JP6075564B2 - Resin composition for display substrate - Google Patents

Resin composition for display substrate Download PDF

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JP6075564B2
JP6075564B2 JP2013545950A JP2013545950A JP6075564B2 JP 6075564 B2 JP6075564 B2 JP 6075564B2 JP 2013545950 A JP2013545950 A JP 2013545950A JP 2013545950 A JP2013545950 A JP 2013545950A JP 6075564 B2 JP6075564 B2 JP 6075564B2
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江原　和也
和也 江原
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
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    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C08G73/14—Polyamide-imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/16—Polyester-imides
    • C—CHEMISTRY; METALLURGY
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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    • C08G73/18—Polybenzimidazoles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133305—Flexible substrates, e.g. plastics, organic film
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements

Description

本発明はディスプレイ基板用樹脂組成物に関し、詳細には適度な線膨張係数、適度な柔軟性を有する有用なポリイミドフィルムを形成することができるディスプレイ基板用樹脂組成物に関する。   The present invention relates to a resin composition for a display substrate, and more particularly to a resin composition for a display substrate capable of forming a useful polyimide film having an appropriate linear expansion coefficient and an appropriate flexibility.

ポリイミド樹脂は、耐熱性が高く難燃性で電気絶縁性に優れていることから、電気・電子材料分野において幅広く使用されている。具体的には、フィルムとしてフレキシブル印刷配線版や耐熱性接着テープの基材、樹脂ワニスとして半導体の絶縁皮膜、保護皮膜などに使用されている。
一方、有機ＥＬ（Ｅｌｅｃｔｒｏｌｕｍｉｎｅｓｃｅｎｃｅ）ディスプレイや液晶ディスプレイなどの表示装置は、高精細のみが要求されてきたが、情報機器などへ急速にその用途を拡大している。例えば、超薄型・軽量化の要求を満たすために、プラスチックフィルムを基板として使用するフレキシブルディスプレイが注目されている。
従来、高精細なディスプレイには、アクティブマトリックス駆動のパネルが使用されている。マトリックス状の画素電極に加えて、薄膜アクティブ素子を含むアクティブマトリックス層を形成するには、その製造プロセスにおいて２００℃以上の高温処理を必要とし、しかも、きわめて正確な位置合わせが必要である。しかし、フレキシブル化のために、ガラス基板からプラスチック材料に変化することで、耐熱性、寸法安定性に劣るため、その上にアクティブ素子をじかに形成するのは非常に困難であった。Polyimide resins are widely used in the field of electrical and electronic materials because of their high heat resistance, flame retardancy, and excellent electrical insulation. Specifically, it is used as a film for flexible printed wiring boards and heat-resistant adhesive tapes as a film, and as a resin varnish for semiconductor insulating films, protective films, and the like.
On the other hand, display devices such as an organic EL (Electroluminescence) display and a liquid crystal display have been demanded only for high definition, but their applications are rapidly expanding to information devices and the like. For example, a flexible display using a plastic film as a substrate is attracting attention in order to satisfy the demand for ultra-thin and light weight.
Conventionally, an active matrix driving panel is used for a high-definition display. In order to form an active matrix layer including a thin film active element in addition to a matrix-like pixel electrode, a high temperature treatment of 200 ° C. or higher is required in the manufacturing process, and extremely accurate alignment is required. However, since it is inferior in heat resistance and dimensional stability by changing from a glass substrate to a plastic material for flexibility, it is very difficult to directly form an active element thereon.

そこで、斯かる問題を回避するために、ガラス基板上にポリイミドフィルムを形成し、製造条件が制限されず、アモルファスシリコンＴＦＴ素子やカラーフィルタなどを高精細で位置合わせて形成して転写層とした後、その転写層をプラスチックフィルム上に転写・形成することにより、表示素子を製造する方法が提案されている（特許文献１及び２）。
ところで、前記工程で必要とされるポリイミドの特性として、線膨張係数が挙げられる。しかし、多くのポリイミド系ではフィルムの線膨張係数は６０乃至８０ｐｐｍ／Ｋの範囲であり、低線膨張特性を有していない。このような中、線膨張係数が低いポリイミドフィルムが開発されているが、汎用性に乏しい酸二無水物を原料に用いているため、得られる製品が高価になってしまう（特許文献３）。Therefore, in order to avoid such a problem, a polyimide film is formed on a glass substrate, the manufacturing conditions are not limited, and an amorphous silicon TFT element, a color filter, etc. are formed with high-definition alignment to form a transfer layer. Thereafter, a method of manufacturing a display element by transferring and forming the transfer layer on a plastic film has been proposed (Patent Documents 1 and 2).
By the way, a linear expansion coefficient is mentioned as a characteristic of the polyimide required at the said process. However, in many polyimide systems, the linear expansion coefficient of the film is in the range of 60 to 80 ppm / K and does not have low linear expansion characteristics. Under such circumstances, a polyimide film having a low linear expansion coefficient has been developed. However, since an acid dianhydride having poor versatility is used as a raw material, the resulting product becomes expensive (Patent Document 3).

特開２００１−３５６３７０号公報JP 2001-356370 A 特表２０１０−５３９２９３号公報Special table 2010-539293 国際公開第２００８／０４７５９１号パンフレットInternational Publication No. 2008/047591 Pamphlet

本発明は、このような事情に鑑みてなされたものであり、汎用性に乏しい酸二無水物を原料に用いなくても、適度な線膨張係数、適度な柔軟性及び満足な耐熱性を有する有用な硬化膜を形成することができるディスプレイ基板用樹脂組成物の提供を目的とする。なお、ここでいう適度な柔軟性とは、自己支持性があり、かつ９０度に曲げても割れない程度の高い柔軟性をいう。   The present invention has been made in view of such circumstances, and has an appropriate coefficient of linear expansion, an appropriate flexibility, and a satisfactory heat resistance without using an acid dianhydride having poor versatility as a raw material. It aims at providing the resin composition for display substrates which can form a useful cured film. In addition, moderate softness | flexibility here means self-supporting property and the high softness | flexibility of the grade which is not cracked even if it bends 90 degree | times.

本発明者は、上記目的を達成するために鋭意検討を重ねた結果、酸二無水物成分としてビフェニル骨格を有する酸無水物と、ジアミン成分としてベンズイミダゾール骨格を有するジアミンとを組み合わせて用いることにより、該酸二無水物成分と該ジアミン成分から誘導されるポリアミック酸又はポリイミドを含むディスプレイ基板用樹脂組成物から、適度な線膨張係数及び適度な柔軟性を有する有用な硬化膜が得られることを見出し、本発明を完成させた。   As a result of intensive studies to achieve the above object, the present inventor has used an acid anhydride having a biphenyl skeleton as an acid dianhydride component and a diamine having a benzimidazole skeleton as a diamine component in combination. From the resin composition for display substrates containing polyamic acid or polyimide derived from the acid dianhydride component and the diamine component, a useful cured film having an appropriate linear expansion coefficient and an appropriate flexibility can be obtained. The headline and the present invention were completed.

すなわち、本発明は、第１観点として、下記式（１）で表される構造単位及び式（３）で表される構造単位を含むポリアミック酸又は下記式（２）で表される構造単位及び式（４）で表される構造単位を含むポリイミドを含有するディスプレイ基板用樹脂組成物に関する。

Figure 0006075564
［式（１）乃至式（４）中、
Ｘ１は芳香族基と２つのカルボニル基を有する４価の有機基を表し、
Ｙ１は２価の芳香族基又は脂肪族基を表し、
Ｙ２は窒素原子を２個以上有する２価の芳香族基を表し、
ｎ及びｍは自然数を表す。］
第２観点として、前記Ｙ２が複素環構造を有する芳香族基を表す、第１観点に記載のディスプレイ基板用樹脂組成物に関する。
第３観点として、前記Ｙ２が下記式（５）で表される、第２観点に記載のディスプレイ基板用樹脂組成物に関する。
Figure 0006075564
 （式中、
Ｒ１乃至Ｒ７は、それぞれ独立して、水素原子、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基、カルボキシル基、Ｗ１で置換されていてもよいフェニル基、Ｗ１で置換されていてもよいナフチル基、Ｗ１で置換されていてもよいチエニル基又はＷ１で置換されていてもよいフリル基を表し、
Ｗ１は、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基又はカルボキシル基を表し、
Ａは、水素原子、炭素原子数１乃至１０のアルキル基又は炭素原子数１乃至１０のハロアルキル基を表す。なお、○は結合手を表す。）
第４観点として、前記Ｒ１乃至Ｒ７及びＡが水素原子を表す、第３観点に記載のディスプレイ基板用樹脂組成物に関する。
第５観点として、前記Ｙ１が下記式（６）で表される、第１観点乃至第４観点のうちいずれか１つに記載のディスプレイ基板用樹脂組成物に関する。
Figure 0006075564
 （式中、
Ｒ８乃至Ｒ１１は、それぞれ独立して、水素原子、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基、カルボキシル基、Ｗ１で置換されていてもよいフェニル基、Ｗ１で置換されていてもよいナフチル基、Ｗ１で置換されていてもよいチエニル基又はＷ１で置換されていてもよいフリル基を表し、
Ｗ１は、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基又はカルボキシル基を表し、
ｑは１又は２を表す。なお、○は結合手を表す。）
第６観点として、前記式（６）で表される２価の芳香族基がフェニレンジアミンから誘導されたものである、第５観点に記載のディスプレイ基板用樹脂組成物に関する。
第７観点として、前記Ｒ８乃至Ｒ１１が水素原子を表す、第６観点に記載のディスプレイ基板用樹脂組成物に関する。
第８観点として、前記Ｘ１が下記式（７）で表される、第１観点乃至第７観点のうちいずれか１つに記載のディスプレイ基板用樹脂組成物に関する。
Figure 0006075564
 （式中、
Ｒ１２乃至Ｒ２１は、それぞれ独立して、水素原子、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基、カルボキシル基、Ｗ１で置換されていてもよいフェニル基、Ｗ１で置換されていてもよいナフチル基、Ｗ１で置換されていてもよいチエニル基又はＷ１で置換されていてもよいフリル基を表し、
Ｗ１は、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基又はカルボキシル基を表し、
Ｚ１及びＺ２は、それぞれ独立して、−ＮＨ−、−ＮＺ３−又は酸素原子を表し、
Ｚ３は、炭素原子数１乃至１０のアルキル基を表し、
ｐは１又は２を表す。なお、○は結合手を表す。）
第９観点として、前記ｐが２を表す、第８観点に記載のディスプレイ基板用樹脂組成物に関する。
第１０の観点として、前記Ｒ１２乃至Ｒ２１が水素原子を表す、第９観点に記載のディスプレイ基板用樹脂組成物に関する。
第１１観点として、前記式（１）中のｎと前記式（３）中のｍとがｎ／ｍ＝７０／３０乃至９９／１の関係である、第１観点乃至第１０観点のうちいずれか１つに記載のディスプレイ基板用樹脂組成物に関する。
第１２観点として、前記式（２）中のｎと前記式（４）中のｍとがｎ／ｍ＝７０／３０乃至９９／１の関係である、第１観点乃至第１０観点のうちいずれか１つに記載のディスプレイ基板用樹脂組成物に関する。
第１３観点として、さらに架橋剤を含む、第１観点乃至第１２観点のうちいずれか１つに記載のディスプレイ基板用樹脂組成物に関する。
第１４観点として、前記架橋剤が２つ以上のエポキシ基を有する化合物である、第１３観点に記載のディスプレイ基板用樹脂組成物に関する。
第１５観点として、前記架橋剤が芳香族基を有する化合物である、第１４観点に記載のディスプレイ基板用樹脂組成物に関する。
第１６観点として、前記架橋剤が６つ以下のエポキシ基を有する化合物であって、かつ該化合物はエポキシ基と芳香族基とを結合する炭素原子数１乃至１０のアルキル基を有する、第１５観点に記載のディスプレイ基板用樹脂組成物に関する。
第１７観点として、前記ポリアミック酸又はポリイミド１００質量部に対して、前記架橋剤が２０質量部以下である、第１３観点乃至第１６観点のうちいずれか１つに記載のディスプレイ基板用樹脂組成物に関する。
第１８観点として、第１観点乃至第１７観点のうちいずれか１つに記載のディスプレイ基板用樹脂組成物が少なくとも１種の溶剤に溶解していることを特徴とする、ワニスに関する。
第１９観点として、第１８観点に記載のワニスを用いて２３０℃以上で焼成することにより得られる、硬化膜に関する。
第２０観点として、基板上に第１９観点に記載の硬化膜からなる層を少なくとも一層備える、構造体に関する。
第２１観点として、下記式（１）で表される構造単位及び式（３）で表される構造単位を含むポリアミック酸に関する。
Figure 0006075564
 ［式（１）及び式（３）中、
Ｘ１は芳香族基と２つのカルボニル基を有する４価の有機基を表し、
Ｙ１は２価の芳香族基又は脂肪族基を表し、
Ｙ２は窒素原子を２個以上有する２価の芳香族基を表し、
ｎ及びｍは自然数を表す。］
第２２観点として、下記式（２）で表される構造単位及び式（４）で表される構造単位を含むポリイミドに関する。
Figure 0006075564
 ［式（２）及び式（４）中、
Ｘ１は芳香族基と２つのカルボニル基を有する４価の有機基を表し、
Ｙ１は２価の芳香族基又は脂肪族基を表し、
Ｙ２は窒素原子を２個以上有する２価の芳香族基を表し、
ｎ及びｍは自然数を表す。］
第２３観点として、第２２観点に記載のポリイミドからなるディスプレイ用基板に関する。That is, as a first aspect, the present invention provides a polyamic acid containing a structural unit represented by the following formula (1) and a structural unit represented by the formula (3), or a structural unit represented by the following formula (2) and It is related with the resin composition for display substrates containing the polyimide containing the structural unit represented by Formula (4).
Figure 0006075564
 [In Formula (1) thru | or Formula (4),
X 1 represents a tetravalent organic group having an aromatic group and two carbonyl groups,
Y 1 represents a divalent aromatic group or aliphatic group,
Y 2 represents a divalent aromatic group having two or more nitrogen atoms,
n and m represent natural numbers. ]
As a second aspect, an aromatic group, wherein Y 2 has a heterocyclic structure, to a display substrate resin composition according to the first aspect.
As a third aspect, the Y 2 is represented by the following formula (5) relates to a display substrate resin composition according to the second aspect.
Figure 0006075564
 (Where
R 1 to R 7 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, or a halogen atom. , nitro group, formyl group, cyano group, carboxyl group, W 1 with an optionally substituted phenyl group, W 1 with an optionally substituted naphthyl group, W 1 with an optionally substituted thienyl group or W Represents a furyl group optionally substituted by 1 ,
W 1 is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, or a carboxyl group. Represents a group,
A represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group having 1 to 10 carbon atoms. In addition, (circle) represents a bond. )
As a fourth aspect, regarding the R 1 to R 7 and A represents a hydrogen atom, a display substrate resin composition according to the third aspect.
As a fifth aspect, relates to the Y 1 is represented by the following formula (6), a display substrate resin composition according to any one of the first aspect to the fourth aspect.
Figure 0006075564
 (Where
R 8 to R 11 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, or a halogen atom. , nitro group, formyl group, cyano group, carboxyl group, W 1 with an optionally substituted phenyl group, W 1 with an optionally substituted naphthyl group, W 1 with an optionally substituted thienyl group or W Represents a furyl group optionally substituted by 1 ,
W 1 is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, or a carboxyl group. Represents a group,
q represents 1 or 2. In addition, (circle) represents a bond. )
As a sixth aspect, the present invention relates to the display substrate resin composition according to the fifth aspect, wherein the divalent aromatic group represented by the formula (6) is derived from phenylenediamine.
As a seventh aspect, the present invention relates to the resin composition for a display substrate according to the sixth aspect, wherein R 8 to R 11 represent a hydrogen atom.
An eighth aspect relates to the X 1 is represented by the following formula (7), a display substrate resin composition according to any one of the first aspect to the seventh aspect.
Figure 0006075564
 (Where
R 12 to R 21 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, or a halogen atom. , nitro group, formyl group, cyano group, carboxyl group, W 1 with an optionally substituted phenyl group, W 1 with an optionally substituted naphthyl group, W 1 with an optionally substituted thienyl group or W Represents a furyl group optionally substituted by 1 ,
W 1 is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, or a carboxyl group. Represents a group,
Z 1 and Z 2 each independently represent —NH—, —NZ 3 — or an oxygen atom,
Z 3 represents an alkyl group having 1 to 10 carbon atoms,
p represents 1 or 2. In addition, (circle) represents a bond. )
As a ninth aspect, the present invention relates to the resin composition for display substrates according to the eighth aspect, wherein p represents 2.
As a tenth aspect, the present invention relates to the resin composition for a display substrate according to the ninth aspect, wherein R 12 to R 21 represent a hydrogen atom.
As an eleventh aspect, any one of the first aspect to the tenth aspect, wherein n in the formula (1) and m in the formula (3) have a relationship of n / m = 70/30 to 99/1. It relates to the resin composition for display substrates as described in any one.
As a twelfth aspect, any one of the first aspect to the tenth aspect, wherein n in the formula (2) and m in the formula (4) have a relationship of n / m = 70/30 to 99/1. It relates to the resin composition for display substrates as described in any one.
As a thirteenth aspect, the present invention relates to the display substrate resin composition according to any one of the first to twelfth aspects, further including a crosslinking agent.
As a fourteenth aspect, the present invention relates to the display substrate resin composition according to the thirteenth aspect, in which the crosslinking agent is a compound having two or more epoxy groups.
As a fifteenth aspect, the present invention relates to the resin composition for a display substrate according to the fourteenth aspect, in which the crosslinking agent is a compound having an aromatic group.
According to a sixteenth aspect, in the fifteenth aspect, the crosslinking agent has a compound having 6 or less epoxy groups, and the compound has an alkyl group having 1 to 10 carbon atoms that bonds the epoxy group and the aromatic group. It is related with the resin composition for display substrates as described in a viewpoint.
As a seventeenth aspect, the resin composition for a display substrate according to any one of the thirteenth aspect to the sixteenth aspect, in which the crosslinking agent is 20 parts by mass or less with respect to 100 parts by mass of the polyamic acid or polyimide. About.
An eighteenth aspect relates to a varnish, wherein the display substrate resin composition according to any one of the first to seventeenth aspects is dissolved in at least one solvent.
As a 19th viewpoint, it is related with the cured film obtained by baking at 230 degreeC or more using the varnish as described in an 18th viewpoint.
As a 20th viewpoint, it is related with a structure provided with at least one layer which consists of a cured film as described in a 19th viewpoint on a board | substrate.
As a twenty-first aspect, the present invention relates to a polyamic acid containing a structural unit represented by the following formula (1) and a structural unit represented by the formula (3).
Figure 0006075564
 [In Formula (1) and Formula (3),
X 1 represents a tetravalent organic group having an aromatic group and two carbonyl groups,
Y 1 represents a divalent aromatic group or aliphatic group,
Y 2 represents a divalent aromatic group having two or more nitrogen atoms,
n and m represent natural numbers. ]
As a twenty-second aspect, the present invention relates to a polyimide containing a structural unit represented by the following formula (2) and a structural unit represented by the formula (4).
Figure 0006075564
 [In Formula (2) and Formula (4),
X 1 represents a tetravalent organic group having an aromatic group and two carbonyl groups,
Y 1 represents a divalent aromatic group or aliphatic group,
Y 2 represents a divalent aromatic group having two or more nitrogen atoms,
n and m represent natural numbers. ]
As a 23rd viewpoint, it is related with the display substrate which consists of a polyimide as described in a 22nd viewpoint.

