JPWO2019208587A1 - Polyimide precursor resin composition - Google Patents

Abstract

A polyimide precursor containing the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), described in the present specification; and the general formula (3-1) or (3-). A resin composition comprising at least one compound of 2) in which m is an integer of 3 or more; and optionally a compound represented by the general formula (4). In the general formula (3-1) or (3-2), the total amount of compounds in which m is an integer of 3 or more is more than 0 ppm and 1,100 ppm or less based on the mass of the resin composition, or In the general formula (3-1) or (3-2), the total amount of the compound in which m is an integer of 3 or more and the compound in which n is an integer of 3 or more in the general formula (4) is the resin composition. It is more than 0 ppm and 1300 ppm or less based on the mass.

Description

  The present invention relates to a polyimide precursor resin composition and a polyimide film. The present invention also relates to methods for making polyimide films, displays, laminates and flexible devices.

  The polyimide resin is an insoluble and infusible super heat resistant resin, and has excellent properties such as heat and oxidation resistance, heat resistance, radiation resistance, low temperature resistance, and chemical resistance. Therefore, the polyimide resin is used in a wide range of fields including electronic materials. Examples of application of the polyimide resin in the field of electronic materials include an insulating coating material, an insulating film, a semiconductor, an electrode protective film of a thin film transistor liquid crystal display (TFT-LCD), and the like. Recently, by utilizing the lightness and flexibility of a polyimide film, it is being considered to use it as a flexible substrate instead of the glass substrate which has been conventionally used in the field of display materials.

  For example, Patent Document 1 describes a resin precursor (weight average molecular weight of 30,000 to 90,000) polymerized from bis (diaminodiphenyl) sulfone (hereinafter, also referred to as DAS) and having a siloxane unit. Patent Document 1 discloses that the polyimide obtained by curing the precursor has low residual stress generated between the precursor such as glass and the like, excellent chemical resistance, and yellowness (YI) depending on the oxygen concentration during the curing step. Value) and that the effect on the total light transmittance is small. Patent Document 2 describes a resin precursor having a siloxane unit, which is polymerized from 2,2'-bis (trifluoromethyl) benzidine (hereinafter, also referred to as TFMB). Patent Document 2 describes that a polyimide film obtained by curing the precursor has a specific glass transition temperature, low residual stress generated between the precursor and the inorganic film, and excellent mechanical properties and thermal stability. is doing.

International Publication No. 2014/148441 International Publication No. 2014/098235 JP, 2016-029126, A JP, 2006-028533, A JP, 2002-012666, A Japanese Patent Publication No. 2007-512568 Special table 2012-511173 gazette JP, 2010-067957, A JP, 2013-179306, A International Publication No. 2005/068535

Shin-Etsu Chemical Co., Ltd. website, “Q & A”, “About silicone grease and oil compounds”, [online], [March 13, 2018 search], Internet <URL: https: //www.silicone.jp/contact /qa/qa103.shtml〉

  Patent Documents 1 and 2 use a siloxane-containing compound as a monomer of a polyimide precursor, but such a siloxane-containing compound contains a low-molecular weight cyclic siloxane (hereinafter, also referred to as a low-molecular cyclic siloxane). It is known that this low molecular weight cyclic siloxane is volatile and may cause contact failure in the manufacturing equipment of the process. See Non-Patent Document 1, for example.

  Patent Documents 3 to 5 are mentioned as prior art documents relating to the polyimide precursor in which the low molecular cyclic siloxane is reduced by purification. In prior art 3, low molecular cyclic siloxane is removed by adding a siloxane-containing compound to acetone, then centrifuging and decanting, and it is described that the obtained polyimide has transparency and less outgas generation. ing. In Patent Documents 4 and 5, the siloxane-containing compound is purified by stripping the siloxane-containing compound under specific conditions, or by dissolving the siloxane-containing compound in 2-butanone and reprecipitating with methanol. It is described that the adhesiveness of the is improved.

  The present inventors synthesized a polyimide precursor using a siloxane-containing compound purified by the same purification method as those described in Patent Documents 3 to 5, and manufactured a polyimide using it. As a result, when a large amount of the polyimide precursor is processed in the polyimide manufacturing process, the evaluation of the number of counts of foreign matters attached to the polyimide film is poor, and the yellowness (YI It was found that the degree of improvement in (value) was insufficient. Therefore, the present invention provides a polyimide precursor resin composition capable of further improving the yellowness (YI value) and reducing foreign substances generated in the polyimide manufacturing process as compared with the case of using an unpurified siloxane compound. The purpose is to

｛式中、Ｐ_１は、２価の有機基を示し、Ｐ_２は、４価の有機基を示し、ｐは正の整数を示す。｝

｛式中、Ｐ_３及びＰ_４は、それぞれ独立に、炭素数１〜５の一価の脂肪族炭化水素、又は炭素数６〜１０の一価の芳香族基であり、ｑは、１〜２００の整数である。｝

｛式中、ｍは１以上の整数である。｝

｛式中、ｎは２以上の整数である。｝
［２］
上記一般式（３−１）又は（３−２）のうちｍが３以上の整数である化合物の総量が、上記樹脂組成物の質量を基準として、０ｐｐｍより多く３００ｐｐｍ以下である、項目１に記載の樹脂組成物。
［３］
下記一般式（１）で表される構造単位、及び下記一般式（２）で表される構造単位を含む、ポリイミド前駆体と；
下記一般式（３−１）又は（３−２）のうちｍが３又は４である、少なくともいずれか一方の化合物と；
任意に、下記一般式（４）で表される化合物と
を含む、樹脂組成物であって、
下記一般式（３−１）又は（３−２）のうちｍが３である化合物の総量が、上記樹脂組成物の質量を基準として、０ｐｐｍより多く６５０ｐｐｍ以下であるか、あるいは、
下記一般式（３−１）又は（３−２）のうちｍが４である化合物の総量が、上記樹脂組成物の質量を基準として、０ｐｐｍより多く３５０ｐｐｍ以下である、
樹脂組成物。

｛式中、Ｐ_１は、２価の有機基を示し、Ｐ_２は、４価の有機基を示し、ｐは正の整数を示す。｝

｛式中、Ｐ_３及びＰ_４は、それぞれ独立に、炭素数１〜５の一価の脂肪族炭化水素、又は炭素数６〜１０の一価の芳香族基であり、ｑは、１〜２００の整数である。｝

｛式中、ｍは１以上の整数である。｝

｛式中、ｎは２以上の整数である。｝
［４］
下記一般式（１）で表される構造単位、及び下記一般式（２）で表される構造単位を含む、ポリイミド前駆体と
下記一般式（３−１）又は（３−２）のうちｍが３以上の整数である少なくともいずれか一方の化合物と；
任意に、下記一般式（４）で表される化合物と
を含む、樹脂組成物であって、
下記一般式（３−１）又は（３−２）のうちｍが３以上の整数である化合物の総量が、上記樹脂組成物中の固形分の質量を基準として、０ｐｐｍより多く７，５００ｐｐｍ以下であり、あるいは、
下記一般式（３−１）又は（３−２）のうちｍが３以上の整数である化合物と、下記一般式（４）のうちｎが３以上の整数である化合物との総量が、上記樹脂組成物中の固形分の質量を基準として、０ｐｐｍより多く８，６００ｐｐｍ以下である、樹脂組成物。

｛式中、Ｐ_１は、２価の有機基を示し、Ｐ_２は、４価の有機基を示し、ｐは正の整数を示す。｝

｛式中、Ｐ_３及びＰ_４は、それぞれ独立に、炭素数１〜５の一価の脂肪族炭化水素、又は炭素数６〜１０の一価の芳香族基であり、ｑは、１〜２００の整数である。｝

｛式中、ｍは１以上の整数である。｝

｛式中、ｎは２以上の整数である。｝
［５］
下記一般式（１）で表される構造単位、及び下記一般式（２）で表される構造単位を含む、ポリイミド前駆体と；
下記一般式（３−１）又は（３−２）のうちｍが３又は４である、少なくともいずれか一方の化合物と；
任意に、下記一般式（４）で表される化合物と
を含む、樹脂組成物であって、
下記一般式（３−１）又は（３−２）のうちｍが３である化合物の総量が、上記樹脂組成物中の固形分の質量を基準として、０ｐｐｍより多く４，５００ｐｐｍ以下であるか、あるいは、
下記一般式（３−１）又は（３−２）のうちｍが４である化合物の総量が、上記樹脂組成物中の固形分の質量を基準として、０ｐｐｍより多く２，５００ｐｐｍ以下である、
樹脂組成物。

｛式中、Ｐ_１は、２価の有機基を示し、Ｐ_２は、４価の有機基を示し、ｐは正の整数を示す。｝

｛式中、Ｐ_３及びＰ_４は、それぞれ独立に、炭素数１〜５の一価の脂肪族炭化水素、又は炭素数６〜１０の一価の芳香族基であり、ｑは、１〜２００の整数である。｝

｛式中、ｍは１以上の整数である。｝

［６］
上記一般式（３−１）又は（３−２）で表される化合物において、ｍは３〜５の整数である、項目１、２及び４のいずれか一項に記載の樹脂組成物。
［７］
上記一般式（４）で表される化合物において、ｎは３〜８の整数である、項目１、２及び４のいずれか一項に記載の樹脂組成物。
［８］
上記ポリイミド前駆体を硬化して得られるポリイミド樹脂膜が、フレキシブル基板に用いられる、項目１〜７のいずれか一項に記載の樹脂組成物。
［９］
上記ポリイミド前駆体を硬化して得られるポリイミド樹脂膜が、フレキシブルディスプレイに用いられる、項目１〜７のいずれか一項に記載の樹脂組成物。
［１０］
下記一般式（１）で表される構造単位、及び下記一般式（２）で表される構造単位を含む、ポリイミド前駆体と；
下記一般式（３−１）又は（３−２）のうちｍが３以上の整数である少なくともいずれか一方の化合物と；
任意に、下記一般式（４）で表される化合物と
を含む、樹脂組成物であって、
上記樹脂組成物は、以下：
下記一般式（５）で表されるケイ素含有化合物と、
下記一般式（３−１）又は（３−２）のうちｍが３以上の整数である少なくともいずれか一方の化合物と、
任意に、下記一般式（４）で表される化合物とを含有する原料組成物を、テトラカルボン酸二無水物及びジアミンと重縮合反応させてポリイミド前駆体を提供することを含む方法により製造され、
上記原料組成物に含まれる、下記一般式（３−１）又は（３−２）のうちｍが３以上の整数である化合物の総量は、下記一般式（３−１）、（３−２）、（４）及び（５）で表されるケイ素含有化合物の合計質量を基準として、０ｐｐｍより多く４６，０００ｐｐｍ以下であるか、あるいは、
上記原料組成物に含まれる、下記一般式（３−１）又は（３−２）のうちｍが３以上の整数である化合物と、下記一般式（４）のうちｎが３以上の整数である化合物との総量は、上記一般式（３−１）、（３−２）、（４）及び（５）のケイ素含有化合物の合計質量を基準として、０ｐｐｍより多く４７，０００ｐｐｍ以下である、
樹脂組成物。

｛式中、Ｐ_１は、２価の有機基を示し、Ｐ_２は、４価の有機基を示し、ｐは正の整数を示す。｝

｛式中、Ｐ_３及びＰ_４は、それぞれ独立に、炭素数１〜５の一価の脂肪族炭化水素、又は炭素数６〜１０の一価の芳香族基であり、ｑは、１〜２００の整数である。｝

｛式中、ｍは１以上の整数である。｝

｛式中、ｎは２以上の整数である。｝

｛式中、Ｒ_１は、それぞれ独立に、単結合又は炭素数１〜１０の二価の有機基であり、Ｒ_２及びＲ_３は、それぞれ独立に、炭素数１〜１０の一価の有機基であり、少なくとも一つは炭素数１〜５の一価の脂肪族炭化水素基であり、Ｒ_４及びＲ_５は、それぞれ独立に、炭素数１〜１０の一価の有機基であり、少なくとも一つは炭素数６〜１０の一価の芳香族基であり、Ｒ_６及びＲ_７は、それぞれ独立に、炭素数１〜１０の一価の有機基で、少なくとも一つは不飽和脂肪族炭化水素基を有する有機基であり、Ｌ_１及びＬ_２は、それぞれ独立に、アミノ基、酸無水物基、イソシアネート基、カルボキシル基、酸エステル基、酸ハライド基、ヒドロキシ基、エポキシ基、又はメルカプト基であり、ｉ及びｊは、それぞれ独立に、１〜２００の整数であり、ｋは、０〜２００の整数であり、０．０５≦ｊ／（ｉ＋ｊ＋ｋ）≦０．５０である。｝
［１１］
上記一般式（３−１）又は（３−２）で表される化合物において、ｍは３〜５の整数である、項目１０に記載の樹脂組成物。
［１２］
上記一般式（４）で表される化合物において、ｎは３〜８の整数である、項目１０に記載の樹脂組成物。
［１３］
下記一般式（１）で表される構造単位、及び下記一般式（２）で表される構造単位を含む、ポリイミド前駆体と；
下記一般式（３−１）又は（３−２）のうちｍが３又は４である、少なくともいずれか一方の化合物と；
任意に、下記一般式（４）で表される化合物と
を含む、樹脂組成物であって、
上記樹脂組成物は、以下：
下記一般式（５）で表されるケイ素含有化合物と、
下記一般式（３−１）又は（３−２）のうちｍが３又は４である、少なくともいずれか一方の化合物と、
任意に、下記一般式（４）で表される化合物とを含有する原料組成物を、テトラカルボン酸二無水物及びジアミンと重縮合反応させてポリイミド前駆体を提供することを含む方法により製造され、
上記原料組成物に含まれる、下記一般式（３−１）又は（３−２）のうちｍが３である化合物の総量が、下記一般式（３−１）、（３−２）、（４）及び（５）のケイ素含有化合物の合計質量を基準として、０ｐｐｍより多く２５，０００ｐｐｍ以下であるか、あるいは、
上記原料組成物に含まれる、下記一般式（３−１）又は（３−２）のうちｍが４である化合物の総量が、下記一般式（３−１）、（３−２）、（４）及び（５）のケイ素含有化合物の合計質量を基準として、０ｐｐｍより多く１５，０００ｐｐｍ以下である、
樹脂組成物。

