to the present embodiment has a yellowness of 7 or less with reference to 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 with less dependence on oxygen concentration in the oven used for producing a thermosetting film. Thermosetting is performed 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 on the basis of a film thickness of 20 μm from the viewpoint of improving yield by being excellent in breaking strength when handling a flexible substrate. It is more preferable.

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

  Moreover, it is preferable that the resin film according to the present embodiment has chemical resistance that can withstand a photoresist stripping solution in a photolithography process used when manufacturing a TFT element.

  There are two types of light extraction methods for flexible displays: a top emission method for extracting light from the front surface side of the TFT element and a bottom emission method for extracting light from the back surface side. The top emission method has a feature that the TFT element does not get in the way, so that the aperture ratio is easily increased, and the bottom emission method has a feature that alignment is easy and manufacture is easy. If the TFT element is transparent, it is possible to improve the aperture ratio even in the bottom emission method. Therefore, it is expected that the bottom emission method, which is easy to manufacture, will be adopted for large organic EL flexible displays. Yes. When a resin substrate is used for the colorless and transparent resin substrate used in the bottom emission method, the resin substrate comes to the side to be visually recognized. Therefore, the optical isotropy, that is, the retardation in the thickness direction derived from the birefringence (Rth ) Is required from the viewpoint of improving image quality. In addition, when used in the top emission method, it is not required that Rth is low, but a material having low Rth is preferred from the viewpoint that it can be commonly used for both types. Specifically, it 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 a film thickness of 20 μm. If Rth is 100 nm or less, and further 90 nm or less, not only the top emission type transparent display transparent substrate, but also the performance to be applied to the bottom emission type flexible display transparent substrate and touch panel electrode substrate is satisfied. ing.

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

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

  The resin film and laminate produced using the resin precursor according to the present embodiment are particularly suitable as a substrate for the production of, for example, semiconductor insulation films, TFT-LCD insulation films, electrode protective films, and flexible devices. Can be used. Here, examples of the flexible device include a flexible display, a flexible solar cell, a flexible touch panel electrode substrate, flexible illumination, and a flexible battery.

EXAMPLES Hereinafter, although this invention is further explained in full detail based on an Example, these are described for description and the range of this invention is not limited to the following Example.
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 the solvent, N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph) was used, and 24.8 mmol / L lithium bromide monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) before the measurement. , Purity 99.5%) and 63.2 mmol / L phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph) were used. A calibration curve for calculating the weight average molecular weight was prepared using standard polystyrene (manufactured by Tosoh Corporation).

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

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

(Production 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 to 10 minutes, and a vertical cure oven (manufactured by Koyo Lindberg, model name VF-2000B). Was heated at 140 ° C. for 60 minutes, and further heated at 350 ° C. for 60 minutes in a nitrogen atmosphere to prepare 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 dependency of the YI value and the total light transmittance was examined. The film thickness of the resin composition of the laminate was 20 μm. After curing at 350 ° C. (curing treatment), the laminate was allowed to stand at room temperature for 24 hours, the resin film was peeled from the glass, and the film was isolated. For the evaluations other than the yellowness and total light transmittance below, a resin film cured for 60 minutes at 350 ° C. with the oxygen concentration in the hot air oven adjusted to 100 ppm was used as a sample.

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

(Yellowness, total light transmittance and its oxygen concentration dependence during curing)
Oxygen concentrations in the oven were adjusted to 50 ppm, 100 ppm, and 500 ppm, respectively, and cured at 350 ° C., and a 20 μm thick resin film 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))
A resin film having a thickness of 20 μm and cured at 350 ° C. was measured using a phase difference birefringence measuring apparatus (manufactured by Oji Scientific Instruments, KOBRA-WR). The wavelength of the measurement light was 589 nm.

(Evaluation of glass transition temperature and linear expansion coefficient)
For measurement of glass transition temperature (referred to as Tg (1)) and linear expansion coefficient (CTE) above the room temperature region, a resin film cured at 350 ° C. and having a sample length of 5 × 50 mm and a thickness of 20 μm was manufactured by Shimadzu Corporation. Using a mechanical analysis apparatus (TMA-50), the elongation of the specimen in a temperature range of 50 to 450 ° C. under a load of 5 g, a heating rate of 10 ° C./min, under a nitrogen atmosphere (flow rate of 20 ml / min) by thermomechanical analysis. 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 method, the above-mentioned resin film is measured at a dynamic viscoelasticity measuring device (within the range of −150 ° C. to 400 ° C.). The inflection point in the temperature region below room temperature of E prime was measured by RHEOVIBRON MODEL RHEO-1021) manufactured by Orientec Co., and the inflection point was determined as the glass transition temperature at a low temperature.