本発明のディスプレイ基板用樹脂組成物は、適度な線膨張係数、適度な柔軟性及び満足な耐熱性を有する有用な硬化膜を形成することができる。したがって、該硬化膜は、フレキシブルディスプレイ用ベースフィルム等に使用することができる。   The resin composition for a display substrate of the present invention can form a useful cured film having an appropriate linear expansion coefficient, an appropriate flexibility, and a satisfactory heat resistance. Therefore, the cured film can be used as a base film for flexible displays.

［ディスプレイ基板用樹脂組成物］
本発明は、下記式（１）で表される構造単位及び式（３）で表される構造単位を含むポリアミック酸又は下記式（２）で表される構造単位及び式（４）で表される構造単位を含むポリイミドを含有するディスプレイ基板用樹脂組成物に関する。

Figure 0006075564
［式（１）乃至式（４）中、
Ｘ１は芳香族基と２つのカルボニル基を有する４価の有機基を表し、
Ｙ１は２価の芳香族基又は脂肪族基を表し、
Ｙ２は窒素原子を２個以上有する２価の芳香族基を表し、
ｎ及びｍは自然数を表す。］[Resin composition for display substrate]
The present invention is represented by a polyamic acid containing a structural unit represented by the following formula (1) and a structural unit represented by the formula (3), or a structural unit represented by the following formula (2) and the formula (4). The present invention relates to a resin composition for a display substrate containing polyimide containing a structural unit.
Figure 0006075564
 [In Formula (1) thru | or Formula (4),
X 1 represents a tetravalent organic group having an aromatic group and two carbonyl groups,
Y 1 represents a divalent aromatic group or aliphatic group,
Y 2 represents a divalent aromatic group having two or more nitrogen atoms,
n and m represent natural numbers. ]

ここで、上記式（１）で表される構造単位及び式（３）で表される構造単位を含むポリアミック酸とは、ｎ個の下記式（ａ）で表される構造単位及びｍ個の下記式（ｂ）で表される構造単位を含み、これら（ｎ＋ｍ）個の構造単位が任意の順序で結合した化合物を意味し、上記式（２）で表される構造単位及び式（４）で表される構造単位を含むポリイミドとは、ｎ個の下記式（ｃ）で表される構造単位及びｍ個の下記式（ｄ）で表される構造単位を含み、これら（ｎ＋ｍ）個の構造単位が任意の順序で結合した化合物を意味する。
なお、上記式（１）で表される構造単位及び式（３）で表される構造単位を含むポリアミック酸は、下記式（ｃ）で表される構造単位及び式（ｄ）で表される構造単位のいずれか又は両方を分子内に有していてもよく、上記式（２）で表される構造単位及び式（４）で表される構造単位を含むポリイミドは、下記式（ａ）で表される構造単位及び式（ｂ）で表される構造単位のいずれか又は両方を分子内に有していてもよい。

Figure 0006075564
［式（ａ）乃至式（ｄ）中、Ｘ１、Ｙ１及びＹ２は、それぞれ前記式（１）乃至式（４）における定義と同じ意味を表す。］Here, the polyamic acid containing the structural unit represented by the above formula (1) and the structural unit represented by the formula (3) means n structural units represented by the following formula (a) and m number of structural units. This means a compound comprising a structural unit represented by the following formula (b), wherein these (n + m) structural units are bonded in any order, and the structural unit represented by the above formula (2) and the formula (4) The polyimide containing a structural unit represented by n includes n structural units represented by the following formula (c) and m structural units represented by the following formula (d), and these (n + m) pieces of structural units are represented by A compound in which structural units are bonded in any order.
In addition, the polyamic acid containing the structural unit represented by the above formula (1) and the structural unit represented by the formula (3) is represented by the structural unit represented by the following formula (c) and the formula (d). Either or both of the structural units may be present in the molecule, and the polyimide containing the structural unit represented by the above formula (2) and the structural unit represented by the formula (4) is represented by the following formula (a): Either or both of the structural unit represented by formula (b) and the structural unit represented by formula (b) may be present in the molecule.
Figure 0006075564
 [In Formula (a) to Formula (d), X 1 , Y 1, and Y 2 represent the same meaning as defined in Formula (1) to Formula (4), respectively. ]

ディスプレイ基板用樹脂組成物における上記ポリアミック酸又はポリイミド（両方とも含まれるときは、ポリアミック酸及びポリイミド）の含有量は、該樹脂組成物の固形分の含有量に基づいて、８乃至９９．９質量％、好ましくは４０乃至９９．９質量％、より好ましくは８０乃至９９．９質量％である。
ここで、固形分とはディスプレイ基板用樹脂組成物の全成分から溶剤を除去した残りの成分である。The content of the polyamic acid or polyimide (when both are included) in the display substrate resin composition is 8 to 99.9 masses based on the solid content of the resin composition. %, Preferably 40 to 99.9% by mass, more preferably 80 to 99.9% by mass.
Here, solid content is the remaining component which removed the solvent from all the components of the resin composition for display substrates.

本発明のディスプレイ基板用樹脂組成物は、ポリアミック酸又はポリイミドを含む。   The resin composition for a display substrate of the present invention contains polyamic acid or polyimide.

＜ポリアミック酸＞
本発明のディスプレイ基板用樹脂組成物に含まれるポリアミック酸は、酸無水物成分とジアミン成分とを溶剤中で重合させることで得られる。
ポリアミック酸は、公知の方法、例えば、窒素などの不活性ガス雰囲気中において、下記式（８）：

Figure 0006075564
（式中、Ｘ１は芳香族基と２つのカルボニル基を有する４価の有機基を表す。）で表される少なくとも１種の酸二無水物と、下記式（９）：
Ｈ２Ｎ−Ｙ１−ＮＨ２ （９）
（式中、Ｙ１は２価の芳香族基又は脂肪族基を表す。）で表される少なくとも１種のジアミンと、下記式（１０）：
Ｈ２Ｎ−Ｙ２−ＮＨ２ （１０）
（式中、Ｙ２は窒素原子を２個以上有する２価の芳香族基を表す。）で表される少なくとも１種のジアミンとを溶剤に溶解し、反応させることで得られる。<Polyamic acid>
The polyamic acid contained in the display substrate resin composition of the present invention is obtained by polymerizing an acid anhydride component and a diamine component in a solvent.
The polyamic acid is represented by the following formula (8) in a known method, for example, in an inert gas atmosphere such as nitrogen:
Figure 0006075564
 (Wherein, X 1 represents a tetravalent organic group having an aromatic group and two carbonyl groups), and the following formula (9):
H 2 N-Y 1 -NH 2 (9)
(Wherein Y 1 represents a divalent aromatic group or aliphatic group) and at least one diamine represented by the following formula (10):
H 2 N-Y 2 -NH 2 (10)
(In the formula, Y 2 represents a divalent aromatic group having two or more nitrogen atoms.) At least one diamine represented by the formula ( 2 ) is dissolved in a solvent and reacted.

この時の反応温度は、−２０乃至１００℃、好ましくは２０乃至６０℃である。反応時間は、１乃至７２時間である。   The reaction temperature at this time is −20 to 100 ° C., preferably 20 to 60 ° C. The reaction time is 1 to 72 hours.