｛式中、Ｐ_１は、２価の有機基を示し、Ｐ_２は、４価の有機基を示し、ｐは正の整数を示す。｝

｛式中、Ｐ_３及びＰ_４は、それぞれ独立に、炭素数１〜５の一価の脂肪族炭化水素、又は炭素数６〜１０の一価の芳香族基であり、ｑは、１〜２００の整数である。｝

｛式中、ｍは１以上の整数である。｝

｛式中、ｎは２以上の整数である。｝

｛式中、Ｒ_１は、それぞれ独立に、単結合又は炭素数１〜１０の二価の有機基であり、Ｒ_２及びＲ_３は、それぞれ独立に、炭素数１〜１０の一価の有機基であり、少なくとも一つは炭素数１〜５の一価の脂肪族炭化水素基であり、Ｒ_４及びＲ_５は、それぞれ独立に、炭素数１〜１０の一価の有機基であり、少なくとも一つは炭素数６〜１０の一価の芳香族基であり、Ｒ_６及びＲ_７は、それぞれ独立に、炭素数１〜１０の一価の有機基で、少なくとも一つは不飽和脂肪族炭化水素基を有する有機基であり、Ｌ_１及びＬ_２は、それぞれ独立に、アミノ基、酸無水物基、イソシアネート基、カルボキシル基、酸エステル基、酸ハライド基、ヒドロキシ基、エポキシ基、又はメルカプト基であり、ｉ及びｊは、それぞれ独立に、１〜２００の整数であり、ｋは、０〜２００の整数であり、０．０５≦ｊ／（ｉ＋ｊ＋ｋ）≦０．５０である。｝
［１４］
上記一般式（５）で表されるケイ素含有化合物の、Ｌ_１及びＬ_２が、それぞれ独立に、アミノ基、酸無水物基及びエポキシ基からなる群から選択される、項目１０〜１３のいずれか一項に記載の樹脂組成物。
［１５］
上記一般式（５）で表されるケイ素含有化合物の、Ｌ_１及びＬ_２が、アミノ基である、項目１０〜１４のいずれか一項に記載の樹脂組成物。
［１６］
上記一般式（３−１）又は（３−２）で表される化合物が、上記一般式（３−１）で表される化合物である、項目１０〜１５のいずれか一項に記載の樹脂組成物。
［１７］
上記テトラカルボン酸二無水物が、ピロメリット酸二無水物、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物、４，４’−オキシジフタル酸無水物、シクロヘキサンテトラカルボン酸二無水物、及びシクロブタンテトラカルボン酸二無水物からなる群から選択される少なくとも１つである、項目１０〜１６のいずれか一項に記載の樹脂組成物。
［１８］
上記ジアミンが、４，４’−ジアミノジフェニルスルホン、ｍ−トリジン、ｐ−フェニレンジアミン、２，２’−ビス（トリフルオロメチル）ベンジジン、及び２，２’−ビス［４−（４−アミノフェノキシ）フェニル］プロパンからなる群から選択される少なくとも１つである、項目１０〜１７のいずれか一項に記載の樹脂組成物。
［１９］
下記一般式（５）で表されるケイ素含有化合物と、
下記一般式（３−１）又は（３−２）のうちｍが３以上の整数である少なくともいずれか一方の化合物と、
任意に、下記一般式（４）で表される化合物とを含有する原料組成物を、テトラカルボン酸二無水物及びジアミンと重縮合反応させてポリイミド前駆体を提供することを含む、樹脂組成物の製造方法であって、
上記原料組成物に含まれる、下記一般式（３−１）又は（３−２）のうちｍが３以上の整数である化合物の総量は、下記一般式（３−１）、（３−２）、（４）及び（５）で表されるケイ素含有化合物の合計質量を基準として、０ｐｐｍより多く４６，０００ｐｐｍ以下であるか、あるいは、
上記原料組成物に含まれる、下記一般式（３−１）又は（３−２）のうちｍが３以上の整数である化合物と、下記一般式（４）のうちｎが３以上の整数である化合物との総量は、上記一般式（３−１）、（３−２）、（４）及び（５）のケイ素含有化合物の合計質量を基準として、０ｐｐｍより多く４７，０００ｐｐｍ以下である、
樹脂組成物の製造方法。

｛式中、ｍは１以上の整数である。｝

｛式中、ｎは２以上の整数である。｝

｛式中、Ｒ_１は、それぞれ独立に、単結合又は炭素数１〜１０の二価の有機基であり、Ｒ_２及びＲ_３は、それぞれ独立に、炭素数１〜１０の一価の有機基であり、少なくとも一つは炭素数１〜５の一価の脂肪族炭化水素基であり、Ｒ_４及びＲ_５は、それぞれ独立に、炭素数１〜１０の一価の有機基であり、少なくとも一つは炭素数６〜１０の一価の芳香族基であり、Ｒ_６及びＲ_７は、それぞれ独立に、炭素数１〜１０の一価の有機基で、少なくとも一つは不飽和脂肪族炭化水素基を有する有機基であり、Ｌ_１及びＬ_２は、それぞれ独立に、アミノ基、酸無水物基、イソシアネート基、カルボキシル基、酸エステル基、酸ハライド基、ヒドロキシ基、エポキシ基、又はメルカプト基であり、ｉ及びｊは、それぞれ独立に、１〜２００の整数であり、ｋは、０〜２００の整数であり、０．０５≦ｊ／（ｉ＋ｊ＋ｋ）≦０．５０である。｝
［２０］
上記一般式（３−１）又は（３−２）で表される化合物において、ｍは３〜５の整数である、項目１９に記載の方法。
［２１］
上記一般式（４）で表される化合物において、ｎは３〜８の整数である、項目１９に記載の方法。
［２２］
下記一般式（５）で表されるケイ素含有化合物と、
下記一般式（３−１）又は（３−２）のうちｍが３又は４である、少なくともいずれか一方の化合物と、
任意に、下記一般式（４）で表される化合物とを含有する原料組成物を、テトラカルボン酸二無水物及びジアミンと重縮合反応させてポリイミド前駆体を提供することを含む、樹脂組成物の製造方法であって、
上記原料組成物に含まれる、下記一般式（３−１）又は（３−２）のうちｍが３である化合物の総量が、下記一般式（３−１）、（３−２）、（４）及び（５）のケイ素含有化合物の合計質量を基準として、０ｐｐｍより多く２５，０００ｐｐｍ以下であるか、あるいは、
上記原料組成物に含まれる、下記一般式（３−１）又は（３−２）のうちｍが４である化合物の総量が、下記一般式（３−１）、（３−２）、（４）及び（５）のケイ素含有化合物の合計質量を基準として、０ｐｐｍより多く１５，０００ｐｐｍ以下である、
樹脂組成物の製造方法。

｛式中、ｍは１以上の整数である。｝

｛式中、ｎは２以上の整数である。｝

｛式中、Ｒ_１は、それぞれ独立に、単結合又は炭素数１〜１０の二価の有機基であり、Ｒ_２及びＲ_３は、それぞれ独立に、炭素数１〜１０の一価の有機基であり、少なくとも一つは炭素数１〜５の一価の脂肪族炭化水素基であり、Ｒ_４及びＲ_５は、それぞれ独立に、炭素数１〜１０の一価の有機基であり、少なくとも一つは炭素数６〜１０の一価の芳香族基であり、Ｒ_６及びＲ_７は、それぞれ独立に、炭素数１〜１０の一価の有機基で、少なくとも一つは不飽和脂肪族炭化水素基を有する有機基であり、Ｌ_１及びＬ_２は、それぞれ独立に、アミノ基、酸無水物基、イソシアネート基、カルボキシル基、酸エステル基、酸ハライド基、ヒドロキシ基、エポキシ基、又はメルカプト基であり、ｉ及びｊは、それぞれ独立に、１〜２００の整数であり、ｋは、０〜２００の整数であり、０．０５≦ｊ／（ｉ＋ｊ＋ｋ）≦０．５０である。｝
［２３］
上記一般式（５）で表されるケイ素含有化合物の、Ｌ_１及びＬ_２が、それぞれ独立に、アミノ基、酸無水物基及びエポキシ基からなる群から選択される、項目１９〜２２のいずれか一項に記載の方法。
［２４］
上記一般式（５）で表されるケイ素含有化合物の、Ｌ_１及びＬ_２が、アミノ基である、項目１９〜２３のいずれか一項に記載の方法。
［２５］
上記一般式（３−１）又は（３−２）で表される化合物が、上記一般式（３−１）で表される化合物である、項目１９〜２４のいずれか一項に記載の方法。
［２６］
上記テトラカルボン酸二無水物が、ピロメリット酸二無水物、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物、４，４’−オキシジフタル酸無水物、シクロヘキサンテトラカルボン酸二無水物、及びシクロブタンテトラカルボン酸二無水物からなる群から選択される少なくとも１つである、項目１９〜２５のいずれか一項に記載の方法。
［２７］
上記ジアミンが、４，４’−ジアミノジフェニルスルホン、ｍ−トリジン、ｐ−フェニレンジアミン、２，２’−ビス（トリフルオロメチル）ベンジジン、及び２，２’−ビス［４−（４−アミノフェノキシ）フェニル］プロパンからなる群から選択される少なくとも１つである、項目１９〜２６のいずれか一項に記載の方法。
［２８］
支持体の表面上に、項目１〜１８のいずれか一項のいずれか一項に記載の樹脂組成物を塗布する塗布工程と、
上記樹脂組成物を加熱してポリイミド樹脂膜を形成する膜形成工程と、
上記ポリイミド樹脂膜を上記支持体から剥離する剥離工程と、
を含む、ポリイミドフィルムの製造方法。
［２９］
上記剥離工程に先立って、上記支持体側から上記樹脂組成物にレーザーを照射する照射工程を含む、項目２８に記載のポリイミドフィルムの製造方法。
［３０］
支持体の表面上に、項目１〜１８のいずれか一項に記載の樹脂組成物を塗布する塗布工程と、
上記樹脂組成物を加熱してポリイミド樹脂膜を形成する膜形成工程と、
上記ポリイミド樹脂膜上に素子を形成する素子形成工程と、
上記素子が形成された上記ポリイミド樹脂膜を上記支持体から剥離する剥離工程と、
を含む、ディスプレイの製造方法。
［３１］
支持体の表面上に、項目１〜１８のいずれか一項に記載の樹脂組成物を塗布する塗布工程と、
上記樹脂組成物を加熱してポリイミド樹脂膜を形成する膜形成工程と、
上記ポリイミド樹脂膜上に素子を形成する素子形成工程と、
を含む、積層体の製造方法。
［３２］
上記素子が形成された上記ポリイミド樹脂膜を上記支持体から剥離する工程をさらに含む、項目３１に記載の積層体の製造方法。
［３３］
項目３１又は３２に記載の方法で積層体を製造することを含む、フレキシブルデバイスの製造方法。
［３４］
項目１〜１８のいずれか一項に記載の樹脂組成物の硬化物である、ポリイミドフィルム。As a result of intensive studies, the present inventors have found that the low-molecular cyclic siloxanes reduced in Patent Documents 3 to 5 are methyl side chains (general formula (4) described later) and phenyl side chains (described later). It was noted that it is not the general formula (3-1) or (3-2)). Then, it was found that the above problem can be solved by purifying the siloxane compound and using the siloxane compound in which the phenyl side chain of the low-molecular cyclic siloxane is reduced to a specific amount as the polyimide precursor. Examples of the embodiments of the present invention are listed below in [1] to [34].
[1]
A polyimide precursor containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2);
At least one of the compounds of the following general formula (3-1) or (3-2), wherein m is an integer of 3 or more;
A resin composition, optionally comprising a compound represented by the following general formula (4):
Whether the total amount of compounds in which m is an integer of 3 or more in the following general formula (3-1) or (3-2) is more than 0 ppm and 1,100 ppm or less based on the mass of the resin composition, Alternatively,
In the following general formula (3-1) or (3-2), the total amount of the compound in which m is an integer of 3 or more and the compound in which n is an integer of 3 or more in the following general formula (4) is the above resin. Greater than 0 ppm and less than or equal to 1,300 ppm, based on the weight of the composition,
Resin composition.

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer. }

{In the formula, P ₃ and P ₄ are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms, and q is 1 to It is an integer of 200. }

{In the formula, m is an integer of 1 or more. }

{In the formula, n is an integer of 2 or more. }
[2]
Item 1 in which the total amount of compounds in which m is an integer of 3 or more in the general formula (3-1) or (3-2) is more than 0 ppm and 300 ppm or less based on the mass of the resin composition. The resin composition described.
[3]
A polyimide precursor containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2);
At least one compound in which m is 3 or 4 in the following general formula (3-1) or (3-2);
A resin composition, optionally comprising a compound represented by the following general formula (4):
In the following general formula (3-1) or (3-2), the total amount of compounds in which m is 3 is more than 0 ppm and 650 ppm or less based on the mass of the resin composition, or
In the following general formula (3-1) or (3-2), the total amount of compounds in which m is 4 is more than 0 ppm and 350 ppm or less based on the mass of the resin composition,
Resin composition.

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer. }

{In the formula, P ₃ and P ₄ are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms, and q is 1 to It is an integer of 200. }

{In the formula, m is an integer of 1 or more. }

{In the formula, n is an integer of 2 or more. }
[4]
M among the polyimide precursor and the following general formula (3-1) or (3-2) containing the structural unit represented by the following general formula (1) and the structural unit represented by the following general formula (2). And at least one compound in which is an integer of 3 or more;
A resin composition, optionally comprising a compound represented by the following general formula (4):
In the following general formula (3-1) or (3-2), the total amount of compounds in which m is an integer of 3 or more is greater than 0 ppm and equal to or less than 7,500 ppm based on the mass of the solid content in the resin composition. Or
In the following general formula (3-1) or (3-2), the total amount of the compound in which m is an integer of 3 or more and the compound in which n is an integer of 3 or more in the following general formula (4) is the above. A resin composition which is more than 0 ppm and not more than 8,600 ppm based on the mass of the solid content in the resin composition.

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer. }

{In the formula, P ₃ and P ₄ are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms, and q is 1 to It is an integer of 200. }

{In the formula, m is an integer of 1 or more. }

{In the formula, n is an integer of 2 or more. }
[5]
A polyimide precursor containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2);
At least one compound in which m is 3 or 4 in the following general formula (3-1) or (3-2);
A resin composition, optionally comprising a compound represented by the following general formula (4):
Is the total amount of compounds in which m is 3 in the following general formula (3-1) or (3-2) is more than 0 ppm and not more than 4,500 ppm based on the mass of the solid content in the resin composition. , Or
In the following general formula (3-1) or (3-2), the total amount of compounds in which m is 4 is more than 0 ppm and 2,500 ppm or less, based on the mass of the solid content in the resin composition,
Resin composition.