(Evaluation of residual stress)
Using a bar coater, the resin composition was measured on a 6-inch silicon wafer having a thickness of 625 μm ± 25 μm, in which the “warping amount” was measured in advance using a residual stress measurement device (manufactured by Tencor, model name FLX-2320). After applying and pre-baking at 140 ° C. for 60 minutes, using a vertical curing furnace (manufactured by Koyo Lindberg Co., model name: VF-2000B), heat-curing treatment is performed at 350 ° C. for 1 hour in a nitrogen atmosphere, and after curing A silicon wafer with a resin film having a thickness of 10 μm was produced. The amount of warpage of the wafer was measured using the above-described residual stress measuring apparatus, 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. is immersed in an NMP layer at room temperature, pulled up every 10 minutes, washed with ion-exchanged water, and then the film surface is observed with a microscope. The time for entering was evaluated in increments of 10 minutes up to 300 minutes.

[Example 1]
To a 3 L separable flask with a stirring rod equipped with an oil bath, while introducing nitrogen gas, NMP 1000 g was added, and 3,3- (diaminodiphenyl) sulfone (defined as diamine 1) was added with stirring 232.4 g. 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. and stirred for 12 hours, and then both terminal amine-modified methyl phenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) (defined as a silicon group-containing diamine) 105.6 g was dissolved in 298 g of NMP and added dropwise using a dropping funnel. After raising the temperature 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). The composition here and the weight average molecular weight (Mw) of the resulting polyamic acid are shown in Table 1. 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 acid anhydride 1, silicon group-containing diamine, and their added mass were changed to those shown in Table 1, respectively. I went and got a varnish. Moreover, the NMP addition amount shown in Table 1 and Table 2 shows 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 here and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 1, Table 2, and Table 7, respectively. The test results of the films cured at 350 ° C. are shown in Table 4, Table 5, and Table 8, respectively. The formal compound names of the abbreviated compound names described in Tables 1 to 6 are shown 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 Product CHDA: cyclohexane-1,2,4,5-tetracarboxylic dianhydride DSDA: 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride BPADA: 2,2-bis [4- ( 3,4-dicarboxyphenoxy) phenyl] propane dianhydride BPAF: 9,9′-bis (3,4-dicarboxyphenyl) fluorene Things TAHQ: 4,4'- biphenyl-bis (trimellitic acid monoester acid anhydride)
BTDA: 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride TPE-R: 1,3-bis (4-aminophenoxy) benzene CBDA: 1,2,3,4-cyclobutane tetracarboxylic acid di Anhydride FM3311: Both-end amine-modified dimethylsilicone oil (Silaplane FM3311 (number average molecular weight 1000) manufactured by Chisso Corporation)
TFMB: 2,2′-bis (trifluoromethyl) benzidine TACl: trimellitic anhydride chloride

[Example 34]
Nitrogen gas is introduced into a 3 L separable flask equipped with an oil bath and equipped with a stirring rod, 1274 g of NMP is added, and 4,4′-oxydiphthalic dianhydride (hereinafter referred to as ODPA) (specified as tetracarboxylic anhydride 1) 2) Amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) (defined as a silicon group-containing diamine) is dissolved in 298 g of NMP while stirring. Was added dropwise using a dropping funnel. After stirring for 1 hour at room temperature, 149.9 g of 2,2′-bis (trifluoromethyl) benzidine (hereinafter referred to as TFMB) (defined as diamine 2) was added with stirring, followed by 3,3-DAS. 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. This was heated to 80 ° C. and stirred for 4 hours, and then 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). The composition here and the weight average molecular weight (Mw) of the resulting polyamic acid are shown in Table 2. Table 5 shows the test results of the film cured at 350 ° C.