本発明では、ポリアミック酸の反応溶液をそのまま、又は、希釈若しくは濃縮し、或いは反応溶液から再沈殿等により回収したポリアミック酸を適当な溶剤に再溶解又は分散させて、ディスプレイ基板用樹脂組成物として使用することができる。希釈、再溶解又は分散に用いる溶剤は、得られたポリアミック酸を溶解又は分散させるものであれば特に限定されないが、例えば、２−ピロリドン、Ｎ−メチル−２−ピロリドン、Ｎ−エチル−２−ピロリドン、Ｎ−ビニル−２−ピロリドン、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、３−メトキシ−Ｎ，Ｎ−ジメチルプロピルアミド、３−エトキシ−Ｎ，Ｎ−ジメチルプロピルアミド、３−プロポキシ−Ｎ，Ｎ−ジメチルプロピルアミド、３−イソプロポキシ−Ｎ，Ｎ−ジメチルプロピルアミド、３−ブトキシ−Ｎ，Ｎ−ジメチルプロピルアミド、３−ｓｅｃ−ブトキシ−Ｎ，Ｎ−ジメチルプロピルアミド、３−ｔｅｒｔ−ブトキシ−Ｎ，Ｎ−ジメチルプロピルアミド、γ−ブチロラクトン等を挙げることができる。これらの溶剤は、単独で又は２種以上を組み合わせて使用してもよい。   In the present invention, the polyamic acid reaction solution as it is, or diluted or concentrated, or the polyamic acid recovered from the reaction solution by reprecipitation or the like is re-dissolved or dispersed in an appropriate solvent to obtain a resin composition for a display substrate. Can be used. The solvent used for dilution, re-dissolution or dispersion is not particularly limited as long as it can dissolve or disperse the obtained polyamic acid. For example, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2- Pyrrolidone, N-vinyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, 3-methoxy-N, N-dimethylpropylamide, 3-ethoxy-N, N-dimethylpropylamide, 3- Propoxy-N, N-dimethylpropylamide, 3-isopropoxy-N, N-dimethylpropylamide, 3-butoxy-N, N-dimethylpropylamide, 3-sec-butoxy-N, N-dimethylpropylamide, 3 -Tert-butoxy-N, N-dimethylpropylamide, γ-butyrolactone, etc.These solvents may be used alone or in combination of two or more.

前記式（８）で表される酸二無水物としては、Ｘ１が下記式（７）で表される構造である酸二無水物が好ましく、Ｘ１が下記式（７−１）で表される構造である酸二無水物が特に好ましい。

Figure 0006075564
（式中、
Ｒ１２乃至Ｒ２１は、それぞれ独立して、水素原子、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基、カルボキシル基、Ｗ１で置換されていてもよいフェニル基、Ｗ１で置換されていてもよいナフチル基、Ｗ１で置換されていてもよいチエニル基又はＷ１で置換されていてもよいフリル基を表し、
Ｗ１は、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基又はカルボキシル基を表し、
Ｚ１及びＺ２は、それぞれ独立して、−ＮＨ−、−ＮＺ３−又は酸素原子を表し、
Ｚ３は、炭素原子数１乃至１０のアルキル基を表し、
ｐは１又は２を表す。なお、○は結合手を表す。）Table Examples of the acid dianhydride represented by the structural dianhydride preferably represented by X 1 is represented by the following formula (7), X 1 is the following formula (7-1) by the formula (8) Particularly preferred are acid dianhydrides having the structure
Figure 0006075564
 (Where
R 12 to R 21 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, or a halogen atom. , nitro group, formyl group, cyano group, carboxyl group, W 1 with an optionally substituted phenyl group, W 1 with an optionally substituted naphthyl group, W 1 with an optionally substituted thienyl group or W Represents a furyl group optionally substituted by 1 ,
W 1 is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, or a carboxyl group. Represents a group,
Z 1 and Z 2 each independently represent —NH—, —NZ 3 — or an oxygen atom,
Z 3 represents an alkyl group having 1 to 10 carbon atoms,
p represents 1 or 2. In addition, (circle) represents a bond. )

前記式（７）において、前記ｐが２であることが好ましい。   In the formula (7), the p is preferably 2.

このような式（８）で表される酸二無水物としては、例えば、ｐ−フェニレンビス（トリメリット酸モノエステル無水物）、２−メチル−１，４−フェニレンビス（トリメリット酸モノエステル無水物）、２，５−ジメチル−１，４−フェニレンビス（トリメリット酸モノエステル無水物）、２，３，５，６−テトラメチル−１，４−フェニレンビス（トリメリット酸モノエステル無水物）、２−トリフルオロメチル−１，４−フェニレンビス（トリメリット酸モノエステル無水物）、２，５−ジトリフルオロメチル−１，４−フェニレンビス（トリメリット酸モノエステル無水物）、２−クロロ−１，４−フェニレンビス（トリメリット酸モノエステル無水物）、２，５−ジクロロ−１，４−フェニレンビス（トリメリット酸モノエステル無水物）、２−フルオロ−１，４−フェニレンビス（トリメリット酸モノエステル無水物）及び２，５−ジフルオロ−１，４−フェニレンビス（トリメリット酸モノエステル無水物）、並びにＮ，Ｎ’−（１，４−フェニレン）ビス（１，３−ジオキソ−１，３−ジヒドロベンゾフラン−５−カルボキシアミド）及びＮ，Ｎ’−（１，４−フェニレン）ビス（Ｎ−メチル−１，３−ジオキソ−１，３−ジヒドロベンゾフラン−５−カルボキシアミド）等が挙げられる。
前記酸二無水物の中でも、本発明の樹脂組成物から得られる硬化膜が十分に低い線膨張係数及び十分に高い強度を有するものとする観点から、前記式（７）中のＲ１２乃至Ｒ２１が水素原子を表し、Ｚ１及びＺ２が酸素原子を表し、かつｐが２を表す化合物である、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）（下記式（１１））が好ましい。

Figure 0006075564
Examples of the acid dianhydride represented by the formula (8) include p-phenylenebis (trimellitic acid monoester anhydride) and 2-methyl-1,4-phenylenebis (trimellitic acid monoester). Anhydride), 2,5-dimethyl-1,4-phenylenebis (trimellitic acid monoester anhydride), 2,3,5,6-tetramethyl-1,4-phenylenebis (trimellitic acid monoester anhydride) Product), 2-trifluoromethyl-1,4-phenylenebis (trimellitic acid monoester anhydride), 2,5-ditrifluoromethyl-1,4-phenylenebis (trimellitic acid monoester anhydride), 2 -Chloro-1,4-phenylenebis (trimellitic acid monoester anhydride), 2,5-dichloro-1,4-phenylenebis (trimellitic acid monoester) Water), 2-fluoro-1,4-phenylenebis (trimellitic acid monoester anhydride) and 2,5-difluoro-1,4-phenylenebis (trimellitic acid monoester anhydride), and N, N '-(1,4-phenylene) bis (1,3-dioxo-1,3-dihydrobenzofuran-5-carboxamide) and N, N'-(1,4-phenylene) bis (N-methyl-1, 3-dioxo-1,3-dihydrobenzofuran-5-carboxamide) and the like.
Among the acid dianhydrides, R 12 to R in the formula (7) from the viewpoint that the cured film obtained from the resin composition of the present invention has a sufficiently low linear expansion coefficient and a sufficiently high strength. 4,4′-biphenylbis (trimellitic acid monoester acid anhydride) ( 21) represents a hydrogen atom, Z 1 and Z 2 represent an oxygen atom, and p represents 2. )) Is preferred.
Figure 0006075564

前記式（９）で表される芳香族又は脂肪族ジアミンは、本発明の樹脂組成物から得られる硬化膜が十分に低い線膨張係数を有するものとする観点から、剛直で直線的な分子構造を有するジアミンを使用することが好ましい。なかでも前記式（９）で表されるジアミンとしては、Ｙ１が下記式（６）で表される構造であるジアミンが好ましく、Ｙ１が下記式（６−１）で表される構造であるジアミンが特に好ましい。

Figure 0006075564
（式中、
Ｒ８乃至Ｒ１１は、それぞれ独立して、水素原子、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基、カルボキシル基、Ｗ１で置換されていてもよいフェニル基、Ｗ１で置換されていてもよいナフチル基、Ｗ１で置換されていてもよいチエニル基又はＷ１で置換されていてもよいフリル基を表し、
Ｗ１は、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基又はカルボキシル基を表し、
ｑは１又は２を表す。なお、○は結合手を表す。）The aromatic or aliphatic diamine represented by the formula (9) is a rigid and linear molecular structure from the viewpoint that the cured film obtained from the resin composition of the present invention has a sufficiently low linear expansion coefficient. It is preferred to use a diamine having Of these examples of the diamine represented by the formula (9), the structure diamine preferably represented by Y 1 is the following formula (6), a structure in which Y 1 is represented by the following formula (6-1) Certain diamines are particularly preferred.
Figure 0006075564
 (Where
R 8 to R 11 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, or a halogen atom. , nitro group, formyl group, cyano group, carboxyl group, W 1 with an optionally substituted phenyl group, W 1 with an optionally substituted naphthyl group, W 1 with an optionally substituted thienyl group or W Represents a furyl group optionally substituted by 1 ,
W 1 is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, or a carboxyl group. Represents a group,
q represents 1 or 2. In addition, (circle) represents a bond. )

前記式（６）で表される２価の芳香族基がフェニレンジアミンから誘導されたものであることが好ましい。
また、本発明の樹脂組成物から得られる硬化膜が十分に低い線膨張係数及び十分に高い強度を有するものとする観点から、前記式（６）において、前記Ｒ８乃至Ｒ１１が水素原子であることが好ましい。The divalent aromatic group represented by the formula (6) is preferably derived from phenylenediamine.
Further, from the viewpoint that the cured film obtained from the resin composition of the present invention has a sufficiently low linear expansion coefficient and a sufficiently high strength, in the formula (6), R 8 to R 11 are hydrogen atoms. Preferably there is.

前記式（９）で表される芳香族ジアミンとしては、例えば、ｐ−フェニレンジアミン、ｏ−フェニレンジアミン、メチル−１，４−フェニレンジアミン、２−トリフルオロメチル−１，４−フェニレンジアミン、２−メトキシ−１，４−フェニレンジアミン、２，５−ジメチル−１，４−フェニレンジアミン、２，５−ビス（トリフルオロメチル）−１，４−フェニレンジアミン、４，４’−ジアミノベンズアニリド、４−アミノフェニル−４’−アミノベンゾエート、ベンジジン、３，３’−ジメトキシベンジジン、３，３’−ジクロロベンジジン、ｏ−トリジン、ｍ−トリジン、２，２’−ビス（トリフルオロメチル）ベンジジン、３，３’−ビス（トリフルオロメチル）ベンジジン、オクタフルオロベンジジン、３，３’，５，５’−テトラメチルベンジジン、２，２’，５，５’−テトラクロロベンジジン等が挙げられるが、これらの中でも、本発明の樹脂組成物から得られる硬化膜が十分に低い線膨張係数及び十分に高い強度を有するものとする観点から、ｐ−フェニレンジアミン及びｍ−フェニレンジアミンが特に好ましい。   Examples of the aromatic diamine represented by the formula (9) include p-phenylenediamine, o-phenylenediamine, methyl-1,4-phenylenediamine, 2-trifluoromethyl-1,4-phenylenediamine, and 2 -Methoxy-1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, 2,5-bis (trifluoromethyl) -1,4-phenylenediamine, 4,4'-diaminobenzanilide, 4-aminophenyl-4′-aminobenzoate, benzidine, 3,3′-dimethoxybenzidine, 3,3′-dichlorobenzidine, o-tolidine, m-tolidine, 2,2′-bis (trifluoromethyl) benzidine, 3,3′-bis (trifluoromethyl) benzidine, octafluorobenzidine, 3,3 ′, 5,5′- Examples include tramethylbenzidine and 2,2 ′, 5,5′-tetrachlorobenzidine. Among these, the cured film obtained from the resin composition of the present invention has a sufficiently low linear expansion coefficient and sufficiently high strength. From the viewpoint of having p, p-phenylenediamine and m-phenylenediamine are particularly preferable.

前記式（９）で表される脂肪族ジアミンとしては、例えば、４，４’−メチレンビス（シクロヘキシルアミン）、４，４’−メチレンビス（３−メチルシクロヘキシルアミン）、イソホロンジアミン、トランス−１，４−シクロヘキサンジアミン、シス−１，４−シクロヘキサンジアミン、１，４−シクロヘキサンビス（メチルアミン）、２，５−ビス（アミノメチル）ビシクロ〔２．２．１〕ヘプタン、２，６−ビス（アミノメチル）ビシクロ〔２．２．１〕ヘプタン、３，８−ビス（アミノメチル）トリシクロ〔５．２．１．０〕デカン、１，３−ジアミノアダマンタン、２，２−ビス（４−アミノシクロヘキシル）プロパン、２，２−ビス（４−アミノシクロヘキシル）ヘキサフルオロプロパン、１，３−プロパンジアミン、１，４−テトラメチレンジアミン、１，５−ペンタメチレンジアミン、１，６−ヘキサメチレンジアミン、１，７−ヘプタメチレンジアミン、１，８−オクタメチレンジアミン、１，９−ノナメチレンジアミン等が挙げられる。
前記脂肪族ジアミンの中でも、本発明の樹脂組成物から得られる硬化膜が十分に低い線膨張係数を有するものとする観点から、剛直で直線的な分子構造を有するジアミンを使用することが好ましく、例えばトランス−１，４−シクロヘキサンジアミンが好適に用いられる。Examples of the aliphatic diamine represented by the formula (9) include 4,4′-methylenebis (cyclohexylamine), 4,4′-methylenebis (3-methylcyclohexylamine), isophoronediamine, and trans-1,4. -Cyclohexanediamine, cis-1,4-cyclohexanediamine, 1,4-cyclohexanebis (methylamine), 2,5-bis (aminomethyl) bicyclo [2.2.1] heptane, 2,6-bis (amino) Methyl) bicyclo [2.2.1] heptane, 3,8-bis (aminomethyl) tricyclo [5.2.1.0] decane, 1,3-diaminoadamantane, 2,2-bis (4-aminocyclohexyl) ) Propane, 2,2-bis (4-aminocyclohexyl) hexafluoropropane, 1,3-propanediamine, 1,4-the La diamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylene diamine, 1,8-octamethylene diamine, 1,9-nonamethylenediamine, and the like.
Among the aliphatic diamines, from the viewpoint that the cured film obtained from the resin composition of the present invention has a sufficiently low linear expansion coefficient, it is preferable to use a diamine having a rigid and linear molecular structure, For example, trans-1,4-cyclohexanediamine is preferably used.