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer. }

{In the formula, P ₃ and P ₄ are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms, and q is 1 to It is an integer of 200. }

{In the formula, m is an integer of 1 or more. }

[6]
The resin composition according to any one of items 1, 2 and 4, wherein m is an integer of 3 to 5 in the compound represented by the general formula (3-1) or (3-2).
[7]
The compound represented by the said General formula (4), n is an integer of 3-8, The resin composition as described in any one of items 1, 2 and 4.
[8]
The resin composition according to any one of Items 1 to 7, wherein the polyimide resin film obtained by curing the polyimide precursor is used for a flexible substrate.
[9]
The resin composition according to any one of Items 1 to 7, wherein the polyimide resin film obtained by curing the polyimide precursor is used for a flexible display.
[10]
A polyimide precursor containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2);
At least one compound of the following general formula (3-1) or (3-2), wherein m is an integer of 3 or more;
A resin composition, optionally comprising a compound represented by the following general formula (4):
The above resin composition has the following:
A silicon-containing compound represented by the following general formula (5),
At least one of the compounds of the following general formula (3-1) or (3-2), wherein m is an integer of 3 or more,
Optionally prepared by a method comprising polycondensing a raw material composition containing a compound represented by the following general formula (4) with a tetracarboxylic dianhydride and a diamine to provide a polyimide precursor. ,
Among the following general formulas (3-1) and (3-2) contained in the above-mentioned raw material composition, the total amount of compounds in which m is an integer of 3 or more is the following general formulas (3-1) and (3-2). ), (4) and (5) based on the total mass of the silicon-containing compounds, more than 0ppm and 46,000ppm or less, or
A compound in which m is an integer of 3 or more in the following general formula (3-1) or (3-2) contained in the raw material composition, and n is an integer of 3 or more in the following general formula (4). The total amount with a certain compound is more than 0 ppm and 47,000 ppm or less, based on the total mass of the silicon-containing compounds of the general formulas (3-1), (3-2), (4) and (5).
Resin composition.

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer. }

{In the formula, P ₃ and P ₄ are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms, and q is 1 to It is an integer of 200. }

{In the formula, m is an integer of 1 or more. }

{In the formula, n is an integer of 2 or more. }

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, and R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms. At least one is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group having 1 to 10 carbon atoms, At least one is a monovalent aromatic group having 6 to 10 carbon atoms, R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one is an unsaturated fatty group. Is an organic group having a group hydrocarbon group, L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid halide group, a hydroxy group, an epoxy group, Or a mercapto group, and i and j are each independently an integer of 1 to 200. And a, k is an integer of 0 to 200, is 0.05 ≦ j / (i + j + k) ≦ 0.50. }
[11]
Item 11. The resin composition according to Item 10, wherein m is an integer of 3 to 5 in the compound represented by the general formula (3-1) or (3-2).
[12]
Item 11. The resin composition according to item 10, wherein n is an integer of 3 to 8 in the compound represented by the general formula (4).
[13]
A polyimide precursor containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2);
At least one compound in which m is 3 or 4 in the following general formula (3-1) or (3-2);
A resin composition, optionally comprising a compound represented by the following general formula (4):
The above resin composition has the following:
A silicon-containing compound represented by the following general formula (5),
At least one compound in which m is 3 or 4 in the following general formula (3-1) or (3-2),
Optionally prepared by a method comprising polycondensing a raw material composition containing a compound represented by the following general formula (4) with a tetracarboxylic dianhydride and a diamine to provide a polyimide precursor. ,
Of the following general formula (3-1) or (3-2) contained in the above raw material composition, the total amount of compounds in which m is 3 is the following general formula (3-1), (3-2), ( 4) and (5) based on the total mass of the silicon-containing compound, more than 0ppm and 25,000ppm or less, or
Of the following general formula (3-1) or (3-2) contained in the above-mentioned raw material composition, the total amount of the compounds in which m is 4 is the following general formula (3-1), (3-2), ( 4) and 15,000 ppm or more based on the total mass of the silicon-containing compounds of (5),
Resin composition.

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer. }

{In the formula, P ₃ and P ₄ are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms, and q is 1 to It is an integer of 200. }

{In the formula, m is an integer of 1 or more. }

{In the formula, n is an integer of 2 or more. }

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, and R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms. At least one is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group having 1 to 10 carbon atoms, At least one is a monovalent aromatic group having 6 to 10 carbon atoms, R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one is an unsaturated fatty group. Is an organic group having a group hydrocarbon group, L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid halide group, a hydroxy group, an epoxy group, Or a mercapto group, and i and j are each independently an integer of 1 to 200. And a, k is an integer of 0 to 200, is 0.05 ≦ j / (i + j + k) ≦ 0.50. }
[14]
Any of Items 10 to 13, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (5) are each independently selected from the group consisting of an amino group, an acid anhydride group and an epoxy group. The resin composition according to item 1.
[15]
The resin composition according to any one of Items 10 to 14, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (5) are amino groups.
[16]
Item 16. The resin according to any one of Items 10 to 15, wherein the compound represented by the general formula (3-1) or (3-2) is a compound represented by the general formula (3-1). Composition.
[17]
The tetracarboxylic dianhydride is pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic anhydride, cyclohexanetetracarboxylic dianhydride. The resin composition according to any one of Items 10 to 16, which is at least one selected from the group consisting of a compound and a cyclobutanetetracarboxylic dianhydride.
[18]
The diamine is 4,4′-diaminodiphenyl sulfone, m-tolidine, p-phenylenediamine, 2,2′-bis (trifluoromethyl) benzidine, and 2,2′-bis [4- (4-aminophenoxy). ) A resin composition according to any one of items 10 to 17, which is at least one selected from the group consisting of phenyl] propane.
[19]
A silicon-containing compound represented by the following general formula (5),
At least one of the compounds of the following general formula (3-1) or (3-2), wherein m is an integer of 3 or more,
A resin composition, which optionally comprises polycondensing a raw material composition containing a compound represented by the following general formula (4) with a tetracarboxylic dianhydride and a diamine to provide a polyimide precursor. The manufacturing method of
Among the following general formulas (3-1) and (3-2) contained in the above-mentioned raw material composition, the total amount of compounds in which m is an integer of 3 or more is the following general formulas (3-1) and (3-2). ), (4) and (5) based on the total mass of the silicon-containing compounds, more than 0ppm and 46,000ppm or less, or
A compound in which m is an integer of 3 or more in the following general formula (3-1) or (3-2) contained in the raw material composition, and n is an integer of 3 or more in the following general formula (4). The total amount with a certain compound is more than 0 ppm and 47,000 ppm or less, based on the total mass of the silicon-containing compounds of the general formulas (3-1), (3-2), (4) and (5).
A method for producing a resin composition.

{In the formula, m is an integer of 1 or more. }

{In the formula, n is an integer of 2 or more. }

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, and R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms. At least one is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group having 1 to 10 carbon atoms, At least one is a monovalent aromatic group having 6 to 10 carbon atoms, R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one is an unsaturated fatty group. Is an organic group having a group hydrocarbon group, L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid halide group, a hydroxy group, an epoxy group, Or a mercapto group, and i and j are each independently an integer of 1 to 200. And a, k is an integer of 0 to 200, is 0.05 ≦ j / (i + j + k) ≦ 0.50. }
[20]
20. The method according to item 19, wherein m is an integer of 3 to 5 in the compound represented by the general formula (3-1) or (3-2).
[21]
20. The method according to Item 19, wherein in the compound represented by the general formula (4), n is an integer of 3 to 8.
[22]
A silicon-containing compound represented by the following general formula (5),
At least one compound in which m is 3 or 4 in the following general formula (3-1) or (3-2),
A resin composition, which optionally comprises polycondensing a raw material composition containing a compound represented by the following general formula (4) with a tetracarboxylic dianhydride and a diamine to provide a polyimide precursor. The manufacturing method of
Of the following general formula (3-1) or (3-2) contained in the above raw material composition, the total amount of compounds in which m is 3 is the following general formula (3-1), (3-2), ( 4) and (5) based on the total mass of the silicon-containing compound, more than 0ppm and 25,000ppm or less, or
Of the following general formula (3-1) or (3-2) contained in the above-mentioned raw material composition, the total amount of the compounds in which m is 4 is the following general formula (3-1), (3-2), ( 4) and 15,000 ppm or more based on the total mass of the silicon-containing compounds of (5),
A method for producing a resin composition.

{In the formula, m is an integer of 1 or more. }

{In the formula, n is an integer of 2 or more. }

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, and R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms. At least one is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group having 1 to 10 carbon atoms, At least one is a monovalent aromatic group having 6 to 10 carbon atoms, R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one is an unsaturated fatty group. Is an organic group having a group hydrocarbon group, L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid halide group, a hydroxy group, an epoxy group, Or a mercapto group, and i and j are each independently an integer of 1 to 200. And a, k is an integer of 0 to 200, is 0.05 ≦ j / (i + j + k) ≦ 0.50. }
[23]
Any of Items 19 to 22, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (5) are each independently selected from the group consisting of an amino group, an acid anhydride group and an epoxy group. The method described in paragraph 1.
[24]
24. The method according to any one of Items 19 to 23, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (5) are amino groups.
[25]
25. The method according to any one of Items 19 to 24, wherein the compound represented by the general formula (3-1) or (3-2) is a compound represented by the general formula (3-1). ..
[26]
The tetracarboxylic dianhydride is pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic anhydride, cyclohexanetetracarboxylic dianhydride. 26. The method according to any one of Items 19 to 25, wherein the method is at least one selected from the group consisting of a compound and cyclobutanetetracarboxylic dianhydride.
[27]
The diamine is 4,4′-diaminodiphenyl sulfone, m-tolidine, p-phenylenediamine, 2,2′-bis (trifluoromethyl) benzidine, and 2,2′-bis [4- (4-aminophenoxy). ) A method according to any one of items 19 to 26, which is at least one selected from the group consisting of phenyl] propane.
[28]
A coating step of coating the resin composition according to any one of items 1 to 18 on the surface of a support,
A film forming step of heating the resin composition to form a polyimide resin film,
A peeling step of peeling the polyimide resin film from the support,
A method for producing a polyimide film, comprising:
[29]
29. The method for producing a polyimide film according to item 28, including an irradiation step of irradiating the resin composition with a laser from the support side prior to the peeling step.
[30]
A coating step of coating the resin composition according to any one of items 1 to 18 on the surface of a support;
A film forming step of heating the resin composition to form a polyimide resin film,
An element forming step of forming an element on the polyimide resin film,
A peeling step of peeling the polyimide resin film on which the element is formed from the support,
A method of manufacturing a display, including:
[31]
A coating step of coating the resin composition according to any one of items 1 to 18 on the surface of a support,
A film forming step of heating the resin composition to form a polyimide resin film,
An element forming step of forming an element on the polyimide resin film,
The manufacturing method of a laminated body containing.
[32]
32. The method for manufacturing a laminate according to item 31, further including a step of peeling the polyimide resin film having the element formed thereon from the support.
[33]
A method for manufacturing a flexible device, which comprises manufacturing a laminate by the method according to Item 31 or 32.
[34]
A polyimide film, which is a cured product of the resin composition according to any one of Items 1 to 18.

  ADVANTAGE OF THE INVENTION According to this invention, compared with the case where an unpurified siloxane compound is used, a yellow degree (YI value) is improved and the polyimide precursor resin composition which can reduce the foreign material which generate | occur | produces in a polyimide manufacturing process is provided. can do. It should be noted that the above description should not be considered as disclosing all the embodiments of the present invention and all advantages related to the present invention. Further embodiments of the invention and its advantages will be apparent with reference to the following description.

FIG. 1 is a schematic view showing a structure of a top emission type flexible organic EL display above a polyimide substrate as an example of the display of the present embodiment.

  Hereinafter, exemplary embodiments of the present invention (hereinafter, abbreviated as “this embodiment”) will be described in detail. The present invention is not limited to this embodiment, and can be variously modified and implemented within the scope of the gist. In the present specification, the upper limit value and the lower limit value of each numerical range can be arbitrarily combined.

<< Resin composition >>
<Polyimide precursor>
Structural Unit of General Formula (1) First Embodiment A resin composition of the present embodiment includes a polyimide precursor containing a structural unit represented by the following general formula (1) in the first embodiment.

｛式中、Ｐ_１は、２価の有機基を示し、Ｐ_２は、４価の有機基を示し、ｐは正の整数を示す。｝

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer. }

The polyimide precursor having the structure represented by the general formula (1) is preferably a copolymer of an acid dianhydride having a P ₂ group and a diamine having a P ₁ group.

Acid dianhydride As the acid dianhydride containing a P ₂ group, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3 ′ -Biphenyltetracarboxylic dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-cyclohexene-1,2 Dicarboxylic acid anhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dianhydride, 2,2 ′, 3,3′-benzophenone Tetracarboxylic acid dianhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, methylene-4,4'-diphthalic acid dianhydride, 1,1-ethylidene-4,4'- Diphthalic dianhydride, 2,2-pro Ridene-4,4'-diphthalic acid dianhydride, 1,2-ethylene-4,4'-diphthalic acid dianhydride, 1,3-trimethylene-4,4'-diphthalic acid dianhydride, 1,4 -Tetramethylene-4,4'-diphthalic acid dianhydride, 1,5-pentamethylene-4,4'-diphthalic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, p-phenylenebis (trimellitate) Acid anhydride), thio-4,4'-diphthalic acid dianhydride, sulfonyl-4,4'-diphthalic acid dianhydride, 1,3-bis (3,4-dicarboxyphenyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,3-bis [2- (3,4 -Dicarboxyphenyl) -2-propyl] benzene dianhydride 1,4-bis [2- (3,4-dicarboxyphenyl) -2-propyl] benzene dianhydride, bis [3- (3,4-dicarboxyphenoxy) phenyl] methane dianhydride, bis [4- (3,4-Dicarboxyphenoxy) phenyl] methane dianhydride, 2,2-bis [3- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [4 -(3,4-Dicarboxyphenoxy) phenyl] propane dianhydride, bis (3,4-dicarboxyphenoxy) dimethylsilane dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1, 1,3,3-Tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2, 5,6- Phthalene tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, and 1,2,7,8- Examples thereof include phenanthrene tetracarboxylic dianhydride.