[Examples 35, 39, 40, 44, 45]
In the same manner as in Example 34, the types of diamine 1, diamine 2, tetracarboxylic acid anhydride 1, and tetracarboxylic acid anhydride 2 and their added masses were changed to those shown in Table 2, respectively, and Example 34 was obtained. A varnish was obtained by performing the same operation as in Example 1. Moreover, the NMP addition amount shown in Table 2 shows 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 here and the weight average molecular weight (Mw) of the resulting polyamic acid are shown in Table 2, respectively. Table 5 shows the test results of 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 stirring rod equipped with an oil bath, and 3,3- (diaminodiphenyl) sulfone (specified as diamine 1). 232.4 g was added with stirring, and the mixture was heated to 50 ° C., and then 147.1 g of BPDA (defined as tetracarboxylic anhydride 1) was added and stirred for 30 minutes. Subsequently, 155.1 g of ODPA (defined as tetracarboxylic anhydride 2) was added and stirred for 8 hours, and then both-end amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400). )) 105.6 g (defined as silicon group-containing diamine) was dissolved in 298 g of NMP and added dropwise using a dropping funnel. After raising the temperature 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). The composition here and the weight average molecular weight (Mw) of the resulting polyamic acid are shown in Table 2. 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, except that the types of diamine 1, tetracarboxylic acid anhydride 1, tetracarboxylic acid anhydride 2, and their added masses were changed to those described in Table 2, respectively, the same as in Example 36 The operation was performed to obtain a varnish. Moreover, the NMP addition amount shown in Table 2 shows 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 here and the weight average molecular weight (Mw) of the resulting polyamic acid are shown in Table 2, respectively. Table 5 shows the test results of films cured at 350 ° C.

[Example 38]
While introducing nitrogen gas, 1200 g of NMP was added to a 3 L separable flask equipped with a stir bar 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 (specified as other monomer components) was dissolved in 200 g of γ-butyrolactone, and then added dropwise and stirred for 30 minutes. Subsequently, 235.4 g of BPDA (defined as tetracarboxylic anhydride 1) was added and stirred for 8 hours, and then both-end amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400). )) 105.6 g (defined as silicon group-containing diamine) was dissolved in 298 g of NMP and added dropwise using a dropping funnel. After heating up to 80 degreeC and stirring for 1 hour, the oil bath was removed and it returned to room temperature, and the solution of the transparent polyamic acid was obtained. To this, 1000 g of NMP was added and diluted, and then added dropwise to 10 L of ion-exchanged water, and a polyamideimide precursor powder was deposited. Then, 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, other monomer components, and their added mass were changed to those shown in Table 2, respectively. And got a varnish. Moreover, the NMP addition amount shown in Table 2 shows the total amount of NMP finally contained in the varnish. The composition here and the weight average molecular weight (Mw) of the obtained polyamideimide precursor are shown in Table 2, respectively. Table 5 shows the test results of films cured at 350 ° C.

[Example 59]
To a 3 L separable flask equipped with a stir bar equipped with an oil bath, NMP 1000 g was added while introducing nitrogen gas, 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 stirred at room temperature for 30 minutes. The temperature was raised to 50 ° C. and stirred for 12 hours, and then 104.58 g of N-terminal acid anhydride-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-168-P5-B (number average molecular weight 4200)) was 298 g of NMP. And added dropwise using a dropping funnel. After raising the temperature 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 here and the weight average molecular weight (Mw) of the resulting 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 diamine 1, tetracarboxylic acid anhydride 1, silicon group-containing diamine, and their added mass were changed to those shown in Table 1, respectively. I went and got a varnish. Moreover, the NMP addition amount shown in Table 1 and Table 2 shows 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 here and the weight average molecular weight (Mw) of the resulting polyamic acid are shown in Table 7, respectively. 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 stir bar equipped with an oil bath, NMP 1065 g was added while introducing nitrogen gas, and 24,3 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. This was heated to 50 ° C. and stirred for 12 hours, and then the oil bath was removed and the temperature was returned to room temperature to obtain a transparent polyamic acid NMP solution (hereinafter also referred to as varnish). The composition here and the weight average molecular weight (Mw) of the resulting polyamic acid are shown in Table 3. 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 diamine 1, the type of tetracarboxylic acid anhydride 1, and their added mass were changed to those described in Table 3, respectively, and the same operation as in Comparative Example 1 was performed to obtain a varnish. It was. The composition here and the weight average molecular weight (Mw) of the resulting polyamic acid are shown in Table 3, respectively. Table 6 shows the test results of films cured at 350 ° C.