また、前記式（１０）で表されるジアミンも、本発明の樹脂組成物から得られる硬化膜が十分に低い線膨張係数を有するものとする観点から、剛直で直線的な分子構造を有するジアミンを使用することが好ましい。
なかでも前記式（１０）で表されるジアミンとしては、Ｙ２が、イミダゾール、オキサゾール、チアゾール、テトラアザピレン、イミダゾピロロン、キサノリン、インドロキサノリン、イソインドロキナゾリンジオンといった複素環構造を有する芳香族基であるジアミンが好ましく、当該複素環構造ベンゼン、ナフタレン、アントラセン等の芳香族環構造を有する芳香族基であるジアミンがより好ましく、Ｙ２が下記式（５）で表される構造であるジアミンが好ましく、Ｙ２が下記式（５−１）で表される構造であるジアミンが特に好ましい。

Figure 0006075564
（式中、
Ｒ１乃至Ｒ７は、それぞれ独立して、水素原子、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基、カルボキシル基、Ｗ１で置換されていてもよいフェニル基、Ｗ１で置換されていてもよいナフチル基、Ｗ１で置換されていてもよいチエニル基又はＷ１で置換されていてもよいフリル基を表し、
Ｗ１は、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基又はカルボキシル基を表し、
Ａは、水素原子、炭素原子数１乃至１０のアルキル基又は炭素原子数１乃至１０のハロアルキル基を表す。なお、○は結合手を表す。）The diamine represented by the formula (10) is also a diamine having a rigid and linear molecular structure from the viewpoint that the cured film obtained from the resin composition of the present invention has a sufficiently low linear expansion coefficient. Is preferably used.
Among them, as the diamine represented by the formula (10), Y 2 has a heterocyclic structure such as imidazole, oxazole, thiazole, tetraazapyrene, imidazopyrrolone, xanoline, indoloxanoline, and isoindoloquinazolinedione. A diamine that is an aromatic group is preferable, a diamine that is an aromatic group having an aromatic ring structure such as the heterocyclic structure benzene, naphthalene, and anthracene is more preferable, and Y 2 is a structure represented by the following formula (5). A certain diamine is preferable, and a diamine having a structure in which Y 2 is represented by the following formula (5-1) is particularly preferable.
Figure 0006075564
 (Where
R 1 to R 7 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, or a halogen atom. , nitro group, formyl group, cyano group, carboxyl group, W 1 with an optionally substituted phenyl group, W 1 with an optionally substituted naphthyl group, W 1 with an optionally substituted thienyl group or W Represents a furyl group optionally substituted by 1 ,
W 1 is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, or a carboxyl group. Represents a group,
A represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group having 1 to 10 carbon atoms. In addition, (circle) represents a bond. )

前記式（１０）で表されるジアミンとしては、２−（４−アミノフェニル）−５−アミノベンズオキサゾール、２−（３−アミノフェニル）−５−アミノベンズオキサゾール、２−（４−アミノフェニル）−５−アミノベンズイミダゾール、２−（３−アミノフェニル）−５−アミノベンズイミダゾール、２−（４−アミノフェニル）−５−アミノベンズチアゾール、２−（３−アミノフェニル）−５−アミノベンズジアゾール等が挙げられる。
前記ジアミンの中でも、その入手容易性及び本発明の樹脂組成物から得られる硬化膜の自己支持性を高める観点から、前記式（５）中のＲ１乃至Ｒ７及びＡが水素原子を表す化合物である、２−（３−アミノフェニル）−５−アミノベンズイミダゾールが好ましい。Examples of the diamine represented by the formula (10) include 2- (4-aminophenyl) -5-aminobenzoxazole, 2- (3-aminophenyl) -5-aminobenzoxazole, and 2- (4-aminophenyl). ) -5-aminobenzimidazole, 2- (3-aminophenyl) -5-aminobenzimidazole, 2- (4-aminophenyl) -5-aminobenzthiazole, 2- (3-aminophenyl) -5-amino Examples include benzdiazole.
Among the diamines, R 1 to R 7 and A in the formula (5) each represent a hydrogen atom from the viewpoint of improving the availability and the self-supporting property of the cured film obtained from the resin composition of the present invention. 2- (3-aminophenyl) -5-aminobenzimidazole is preferred.

ポリアミック酸の生成反応に使用される溶剤としては特に限定されないが、例えば、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジエチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチルピロリドン、３−メトキシ−Ｎ，Ｎ−ジメチルプロピルアミド、３−エトキシ−Ｎ，Ｎ−ジメチルプロピルアミド、３−プロポキシ−Ｎ，Ｎ−ジメチルプロピルアミド、３−イソプロポキシ−Ｎ，Ｎ−ジメチルプロピルアミド、３−ブトキシ−Ｎ，Ｎ−ジメチルプロピルアミド、３−ｓｅｃ−ブトキシ−Ｎ，Ｎ−ジメチルプロピルアミド、３−ｔｅｒｔ−ブトキシ−Ｎ，Ｎ−ジメチルプロピルアミド、ヘキサメチルホスホルアミド、ジメチルスルホオキシド、γ−ブチロラクトン、１，３−ジメチル−２−イミダゾリジノン、１，２−ジメトキシエタン−ビス（２−メトキシエチル）エーテル、テトラヒドロフラン、１，４−ジオキサン、ピコリン、ピリジン、アセトン、クロロホルム、トルエン、キシレン等の非プロトン性溶剤、及びフェノール、ｏ−クレゾール、ｍ−クレゾール、ｐ−クレゾール、ｏ−クロロフェノール、ｍ−クロロフェノール、ｐ−クロロフェノール等のプロトン性溶剤等が挙げられる。これらの溶剤は単独で又は２種類以上を組み合わせて使用してもよい。   Although it does not specifically limit as a solvent used for the production | generation reaction of a polyamic acid, For example, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, 3-methoxy-N , N-dimethylpropylamide, 3-ethoxy-N, N-dimethylpropylamide, 3-propoxy-N, N-dimethylpropylamide, 3-isopropoxy-N, N-dimethylpropylamide, 3-butoxy-N, N-dimethylpropylamide, 3-sec-butoxy-N, N-dimethylpropylamide, 3-tert-butoxy-N, N-dimethylpropylamide, hexamethylphosphoramide, dimethylsulfoxide, γ-butyrolactone, 1, 3-dimethyl-2-imidazolidinone, 1,2-dimethoxy Aprotic solvents such as tan-bis (2-methoxyethyl) ether, tetrahydrofuran, 1,4-dioxane, picoline, pyridine, acetone, chloroform, toluene, xylene, and phenol, o-cresol, m-cresol, p- Examples include protic solvents such as cresol, o-chlorophenol, m-chlorophenol, and p-chlorophenol. These solvents may be used alone or in combination of two or more.

上記反応において、ジアミン成分の割合は、上記式（９）で表されるジアミンと上記式（１０）で表されるジアミンとのモル比が、７０／３０乃至９９／１であることが好ましく、本発明の樹脂組成物から得られる硬化膜が十分に低い線膨張係数及び十分に高い強度を有するものとする観点から、７５／２５乃至９５／５であることがより好ましい。   In the above reaction, the ratio of the diamine component is such that the molar ratio of the diamine represented by the above formula (9) and the diamine represented by the above formula (10) is 70/30 to 99/1, From the viewpoint that the cured film obtained from the resin composition of the present invention has a sufficiently low linear expansion coefficient and a sufficiently high strength, it is more preferably 75/25 to 95/5.

また、上記反応において、酸二無水物成分とジアミン成分との割合は、モル比で酸二無水物成分／ジアミン成分＝０．８乃至１．２であることが好ましい。通常の重縮合反応と同様に、このモル比が１に近いほど生成する重合体の重合度は大きくなる。重合度が小さすぎるとポリイミド硬化膜の強度が不十分となり、また重合度が大きすぎるとポリイミド硬化膜形成時の作業性が悪くなる場合がある。   Moreover, in the said reaction, it is preferable that the ratio of an acid dianhydride component and a diamine component is acid dianhydride component / diamine component = 0.8 thru | or 1.2 by molar ratio. Similar to the normal polycondensation reaction, the closer the molar ratio is to 1, the higher the degree of polymerization of the polymer produced. When the degree of polymerization is too small, the strength of the polyimide cured film becomes insufficient, and when the degree of polymerization is too large, workability at the time of forming the polyimide cured film may be deteriorated.

生成されるポリアミック酸の重量平均分子量は、ポリアミック酸を含むディスプレイ基板用樹脂組成物から得られる硬化膜の強度を維持するために、ポリスチレン換算にて３，０００乃至２００，０００が好ましい。重量平均分子量が３，０００未満では、できあがったフィルムが脆くなる可能性があり、一方、重量平均分子量が２００，０００を超えるとポリアミック酸のワニスの粘度が高くなり過ぎる可能性があり、その結果、取扱いが難しくなるからである。   The weight average molecular weight of the produced polyamic acid is preferably 3,000 to 200,000 in terms of polystyrene in order to maintain the strength of the cured film obtained from the resin composition for display substrate containing polyamic acid. If the weight average molecular weight is less than 3,000, the resulting film may be brittle. On the other hand, if the weight average molecular weight exceeds 200,000, the viscosity of the polyamic acid varnish may be too high. This is because handling becomes difficult.

生成されるポリアミック酸中の式（１）で表される構造単位の数ｎ及び式（３）で表される構造単位の数ｍの関係は、好ましくはｎ／ｍ＝７０／３０乃至９９／１であり、より好ましくは７５／２５乃至９５／５である。
また、特に、得られる硬化膜が十分に低い線膨張係数及び十分に高い強度を有するものとする観点から、Ｘ１が、Ｒ１２乃至Ｒ２１が水素原子であり、Ｚ１及びＺ２が酸素原子である式（７）で表される構造であり、Ｙ１が、Ｒ８乃至Ｒ１１が水素原子である式（６）で表される構造である式（１）で表される構造単位（下記式（１−１）で表される構造単位）及びＸ１が、Ｒ１２乃至Ｒ２１が水素原子であり、Ｚ１及びＺ２が酸素原子である式（７）で表される構造であり、Ｙ２が、Ｒ１乃至Ｒ７及びＡが水素原子である式（５）で表される構造である式（３）で表される構造単位（下記式（３−１）で表される構造単位）の割合は、両方の合計で、生成されるポリアミック酸の繰返し単位中、好ましくは７０モル％以上、より好ましくは８０モル％以上、より一層好ましくは８５モル％以上である。The relationship between the number n of structural units represented by formula (1) and the number m of structural units represented by formula (3) in the produced polyamic acid is preferably n / m = 70/30 to 99 / 1, more preferably 75/25 to 95/5.
In particular, from the viewpoint that the obtained cured film has a sufficiently low linear expansion coefficient and a sufficiently high strength, X 1 is R 12 to R 21 are hydrogen atoms, and Z 1 and Z 2 are oxygen. A structural unit represented by formula (1), which is a structure represented by formula (7) which is an atom, and Y 1 is a structure represented by formula (6), wherein R 8 to R 11 are hydrogen atoms. (Structural unit represented by the following formula (1-1)) and X 1 are structures represented by the formula (7) in which R 12 to R 21 are hydrogen atoms, and Z 1 and Z 2 are oxygen atoms. Y 2 is a structural unit represented by formula (3) which is a structure represented by formula (5) wherein R 1 to R 7 and A are hydrogen atoms (represented by formula (3-1) below) The proportion of the structural units) is preferably the sum of both of the repeating units of the polyamic acid produced, preferably 70 mol% or more, and more Preferably it is 80 mol% or more, More preferably, it is 85 mol% or more.

Figure 0006075564
［式中、ｑ及びｐは、それぞれ前記式（６）及び式（７）における定義と同じ意味を表す。］
Figure 0006075564
 [Wherein q and p represent the same meanings as defined in the above formulas (6) and (7), respectively. ]

以上説明した方法により得られるポリアミック酸を用いてディスプレイ基板用樹脂組成物を作製、特に溶媒に溶解又は分散させてワニス形態で該樹脂組成物を作製する場合、Ｘ１が、下記式（７−２）で表される構造であり、Ｙ１が、下記式（６−２）で表される構造である式（１）で表される構造単位及びＸ１が、下記式（７−２）で表される構造であり、Ｙ２が、下記式（５−２）で表される構造である式（３）で表される構造単位を含むポリアミック酸が好ましく（以下、構成Ａ）、Ｘ１が、下記式（７−３）で表される構造であり、Ｙ１が、下記式（６−３）で表される構造である式（１）で表される構造単位及びＸ１が、下記式（７−３）で表される構造であり、Ｙ２が、下記式（５−３）で表される構造である式（３）で表される構造単位を含むポリアミック酸がより好ましく（以下、構成Ｂ）、Ｘ１が、ｐが２である下記式（７−３）で表される構造であり、Ｙ１が、ｑが１である下記式（６−３）で表される構造である式（１）で表される構造単位及びＸ１が、ｐが２である下記式（７−３）で表される構造であり、Ｙ２が、下記式（５−３）で表される構造である式（３）で表される構造単位を含むポリアミック酸がより一層好ましい（以下、構成Ｃ）。When a resin composition for a display substrate is produced using the polyamic acid obtained by the above-described method, particularly when the resin composition is produced in a varnish form by dissolving or dispersing in a solvent, X 1 is represented by the following formula (7- 2), wherein Y 1 is a structure represented by the following formula (6-2) and a structural unit represented by the formula (1) and X 1 are represented by the following formula (7-2) A polyamic acid containing a structural unit represented by formula (3) wherein Y 2 is a structure represented by the following formula (5-2) is preferred (hereinafter referred to as configuration A), X 1 is a structure represented by the following formula (7-3), Y 1 is a structure represented by the following formula (6-3), and the structural unit represented by the formula (1) and X 1 are a structure represented by the following formula (7-3), Y 2 is the formula (3) is a structure represented by the following formula (5-3) Is the more preferred polyamic acid having a structural unit (hereinafter, configuration B), X 1 is, p has a structure which is represented by the following formula is 2 (7-3), Y 1 is, q is 1 A structural unit represented by the formula (1) which is a structure represented by the following formula (6-3) and X 1 are structures represented by the following formula (7-3) in which p is 2. A polyamic acid containing a structural unit represented by the formula (3) in which Y 2 is a structure represented by the following formula (5-3) is even more preferable (hereinafter referred to as configuration C).