  The acid dianhydride may be used alone or in combination of two or more. Among them, pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic dianhydride (BPDA) are optical materials such as mechanical properties of polyimide film, low thickness direction retardation (Rth) and low yellowness (YI value). It is preferable from the viewpoint of properties and high glass transition temperature. The polyimide precursor having the structure represented by the general formula (1) is a copolymer of tetracarboxylic dianhydride and diamine, and the tetracarboxylic dianhydride is pyromellitic dianhydride (PMDA). It is more preferable to include).

  The total content of pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic dianhydride (BPDA) in the total acid dianhydride is determined from the viewpoints of low Rth and YI values of the polyimide film and high glass transition temperature. Therefore, it is preferably 60 mol% or more, more preferably 80 mol% or more, still more preferably 100 mol%.

  The content of pyromellitic dianhydride (PMDA) in the total acid dianhydride is preferably 0 mol% or more, preferably 10 mol% or more, and 20 mol% from the viewpoint of the high glass transition temperature of the polyimide film. The above is preferable, 100 mol% or less is preferable, and 90 mol% or less is preferable.

  The content of biphenyltetracarboxylic dianhydride (BPDA) in the total acid dianhydride is preferably 0 mol% or more, and more preferably 10 mol% or more, from the viewpoint of low Rth and YI value of the polyimide film. It is preferably at least mol%, more preferably at most 100 mol%, and preferably at most 90 mol%.

  The content ratio of pyromellitic dianhydride (PMDA): biphenyltetracarboxylic dianhydride (BPDA) in the acid dianhydride is such that the polyimide film has a low Rth and YI value, a high glass transition temperature, and elongation. From the viewpoint of satisfying both, 20:80 to 80:20 are preferable, and 30:70 to 70:30 are more preferable.

Diamine As the diamine containing a P ₁ group in the formula (1), diaminodiphenyl sulfone (eg, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone), p-phenylenediamine, m-phenylenediamine, 4 , 4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, 4,4-bis (4-aminophenoxy) biphenyl , 4,4-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, 1,4-bis (4- Aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 9,10-bis (4-aminophenyl) anthracene, 2,2-bis (4-aminophenyl) propane, 2,2-bis ( 4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl) propane, 2,2-bis [4- 4-aminophenoxy) phenyl) hexafluoropropane and 1,4-bis (3-aminopropyl dimethyl silyl) benzene.

The diamine containing a P ₁ group in formula (1) preferably contains diaminodiphenyl sulfone, for example, 4,4′-diaminodiphenyl sulfone, and / or 3,3′-diaminodiphenyl sulfone.

  The content of diaminodiphenyl sulfone in all the diamines may be 50 mol% or more, or 70 mol% or more, or 90 mol% or more, or 95 mol% or more. It is preferable that the amount of diaminodiphenyl sulfone is larger because the YI value of the polyimide film is reduced and a high glass transition temperature is obtained. As the diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone is particularly preferable from the viewpoint of reducing the YI value.

  The diamine may be used alone or in combination of two or more. It is preferable to copolymerize diaminodiphenyl sulfone with another diamine. Other diamines to be copolymerized with diaminodiphenyl sulfone include preferably diamidobiphenyls, more preferably diaminobis (trifluoromethyl) biphenyl (TFMB), from the viewpoint of high heat resistance of polyimide film and low YI value. .. The content of diaminobis (trifluoromethyl) biphenyl (TFMB) in all the diamines is preferably 20 mol% or more, more preferably 30 mol% or more from the viewpoint of the low YI value of the polyimide film. From a design point of view allowing the diamine to contain other advantageous diamines such as diaminodiphenyl sulfone, the content of TFMB is preferably 80 mol% or less, more preferably 70 mol% or less.

Structural Unit of General Formula (2) The polyimide precursor in the resin composition of the present embodiment further includes a structural unit represented by the following general formula (2).

｛式中、Ｐ_３及びＰ_４は、それぞれ独立に、炭素数１〜５の一価の脂肪族炭化水素、又は炭素数６〜１０の一価の芳香族基であり、ｑは、１〜２００の整数である。｝

{In the formula, P ₃ and P ₄ are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms, and q is 1 to It is an integer of 200. }

Based on the mass of the polyimide precursor, the lower limit of the ratio of the structural sites represented by the general formula (2) is preferably 5 mass% from the viewpoint of reducing the residual stress of the polyimide film generated between the support and the support. As described above, the content is more preferably 6% by mass or more, and further preferably 7% by mass or more. Based on the mass of the polyimide precursor, the upper limit of the ratio of the structural sites represented by the general formula (2) is preferably 40% by mass or less, more preferably 30% from the viewpoint of transparency and heat resistance of the polyimide film. It is not more than 25% by mass, more preferably not more than 25% by mass.
In the general formula (2), q is an integer of 1 to 200, and an integer of 3 to 200 is preferable from the viewpoint of heat resistance of the obtained polyimide.

  The polyimide precursor may have the structure of the general formula (2) at any site in the molecule, but from the viewpoint of the type of siloxane monomer, the cost, and the molecular weight of the obtained polyimide precursor, the general formula The structure (2) is preferably derived from a silicon-containing compound, for example, a silicon-containing diamine. As the silicon-containing diamine, for example, diamino (poly) siloxane represented by the following formula (6) is preferable.

｛式中、Ｐ_５は、それぞれ独立に、二価の炭化水素基を示し、同一でも異なっていてもよく、Ｐ_３及びＰ_４は、一般式（２）において定義したものと同様であり、ｌは、１〜２００の整数を表す。｝

{In the formula, P ₅ each independently represents a divalent hydrocarbon group, which may be the same or different, and P ₃ and P ₄ are the same as defined in the general formula (2), l represents an integer of 1 to 200. }

Examples of a preferable structure of P _{5 in} the general formula (2) include a methylene group, an ethylene group, a propylene group, a butylene group and a phenylene group. Preferable structures of P ₃ and P ₄ include a methyl group, an ethyl group, a propyl group, a butyl group and a phenyl group. In the general formula (6), l is an integer of 1 to 200, and an integer of 3 to 200 is preferable from the viewpoint of heat resistance of the polyimide used in (6).

  The number average molecular weight of the compound represented by the general formula (6) is preferably 500 or more, more preferably 1,000 or more, from the viewpoint of reducing the residual stress generated between the obtained polyimide film and the support. More preferably, it is 2,000 or more. From the viewpoint of transparency (particularly low Haze) of the obtained polyimide film, the number average molecular weight is preferably 12,000 or less, more preferably 10,000 or less, and further preferably 8,000 or less.

  Specific examples of the compound represented by the general formula (6) include amine-modified methylphenyl silicone oil modified at both terminals (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400), X22-9409 (number average). Molecular weight 1340)), both ends acid anhydride-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-168-P5-B (number average molecular weight 4200)), both ends epoxy-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-2000 (number average molecular weight 1240)), amino-modified dimethyl silicone at both ends (manufactured by Shin-Etsu Chemical: X22-161A (number average molecular weight 1600), X22-161B (number average molecular weight 3000), KF8021 (number average molecular weight 4400). Manufactured by Toray Dow Corning: BY16-835U (number average molecular weight 900) Company Ltd. Silaplane FM3311 (number average molecular weight 1000)) and the like. Among these, amine-modified methylphenyl silicone oil modified at both ends is preferable from the viewpoint of improving chemical resistance and Tg.

  The copolymerization ratio of the silicon-containing diamine is preferably 0.5 to 30% by mass, more preferably 1.0% to 25% by mass, further preferably 1.5% by mass, based on the total mass of the polyimide precursor. Is about 20% by mass. When the silicon-containing diamine is 0.5% by mass or more, the residual stress generated between the diamine and the support can be effectively reduced. When the content of silicon-containing diamine is 30% by mass or less, the transparency (particularly low HAZE) of the obtained polyimide film is good, and it is preferable from the viewpoint of achieving high total light transmittance and high glass transition temperature.

Dicarboxylic acid As the acid component for forming the polyimide precursor in the present embodiment, dicarboxylic acid is added in addition to the acid dianhydride (for example, the tetracarboxylic acid dianhydride exemplified above) as long as the performance is not impaired. Acids may be used. That is, the polyimide precursor of the present disclosure may be a polyamideimide precursor. A film obtained from such a polyimide precursor may have good properties such as mechanical elongation, glass transition temperature Tg, and YI value. Examples of the dicarboxylic acid used include an aromatic ring-containing dicarboxylic acid and an alicyclic dicarboxylic acid. Particularly, at least one compound selected from the group consisting of aromatic dicarboxylic acids having 8 to 36 carbon atoms and alicyclic dicarboxylic acids having 6 to 34 carbon atoms is preferable. The number of carbons referred to here also includes the number of carbons contained in the carboxyl group. Of these, dicarboxylic acids having an aromatic ring are preferable.

  Specific examples of the dicarboxylic acid having an aromatic ring include isophthalic acid, terephthalic acid, 4,4′-biphenyldicarboxylic acid, 3,4′-biphenyldicarboxylic acid, 3,3′-biphenyldicarboxylic acid, 1, 4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-sulfonylbisbenzoic acid, 3,4′-sulfonylbisbenzoic acid, 3,3'-sulfonylbisbenzoic acid, 4,4'-oxybisbenzoic acid, 3,4'-oxybisbenzoic acid, 3,3'-oxybisbenzoic acid, 2,2-bis (4-carboxyphenyl) propane, 2,2-bis (3-carboxyphenyl) propane, 2,2'-dimethyl-4,4'-biphenyldicarboxylic acid, 3,3'-di Tyl-4,4′-biphenyldicarboxylic acid, 2,2′-dimethyl-3,3′-biphenyldicarboxylic acid, 9,9-bis (4- (4-carboxyphenoxy) phenyl) fluorene, 9,9-bis (4- (3-carboxyphenoxy) phenyl) fluorene, 4,4′-bis (4-carboxyphenoxy) biphenyl, 4,4′-bis (3-carboxyphenoxy) biphenyl, 3,4′-bis (4- Carboxyphenoxy) biphenyl, 3,4'-bis (3-carboxyphenoxy) biphenyl, 3,3'-bis (4-carboxyphenoxy) biphenyl, 3,3'-bis (3-carboxyphenoxy) biphenyl, 4,4 '-Bis (4-carboxyphenoxy) -p-terphenyl, 4,4'-bis (4-carboxyphenoxy) -m- -Phenyl, 3,4'-bis (4-carboxyphenoxy) -p-terphenyl, 3,3'-bis (4-carboxyphenoxy) -p-terphenyl, 3,4'-bis (4-carboxyphenoxy) -M-terphenyl, 3,3'-bis (4-carboxyphenoxy) -m-terphenyl, 4,4'-bis (3-carboxyphenoxy) -p-terphenyl, 4,4'-bis (3 -Carboxyphenoxy) -m-terphenyl, 3,4'-bis (3-carboxyphenoxy) -p-terphenyl, 3,3'-bis (3-carboxyphenoxy) -p-terphenyl, 3,4 ' -Bis (3-carboxyphenoxy) -m-terphenyl, 3,3'-bis (3-carboxyphenoxy) -m-terphenyl, 1,1-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4,4′-benzophenonedicarboxylic acid, 1,3-phenylenediacetic acid, 1,4-phenylenediacetic acid and the like; and WO 2005/068535. And the 5-aminoisophthalic acid derivative described in 1. When these dicarboxylic acids are actually copolymerized with the polymer, they may be used in the form of an acid chloride derivative derived from thionyl chloride or the like, an active ester derivative or the like.

Second Embodiment In the second embodiment, the polyimide precursor in the resin composition comprises a silicon-containing compound represented by the following general formula (5), a tetracarboxylic dianhydride, and a diamine as a monomer unit. Can also be described as a copolymer containing.

｛式中、Ｒ_１は、それぞれ独立に、単結合又は炭素数１〜１０の二価の有機基であり、Ｒ_２及びＲ_３は、それぞれ独立に、炭素数１〜１０の一価の有機基であり、少なくとも一つは炭素数１〜５の一価の脂肪族炭化水素基であり、Ｒ_４及びＲ_５は、それぞれ独立に、炭素数１〜１０の一価の有機基であり、少なくとも一つは炭素数６〜１０の一価の芳香族基であり、Ｒ_６及びＲ_７は、それぞれ独立に、炭素数１〜１０の一価の有機基で、少なくとも一つは不飽和脂肪族炭化水素基を有する有機基であり、Ｌ_１及びＬ_２は、それぞれ独立に、アミノ基、酸無水物基、イソシアネート基、カルボキシル基、酸エステル基、酸ハライド基、ヒドロキシ基、エポキシ基、又はメルカプト基であり、ｉ及びｊは、それぞれ独立に、１〜２００の整数であり、ｋは、０〜２００の整数であり、０．０５≦ｊ／（ｉ＋ｊ＋ｋ）≦０．５０である。｝

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, and R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms. At least one is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group having 1 to 10 carbon atoms, At least one is a monovalent aromatic group having 6 to 10 carbon atoms, R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one is an unsaturated fatty group. Is an organic group having a group hydrocarbon group, L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid halide group, a hydroxy group, an epoxy group, Or a mercapto group, and i and j are each independently an integer of 1 to 200. And a, k is an integer of 0 to 200, is 0.05 ≦ j / (i + j + k) ≦ 0.50. }

L ₁ and L ₂ of the silicon-containing compound represented by the general formula (5) are, but not limited to, each independently an amino group or an acid anhydride group from the viewpoint of the molecular weight of the obtained polyimide precursor. Preferably, it is more preferably an amino group.

In general formula (5), R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms. The divalent organic group having 1 to 10 carbon atoms may be linear, cyclic or branched, and may be saturated or unsaturated. Examples of the divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms include methylene, ethylene, n-propylene, i-propylene, n-butylene, s-butylene, t-butylene, n-pentylene, neopentylene and n. Straight-chain or branched-chain alkylene groups such as -hexylene, n-heptylene, n-octylene, n-nonylene, and n-decylene groups; and cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, and cyclooctylene. Examples include cycloalkylene groups such as groups. The divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferably at least one selected from the group consisting of ethylene, n-propylene and i-propylene.