[Comparative Example 22]
Nitrogen gas was introduced into a 3 L separable flask equipped with an oil bath and 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) 1) and was heated to 50 ° C. and stirred for 12 hours. To this, a dripping funnel was prepared by dissolving 105.6 g of both-end amine-modified methyl phenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) (defined as a silicon group-containing diamine) in NMP 298 g. Was added dropwise. After completion of the dropwise addition, this was heated to 80 ° C. and stirred for 1 hour, and then the oil bath was removed and the temperature was returned to room temperature to obtain a slightly turbid opaque polyamic acid NMP solution (hereinafter also referred to as varnish). The composition here and the weight average molecular weight (Mw) of the resulting polyamic acid are shown in Table 3. Table 6 shows the test results of the film cured at 350 ° C.

[Example 23]
Pyromellitic anhydride (PMDA) 4. 36 g (0.02 mol) and BTDA 25.78 g are dispersed in N-methyl-2-pyrrolidone (NMP) 240 g, 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 stirred for 1 hour to react. Thus, after reacting diaminosiloxane and tetracarboxylic dianhydride, 14.3-62 g (0.05 mol) of 1,3-bis (4-aminophenoxy) benzene (TPE-R), then 3,3 DAS11. 17 g of powder was added in small portions.

[Example 24]
A 1 liter flask equipped with a stirrer, dropping funnel, thermometer, condenser and nitrogen purge was fixed in cold water. After replacing the flask with nitrogen gas, 500 g of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) purified by dehydration, 3,3'4,4'-benzophenonetetracarboxylic dianhydride (BTDA) 25.11 g (0.0779 mol), 15.48 g (0.0623 mol) of 3,3′-diaminodiphenylsulfone (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.

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

[Example 26]
A 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl (hereinafter referred to as “TFMB”) as a component (B) was added to a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, and a cooling tube. 7.85 g (24.5 mmol) and 2.03 g (1.6 mmol) of both terminal amino-modified methylphenyl silicone (X22-9409) were added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide was added and stirred until uniform. To the resulting solution, 5.12 g (26.1 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (hereinafter also referred to as “CBDA”) as component (A) was added at room temperature, and the temperature was maintained. Then, stirring was continued for 24 hours to obtain a composition (polyamic acid solution).

  The YI values and total light transmittances shown in Tables 4 to 6 and Table 8 indicate 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 satisfied the following conditions simultaneously in film properties.

(1) Residual stress is 25 MPa or less (2) Yellowness is 7 or less and is less affected by oxygen concentration (3) Glass transition temperature is 250 ° C. or higher in the temperature range above room temperature (4) Total light transmittance is 88% or more, less affected by oxygen concentration (5) Tensile elongation: 30% or more (6) NMP chemical resistance test: 30 minutes or more (7) Even if a varnish is prepared with NMP alone, the thermosetting film is cloudy High total light transmittance

  These satisfy the performance for application 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. Moreover, the retardation Rth in the thickness direction is a polyimide that does not use a silicon group-containing monomer as a copolymerization monomer (Comparative Examples 1 to 22) and a polyimide that uses a silicon group-containing monomer (Examples 1 to 33). The polyimide using the silicon group-containing monomer has a smaller Rth, and it can be seen that the silicon group-containing monomer contributes to the Rth reduction of the polyimide.

  On the other hand, Comparative Examples 1 to 26 have low residual stress, chemical resistance, and tensile elongation, and the YI value and total light transmittance are affected by the oxygen concentration during curing and deteriorate.

  From this result, the resin obtained from the resin precursor according to the present invention is colorless and transparent, has low residual stress generated between the inorganic film, excellent chemical resistance, and YI due to oxygen concentration during curing. It was confirmed that the resin film had little influence on the value and the total light transmittance.

  In addition, this invention is not limited to the said embodiment, It can change and implement variously.