Figure 0006075564
［式中、ｑ及びｐは、それぞれ前記式（６）及び式（７）における定義と同じ意味を表す。なお、○は結合手を表す。］
Figure 0006075564
 [Wherein q and p represent the same meanings as defined in the above formulas (6) and (7), respectively. In addition, (circle) represents a bond. ]

そして、更に、これら好ましい各構成（構成Ａ，Ｂ又はＣ）の下で、式（１）で表される構造単位の数ｎ及び式（３）で表される構造単位の数ｍが、ｎ／ｍ＝７０／３０乃至９９／１の関係、好ましくはｎ／ｍ＝７５／２５乃至９５／５の関係、を満たし、上記式（１−１）で表される構造単位及び上記式（３−１）で表される構造単位の割合が、両方の合計で、ポリアミック酸の繰返し単位中、７０モル％以上、好ましくは８０モル％以上、より好ましくは８５モル％以上、であり、かつ、ポリアミック酸の重量平均分子量が３，０００乃至２００，０００（ポリスチレン換算）であることが好ましい。
なお、上記で説明した、式（１）で表される構造単位及び式（３）で表される構造単位を含むポリアミック酸も、本発明の対象である。Further, under each of these preferable configurations (configurations A, B, or C), the number n of structural units represented by formula (1) and the number m of structural units represented by formula (3) are n / M = 70/30 to 99/1, preferably n / m = 75/25 to 95/5, and the structural unit represented by the above formula (1-1) and the above formula (3 The ratio of the structural unit represented by -1) is 70 mol% or more, preferably 80 mol% or more, more preferably 85 mol% or more in the repeating unit of the polyamic acid in the total of both, and The weight average molecular weight of the polyamic acid is preferably 3,000 to 200,000 (polystyrene conversion).
In addition, the polyamic acid containing the structural unit represented by Formula (1) and the structural unit represented by Formula (3) demonstrated above is also the object of this invention.

＜ポリイミド＞
本発明のディスプレイ基板用樹脂組成物に含まれるポリイミドは、上述のように合成したポリアミック酸を、加熱により脱水閉環（熱イミド化）して得ることができる。なお、この際、ポリアミック酸を溶剤中でイミドに転化させ、溶剤可溶性のポリイミドとして用いることも可能である。また、公知の脱水閉環触媒を使用して化学的に閉環する方法も採用することができる。加熱による方法は、１００乃至３００℃、好ましくは１２０乃至２５０℃の任意の温度で行うことができる。化学的に閉環する方法は、例えば、ピリジンやトリエチルアミンなどと、無水酢酸などとの存在下で行うことができ、この際の温度は、−２０乃至２００℃の任意の温度を選択することができる。<Polyimide>
The polyimide contained in the resin composition for display substrates of the present invention can be obtained by subjecting the polyamic acid synthesized as described above to dehydration ring closure (thermal imidization) by heating. At this time, polyamic acid can be converted to imide in a solvent and used as a solvent-soluble polyimide. Moreover, the method of chemically ring-closing using a well-known dehydration ring-closing catalyst is also employable. The method by heating can be performed at an arbitrary temperature of 100 to 300 ° C., preferably 120 to 250 ° C. The chemical ring closure method can be performed, for example, in the presence of pyridine, triethylamine, and the like, and acetic anhydride, and the temperature at this time can be selected from -20 to 200 ° C. .

本発明では、ポリイミドの反応溶液をそのまま、又は、希釈若しくは濃縮し、或いは反応溶液から再沈殿等により回収したポリイミドを適当な溶剤に再溶解又は分散させて、ディスプレイ基板用樹脂組成物として使用することができる。希釈、再溶解又は分散に用いる溶剤は、得られたポリイミドを溶解又は分散させるものであれば特に限定されないが、例えば、ｍ−クレゾール、２−ピロリドン、Ｎ−メチル−２−ピロリドン、Ｎ−エチル−２−ピロリドン、Ｎ−ビニル−２−ピロリドン、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、３−メトキシ−Ｎ，Ｎ−ジメチルプロピルアミド、３−エトキシ−Ｎ，Ｎ−ジメチルプロピルアミド、３−プロポキシ−Ｎ，Ｎ−ジメチルプロピルアミド、３−イソプロポキシ−Ｎ，Ｎ−ジメチルプロピルアミド、３−ブトキシ−Ｎ，Ｎ−ジメチルプロピルアミド、３−ｓｅｃ−ブトキシ−Ｎ，Ｎ−ジメチルプロピルアミド、３−ｔｅｒｔ−ブトキシ−Ｎ，Ｎ−ジメチルプロピルアミド、γ−ブチロラクトン、などが挙げられる。これらの溶剤は、単独で又は２種以上を組み合わせて使用してもよい。   In the present invention, the polyimide reaction solution is used as it is, or diluted or concentrated, or the polyimide recovered from the reaction solution by reprecipitation or the like is dissolved or dispersed in an appropriate solvent and used as a resin composition for a display substrate. be able to. The solvent used for dilution, re-dissolution or dispersion is not particularly limited as long as it can dissolve or disperse the obtained polyimide. For example, m-cresol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl -2-pyrrolidone, N-vinyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, 3-methoxy-N, N-dimethylpropylamide, 3-ethoxy-N, N-dimethylpropylamide , 3-propoxy-N, N-dimethylpropylamide, 3-isopropoxy-N, N-dimethylpropylamide, 3-butoxy-N, N-dimethylpropylamide, 3-sec-butoxy-N, N-dimethylpropyl Amide, 3-tert-butoxy-N, N-dimethylpropylamide, γ-butyrolactone, etc. It is. These solvents may be used alone or in combination of two or more.

生成されるポリイミドの重量平均分子量は、ポリイミドを含むディスプレイ基板用樹脂組成物から得られる硬化膜の強度を維持するために、ポリスチレン換算にて３，０００乃至２００，０００が好ましい。重量平均分子量が３，０００未満では、できあがったフィルムが脆くなる可能性があり、一方、重量平均分子量が２００，０００を超えるとポリイミドのワニスの粘度が高くなり過ぎる可能性があり、その結果、取扱いが難しくなるからである。   The weight average molecular weight of the produced polyimide is preferably 3,000 to 200,000 in terms of polystyrene in order to maintain the strength of the cured film obtained from the resin composition for display substrate containing polyimide. If the weight average molecular weight is less than 3,000, the resulting film may become brittle, while if the weight average molecular weight exceeds 200,000, the viscosity of the polyimide varnish may be too high, and as a result, This is because handling becomes difficult.

生成されるポリイミド中の式（２）で表される構造単位の数ｎ及び式（４）で表される構造単位の数ｍの関係は、好ましくはｎ／ｍ＝７０／３０乃至９９／１であり、より好ましくは７５／２５乃至９５／５である。
また、特に、得られる硬化膜が十分に低い線膨張係数及び十分に高い強度を有するものとする観点から、Ｘ１が、Ｒ１２乃至Ｒ２１が水素原子であり、Ｚ１及びＺ２が酸素原子である式（７）で表される構造であり、Ｙ１が、Ｒ８乃至Ｒ１１が水素原子である式（６）で表される構造である式（２）で表される構造単位（下記式（２−１）で表される構造単位）及びＸ１が、Ｒ１２乃至Ｒ２１が水素原子であり、Ｚ１及びＺ２が酸素原子である式（７）で表される構造であり、Ｙ２が、Ｒ１乃至Ｒ７及びＡが水素原子である式（５）で表される構造である式（４）で表される構造単位（下記式（４−１）で表される構造単位）の割合は、両方の合計で、生成されるポリイミドの繰返し単位中、好ましくは７０モル％以上、より好ましくは８０モル％以上、より一層好ましくは８５モル％以上である。The relationship between the number n of structural units represented by formula (2) and the number m of structural units represented by formula (4) in the polyimide produced is preferably n / m = 70/30 to 99/1. More preferably, it is 75/25 to 95/5.
In particular, from the viewpoint that the obtained cured film has a sufficiently low linear expansion coefficient and a sufficiently high strength, X 1 is R 12 to R 21 are hydrogen atoms, and Z 1 and Z 2 are oxygen. A structural unit represented by formula (2), which is a structure represented by formula (7) which is an atom, and Y 1 is a structure represented by formula (6), wherein R 8 to R 11 are hydrogen atoms (Structural unit represented by the following formula (2-1)) and X 1 are structures represented by the formula (7) in which R 12 to R 21 are hydrogen atoms, and Z 1 and Z 2 are oxygen atoms. Y 2 is a structural unit represented by the formula (4) which is a structure represented by the formula (5) in which R 1 to R 7 and A are hydrogen atoms (represented by the following formula (4-1)) The proportion of the structural units) is preferably 70 mol% or more, more preferably in the total of both of the repeating units of the polyimide produced. Alternatively, it is 80 mol% or more, more preferably 85 mol% or more.

Figure 0006075564
［式中、ｑ及びｐは、それぞれ前記式（６）及び式（７）における定義と同じ意味を表す。］
Figure 0006075564
 [Wherein q and p represent the same meanings as defined in the above formulas (6) and (7), respectively. ]

以上説明した方法により得られるポリイミドを用いてディスプレイ基板用樹脂組成物を作製、特に溶媒に溶解又は分散させてワニス形態で該樹脂組成物を作製する場合、Ｘ１が、上記式（７−２）で表される構造であり、Ｙ１が、上記式（６−２）で表される構造である式（２）で表される構造単位及びＸ１が、上記式（７−２）で表される構造であり、Ｙ２が、上記式（５−２）で表される構造である式（４）で表される構造単位を含むポリイミドが好ましく（以下、構成Ｄ）、Ｘ１が、上記式（７−３）で表される構造であり、Ｙ１が、上記式（６−３）で表される構造である式（２）で表される構造単位及びＸ１が、上記式（７−３）で表される構造であり、Ｙ２が、上記式（５−３）で表される構造である式（４）で表される構造単位を含むポリイミドがより好ましく（以下、構成Ｅ）、Ｘ１が、ｐが２である上記式（７−３）で表される構造であり、Ｙ１が、ｑが１である上記式（６−３）で表される構造である式（２）で表される構造単位及びＸ１が、ｐが２である上記式（７−３）で表される構造であり、Ｙ２が、上記式（５−３）で表される構造である式（４）で表される構造単位を含むポリイミドがより一層好ましい（以下、構成Ｆ）。
そして、更に、これら好ましい各構成（構成Ｄ，Ｅ又はＦ）の下で、式（２）で表される構造単位の数ｎ及び式（４）で表される構造単位の数ｍが、ｎ／ｍ＝７０／３０乃至９９／１の関係、好ましくはｎ／ｍ＝７５／２５乃至９５／５の関係、を満たし、上記式（２−１）で表される構造単位及び上記式（４−１）で表される構造単位の割合が、両方の合計で、ポリイミドの繰返し単位中、７０モル％以上、好ましくは８０モル％以上、より好ましくは８５モル％以上、であり、かつ、ポリイミドの重量平均分子量が３，０００乃至２００，０００（ポリスチレン換算）であることが好ましい。
なお、上記で説明した、式（２）で表される構造単位及び式（４）で表される構造単位を含むポリイミドも本発明の対象である。When a resin composition for a display substrate is produced using the polyimide obtained by the above-described method, particularly when the resin composition is produced in a varnish form by dissolving or dispersing in a solvent, X 1 represents the above formula (7-2). ), Wherein Y 1 is a structure represented by the above formula (6-2) and the structural unit represented by the formula (2) and X 1 are represented by the above formula (7-2). Polyimide containing a structural unit represented by the formula (4) in which Y 2 is a structure represented by the above formula (5-2) is preferable (hereinafter referred to as configuration D), and X 1 is The structural unit represented by the formula (7-3) and Y 1 is the structure represented by the formula (6-3) and the structural unit represented by the formula (2) and X 1 are a structure represented by formula (7-3), Y 2 is represented by the formula (4) is a structure represented by the formula (5-3) More preferably polyimide comprising forming units (hereinafter, Configuration E), X 1 is, p is a structure represented by the above formula is 2 (7-3), Y 1 is the formula q is 1 (6-3) is a structure represented by the formula (2) and X 1 is a structure represented by the above formula (7-3) in which p is 2, and Y 2 is The polyimide containing the structural unit represented by the formula (4) which is the structure represented by the above formula (5-3) is more preferable (hereinafter referred to as configuration F).
Further, under these preferable configurations (configurations D, E, or F), the number n of structural units represented by formula (2) and the number m of structural units represented by formula (4) are n / M = 70/30 to 99/1, preferably n / m = 75/25 to 95/5, and the structural unit represented by the above formula (2-1) and the above formula (4) The proportion of the structural unit represented by -1) is 70 mol% or more, preferably 80 mol% or more, more preferably 85 mol% or more in the repeating unit of polyimide in the total of both, and polyimide Is preferably 3,000 to 200,000 (in terms of polystyrene).
In addition, the polyimide containing the structural unit represented by Formula (2) and the structural unit represented by Formula (4) demonstrated above is also the object of this invention.