In formula (5), R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms. Is. The monovalent organic group having 1 to 10 carbon atoms may be linear, cyclic or branched, and may be saturated or unsaturated. For example, as the monovalent organic group having 1 to 10 carbon atoms, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, linear or branched alkyl groups such as n-heptyl, n-octyl, n-nonyl, and n-decyl groups; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups, Aromatic groups such as phenyl, tolyl, xylyl, α-naphthyl, and β-naphthyl groups. The monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms may be linear, cyclic or branched, and may be saturated or unsaturated. For example, as the monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, and neopentyl groups can be given. And straight chain or branched chain alkyl groups; and cycloalkyl groups such as cyclopropyl, cyclobutyl, and cyclopentyl groups. The monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferably at least one selected from the group consisting of methyl, ethyl, and n-propyl.

In the general formula (5), R ₄ and R ₅ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one is a monovalent aromatic group having 6 to 10 carbon atoms. .. The monovalent organic group having 1 to 10 carbon atoms may be linear, cyclic or branched, and may be saturated or unsaturated. For example, as the monovalent organic group having 1 to 10 carbon atoms, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, linear or branched alkyl groups such as n-heptyl, n-octyl, n-nonyl, and n-decyl groups; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups, Aromatic groups such as phenyl, tolyl, xylyl, α-naphthyl, and β-naphthyl groups. Examples of the monovalent aromatic group having 6 to 10 carbon atoms include phenyl, tolyl, xylyl, α-naphthyl, and β-naphthyl groups and the like, with phenyl, tolyl, and xylyl being preferred.

In the general formula (5), R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one is an organic group having an unsaturated aliphatic hydrocarbon group. The monovalent organic group having 1 to 10 carbon atoms may be linear, cyclic or branched and includes, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, Linear or branched alkyl groups such as t-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl groups; and cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl. And cycloalkyl groups such as cycloheptyl and cyclooctyl groups, and aromatic groups such as phenyl, tolyl, xylyl, α-naphthyl, and β-naphthyl groups. The monovalent organic group having 1 to 10 carbon atoms is preferably at least one selected from the group consisting of methyl, ethyl and phenyl. The organic group having an unsaturated aliphatic hydrocarbon group may be an unsaturated aliphatic hydrocarbon group having 3 to 10 carbon atoms, and may be linear, cyclic or branched. Examples of the unsaturated aliphatic hydrocarbon group having 3 to 10 carbon atoms include vinyl, allyl, propenyl, 3-butenyl, 2-butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, octenyl, nonenyl, decenyl, Examples include ethynyl, propynyl, butynyl, pentynyl, and hexynyl groups. The unsaturated aliphatic hydrocarbon group having 3 to 10 carbon atoms is preferably at least one selected from the group consisting of vinyl, allyl, and 3-butenyl.

In the general formula (5), some or all of the hydrogen atoms of R _{1 to} R ₇ may be substituted with a substituent such as a halogen atom of F, Cl, Br or the like, or may be unsubstituted. .

  i and j are each independently an integer of 1 to 200, preferably an integer of 2 to 100, more preferably an integer of 4 to 80, and still more preferably an integer of 8 to 40. k is an integer of 0 to 200, preferably an integer of 0 to 50, more preferably an integer of 0 to 20, and still more preferably an integer of 0 to 50.

  The tetracarboxylic acid dianhydride in the second embodiment may be the tetracarboxylic acid dianhydride described for the general formula (1). The tetracarboxylic dianhydride in the second embodiment is pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic anhydride, cyclohexanetetra. It is preferably at least one selected from the group consisting of carboxylic dianhydride and cyclobutanetetracarboxylic dianhydride.

  The diamine in the second embodiment may be the diamine mentioned for the general formula (1). The diamine in the second embodiment is 4,4′-diaminodiphenyl sulfone, m-tolidine, p-phenylenediamine, 2,2′-bis (trifluoromethyl) benzidine, and 2,2′-bis [4- ( It is preferably at least one selected from the group consisting of 4-aminophenoxy) phenyl] propane.

Weight average molecular weight In the present embodiment, the weight average molecular weight of the polyimide precursor is preferably 50,000 or more, more preferably 60,000 or more from the viewpoint of reducing the YI value of the polyimide film. From the viewpoint of reducing the haze of the polyimide film, the weight average molecular weight of the polyimide precursor is preferably 150,000 or less, more preferably 120,000 or less. The desirable weight average molecular weight of the polyimide precursor may vary depending on the desired application, the type of polyimide precursor, the solid content of the resin composition, the type of solvent that the resin composition may contain, and the like.

Preferred Embodiment of Polyimide Precursor The following (1) to (9) are mentioned as particularly preferred polyimide precursors in the present embodiment.
(1) A polycondensate in which the acid dianhydride component is pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic dianhydride (BPDA) and the diamine component is diaminodiphenylsulfone (DAS) and a silicon-containing diamine. . More preferably, the weight average molecular weight is 80,000 to 100,000 and the solid content is 10 to 25% by mass.
(2) The acid dianhydride component is pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic dianhydride (BPDA), and the diamine component is diaminobis (trifluoromethyl) biphenyl (TFMB) and silicon-containing diamine. A polycondensate. More preferably, the weight average molecular weight is 65,000 to 90,000 and the solid content is 10 to 25 mass%.
(3) The acid dianhydride component is pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic dianhydride (BPDA), and the diamine component is diaminodiphenylsulfone (DAS), diaminobis (trifluoromethyl) biphenyl ( TFMB) and a polycondensate which is a silicon-containing diamine. More preferably, the weight average molecular weight is 95,000 to 120,000 and the solid content is 10 to 25% by mass.
(4) A polycondensate in which the acid dianhydride component is pyromellitic dianhydride (PMDA) and the diamine component is diaminodiphenyl sulfone (DAS) and a silicon-containing diamine. More preferably, the weight average molecular weight is 100,000 to 110,000 and the solid content is 10 to 25% by mass.
(5) A polycondensate in which the acid dianhydride component is pyromellitic dianhydride (PMDA) and the diamine component is diaminobis (trifluoromethyl) biphenyl (TFMB) and a silicon-containing diamine. More preferably, the weight average molecular weight is 100,000 to 110,000 and the solid content is 10 to 25% by mass.
(6) Polycondensate in which the acid dianhydride component is pyromellitic dianhydride (PMDA) and the diamine component is diaminodiphenyl sulfone (DAS), diaminobis (trifluoromethyl) biphenyl (TFMB) and silicon-containing diamine . More preferably, the weight average molecular weight is 110,000 to 120,000 and the solid content is 10 to 25% by mass.

(7) A polycondensate in which the acid dianhydride component is biphenyltetracarboxylic dianhydride (BPDA) and the diamine component is diaminodiphenylsulfone (DAS) and a silicon-containing diamine. More preferably, the weight average molecular weight is 70,000 to 80,000 and the solid content is 10 to 25% by mass.
(8) Polycondensation in which the acid dianhydride component is biphenyltetracarboxylic dianhydride (BPDA) and the diamine component is diaminodiphenylsulfone (DAS), diaminobis (trifluoromethyl) biphenyl (TFMB) and silicon-containing diamine object. More preferably, the weight average molecular weight is 90,000 to 100,000 and the solid content is 10 to 25 mass%.
(9) A polycondensate in which the acid dianhydride component is biphenyltetracarboxylic dianhydride (BPDA) and the diamine component is diaminobis (trifluoromethyl) biphenyl (TFMB) and a silicon-containing diamine. More preferably, the weight average molecular weight is 70,000 to 80,000 and the solid content is 10 to 25% by mass.

  In the material component of the polycondensate of (1) to (9), the silicon-containing diamine is preferably diamino (poly) siloxane represented by the general formula (6). In this case, the number average molecular weight of the diamino (poly) siloxane is preferably 500 to 12,000, and more preferably the diamino (poly) siloxane is an amine-modified methylphenyl silicone oil modified at both ends.

<Low molecular cyclic siloxane>
Compound of General Formula (3) In the resin composition of the present embodiment, at least m is an integer of 3 or more among the low molecular weight cyclic siloxanes represented by the following general formula (3-1) or (3-2). One of the low molecular cyclic siloxanes is included (when simply referred to as “(3)”, it means “(3-1) or (3-2)”). The composition of the present embodiment may or may not include a compound in which m is 1 or 2 in the general formula (3-1) or (3-2). The resin composition of the present embodiment may include only one of general formula (3-1) or (3-2), or may include both of them. The compound represented by formula (3-1) or (3-2) is preferably the compound represented by formula (3-1). That is, the resin composition of the present embodiment preferably contains at least the compound represented by the general formula (3-1).

｛式中、ｍは１以上の整数である。｝

{In the formula, m is an integer of 1 or more. }

  In the general formula (3), the total amount of compounds in which m is an integer of 3 or more is preferably more than 0 ppm and 1,100 ppm or less, more preferably more than 0 ppm and 800 ppm or less, further preferably based on the mass of the resin composition. Is more than 0 ppm and 600 ppm or less, particularly preferably more than 0 ppm and 300 ppm or less, particularly preferably more than 0 ppm and 180 ppm or less. Here, the total amount of the compound represented by the general formula (3) includes the total amount when the resin composition includes only one of the general formulas (3-1) and (3-2), or both of them. The case means the total amount.

  More specifically, the total amount of compounds in which m is 3 to 5 in the general formula (3) is preferably more than 0 ppm and 1,100 ppm or less, more preferably more than 0 ppm, based on the mass of the resin composition. It is 800 ppm or less, more preferably more than 0 ppm and 600 ppm or less, particularly preferably more than 0 ppm and 300 ppm or less, particularly preferably more than 0 ppm and 180 ppm or less.

  The total amount of compounds in which m is 3 in the general formula (3) is preferably more than 0 ppm and 650 ppm or less, more preferably more than 0 ppm and 150 ppm or less, still more preferably more than 0 ppm and 80 ppm, based on the mass of the resin composition. It is below. The total amount of the compounds of m = 4 in the general formula (3) is preferably more than 0 ppm and less than 350 ppm, more preferably more than 0 ppm and less than 100 ppm, still more preferably more than 0 ppm and less than 60 ppm, based on the mass of the resin composition. is there. It is preferable that the total amount of the compound represented by the general formula (3) is within the above range because the YI value of the polyimide resin film obtained from the resin composition is further lowered.

  When based on the mass of the solid content in the resin composition, the total amount of the compounds of the general formula (3) in which m is an integer of 3 or more is preferably more than 0 ppm and 7,500 ppm or less, more preferably 0 ppm. It is more than 2,000 ppm and more preferably more than 0 ppm and not more than 1,100 ppm. When based on the mass of the solid content in the resin composition, the total amount of compounds in which m is 3 in the general formula (3) is preferably more than 0 ppm and 4,500 ppm or less, more preferably more than 0 ppm 1, It is 000 ppm or less, more preferably more than 0 ppm and 500 ppm or less. When based on the mass of the solid content in the resin composition, the total amount of compounds in which m is 4 in the general formula (3) is preferably more than 0 ppm and 2,500 ppm or less, more preferably more than 0 ppm and 700 ppm or less. And more preferably more than 0 ppm and 400 ppm or less. It is preferable that the total amount of the compound represented by the general formula (3) is within the above range because the YI value of the polyimide resin film obtained from the resin composition is further lowered.

  In the present specification, the "solid content" refers to all the components other than the solvent in the resin composition, and the liquid monomer component is also included in the mass of the solid content. When the resin composition contains only the solvent and the polyimide precursor, the polyimide precursor corresponds to the solid content. When the resin composition contains only the solvent and the polyimide precursor, the mass of the solid content corresponds to the total mass of all the monomers contained in the polyimide precursor. The mass of the solid content can also be determined by determining the mass of the solvent by analyzing the resin composition by gas chromatography (hereinafter also referred to as GC) and subtracting the mass of the solvent from the mass of the resin composition. The mass of the solid content can also be determined by heating the resin composition, volatilizing and removing the solvent, determining the mass of the solvent, and subtracting the mass of the solvent from the mass of the resin composition.

  The polyimide precursor of the present embodiment is represented by a silicon-containing compound represented by the general formula (5), a compound represented by the general formula (3-1) or (3-2), and a general formula (4). It can be obtained by subjecting a raw material composition containing the compound described above to a polycondensation reaction with tetracarboxylic dianhydride and diamine. In that case, the total amount of compounds in the general formula (3) in which m is an integer of 3 or more is the silicon represented by the general formulas (3), (4), and (5). It is preferably more than 0 ppm and 280 ppm or less, more preferably more than 0 ppm and 30 ppm or less, still more preferably more than 0 ppm and 6 ppm or less, based on the mass of the contained compound. Based on the total mass of the silicon-containing compounds represented by the general formulas (3), (4) and (5), the total amount of the compounds in which m is 3 in the general formula (3) is preferably more than 0 ppm and 200 ppm. Or less, more preferably more than 0 ppm and 25 ppm or less, still more preferably more than 0 ppm and 3 ppm or less. Based on the total mass of the silicon-containing compounds of the general formulas (3), (4) and (5), the total amount of compounds of the general formula (3) in which m is 4 is preferably more than 0 ppm and 80 ppm or less. , More preferably more than 0 ppm and 5 ppm or less, still more preferably more than 0 ppm and 3 ppm or less. It is preferable that the total amount of the compound represented by the general formula (3) is within the above range because the YI value of the polyimide resin film obtained from the resin composition is further lowered.

Compound of General Formula (4) The resin composition of the present embodiment may further include a compound represented by the following general formula (4) in addition to the compound represented by the general formula (3).

｛式中、ｎは２以上の整数である。｝

{In the formula, n is an integer of 2 or more. }

  Of the general formula (4), the total amount of compounds in which n is an integer of 3 or more is preferably more than 0 ppm and 200 ppm or less, more preferably more than 0 ppm and 100 ppm or less, further preferably 0 ppm, based on the mass of the resin composition. It is more than 50 ppm.

  Of the general formula (4), the total amount of compounds in which n is 3 to 8 is preferably more than 0 ppm and 200 ppm or less, more preferably more than 0 ppm and 100 ppm or less, further preferably more than 0 ppm, based on the mass of the resin composition. Many are 50 ppm or less.