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

Claims (18)

Ri der Rth is 200nm or less in the thickness 20 [mu] m, a polyimide resin film used in the manufacture of a display substrate,
The polyimide resin film is
Following formula (1):

A skeleton derived from a diamine represented by:
Pyromellitic dianhydride, 4,4'-oxydiphthalic dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride Anhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride, and 4, A skeleton derived from at least one tetracarboxylic acid selected from the group consisting of 4′-biphenylbis (trimellitic acid monoester anhydride);
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. } A skeleton derived from a silicon group-containing compound having a structure represented by:
Have
The polyimide resin film is obtained by polymerizing a polymerization component including a diamine represented by the formula (1), the tetracarboxylic acid, and a silicon group-containing compound having a structure represented by the general formula (2). It is a film that is a cured product of the resulting polyimide precursor,
In the polymerization component, the content of the silicon group-containing compound having the structure represented by the general formula (2) is such that the diamine represented by the formula (1), the tetracarboxylic acid, and the general formula (2). The polyimide resin film | membrane which is 6-25 mass% on the basis of the total amount with the silicon group containing compound which has a structure represented by this.   The polyimide resin film according to claim 1, wherein Rth at a thickness of 20 μm is 20 nm or more.   The polyimide resin film of Claim 1 or 2 whose Rth in 20 micrometers in thickness is 20 nm-90 nm.   The polyimide resin film according to any one of claims 1 to 3, wherein the yellowness at a thickness of 20 µm is 7 or less.   The polyimide resin film according to any one of claims 1 to 4, wherein a residual stress at a thickness of 10 µm is 25 MPa or less.   The polyimide resin film according to any one of claims 1 to 5, wherein the transmittance of light having a wavelength of 550 nm at a thickness of 20 µm is 85% or more.   The polyimide resin film according to claim 1, which has at least one glass transition temperature in a range of 200 ° C. to 380 ° C. 7.   The polyimide resin film according to claim 7, which has at least one glass transition temperature in a range of 310 ° C. to 380 ° C.   The polyimide resin film according to claim 1, wherein the mechanical elongation at a thickness of 20 μm is 30% or more. Developing a resin composition containing a polyimide precursor on the surface of the support;
Said support and by imidizing a polyimide precursor by heating the resin composition, and forming a polyimide resin film,
Forming an element on the polyimide resin film;
And a step of peeling the polyimide resin film on which the element is formed from the support ,
The polyimide resin film is
Rth at a thickness of 20 μm is 200 nm or less,
Following formula (1):

A skeleton derived from a diamine represented by:
Pyromellitic dianhydride, 4,4'-oxydiphthalic dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride Anhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride, and 4, A skeleton derived from at least one tetracarboxylic acid selected from the group consisting of 4′-biphenylbis (trimellitic acid monoester anhydride);
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. } A skeleton derived from a silicon group-containing compound having a structure represented by:
Have
The polyimide resin film is obtained by polymerizing a polymerization component including a diamine represented by the formula (1), the tetracarboxylic acid, and a silicon group-containing compound having a structure represented by the general formula (2). It is a film that is a cured product of the resulting polyimide precursor,
In the polymerization component, the content of the silicon group-containing compound having the structure represented by the general formula (2) is such that the diamine represented by the formula (1), the tetracarboxylic acid, and the general formula (2). The method is a polyimide resin film that is 6% by mass to 25% by mass based on the total amount with the silicon group-containing compound having a structure represented by:   The method according to claim 10, wherein Rth at a thickness of 20 μm of the polyimide resin film is 20 nm or more.   12. The method according to claim 10, wherein Rth at a thickness of 20 μm of the polyimide resin film is 20 nm to 90 nm.   The method according to claim 10, wherein the polyimide resin film has a yellowness of 7 or less at a thickness of 20 μm.   The method according to claim 10, wherein a residual stress at a thickness of 10 μm of the polyimide resin film is 25 MPa or less.   The method according to any one of claims 10 to 14, wherein a transmittance of light having a wavelength of 550 nm at a thickness of 20 µm of the polyimide resin film is 85% or more.   The method according to any one of claims 10 to 15, wherein the polyimide resin film has at least one glass transition temperature in a range of 200C to 380C.   The method of claim 16, wherein the polyimide resin film has at least one glass transition temperature in the region of 310 ° C. to 380 ° C.   The method according to any one of claims 10 to 17, wherein a mechanical elongation at a thickness of 20 µm of the polyimide resin film is 30% or more.