本発明のディスプレイ基板用樹脂組成物は、上記式（１）で表される構造単位及び式（３）で表される構造単位を含むポリアミック酸と上記式（２）で表される構造単位及び式（４）で表される構造単位を含むポリイミドの両方を含んでいてもよい。   The resin composition for display substrates of the present invention comprises a structural unit represented by the above formula (1) and a polyamic acid containing a structural unit represented by the formula (3), a structural unit represented by the above formula (2), and Both of the polyimide containing the structural unit represented by the formula (4) may be included.

本発明のディスプレイ基板用樹脂組成物は、溶剤を含み、ポリアミック酸又はポリイミドが溶解又は均一に分散していることが好ましく、ポリアミック酸又はポリイミドが溶剤に溶解していることがより好ましい。そのような溶剤としては、例えば、段落［００１４］に記載された溶剤等が挙げられる。   The resin composition for a display substrate of the present invention contains a solvent, and preferably the polyamic acid or polyimide is dissolved or uniformly dispersed, and more preferably the polyamic acid or polyimide is dissolved in the solvent. Examples of such solvents include the solvents described in paragraph [0014].

また、本発明のディスプレイ基板用樹脂組成物は、架橋剤（以下、架橋性化合物ともいう。）を含むことができる。
＜架橋剤＞
架橋性化合物は、そのポジ型感光性樹脂組成物を用いて得られる塗膜を、硬化膜に転換する工程で、ポリアミック酸、又はポリイミドの少なくとも一方に含有される有機基と、反応し得る基を有する化合物であれば特に限定されない。そのような化合物としては、例えば、エポキシ基を２個以上含有する化合物や、アミノ基の水素原子が、メチロール基、アルコキシメチル基又はその両方で置換された基を有する、メラミン誘導体、ベンゾグアナミン誘導体又はグリコールウリル等が挙げられる。このメラミン誘導体及びベンゾグアナミン誘導体は、二量体又は三量体であっても良く、又、単量体、二量体及び三量体から任意に選ばれる混合物であっても良い。これらのメラミン誘導体及びベンゾグアナミン誘導体は、トリアジン環１個当たり、メチロール基又はアルコキシメチル基を平均３個以上６個未満有するものが好ましい。
また、本発明に用いられる架橋剤は、単独で又は２種以上を組み合わせて使用してもよい。Moreover, the resin composition for display substrates of this invention can contain a crosslinking agent (henceforth a crosslinkable compound).
<Crosslinking agent>
The crosslinkable compound is a group capable of reacting with an organic group contained in at least one of polyamic acid and polyimide in a step of converting a coating film obtained by using the positive photosensitive resin composition into a cured film. If it is a compound which has this, it will not specifically limit. Examples of such a compound include a compound containing two or more epoxy groups, a melamine derivative, a benzoguanamine derivative, or a group in which a hydrogen atom of an amino group is substituted with a methylol group, an alkoxymethyl group, or both. Examples include glycoluril. The melamine derivative and benzoguanamine derivative may be a dimer or a trimer, or may be a mixture arbitrarily selected from a monomer, a dimer and a trimer. These melamine derivatives and benzoguanamine derivatives preferably have an average of 3 or more and less than 6 methylol groups or alkoxymethyl groups per one triazine ring.
Moreover, you may use the crosslinking agent used for this invention individually or in combination of 2 or more types.

以下に、架橋性化合物の具体例を挙げるが、これに限定されない。
エポキシ基を２個以上含有する化合物としては、エポリードＧＴ−４０１、エポリードＧＴ−４０３、エポリードＧＴ−３０１、エポリードＧＴ−３０２、セロキサイド２０２１、セロキサイド３０００（以上、ダイセル化学工業（株）製）等のシクロヘキセン構造を有するエポキシ化合物；エピコート１００１、エピコート１００２、エピコート１００３、エピコート１００４、エピコート１００７、エピコート１００９、エピコート１０１０、エピコート８２８（以上、ジャパンエポキシレジン（株）製）等のビスフェノールＡ型エポキシ化合物；エピコート８０７（ジャパンエポキシレジン（株）製）等のビスフェノールＦ型エポキシ化合物；エピコート１５２、エピコート１５４（以上、ジャパンエポキシレジン（株）製）、ＥＰＰＮ２０１、ＥＰＰＮ２０２（以上、日本化薬（株）製）等のフェノールノボラック型エポキシ化合物；ＥＣＯＮ−１０２、ＥＣＯＮ−１０３Ｓ、ＥＣＯＮ−１０４Ｓ、ＥＣＯＮ−１０２０、ＥＣＯＮ−１０２５、ＥＣＯＮ−１０２７（以上、日本化薬（株）製）、エピコート１８０Ｓ７５（ジャパンエポキシレジン（株）製）等のクレゾールノボラック型エポキシ化合物；Ｖ８０００−Ｃ７（ＤＩＣ（株）製）等のナフタレン型エポキシ化合物；デナコールＥＸ−２５２（ナガセケムテックス（株）製）、ＣＹ１７５、ＣＹ１７７、ＣＹ１７９、アラルダイトＣＹ−１８２、アラルダイトＣＹ−１９２、アラルダイトＣＹ−１８４（以上、ＢＡＳＦ社製）、エピクロン２００、エピクロン４００（以上、ＤＩＣ（株）製）、エピコート８７１、エピコート８７２（以上、ジャパンエポキシレジン（株）製）、ＥＤ−５６６１、ＥＤ−５６６２（以上、セラニーズコーティング（株）製）等の脂環式エポキシ化合物；デナコールＥＸ−６１１、デナコールＥＸ−６１２、デナコールＥＸ−６１４、デナコールＥＸ−６２２、デナコールＥＸ−４１１、デナコールＥＸ−５１２、デナコールＥＸ−５２２、デナコールＥＸ−４２１、デナコールＥＸ−３１３、デナコールＥＸ−３１４、デナコールＥＸ−３１２（以上、ナガセケムテックス（株）製）等の脂肪族ポリグリシジルエーテル化合物が挙げられる。Although the specific example of a crosslinkable compound is given to the following, it is not limited to this.
Examples of the compound containing two or more epoxy groups include Epolide GT-401, Epolide GT-403, Epolide GT-301, Epolide GT-302, Celoxide 2021, and Celoxide 3000 (manufactured by Daicel Chemical Industries, Ltd.). Epoxy compounds having a cyclohexene structure; bisphenol A type epoxy compounds such as Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004, Epicoat 1007, Epicoat 1009, Epicoat 1010, Epicoat 828 (above, manufactured by Japan Epoxy Resins Co., Ltd.); Bisphenol F type epoxy compound such as 807 (manufactured by Japan Epoxy Resin Co., Ltd.); Epicoat 152, Epicoat 154 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPP 201, EPPN202 (above, Nippon Kayaku Co., Ltd.) and other phenol novolac type epoxy compounds; ECON-102, ECON-103S, ECON-104S, ECON-1020, ECON-1025, ECON-1027 (above, Nippon Kayaku) Cresol novolak type epoxy compounds such as Yakuhin Co., Ltd., Epicoat 180S75 (made by Japan Epoxy Resin Co., Ltd.); naphthalene type epoxy compounds such as V8000-C7 (made by DIC Corporation); Denacol EX-252 (Nagase Chem) Manufactured by Tex Co., Ltd.), CY175, CY177, CY179, Araldite CY-182, Araldite CY-192, Araldite CY-184 (above, manufactured by BASF), Epicron 200, Epicron 400 (above, manufactured by DIC Corporation), Epicote 871 Alicyclic epoxy compounds such as Epicoat 872 (above, Japan Epoxy Resin Co., Ltd.), ED-5661, ED-5661 (above, Celanese Coating Co., Ltd.); Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-411, Denacol EX-512, Denacol EX-522, Denacol EX-421, Denacol EX-313, Denacol EX-314, Denacol EX-312 (above, Nagase ChemteX Aliphatic polyglycidyl ether compounds such as those manufactured by KK

アミノ基の水素原子がメチロール基、アルコキシメチル基又はその両方で置換された基を有する、メラミン誘導体、ベンゾグアナミン誘導体又はグリコールウリルとしては、トリアジン環１個当たりメトキシメチル基が平均３．７個置換されているＭＸ−７５０、トリアジン環１個当たりメトキシメチル基が平均５．８個置換されているＭＷ−３０（以上、（株）三和ケミカル製）；サイメル３００、サイメル３０１、サイメル３０３、サイメル３５０、サイメル３７０、サイメル７７１、サイメル３２５、サイメル３２７、サイメル７０３、サイメル７１２等のメトキシメチル化メラミン；サイメル２３５、サイメル２３６、サイメル２３８、サイメル２１２、サイメル２５３、サイメル２５４等のメトキシメチル化ブトキシメチル化メラミン；サイメル５０６、サイメル５０８等のブトキシメチル化メラミン；サイメル１１４１のようなカルボキシル基含有メトキシメチル化イソブトキシメチル化メラミン；サイメル１１２３のようなメトキシメチル化エトキシメチル化ベンゾグアナミン；サイメル１１２３−１０のようなメトキシメチル化ブトキシメチル化ベンゾグアナミン；サイメル１１２８のようなブトキシメチル化ベンゾグアナミン；サイメル１１２５−８０のようなカルボキシル基含有メトキシメチル化エトキシメチル化ベンゾグアナミン；サイメル１１７０のようなブトキシメチル化グリコールウリル；サイメル１１７２のようなメチロール化グリコールウリル（以上、三井サイアナミッド（株）製）等が挙げられる。
また、本発明のディスプレイ基板用樹脂組成物における架橋剤の含有量は樹脂組成物の保存安定性を向上させる観点から、ポリアミック酸又はポリイミド（両方が含まれるときは、ポリアミック酸及びポリイミド）１００質量部に対して、２０質量部以下が好ましく、本発明の樹脂組成物から得られる硬化膜が十分に低い線膨張係数を有するものとする観点から、１５質量部以下がより好ましい。As the melamine derivative, benzoguanamine derivative, or glycoluril having a group in which the hydrogen atom of the amino group is substituted with a methylol group, an alkoxymethyl group, or both, an average of 3.7 methoxymethyl groups are substituted per triazine ring. MX-750, MW-30 substituted with an average of 5.8 methoxymethyl groups per triazine ring (above, manufactured by Sanwa Chemical Co., Ltd.); Cymel 300, Cymel 301, Cymel 303, Cymel 350 Methoxymethylated melamine such as Cymel 370, Cymel 771, Cymel 325, Cymel 327, Cymel 703, Cymel 712, etc .; Mela Butylmethylated melamines such as Cymel 506 and Cymel 508; carboxyl group-containing methoxymethylated isobutoxymethylated melamines such as Cymel 1141; methoxymethylated ethoxymethylated benzoguanamines such as Cymel 1123; Methoxymethylated butoxymethylated benzoguanamine; butoxymethylated benzoguanamine such as Cymel 1128; carboxyl-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80; butoxymethylated glycoluril such as Cymel 1170; Cymel 1172 Such as methylolated glycoluril (manufactured by Mitsui Cyanamid Co., Ltd.).
Moreover, content of the crosslinking agent in the resin composition for display substrates of this invention is 100 masses of polyamic acid or polyimide (when both are included, polyamic acid and polyimide) from a viewpoint of improving the storage stability of the resin composition. From the viewpoint that the cured film obtained from the resin composition of the present invention has a sufficiently low linear expansion coefficient, 15 parts by mass or less is more preferable.

［ワニス及び硬化膜］
本発明のディスプレイ基板用樹脂組成物を用いて硬化膜を形成する具体的な方法は、次の通りである。
まず、上記式（１）で表される構造単位及び式（３）で表される構造単位を含むポリアミック酸又は上記式（２）で表される構造単位及び式（４）で表される構造単位を含むポリイミドを溶剤に溶解又は分散して、ワニスの形態（膜形成材料）で樹脂組成物を作製する。あるいは、上記説明したポリアミック酸又はポリイミドの反応溶液をそのまま用い、又は希釈若しくは濃縮することで、ワニスの形態の樹脂組成物を準備する。
そして、該ワニスを基板上にキャストコート法、スピンコート法、ブレードコート法、ディップコート法、ロールコート法、バーコート法、ダイコート法、インクジェット法、印刷法（凸版、凹版、平版、スクリーン印刷等）等によって塗布して塗膜を得る。そして得られた塗膜を、ホットプレート、オーブン等で焼成することにより硬化膜が形成される。
硬化膜を形成するための焼成温度は、通常１００乃至４００℃、好ましくは１００乃至３５０℃であり、この焼成処理によって、溶剤が蒸発し、ポリアミック酸が脱水閉環（イミド化）してポリイミドとなる。この際、より高い均一成膜性を発現させたり、基板上で反応を進行させたりする目的で、２段階以上の温度変化をつけてもよい。
また、用いる基板としては、例えば、プラスチック（ポリカーボネート、ポリメタクリレート、ポリスチレン、ポリエステル、ポリオレフィン、エポキシ、メラミン、トリアセチルセルロース、ＡＢＳ、ＡＳ、ノルボルネン系樹脂等）、金属、木材、紙、ガラス、スレート等を挙げることができる。[Varnish and cured film]
The specific method of forming a cured film using the resin composition for display substrates of this invention is as follows.
First, the polyamic acid containing the structural unit represented by the above formula (1) and the structural unit represented by the formula (3), or the structural unit represented by the above formula (2) and the structure represented by the formula (4) A resin composition is prepared in the form of a varnish (film forming material) by dissolving or dispersing polyimide containing units in a solvent. Or the resin composition of the form of a varnish is prepared by using the reaction solution of the polyamic acid or polyimide demonstrated above as it is, or diluting or concentrating.
Then, the varnish is cast on a substrate by a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a bar coating method, a die coating method, an ink jet method, a printing method (letter plate, intaglio plate, planographic plate, screen printing, etc. ) To obtain a coating film. And the cured film is formed by baking the obtained coating film with a hotplate, oven, etc. FIG.
The baking temperature for forming the cured film is usually 100 to 400 ° C., preferably 100 to 350 ° C. By this baking treatment, the solvent evaporates and the polyamic acid is dehydrated and closed (imidized) to become polyimide. . At this time, the temperature may be changed in two or more steps for the purpose of developing a higher uniform film forming property or causing the reaction to proceed on the substrate.
Examples of the substrate to be used include plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal, wood, paper, glass, slate, etc. Can be mentioned.