  The total amount of the compound in which m is an integer of 3 or more in the general formula (3) and the compound in which n is an integer of 3 or more in the general formula (4) is preferably based on the mass of the resin composition. It may be more than 0 ppm and less than or equal to 1,300 ppm, more preferably more than 0 ppm and less than or equal to 400 ppm, still more preferably more than 0 ppm and less than or equal to 230 ppm. The total amount of the compound in which m is an integer of 3 or more in the general formula (3) and the compound in which n is an integer of 3 or more in the general formula (4) is within the above range, and the general formula (3) Among them, the total amount of compounds in which m is an integer of 3 or more is preferably more than 0 ppm and 1,100 ppm or less, more preferably more than 0 ppm and 800 ppm or less, still more preferably more than 0 ppm and 600 ppm, based on the mass of the resin composition. The following is more preferable, more preferably more than 0 ppm and not more than 300 ppm, particularly preferably more than 0 ppm and not more than 180 ppm.

  The total amount of the compound in which m is an integer of 3 or more in the general formula (3) and the compound in which n is an integer of 3 or more in the general formula (4) is within the above range, and the general formula (3 In the above, the total amount of compounds in which m is 3 to 5 is preferably more than 0 ppm and 1,100 ppm or less, more preferably more than 0 ppm and 800 ppm or less, still more preferably more than 0 ppm and 600 ppm, based on the mass of the resin composition. The following is more preferable, more preferably more than 0 ppm and not more than 300 ppm, particularly preferably more than 0 ppm and not more than 180 ppm. When the total amount of the compound represented by the general formula (3) and the compound represented by the general formula (4) is within the above range, the total number of foreign substances attached in the manufacturing process of the polyimide resin film is reduced. preferable.

  When based on the mass of the solid content in the resin composition, the total amount of compounds of the general formula (4) in which n is an integer of 3 or more is preferably more than 0 ppm and 1,100 ppm or less, more preferably 0 ppm or more. It is more than 700 ppm and more preferably more than 0 ppm and less than 400 ppm. Based on the mass of the solid content in the resin composition, a compound of the general formula (3) in which m is an integer of 3 or more and a compound of the general formula (4) in which n is an integer of 3 or more. Is preferably more than 0 ppm and not more than 8,600 ppm, more preferably more than 0 ppm and not more than 2,700 ppm, still more preferably more than 0 ppm and not more than 1,500 ppm. When the total amount of the compound represented by the general formula (3) and the compound represented by the general formula (4) is within the above range, the total number of foreign substances attached in the manufacturing process of the polyimide resin film is reduced. preferable.

  Based on the mass of the silicon-containing compounds of the general formulas (3), (4) and (5), the total amount of compounds of the general formula (4) in which n is an integer of 3 or more is preferably more than 0 ppm. It is 200 ppm or less, more preferably more than 0 ppm and 100 ppm or less, still more preferably more than 0 ppm and 50 ppm or less. Based on the total mass of the silicon-containing compounds of the general formulas (3), (4) and (5), a compound of the general formula (3) in which m is an integer of 3 or more and a compound of the general formula (4) Of these, the total amount with the compound in which n is an integer of 3 or more is preferably more than 0 ppm and 4,700 ppm or less, more preferably more than 0 ppm and 1,100 ppm or less, still more preferably more than 0 ppm and 6,300 ppm or less. When the total amount of the compound represented by the general formula (3) and the compound represented by the general formula (4) is within the above range, the total number of foreign substances attached in the manufacturing process of the polyimide resin film is reduced. preferable.

Foreign matter count number A cyclic siloxane in which m is an integer of 3 or more (preferably m is 3 to 5) in the general formula (3) based on the mass of each of the resin composition, the solid content, and the silicon-containing compound, and the general formula In (4), the smaller the total amount of cyclic siloxanes in which n is an integer of 3 or more (preferably n is 3 to 8), the smaller the amount of foreign matter attached in the process for producing the polyimide resin film, which is preferable. Although the mechanism is unknown, the inventors presume as follows. That is, in the production of a polyimide resin film, typically, a resin composition containing a polyimide precursor composition is applied to a support such as a glass substrate and heated in one oven at, for example, 100 ° C. for 30 minutes. The solvent is removed by, and the polyimide resin film is formed by continuous imidization by heating at a higher temperature, for example, 350 ° C. for 1 hour in the same oven. Here, the cyclic siloxane of the general formula (4) is more volatile than the cyclic siloxane of the general formula (3). Therefore, it is considered that when the solvent is removed, the cyclic siloxane of the general formula (4) is volatilized, and at the time of imidization, the cyclic siloxane of the general formula (3) is volatilized and attached to the oven. Especially when a large number of samples are put into the oven, it is considered that more cyclic siloxanes of the general formulas (3) and (4) are deposited in the oven, and when they fall, they become foreign matter attached to the polyimide resin film. Be done. Therefore, it is considered that the smaller the total amount of the cyclic siloxane represented by the general formula (3) and the cyclic siloxane represented by the general formula (4) is, the smaller the amount of foreign matter attached in the process of manufacturing the polyimide resin film is.

<solvent>
The resin composition typically comprises a solvent. As the solvent, those having good solubility of the polyimide precursor and capable of appropriately controlling the solution viscosity of the resin composition are preferable, and the reaction solvent of the polyimide precursor can be used as the solvent of the composition. Among them, N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), the compound represented by the general formula (4), and the like are preferable. Specific examples of the solvent composition include N-methyl-2-pyrrolidone (NMP) alone or a mixed solvent of N-methyl-2-pyrrolidone (NMP) and γ-butyrolactone (GBL). The mass ratio of NMP and GBL may be, for example, NMP: GBL (mass ratio) = 10: 90 to 90:10.

<Additional ingredients>
The resin composition of the present embodiment may further include additional components in addition to the polyimide precursor, the low molecular weight cyclic siloxane, and the solvent. Examples of the additional component include a surfactant and an alkoxysilane compound.

Surfactant By adding a surfactant to the resin composition of the present embodiment, the coatability of the resin composition can be improved. Specifically, it is possible to prevent the occurrence of streaks in the coating film.
Examples of such a surfactant include a silicone-based surfactant, a fluorine-based surfactant, and a nonionic surfactant other than these. Examples of silicone-based surfactants include organosiloxane polymers KF-640, 642, 643, KP341, X-70-092, X-70-093 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.); SH-28PA, SH. -190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (trade name, manufactured by Toray Dow Corning Silicone Co.); SILWET L-77, L-7001, FZ-2105, FZ. -2120, FZ-2154, FZ-2164, FZ-2166, L-7604 (trade name, manufactured by Nippon Unicar Co., Ltd.); DBE-814, DBE-224, DBE-621, CMS-626, CMS-222, KF-. 352A, KF-354L, KF-355A, KF-6020, DBE-821, DBE-712 (Geles) t), BYK-307, BYK-310, BYK-378, BYK-333 (trade name, manufactured by Big Chemie Japan); Granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and the like. Examples of the fluorine-based surfactant include Megafac F171, F173, R-08 (manufactured by Dainippon Ink and Chemicals, Inc., trade name); Florard FC4430, FC4432 (Sumitomo 3M, trade name) and the like. . Examples of nonionic surfactants other than these include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenol ether.

  Among these surfactants, silicone-based surfactants and fluorine-based surfactants are preferable from the viewpoint of coatability (strain suppression) of the resin composition, and the YI value and total light transmission depending on the oxygen concentration during the curing step. From the viewpoint of reducing the influence on the rate, a silicone-based surfactant is preferable. When a surfactant is used, its blending amount is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, relative to 100 parts by mass of the polyimide precursor in the resin composition.

Alkoxysilane compound When a polyimide film obtained from the resin composition of the present embodiment is used for a flexible substrate or the like, the resin composition is a polyimide precursor from the viewpoint of obtaining good adhesion between the support and the polyimide film in the manufacturing process. The alkoxysilane compound may be contained in an amount of 0.01 to 20 parts by mass with respect to 100 parts by mass. When the content of the alkoxysilane compound with respect to 100 parts by mass of the polyimide precursor is 0.01 parts by mass or more, good adhesion can be obtained between the support and the polyimide film. Further, the content of the alkoxysilane compound is preferably 20 parts by mass or less from the viewpoint of storage stability of the resin composition. The content of the alkoxysilane compound is preferably 0.02 to 15 parts by mass, more preferably 0.05 to 10 parts by mass, and further preferably 0.1 to 8 parts by mass with respect to 100 parts by mass of the polyimide precursor. is there. By using an alkoxysilane compound, in addition to the above-mentioned improvement in adhesiveness, the coating property of the resin composition is improved (suppressing uneven streaks), and the effect of oxygen concentration during curing on the YI value of the polyimide film is reduced. You can also do it.

  Examples of the alkoxysilane compound include 3-ureidopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltripropoxysilane, γ-aminopropyltributoxysilane, γ-aminoethyltriethoxysilane, γ-aminoethyltripropoxysilane, γ-aminoethyltributoxysilane, γ-aminobutyltriethoxysilane, γ- Aminobutyltrimethoxysilane, γ-aminobutyltripropoxysilane, γ-aminobutyltributoxysilane, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy (p-tolyl) silane, diphenylsilanediol , Dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and alkoxysilane compounds represented by each of the following structures. The alkoxysilane compounds may be used alone or in combination of two or more.

<< Method for producing resin composition >>
The method for producing the resin composition in the present embodiment is not particularly limited, and for example, the following method can be used.

<Purification of silicon-containing compound>
The resin composition of this embodiment can be produced by subjecting a polycondensation component containing an acid dianhydride, a diamine, and a silicon-containing compound to a polycondensation reaction. As a method of reducing the total amount of the compound of the general formula (3) contained in the resin composition of the present embodiment, for example, the silicon-containing compound is purified before the polycondensation reaction to obtain the general formula (3). And reducing the total amount of compounds of Alternatively, the resin composition may be purified after the polycondensation reaction to reduce the total amount of the compound of the general formula (3).

  Examples of the method for purifying the silicon-containing compound include stripping while blowing an inert gas, for example, nitrogen gas, into the silicon-containing compound in an arbitrary container. The stripping temperature is preferably 200 ° C or higher and 300 ° C or lower, more preferably 220 ° C or higher and 300 ° C or lower, and further preferably 240 ° C or higher and 300 ° C or lower. The vapor pressure for stripping is preferably as low as possible, and is preferably 1000 Pa or less, more preferably 300 Pa or less, still more preferably 200 Pa or less, still more preferably 133.32 Pa (1 mmHg) Pa or less. The stripping time is preferably 4 hours or more and 12 hours or less, more preferably 6 hours or more and 10 hours or less. By adjusting the above conditions, the compound of the general formula (3) can be efficiently removed, and the total amount of the general formulas (3) and (4) can be controlled within a preferable range.

<Synthesis of polyimide precursor>
The polyimide precursor of this embodiment can be synthesized by subjecting a polycondensation component containing an acid dianhydride, a diamine, and a silicon-containing compound to a polycondensation reaction. As the silicon-containing compound, it is preferable to use the above-mentioned purified one. In a preferred embodiment, the polycondensation component comprises an acid dianhydride, a diamine, and a silicon-containing compound. The polycondensation reaction is preferably carried out in a suitable solvent. Specifically, for example, a method in which a predetermined amount of a diamine component and a silicon-containing compound are dissolved in a solvent, a predetermined amount of acid dianhydride is added to the obtained diamine solution, and stirring is performed.

  The molar ratio of the acid dianhydride and the diamine when synthesizing the polyimide precursor is such that the acid dianhydride: diamine = 100: 90 from the viewpoint of increasing the molecular weight of the polyimide precursor resin and the slit coating properties of the resin composition. To 100: 110 (diamine 0.90 to 1.10 parts by mole relative to 1 part by mole of acid dianhydride) is preferable, and 100: 95 to 100: 105 (diamine based on 1 part by mole of acid dianhydride). The range of 0.95 to 1.05 parts by mole) is more preferable.

  The molecular weight of the polyimide precursor can be controlled by adjusting the dianhydride, the type of the diamine and the silicon-containing compound, adjusting the molar ratio of the acid dianhydride and the diamine, adding the terminal blocking agent, adjusting the reaction conditions, and the like. It is possible. The closer the molar ratio of the acid dianhydride component to the diamine component is to 1: 1, and the smaller the amount of the end-capping agent used, the higher the molecular weight of the polyimide precursor can be made.

  It is recommended to use high purity products as the acid dianhydride component and the diamine component. The purity is preferably 98% by mass or more, more preferably 99% by mass or more, and further preferably 99.5% by mass or more. It can also be highly purified by reducing the water content in the acid dianhydride component and the diamine component. When using a plurality of types of acid dianhydride components, and / or a plurality of types of diamine components, it is preferable that the acid dianhydride component as a whole and the diamine component as a whole have the above-mentioned purity, and all types used. It is more preferable that the acid dianhydride component and the diamine component of are each of the above-mentioned purity.

｛式中、Ｒ_１２＝メチル基で表されるエクアミドＭ１００（商品名：出光興産社製）、及び、Ｒ_１２＝ｎ−ブチル基で表されるエクアミドＢ１００（商品名：出光興産社製）｝；γ−ブチロラクトン、γ−バレロラクトン等のラクトン系溶媒；ヘキサメチルホスホリックアミド、ヘキサメチルホスフィントリアミド等の含リン系アミド系溶媒；ジメチルスルホン、ジメチルスルホキシド、スルホラン等の含硫黄系溶媒；シクロヘキサノン、メチルシクロヘキサノン等のケトン系溶媒；ピコリン、ピリジン等の３級アミン系溶媒；酢酸（２−メトキシ−１−メチルエチル）等のエステル系溶媒等が挙げられる。
フェノ−ル系溶媒としては、例えば、フェノール、ｏ−クレゾール、ｍ−クレゾール、ｐ−クレゾール、２，３−キシレノール、２，４−キシレノール、２，５−キシレノール、２，６−キシレノール、３，４−キシレノール、３，５−キシレノール等が挙げられる。
エーテル及びグリコール系溶媒としては、例えば、１，２−ジメトキシエタン、ビス（２−メトキシエチル）エーテル、１，２−ビス（２−メトキシエトキシ）エタン、ビス［２−（２−メトキシエトキシ）エチル］エーテル、テトラヒドロフラン、１，４−ジオキサン等が挙げられる。
これらの溶媒は、単独で又は２種類以上混合して用いてもよい。The solvent for the reaction is not particularly limited as long as it can dissolve the acid dianhydride component, the diamine component, and the resulting polyimide precursor, and can obtain a high molecular weight polymer. Examples of such a solvent include an aprotic solvent, a phenolic solvent, an ether solvent and a glycol solvent. Examples of the aprotic solvent include N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N-methylcaprolactam and 1,3-dimethyl. Imidazolidinone, tetramethylurea, and an amide solvent of the following general formula (6):

{In the formula, Examide M100 represented by R ₁₂ = methyl group (trade name: manufactured by Idemitsu Kosan Co., Ltd.) and Examide B100 represented by R ₁₂ = n-butyl group (trade name: manufactured by Idemitsu Kosan Co., Ltd.)} Lactone solvents such as γ-butyrolactone and γ-valerolactone; phosphorus-containing amide solvents such as hexamethylphosphoric amide and hexamethylphosphine triamide; sulfur-containing solvents such as dimethyl sulfone, dimethyl sulfoxide, sulfolane; cyclohexanone A ketone-based solvent such as methylcyclohexanone; a tertiary amine-based solvent such as picoline and pyridine; an ester-based solvent such as acetic acid (2-methoxy-1-methylethyl).
Examples of the phenol solvent include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3, 4-xylenol, 3,5-xylenol and the like can be mentioned.
Examples of ether and glycol solvents include 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl. ] Ether, tetrahydrofuran, 1,4-dioxane and the like can be mentioned.
You may use these solvent individually or in mixture of 2 or more types.

  The boiling point of the solvent used in the synthesis of the polyimide precursor at atmospheric pressure is preferably 60 to 300 ° C, more preferably 140 to 280 ° C, and further preferably 170 to 270 ° C. When the boiling point of the solvent is lower than 300 ° C., the drying process becomes short. When the boiling point of the solvent is 60 ° C. or higher, the surface of the resin film is less likely to be roughened, air bubbles are not mixed into the resin film during the drying step, and a more uniform film can be obtained. In particular, it is preferable to use a solvent having a boiling point of 170 to 270 ° C. and / or a vapor pressure at 20 ° C. of 250 Pa or less from the viewpoint of solubility and reduction of edge abnormality during coating. More specifically, one or more selected from the group consisting of N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), and the compound represented by the general formula (6) is preferable.

  The water content in the solvent is preferably, for example, 3,000 mass ppm or less in order to allow the polycondensation reaction to proceed well. In the resin composition in this embodiment, the content of molecules having a molecular weight of less than 1,000 is preferably less than 5% by mass. The presence of molecules having a molecular weight of less than 1,000 in the resin composition is considered to be related to the water content of the solvent and the raw materials (acid dianhydride, diamine) used during the synthesis. That is, it is considered that the acid anhydride group of a part of the acid dianhydride monomer is hydrolyzed by water to become a carboxyl group and remains in a low molecular state without increasing the molecular weight. Therefore, the smaller the water content of the solvent used in the polycondensation reaction, the more preferable. The water content of the solvent is preferably 3,000 mass ppm or less, and more preferably 1,000 mass ppm or less. Similarly, the amount of water contained in the raw material is preferably 3,000 mass ppm or less, more preferably 1,000 mass ppm or less.

  The water content of the solvent is the grade of the solvent used (dehydration grade, general-purpose grade, etc.), solvent container (bottle, 18 L can, canister can, etc.), storage state of the solvent (presence or absence of rare gas, etc.), from opening to use It is considered that the time (such as whether to use immediately after opening or after a lapse of time after opening) is involved. It is considered that the replacement of the rare gas in the reactor before the synthesis, the presence or absence of circulation of the rare gas during the synthesis, etc. are also involved. Therefore, when synthesizing the polyimide precursor, it is recommended to use a high-purity material as a raw material, use a solvent with a low water content, and take measures to prevent water from entering the system before and during the reaction. To be done.

  When each polycondensation component is dissolved in the solvent, it may be heated if necessary. From the viewpoint of obtaining a polyimide precursor having a high degree of polymerization, the reaction temperature during the synthesis of the polyimide precursor may be preferably 0 ° C to 120 ° C, 40 ° C to 100 ° C, or 60 to 100 ° C, and the polymerization time is May preferably be 1 to 100 hours, or 2 to 10 hours. By setting the polymerization time to 1 hour or more, a polyimide precursor having a uniform polymerization degree can be obtained, and by setting the polymerization time to 100 hours or less, a polyimide precursor having a high polymerization degree can be obtained.

  The resin composition of this embodiment may include other additional polyimide precursors in addition to the polyimide precursor of this embodiment. However, the mass ratio of the additional polyimide precursor is preferably 30 mass with respect to the total amount of the polyimide precursor in the resin composition from the viewpoint of reducing the oxygen dependency of the YI value and the total light transmittance of the polyimide film. % Or less, more preferably 10% by mass or less.

  A part of the polyimide precursor in the present embodiment may be imidized (partial imidization). By partially imidizing the polyimide precursor, the viscosity stability during storage of the resin composition can be improved. The imidization ratio in this case is preferably 5% or more, more preferably 8% or more, and preferably from the viewpoint of balancing the solubility of the polyimide precursor in the resin composition and the storage stability of the solution. It is 80% or less, more preferably 70% or less, and further preferably 50% or less. This partial imidization is obtained by heating the polyimide precursor to perform dehydration ring closure. This heating can be carried out at a temperature of preferably 120 to 200 ° C, more preferably 150 to 180 ° C, preferably 15 minutes to 20 hours, more preferably 30 minutes to 10 hours.

  To the polyamic acid obtained by the above reaction, N, N-dimethylformamide dimethyl acetal or N, N-dimethylformamide diethyl acetal is added and heated to esterify a part or all of the carboxylic acid. You may use as a polyimide precursor of embodiment. Esterification can improve the viscosity stability during storage. These ester-modified polyamic acids are obtained by sequentially reacting the above-mentioned acid dianhydride component with 1 equivalent of a monohydric alcohol based on an acid anhydride group, and a dehydration condensing agent such as thionyl chloride or dicyclohexylcarbodiimide. It can also be obtained by a method of causing a condensation reaction with a diamine component.

<Preparation of resin composition>
When the solvent used when synthesizing the polyimide precursor is the same as the solvent contained in the resin composition, the synthesized polyimide precursor solution can be used as it is as the resin composition. If necessary, in the temperature range of room temperature (25 ° C.) to 80 ° C., one or more additional solvents and additional components are added to the polyimide precursor, and the mixture is stirred and mixed to adjust the resin composition. May be. This stirring and mixing can be performed using an appropriate device such as a three-one motor (manufactured by Shinto Kagaku Co., Ltd.) equipped with a stirring blade and a rotation / revolution mixer. You may heat a resin composition to 40 degreeC-100 degreeC as needed.

  On the other hand, when the solvent used when synthesizing the polyimide precursor and the solvent to be contained in the resin composition are different, the solvent in the synthesized polyimide precursor solution, for example, reprecipitation, solvent evaporation and the like appropriately The polyimide precursor may be isolated by removing the polyimide precursor by the above method. Then, in a temperature range of room temperature (25 ° C.) to 80 ° C., a desired solvent and, if necessary, additional components are added to the isolated polyimide precursor, and mixed by stirring to prepare a resin composition. You may.

  After preparing the resin composition as described above, by heating the resin composition at, for example, 130 to 200 ° C. for, for example, 5 minutes to 2 hours, a part of the polyimide precursor is polymerized to such an extent that precipitation does not occur in the polymer. It may be dehydrated and imidized (partial imidization). The imidation ratio can be controlled by controlling the heating temperature and the heating time. By partially imidizing the polyimide precursor, the viscosity stability during storage of the resin composition can be improved.

  From the viewpoint of slit coat performance, the solution viscosity of the resin composition is preferably 500 to 100,000 mPa · s, more preferably 1,000 to 50,000 mPa · s, and further preferably 3,000 to 20,000 mPa · s. s. Specifically, it is preferably 500 mPa · s or more, more preferably 1,000 mPa · s or more, still more preferably 3,000 mPa · s or more, from the viewpoint of preventing liquid leakage from the slit nozzle. It is preferably 100,000 mPa · s or less, more preferably 50,000 mPa · s or less, still more preferably 20,000 mPa · s or less, from the viewpoint that the slit nozzle is less likely to be clogged.

  If the solution viscosity of the resin composition at the time of synthesizing the polyimide precursor is higher than 200,000 mPa · s, a problem that stirring at the time of synthesis becomes difficult may occur. However, even if the solution has a high viscosity during the synthesis, it is possible to obtain a resin composition having a viscosity that is easy to handle by adding a solvent and stirring after the completion of the reaction. The solution viscosity of the resin composition in the present embodiment is a value measured at 23 ° C. using an E-type viscometer (for example, VISCONICE HD, manufactured by Toki Sangyo).

  The water content of the resin composition of the present embodiment is preferably 3,000 mass ppm or less, more preferably 2,500 mass ppm or less, and further preferably 2 from the viewpoint of viscosity stability when the resin composition is stored. 1,000 mass ppm or less, more preferably 1,500 mass ppm or less, particularly preferably 1,000 mass ppm or less, particularly preferably 500 mass ppm or less, particularly preferably 300 mass ppm or less, particularly preferably 100 mass ppm or less. Is.

<< Polyimide film and its manufacturing method >>
A polyimide film (hereinafter, also referred to as a polyimide resin film) can be provided by using the resin composition of this embodiment. The method for producing a polyimide film of the present embodiment comprises a coating step of applying the resin composition of the present embodiment on the surface of a support; and a film forming step of heating the resin composition to form a polyimide resin film. A peeling step of peeling the polyimide resin film from the support.

<Coating process>
In the coating step, the resin composition of the present embodiment is coated on the surface of the support. The support is not particularly limited as long as it has heat resistance against the heating temperature in the subsequent film forming step (heating step) and has good releasability in the peeling step. Examples of the support include a glass substrate, for example, a non-alkali glass substrate; a silicon wafer; PET (polyethylene terephthalate), OPP (stretched polypropylene), polyethylene glycol terephthalate, polyethylene glycol naphthalate, polycarbonate, polyimide, polyamideimide, polyetherimide. Resin substrates such as polyether ether ketone, polyether sulfone, polyphenylene sulfone, and polyphenylene sulfide; metal substrates such as stainless steel, alumina, copper, and nickel.

  When forming a thin film-shaped polyimide molded body, for example, a glass substrate, a silicon wafer or the like is preferable, and when forming a thick film-shaped or sheet-shaped polyimide molded body, for example, PET (polyethylene terephthalate) is used. ), OPP (oriented polypropylene) and the like are preferable.

  As a coating method, generally, a doctor blade knife coater, an air knife coater, a roll coater, a rotary coater, a flow coater, a die coater, a bar coater or the like, a spin coat, a spray coat, a dip coat or the like; a screen printing method. And printing techniques typified by gravure printing and the like. The resin composition of the present embodiment is preferably applied by slit coating. The coating thickness should be appropriately adjusted according to the desired thickness of the resin film and the content of the polyimide precursor in the resin composition, but is preferably about 1 to 1,000 μm. The temperature in the coating step may be room temperature, and the resin composition may be heated to, for example, 40 to 80 ° C. in order to reduce the viscosity and improve workability.

<Any drying process>
A drying step may be performed after the coating step, or the drying step may be omitted and the process may directly proceed to the next film forming step (heating step). The drying step is performed for the purpose of removing the organic solvent in the resin composition. When carrying out the drying step, an appropriate device such as a hot plate, a box-type dryer, a conveyor-type dryer or the like can be used. The temperature of the drying step is preferably 80 to 200 ° C, more preferably 100 to 150 ° C. The time for carrying out the drying step is preferably 1 minute to 10 hours, more preferably 3 minutes to 1 hour. As described above, the coating film containing the polyimide precursor is formed on the support.

<Film forming process>
Then, a film forming process (heating process) is performed. The heating step is a step of removing the organic solvent contained in the coating film and advancing the imidization reaction of the polyimide precursor in the coating film to obtain a polyimide resin film. This heating step can be performed using an apparatus such as an inert gas oven, a hot plate, a box dryer, a conveyor dryer, or the like. This step may be performed simultaneously with the drying step, or both steps may be sequentially performed.

  The heating step may be performed in an air atmosphere, but from the viewpoint of obtaining safety and good transparency of the polyimide film to be obtained, low thickness direction retardation (Rth) and low YI value, an inert gas atmosphere is used. It is preferable to carry out. Examples of the inert gas include nitrogen and argon. The heating temperature may be appropriately set depending on the type of polyimide precursor and the type of solvent in the resin composition, but is preferably 250 ° C to 550 ° C, more preferably 300 to 450 ° C. If the temperature is 250 ° C. or higher, imidization proceeds well, and if the temperature is 550 ° C. or lower, inconveniences such as deterioration of transparency and deterioration of heat resistance of the obtained polyimide film can be avoided. The heating time is preferably about 0.1 to 10 hours.

  In the present embodiment, the oxygen concentration of the ambient atmosphere in the heating step is preferably 2,000 mass ppm or less, more preferably 100 mass ppm or less, further preferably from the viewpoint of the transparency and YI value of the obtained polyimide film. Is 10 mass ppm or less. By heating in an atmosphere having an oxygen concentration of 2,000 mass ppm or less, the YI value of the obtained polyimide film can be set to 30 or less.

<Peeling process>
In the peeling step, the polyimide resin film on the support is peeled after being cooled to, for example, room temperature (25 ° C.) to 50 ° C. Examples of this peeling step include the following aspects (1) to (4).

(1) After the structure including the polyimide resin film / support is manufactured by the above method, laser is irradiated from the support side of the structure to ablate the interface between the support and the polyimide resin film, Method of peeling polyimide resin. Examples of the type of laser include a solid (YAG) laser and a gas (UV excimer) laser. It is preferable to use a spectrum having a wavelength of 308 nm or the like (see Japanese Patent Publication No. 2007-512568 and Japanese Patent Publication No. 2012-511173).
(2) A method of forming a release layer on the support before applying the resin composition to the support, and then obtaining a composition including a polyimide resin film / a release layer / support to remove the polyimide resin film. .. Examples of the release layer include Parylene (registered trademark, manufactured by Japan Parylene Godo Kaisha) and tungsten oxide; vegetable oil-based, silicone-based, fluorine-based, alkyd-based release agents and the like may be used (JP 2010-067957 A). Japanese Patent Laid-Open No. 2013-179306, etc.).
This method (2) and the laser irradiation of method (1) may be used in combination.