前記ワニスの形態において使用する溶剤としては、ポリアミック酸又はポリイミドを溶解又は分散させるものであれば特に限定されないが、例えば、上記ポリアミック酸の生成反応において使用される溶剤等が挙げられる。これら溶剤は単独で又は２種以上を組み合わせて使用してもよい。
また上記溶剤にポリアミック酸又はポリイミド（両方が含まれるときは、ポリアミック酸及びポリイミド。以下、同じ。）を溶解又は分散させる濃度は、通常、ポリアミック酸又はポリイミドと溶剤の総質量（合計質量）に対して５乃至４０質量％であり、樹脂組成物の保存安定性を向上させる観点から好ましくは５乃至２０質量％であり、ワニスの塗布性を向上させる観点からより好ましくは５乃至１５質量％である。
ディスプレイ基板用樹脂組成物から形成される硬化膜の厚さは特に限定されないが、通常１乃至５０μｍ、好ましくは５乃至４０μｍである。The solvent used in the form of the varnish is not particularly limited as long as it dissolves or disperses the polyamic acid or the polyimide, and examples thereof include a solvent used in the reaction for producing the polyamic acid. These solvents may be used alone or in combination of two or more.
In addition, the concentration of dissolving or dispersing polyamic acid or polyimide (when both are included, polyamic acid and polyimide; the same shall apply hereinafter) in the solvent is usually the total mass (total mass) of the polyamic acid or polyimide and the solvent. It is 5 to 40% by mass, preferably 5 to 20% by mass from the viewpoint of improving the storage stability of the resin composition, and more preferably 5 to 15% by mass from the viewpoint of improving the coatability of the varnish. is there.
Although the thickness of the cured film formed from the resin composition for display substrates is not specifically limited, Usually, 1-50 micrometers, Preferably it is 5-40 micrometers.

以下、実施例を挙げて、本発明をより具体的に説明するが、本発明は下記の実施例に限定されるものではない。
［実施例で用いる略記号］
以下の実施例で用いる略記号の意味は、次のとおりである。
＜酸二無水物＞
ＢＰ−ＴＭＥ：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）（本州化学工業（株）製）（下記式（１１））

Figure 0006075564
ＴＡＨＱ：ｐ−フェニレンビス（トリメリット酸モノエステル酸無水物）（マナック（株）製）（（下記式（１２））
Figure 0006075564
 ＜ジアミン＞
ＰＤＡ：ｐ−フェニレンジアミン（東京化成（株）製）
ＡＰＡＢＩ：２−（３−アミノフェニル）−５−アミノベンズイミダゾール（Ｃｈａｎｇｚｈｏｕ Ｓｕｎｌｉｇｈｔ Ｐｈａｒｍａｃｅｕｔｉｃａｌ Ｃｏ．， Ｌｔｄ.製）
ＢＡＢＰ：４，４’−ビス（３−アミノフェノキシ）ベンゾフェノン（Ｃｈａｎｇｚｈｏｕ Ｓｕｎｌｉｇｈｔ Ｐｈａｒｍａｃｅｕｔｉｃａｌ Ｃｏ．， Ｌｔｄ. 製）
ＢＡＰＢ：４，４’−ビス（４−アミノフェノキシ）ビフェニル（東京化成（株）製）
＜架橋剤＞
Ｖ８０００−Ｃ７：ナフタレン型エポキシ化合物（ＤＩＣ（株）製）
＜溶剤＞
ＮＭＰ：Ｎ−メチルピロリドンEXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to the following Example.
[Abbreviations used in Examples]
The meanings of the abbreviations used in the following examples are as follows.
<Acid dianhydride>
BP-TME: 4,4′-biphenylbis (trimellitic acid monoester anhydride) (manufactured by Honshu Chemical Industry Co., Ltd.) (the following formula (11))
Figure 0006075564
 TAHQ: p-phenylenebis (trimellitic acid monoester acid anhydride) (manac Co., Ltd.) ((formula (12) below)
Figure 0006075564
 <Diamine>
PDA: p-phenylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
APABI: 2- (3-aminophenyl) -5-aminobenzimidazole (manufactured by Changzhou Sunlight Pharmaceutical Co., Ltd.)
BABP: 4,4′-bis (3-aminophenoxy) benzophenone (manufactured by Changzhou Sunlight Pharmaceutical Co., Ltd.)
BAPB: 4,4′-bis (4-aminophenoxy) biphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.)
<Crosslinking agent>
V8000-C7: naphthalene type epoxy compound (manufactured by DIC Corporation)
<Solvent>
NMP: N-methylpyrrolidone

［数平均分子量及び重量平均分子量の測定］
ポリマーの重量平均分子量（以下、Ｍｗと略す。）と分子量分布は、日本分光（株）製ＧＰＣ装置（Ｓｈｏｄｅｘ［登録商標］カラムＫＦ８０３Ｌ及びＫＦ８０５Ｌ）を用い、溶出溶媒としてジメチルホルムアミドを流量１ｍＬ／分、カラム温度５０℃の条件で測定した。なお、Ｍｗはポリスチレン換算値とした。[Measurement of number average molecular weight and weight average molecular weight]
The weight average molecular weight (hereinafter abbreviated as Mw) and the molecular weight distribution of the polymer were measured using a GPC apparatus (Shodex [registered trademark] columns KF803L and KF805L) manufactured by JASCO Corporation, with dimethylformamide as the elution solvent at a flow rate of 1 mL / min The column temperature was measured at 50 ° C. In addition, Mw was made into the polystyrene conversion value.

＜合成例Ｐ１：ポリアミック酸（Ｐ１）の合成＞
ＰＤＡ １．６６ｇ（０．０１５モル）とＡＰＡＢＩ ０．８６２ｇ（０．００４モル）をＮＭＰ ７０ｇに溶解し、ＢＰ−ＴＭＥ １０．１ｇ（０．０１９モル）を添加した後、再度ＮＭＰ ７．４ｇを添加し、窒素雰囲気下、２３℃で２４時間反応させた。得られたポリマーのＭｗは１３４，０００、分子量分布は２．８であった。<Synthesis Example P1: Synthesis of polyamic acid (P1)>
1.66 g (0.015 mol) of PDA and 0.862 g (0.004 mol) of APABI were dissolved in 70 g of NMP, 10.1 g (0.019 mol) of BP-TME was added, and then 7.4 g of NMP was again added. And reacted at 23 ° C. for 24 hours under a nitrogen atmosphere. Mw of the obtained polymer was 134,000 and molecular weight distribution was 2.8.

＜合成例Ｐ２：ポリアミック酸（Ｐ２）の合成＞
ＰＤＡ １．８２ｇ（０．０１７モル）とＡＰＡＢＩ ０．４２ｇ（０．００２モル）をＮＭＰ ８０ｇに溶解し、ＢＰ−ＴＭＥ ９．７７ｇ（０．０１８モル）を添加した後、再度ＮＭＰ ８ｇを添加し、窒素雰囲気下、２３℃で２４時間反応させた。得られたポリマーのＭｗは１３８，６００、分子量分布は２．３であった。<Synthesis Example P2: Synthesis of polyamic acid (P2)>
PDA 1.82 g (0.017 mol) and APABI 0.42 g (0.002 mol) were dissolved in NMP 80 g, BP-TME 9.77 g (0.018 mol) was added, and NMP 8 g was added again. And reacted at 23 ° C. for 24 hours under a nitrogen atmosphere. Mw of the obtained polymer was 138,600 and molecular weight distribution was 2.3.

＜合成例Ｐ３：ポリアミック酸（Ｐ３）の合成＞
ＰＤＡ １．４２ｇ（０．０１３モル）と、ＡＰＡＢＩ ０．１６ｇ（０．００１モル）と、ＢＡＢＰ ０．６ｇ（０．００２モル）をＮＭＰ ７０ｇに溶解し、ＢＰ−ＴＭＥ ８．７８ｇ（０．０１６モル）を添加した後、再度ＮＭＰ ９．２ｇを添加し、窒素雰囲気下、２３℃で２４時間反応させた。得られたポリマーのＭｗは１５１，４００、分子量分布は２．８であった。<Synthesis Example P3: Synthesis of polyamic acid (P3)>
PDA 1.42 g (0.013 mol), APABI 0.16 g (0.001 mol), and BABP 0.6 g (0.002 mol) were dissolved in NMP 70 g, and BP-TME 8.78 g (0. 016 g) was added, and 9.2 g of NMP was added again, and the mixture was reacted at 23 ° C. for 24 hours under a nitrogen atmosphere. Mw of the obtained polymer was 151,400 and molecular weight distribution was 2.8.

＜合成例Ｐ４：ポリアミック酸（Ｐ４）の合成＞
ＰＤＡ １．４２ｇ（０．０１３モル）と、ＡＰＡＢＩ ０．１６ｇ（０．００１モル）と、ＢＡＰＢ ０．５ｇ（０．００２モル）をＮＭＰ ７０ｇに溶解し、ＢＰ−ＴＭＥ ７．３６ｇ（０．０１４モル）を添加した後、再度ＮＭＰ １１．０ｇを添加し、窒素雰囲気下、２３℃で２４時間反応させた。得られたポリマーのＭｗは１３８，６００、分子量分布は２．３であった。<Synthesis Example P4: Synthesis of Polyamic Acid (P4)>
PDA 1.42 g (0.013 mol), APABI 0.16 g (0.001 mol), and BAPB 0.5 g (0.002 mol) were dissolved in NMP 70 g, and BP-TME 7.36 g (0. 014 mol), 11.0 g of NMP was added again, and the mixture was reacted at 23 ° C. for 24 hours under a nitrogen atmosphere. Mw of the obtained polymer was 138,600 and molecular weight distribution was 2.3.

＜比較例ＨＰ１：ポリアミック酸（ＨＰ１）の合成＞
ＰＤＡ ２２．７ｇ（０．２１０モル）をＮＭＰ ７００ｇに溶解し、ＴＡＨＱ ９４．３ｇ（０．２０５モル）を添加した後、再度ＮＭＰ ８３ｇを添加し、窒素雰囲気下、２３℃で２４時間反応させた。得られたポリマーのＭｗは１４２，７００、分子量分布は２．５であった。<Comparative Example HP1: Synthesis of polyamic acid (HP1)>
Dissolve 22.7 g (0.210 mol) of PDA in 700 g of NMP, add 94.3 g (0.205 mol) of TAHQ, add 83 g of NMP again, and react at 23 ° C. for 24 hours in a nitrogen atmosphere. It was. Mw of the obtained polymer was 142,700, and molecular weight distribution was 2.5.

＜比較例ＨＰ２：ポリアミック酸（ＨＰ２）の合成＞
ＡＰＡＢＩ ３．７８ｇ（０．０１７モル）をＮＭＰ ７０ｇに溶解し、ＢＰ−ＴＭＥ ８．８２ｇ（０．０１７モル）を添加した後、再度ＮＭＰ ７．４ｇを添加し、窒素雰囲気下、２３℃で２４時間反応させた。得られたポリマーのＭｗは１４８，４００、分子量分布は２．５であった。<Comparative Example HP2: Synthesis of polyamic acid (HP2)>
APABI (3.78 g, 0.017 mol) was dissolved in NMP (70 g), BP-TME (8.82 g, 0.017 mol) was added, and NMP (7.4 g) was added again. The reaction was performed for 24 hours. The obtained polymer had Mw of 148,400 and a molecular weight distribution of 2.5.

＜比較例ＨＰ３：ポリアミック酸（ＨＰ３）の合成＞
ＰＤＡ １．４６ｇ（０．０１４モル）とＢＡＢＰ ２．３０ｇ（０．００６モル）をＮＭＰ ７０ｇに溶解し、ＢＰ−ＴＭＥ ８．７９ｇ（０．０１９モル）を添加した後、再度ＮＭＰ ７．４ｇを添加し、窒素雰囲気下、２３℃で２４時間反応させた。得られたポリマーのＭｗは１０２，０００、分子量分布は３．３であった。<Comparative Example HP3: Synthesis of polyamic acid (HP3)>
1.46 g (0.014 mol) of PDA and 2.30 g (0.006 mol) of BABP were dissolved in 70 g of NMP, and 8.79 g (0.019 mol) of BP-TME was added, followed by 7.4 g of NMP again. And reacted at 23 ° C. for 24 hours under a nitrogen atmosphere. Mw of the obtained polymer was 102,000 and molecular weight distribution was 3.3.

＜比較例ＨＰ４：ポリアミック酸（ＨＰ４）の合成＞
ＡＰＡＢＩ ４．４６ｇ（０．０１８モル）をＮＭＰ ８０ｇに溶解し、ＴＡＨＱ ８．００ｇ（０．０１７モル）を添加した後、再度ＮＭＰ ８ｇを添加し、窒素雰囲気下、２３℃で２４時間反応させた。得られたポリマーのＭｗは１４２，７００、分子量分布は２．５であった。<Comparative Example HP4: Synthesis of polyamic acid (HP4)>
APABI (4.46 g, 0.018 mol) was dissolved in NMP (80 g), TAHQ (8.00 g, 0.017 mol) was added, NMP (8 g) was added again, and the mixture was reacted at 23 ° C. for 24 hours in a nitrogen atmosphere. It was. Mw of the obtained polymer was 142,700, and molecular weight distribution was 2.5.

＜サンプル作製：ワニス＞
表１に示す組成に従い、ポリマー溶液、架橋剤及び溶剤としてＮＭＰを混合し、室温（およそ２３℃）で６時間以上攪拌して均一な溶液とすることにより、ディスプレイ基板用樹脂組成物（ワニス）を調製した。<Sample preparation: Varnish>
According to the composition shown in Table 1, NMP is mixed as a polymer solution, a crosslinking agent, and a solvent, and stirred at room temperature (approximately 23 ° C.) for 6 hours or more to obtain a uniform solution, whereby a resin composition for a display substrate (varnish) Was prepared.

Figure 0006075564
Figure 0006075564

＜塗布膜、及び線膨張係数評価＞
上記で調製したディスプレイ基板用樹脂組成物（ワニス）を次の手法で評価した。評価結果を表２に示す。
［キュア前膜厚・剥離方法］
表１のディスプレイ基板用樹脂組成物（ワニス）をそれぞれ、１００ｍｍ×１００ｍｍのガラス基板上にバーコーター（段差２５０μｍ）を用いて塗布し、温度１１０℃で１０分間、温度２５０℃で３０分間、温度３００℃で３０分間オーブンで焼成した。得られた塗布膜の膜厚は接触式膜厚測定器（（株）ＵＬＶＡＣ製Ｄｅｋｔａｋ ３ＳＴ）を使用し、測定した。その後、ガラス基板ごとに１Ｌビーカー内の７０度の純水中に静置し、フィルムの剥離を行った。<Evaluation of coating film and linear expansion coefficient>
The resin composition for display substrates (varnish) prepared above was evaluated by the following method. The evaluation results are shown in Table 2.
[Pre-cure film thickness and peeling method]
Each of the resin compositions for display substrates (varnishes) shown in Table 1 was applied onto a 100 mm × 100 mm glass substrate using a bar coater (step difference 250 μm), and the temperature was 110 ° C. for 10 minutes, the temperature 250 ° C. for 30 minutes, and the temperature. Baking in an oven at 300 ° C. for 30 minutes. The film thickness of the obtained coating film was measured using a contact-type film thickness measuring device (Dektak 3ST manufactured by ULVAC). Then, it left still in the 70 degree pure water in a 1L beaker for every glass substrate, and peeled the film.

［線膨張係数］
上記で得られたフィルムから２０ｍｍ×５ｍｍ状の短冊を作製し、ＴＭＡ−４０００ＳＡ（ブルカー・エイエックスエス（株）製）を用いて、５０℃から４００℃まで５℃／分の条件で昇温し、冷却後、再度５０℃から４００℃までの線膨張係数を測定した。なお、線膨張係数は低温（５０℃〜３００℃）側と高温（３００℃〜４００℃）側の係数で示した。[Linear expansion coefficient]
A 20 mm × 5 mm strip is prepared from the film obtained above, and the temperature is increased from 50 ° C. to 400 ° C. under the condition of 5 ° C./minute using TMA-4000SA (manufactured by Bruker AXS Co., Ltd.). Then, after cooling, the linear expansion coefficient from 50 ° C. to 400 ° C. was measured again. In addition, the linear expansion coefficient was shown by the coefficient of the low temperature (50 degreeC-300 degreeC) side and the high temperature (300 degreeC-400 degreeC) side.

Figure 0006075564
Figure 0006075564

表２に示される通り、本発明のディスプレイ基板用樹脂組成物から得られた薄膜が、適度な線膨張係数、適度な柔軟性及び満足な耐熱性を有することがわかった。   As shown in Table 2, it was found that the thin film obtained from the resin composition for display substrates of the present invention has an appropriate linear expansion coefficient, an appropriate flexibility, and a satisfactory heat resistance.

Claims (17)

下記式（１）で表される構造単位及び式（３）で表される構造単位を含むポリアミック酸又は下記式（２）で表される構造単位及び式（４）で表される構造単位を含むポリイミドを含有するディスプレイ基板用樹脂組成物。
Figure 0006075564
 ［式（１）乃至式（４）中、
Ｘ1は下記式（７）：
Figure 0006075564
 （式中、
Ｒ 12 乃至Ｒ 21 は、それぞれ独立して、水素原子、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基、カルボキシル基、Ｗ 1 で置換
されていてもよいフェニル基、Ｗ 1 で置換されていてもよいナフチル基、Ｗ 1 で置換されていてもよいチエニル基又はＷ 1 で置換されていてもよいフリル基を表し、
Ｗ 1 は、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基
、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基又はカルボキシル基を表し、
Ｚ 1 及びＺ 2 は、それぞれ独立して、−ＮＨ−、−ＮＺ 3 −又は酸素原子を表し、
Ｚ 3 は、炭素原子数１乃至１０のアルキル基を表し、
ｐは１又は２を表す。なお、○は結合手を表す。）で表される芳香族基と２つのカルボニル基を有する４価の有機基を表し、
Ｙ1は下記式（６）：
Figure 0006075564
 （式中、
Ｒ 8 乃至Ｒ 11 は、それぞれ独立して、水素原子、炭素原子数１乃至１０のアルキル基、
炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基、カルボキシル基、Ｗ 1 で置換
されていてもよいフェニル基、Ｗ 1 で置換されていてもよいナフチル基、Ｗ 1 で置換されていてもよいチエニル基又はＷ 1 で置換されていてもよいフリル基を表し、
Ｗ 1 は、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基
、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基又はカルボキシル基を表し、
ｑは１又は２を表す。なお、○は結合手を表す。）で表される、２価の芳香族基又は脂肪族基を表し、
Ｙ2は下記式（５）：
Figure 0006075564
 （式中、
Ｒ 1 乃至Ｒ 7 は、それぞれ独立して、水素原子、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基、カルボキシル基、Ｗ 1 で置換さ
れていてもよいフェニル基、Ｗ 1 で置換されていてもよいナフチル基、Ｗ 1 で置換されていてもよいチエニル基又はＷ 1 で置換されていてもよいフリル基を表し、
Ｗ 1 は、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基
、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基又はカルボキシル基を表し、
Ａは、水素原子、炭素原子数１乃至１０のアルキル基又は炭素原子数１乃至１０のハロアルキル基を表す。なお、○は結合手を表す。）で表される窒素原子を２個以上有する２価の芳香族基を表し、
ｎ及びｍは自然数を表す。］ A structural unit represented by the following formula (1) and a polyamic acid containing a structural unit represented by the formula (3) or a structural unit represented by the following formula (2) and a structural unit represented by the formula (4) The resin composition for display substrates containing the containing polyimide.
Figure 0006075564
 [In Formula (1) thru | or Formula (4),
X 1 is the following formula (7) :
Figure 0006075564
 (Where
R 12 to R 21 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, or a halogen atom. , Nitro group, formyl group, cyano group, carboxyl group, substituted with W 1
Which may be a phenyl group, W 1 with an optionally substituted naphthyl group, W 1 in represents an optionally substituted furyl group thienyl group or W 1 may be substituted,
W 1 is an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms.
Represents an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group or a carboxyl group,
Z 1 and Z 2 each independently represent —NH—, —NZ 3 — or an oxygen atom,
Z 3 represents an alkyl group having 1 to 10 carbon atoms,
p represents 1 or 2. In addition, (circle) represents a bond. ) Represents a tetravalent organic group having an aromatic group and two carbonyl groups,
Y 1 represents the following formula (6):
Figure 0006075564
 (Where
R 8 to R 11 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,
1 to 10 carbon atoms haloalkyl group, 1 to 10 carbon atoms alkoxy group, hydroxy group, halogen atom, nitro group, formyl group, cyano group, carboxyl group, substituted with W 1
Which may be a phenyl group, W 1 with an optionally substituted naphthyl group, W 1 in represents an optionally substituted furyl group thienyl group or W 1 may be substituted,
W 1 is an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms.
Represents an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group or a carboxyl group,
q represents 1 or 2. In addition, (circle) represents a bond. Represents a divalent aromatic group or aliphatic group represented by
Y 2 represents the following formula (5):
Figure 0006075564
 (Where
R 1 to R 7 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, or a halogen atom. , Substituted with nitro group, formyl group, cyano group, carboxyl group, W 1
Which may have a phenyl group, W 1 with an optionally substituted naphthyl group, W 1 in represents an optionally substituted furyl group thienyl group or W 1 may be substituted,
W 1 is an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms.
Represents an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group or a carboxyl group,
A represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group having 1 to 10 carbon atoms. In addition, (circle) represents a bond. Represents a divalent aromatic group having two or more nitrogen atoms represented by
n and m represent natural numbers. ] 前記Ｒ1乃至Ｒ7及びＡが水素原子を表す、請求項１に記載のディスプレイ基板用樹脂組成物。 The resin composition for display substrates according to claim 1 , wherein R 1 to R 7 and A each represent a hydrogen atom. 前記式（６）で表される２価の芳香族基がフェニレンジアミンから誘導されたものである、請求項１又は請求項２に記載のディスプレイ基板用樹脂組成物。 The resin composition for display substrates according to claim 1 or 2, wherein the divalent aromatic group represented by the formula (6) is derived from phenylenediamine. 前記Ｒ8乃至Ｒ11が水素原子を表す、請求項３に記載のディスプレイ基板用樹脂組成物
。 The resin composition for display substrates according to claim 3 , wherein R 8 to R 11 represent a hydrogen atom. 前記ｐが２を表す、請求項１乃至請求項４のうちいずれか１項に記載のディスプレイ基板用樹脂組成物。 The resin composition for display substrates according to any one of claims 1 to 4 , wherein p represents 2. 前記Ｒ12乃至Ｒ21が水素原子を表す、請求項５に記載のディスプレイ基板用樹脂組成物。 The resin composition for display substrates according to claim 5 , wherein R 12 to R 21 represent hydrogen atoms. 前記式（１）中のｎと前記式（３）中のｍとがｎ／ｍ＝７０／３０乃至９９／１の関係である、請求項１乃至請求項６のうちいずれか１項に記載のディスプレイ基板用樹脂組成物。 The n in said Formula (1) and the m in said Formula (3) are the relationship of any one of Claim 1 thru | or 6 which are the relationship of n / m = 70/30 thru | or 99/1. Resin composition for display substrates. 前記式（２）中のｎと前記式（４）中のｍとがｎ／ｍ＝７０／３０乃至９９／１の関係である、請求項１乃至請求項６のうちいずれか１項に記載のディスプレイ基板用樹脂組成物。 The n in said Formula (2) and the m in said Formula (4) are the relationship of any one of Claim 1 thru | or 6 which are the relationship of n / m = 70/30 thru | or 99/1. Resin composition for display substrates. さらに架橋剤を含む、請求項１乃至請求項８のうちいずれか１項に記載のディスプレイ基板用樹脂組成物。 Furthermore, the resin composition for display substrates of any one of Claims 1 thru | or 8 containing a crosslinking agent. 前記架橋剤が２つ以上のエポキシ基を有する化合物である、請求項９に記載のディスプレイ基板用樹脂組成物。 The resin composition for display substrates according to claim 9 , wherein the crosslinking agent is a compound having two or more epoxy groups. 前記架橋剤が芳香族基を有する化合物である、請求項１０に記載のディスプレイ基板用樹脂組成物。 The resin composition for display substrates of Claim 10 whose said crosslinking agent is a compound which has an aromatic group. 前記架橋剤が６つ以下のエポキシ基を有する化合物であって、かつ該化合物はエポキシ基と芳香族基とを結合する炭素原子数１乃至１０のアルキル基を有する、請求項１１に記載のディスプレイ基板用樹脂組成物。 The display according to claim 11 , wherein the cross-linking agent is a compound having 6 or less epoxy groups, and the compound has an alkyl group having 1 to 10 carbon atoms for bonding an epoxy group and an aromatic group. Resin composition for substrates. 前記ポリアミック酸又はポリイミド１００質量部に対して、前記架橋剤が２０質量部以
下である、請求項９乃至請求項１２のうちいずれか１項に記載のディスプレイ基板用樹脂組成物。 The resin composition for display substrates according to any one of claims 9 to 12 , wherein the crosslinking agent is 20 parts by mass or less with respect to 100 parts by mass of the polyamic acid or polyimide. 請求項１乃至請求項１３のうちいずれか１項に記載のディスプレイ基板用樹脂組成物が少なくとも１種の溶剤に溶解していることを特徴とする、ワニス。 A varnish, wherein the resin composition for a display substrate according to any one of claims 1 to 13 is dissolved in at least one solvent. 請求項１４に記載のワニスを用いて得られた、硬化膜。 Obtained using the varnish according to claim 14, cured film. 基板上に請求項１５に記載の硬化膜からなる層を少なくとも一層備える、構造体。 A structure comprising at least one layer comprising the cured film according to claim 15 on a substrate. 請求項１４に記載のワニスを２３０℃以上で焼成することを特徴とする、硬化膜の製造方法。The manufacturing method of the cured film characterized by baking the varnish of Claim 14 at 230 degreeC or more.
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