(3) A method of obtaining a polyimide resin film by using a metal substrate that can be etched as a support to obtain a structure containing a polyimide resin film / support and then etching the metal with an etchant. As the metal, for example, copper (specifically, electrolytic copper foil “DFF” manufactured by Mitsui Mining & Smelting Co., Ltd.), aluminum or the like can be used. As the etchant, ferric chloride or the like can be used for copper and dilute hydrochloric acid or the like can be used for aluminum.
(4) After obtaining a structure containing a polyimide resin film / support by the above method, an adhesive film is attached to the surface of the polyimide resin film to separate the adhesive film / polyimide resin film from the support, and then from the adhesive film. Method for separating polyimide resin film.

  Among these peeling methods, the method (1) or (2) is preferable from the viewpoint of the difference in refractive index between the front and back of the obtained polyimide resin film, the YI value, and the elongation. From the viewpoint of the refractive index difference between the front and back of the obtained polyimide resin film, it is more preferable to perform the irradiation step of irradiating the laser from the support side prior to the peeling step (1). In the method (3), when copper is used as the support, the obtained polyimide resin film tends to have a large YI value and a small elongation. This is considered to be the effect of copper ions.

  The thickness of the obtained polyimide film is not limited, but is preferably 1 to 200 μm, more preferably 5 to 100 μm.

<Yellowness (YI value)>
The YI value at a film thickness of 10 μm of the polyimide film obtained from the resin composition of the present embodiment is preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, particularly preferably from the viewpoint of obtaining good optical characteristics. Is 14 or less, particularly preferably 13 or less, particularly preferably 10 or less, particularly preferably 7 or less. The YI value varies depending on the monomer skeleton of the polyimide precursor, but if the monomer skeleton is the same, the YI value tends to decrease as the weight average molecular weight of the polyimide precursor increases.

  The YI value is influenced by, for example, the amine value of the silicon-containing compound used. When the amine value is high, the YI value is large, and when the amine value is small, the YI value tends to be small. However, a polyimide precursor using a purified silicon-containing compound, that is, a polyimide precursor in which the total amount of the compounds represented by the general formula (3) is within the above range, uses an unpurified silicon-containing compound having the same amine value. The YI value of the obtained polyimide resin film tends to be lower than that of the conventional polyimide precursor. Although this mechanism is not yet clear, the present inventors presume as follows. That is, in the conventional purification method, the non-cyclic low molecular weight diamine used in the production of the polyimide precursor remains, decomposes during polyimide curing to generate radicals, and causes a YI value increase (deterioration). Can be. By reducing the amount of the cyclic siloxane represented by the general formula (3), not only the cyclic siloxane represented by the general formula (3) is removed at the time of purification, but also among diamine components that increase the amine value. It is considered that low molecular weight diamine, which is relatively volatile, is also removed. Therefore, it is estimated that the YI value of the polyimide resin film is further improved in the polyimide precursor in which the total amount of the compound represented by the general formula (3) is reduced according to the present embodiment. Since it is difficult to reduce the low molecular weight diamine which is not cyclic by the conventional purification method, it is considered that the degree of improvement in the YI value of the polyimide resin film is smaller than that of the present embodiment even if the purification is performed. ..

In the present embodiment, the difference in YI value between the polyimide precursor using the purified silicon-containing compound and the polyimide precursor using the non-purified silicon-containing compound is obtained from the following formula.
(Difference in YI value) = (YI value of polyimide resin film obtained by curing polyimide precursor obtained by using unpurified silicon compound)-(Polyimide precursor obtained by using purified silicon compound) (YI value of cured polyimide resin film)
The larger the difference in YI value, the better the YI is, which is preferable. In the present embodiment, the difference in YI value is preferably 1.5 or more, more preferably 2 or more, still more preferably 2.5 or more. For the method of measuring the YI value, see the section of Examples.

<< Use of polyimide film >>
The polyimide film obtained from the resin composition of the present embodiment is, for example, a semiconductor insulating film, a thin film transistor liquid crystal display (TFT-LCD) insulating film, an electrode protective film, a liquid crystal display, an organic electroluminescent display, a field emission display, It can be applied as a transparent substrate of a display device such as electronic paper. In particular, the polyimide film obtained from the resin composition of the present embodiment is suitable as a substrate of a thin film transistor (TFT) substrate, a color filter substrate, a touch panel substrate, a transparent conductive film (ITO, Indium Thin Oxide) in the production of flexible devices. Can be used. Examples of the flexible device to which the polyimide film according to the present embodiment can be applied include TFT devices for flexible displays, flexible solar cells, flexible touch panels, flexible lighting, flexible batteries, flexible printed boards, flexible color filters, surface cover lenses for smartphones, and the like. Can be mentioned.

  The process of forming a TFT on a flexible substrate using a polyimide film is typically performed at a wide temperature range of 150 to 650 ° C. Specifically, when manufacturing a TFT device using amorphous silicon, a process temperature of 250 ° C. to 350 ° C. is generally required, and the polyimide film of the present embodiment needs to be able to withstand that temperature. Specifically, it is necessary to appropriately select a polymer structure having a glass transition temperature above the process temperature and a thermal decomposition initiation temperature.

  When manufacturing a TFT device using a metal oxide semiconductor (IGZO or the like), a process temperature of 320 ° C. to 400 ° C. is generally required, and the polyimide film of this embodiment needs to be able to withstand the temperature. Therefore, it is necessary to appropriately select a polymer structure having a glass transition temperature and a thermal decomposition initiation temperature which are higher than the maximum temperature of the TFT manufacturing process.

When manufacturing a TFT device using low temperature polysilicon (LTPS), a process temperature of 380 ° C. to 520 ° C. is generally required, and the polyimide film of this embodiment needs to be able to withstand that temperature. It is necessary to properly select the glass transition temperature and the thermal decomposition starting temperature which are higher than the maximum temperature of the TFT manufacturing process.
On the other hand, due to these thermal histories, the optical properties of the polyimide film (particularly, the light transmittance, retardation property and YI value) tend to decrease as it is exposed to a high temperature process. However, the polyimide obtained from the polyimide precursor of this embodiment has good optical characteristics even after undergoing thermal history.

  Hereinafter, a method for manufacturing a display and a laminate will be described as an application example of the polyimide film of the present embodiment.

<Display manufacturing method>
The display manufacturing method of the present embodiment includes a coating step of applying the resin composition of the present embodiment on the surface of a support; a film forming step of heating the resin composition to form a polyimide resin film; An element forming step of forming an element on the polyimide resin film; and a peeling step of peeling the polyimide resin film having the element formed thereon from the support.

Manufacturing Example of Flexible Organic EL Display FIG. 1 is a schematic view showing a structure above a polyimide substrate of a top emission type flexible organic EL display as an example of the display of the present embodiment. The organic EL structure 25 of FIG. 1 will be described. For example, an organic EL element 250a that emits red light, an organic EL element 250b that emits green light, and an organic EL element 250c that emits blue light are arranged in a matrix as one unit, and partition walls (banks) are provided. The light emitting area of each organic EL element is defined by 251. Each organic EL element is composed of a lower electrode (anode) 252, a hole transport layer 253, a light emitting layer 254, and an upper electrode (cathode) 255. On the lower layer 2a showing the CVD multilayer film (multi-barrier layer) made of silicon nitride (SiN) or silicon oxide (SiO), the TFT 256 (low temperature polysilicon (LTPS) or metal oxide) for driving the organic EL element is formed. A plurality of semiconductors (selected from IGZO, etc.), an interlayer insulating film 258 having a contact hole 257, and a plurality of lower electrodes 259 are provided. The organic EL element is enclosed by the sealing substrate 2b, and a hollow portion 261 is formed between each organic EL element and the sealing substrate 2b.

  The manufacturing process of the flexible organic EL display includes the steps of manufacturing a polyimide film on a glass substrate support and manufacturing the organic EL substrate shown in FIG. 1 above the polyimide film, manufacturing a sealing substrate, and both substrates. And an exfoliation step of exfoliating the organic EL display formed on the polyimide film from the glass substrate support. Well-known manufacturing processes can be applied to the organic EL substrate manufacturing process, the sealing substrate manufacturing process, and the assembly process. An example thereof will be given below, but the present invention is not limited to this. The peeling process is the same as the above-described polyimide film peeling process.

  For example, referring to FIG. 1, first, a polyimide film is prepared on a glass substrate support by the method described above, and a multilayer film of silicon nitride (SiN) and silicon oxide (SiO) is formed on the polyimide film by a CVD method or a sputtering method. A multi-barrier layer (lower substrate 2a in FIG. 1) having a structure is formed, and a metal wiring layer for driving the TFT is formed on the multi-barrier layer using a photoresist or the like. An active buffer layer of SiO or the like is formed on the upper portion of the same by using a CVD method, and a TFT device (TFT 256 in FIG. 1) such as a metal oxide semiconductor (IGZO) or low temperature polysilicon (LTPS) is formed on the upper portion of the active buffer layer. After manufacturing the TFT substrate for flexible display, an interlayer insulating film 258 having a contact hole 257 is formed with a photosensitive acrylic resin or the like. An ITO film is formed by a sputtering method or the like, and a lower electrode 259 is formed so as to form a pair with the TFT.

  Next, after forming partition walls (banks) 251 with photosensitive polyimide or the like, a hole transport layer 253 and a light emitting layer 254 are formed in each space partitioned by the partition walls. An upper electrode (cathode) 255 is formed so as to cover the light emitting layer 254 and the partition (bank) 251. Then, using a fine metal mask or the like as a mask, an organic EL material that emits red light (corresponding to the organic EL element 250a that emits red light in FIG. 1) and an organic EL material that emits green light (in FIG. 1) Of the organic EL element 250b that emits green light) and an organic EL material that emits blue light (corresponding to the organic EL element 250c that emits blue light in FIG. 1) are deposited by a known method. Then, an organic EL substrate is manufactured. By sealing the organic EL substrate with a sealing film or the like (sealing substrate 2b in FIG. 1) and peeling the device above the polyimide substrate from the glass substrate support by a known peeling method such as laser peeling, An emission type flexible organic EL display can be manufactured. When the polyimide of this embodiment is used, a see-through type flexible organic EL display can be manufactured. A bottom emission type flexible organic EL display may be manufactured by a known method.

Manufacturing Example of Flexible Liquid Crystal Display A flexible liquid crystal display can be manufactured using the polyimide film of the present embodiment. As a specific manufacturing method, a polyimide film is manufactured on the glass substrate support by the above method, and is made of, for example, amorphous silicon, metal oxide semiconductor (IGZO, etc.), and low temperature polysilicon. A TFT substrate is manufactured. Separately, a polyimide film is prepared on a glass substrate support according to the coating process and the film forming process of the present embodiment, and a color filter glass substrate (CF substrate) provided with the polyimide film using a color resist or the like according to a known method. ) Is produced. One of the TFT substrate and the CF substrate is screen-printed with a sealing material such as a thermosetting epoxy resin in a frame-shaped pattern lacking the liquid crystal injection port, and the other substrate is equivalent to the thickness of the liquid crystal layer. Disperse spherical spacers of plastic or silica with a diameter of

  Next, the TFT substrate and the CF substrate are bonded together, and the sealing material is cured. Then, a liquid crystal material is injected into the space surrounded by the TFT substrate, the CF substrate, and the sealing material by a decompression method, a thermosetting resin is applied to the liquid crystal injection port, and the liquid crystal material is sealed by heating to form a liquid crystal layer. To do. Finally, the CF side glass substrate and the TFT side glass substrate are peeled off at the interface between the polyimide film and the glass substrate by a laser peeling method or the like, whereby a flexible liquid crystal display can be manufactured.

<Method of manufacturing laminated body>
The method for manufacturing a laminate of the present embodiment includes a coating step of applying the resin composition of the present embodiment on the surface of a support; a film forming step of heating the resin composition to form a polyimide resin film. An element forming step of forming an element on the polyimide resin film.

  Examples of the element in the laminated body include those exemplified in the production of the above flexible device. As the support, for example, a glass substrate can be used. Preferable specific procedures of the coating step and the film forming step are the same as those described in the above-mentioned method for producing a polyimide film. In the element forming step, the above element is formed on the polyimide resin film as a flexible substrate formed on the support. After that, the polyimide resin film and the element may be optionally peeled from the support in a peeling step.

  Hereinafter, the embodiments of the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples.

<< Measurement and evaluation method >>
<Solid content>
The total mass of the monomers used for the polyimide precursor can be used as the mass of the solid content contained in the resin composition. Alternatively, the mass of the solid content can be determined by gas chromatography (hereinafter also referred to as GC) analysis of the resin composition to determine the mass of the solvent and subtracting the mass of the solvent from the mass of the resin composition.
The following conditions are mentioned as conditions of GC.
Equipment: Gas chromatograph (Agilent gas chromatograph 6890N type)
Inlet temperature: 280 ℃
Injection volume: 1 μL
Oven temperature: Hold at 50 ° C. for 1 minute, then raise to 350 ° C. at a temperature rising rate of 20 ° C./minute, and hold at 350 ° C. for 5 minutes.
Carrier gas: He, 1.0 ml / min
Column: SGE, BPX5 (0.25 mmφ × 30 m, film thickness 0.25 μm)
Split ratio: 50: 1
Detector: Hydrogen flame ionization detector Detector temperature: 355 ° C

<Weight average molecular weight>
The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) under the following conditions.
As a solvent, NMP (manufactured by Wako Pure Chemical Industries, for high performance liquid chromatography, 24.8 mmol / L of lithium bromide monohydrate (manufactured by Wako Pure Chemical Industries, purity 99.5%) immediately before measurement and 63 0.2 mmol / L phosphoric acid (made by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatography) was added and dissolved) was used. The calibration curve for calculating the weight average molecular weight was prepared using standard polystyrene (manufactured by Tosoh Corporation).
Column: Shodex KD-806M (manufactured by Showa Denko KK)
Flow rate: 1.0 mL / min Column temperature: 40 ° C
Pump: PU-2080Plus (made by JASCO)
Detector: RI-2031Plus (RI: differential refractometer, manufactured by JASCO) and UV-2075Plus (UV-VIS: ultraviolet-visible absorption meter, manufactured by JASCO)

<Analysis of low molecular cyclic siloxane concentration>
The analysis of the low molecular cyclic siloxane concentration of the general formula (3) and the general formula (4) contained in the resin composition containing the polyimide precursor and the silicon-containing compound (the general formulas (3) and (4)) is as follows. As shown below, quantification was performed by GC (gas chromatography analysis) (see the following analysis of low molecular cyclic siloxane concentration (silicon-containing compound standard)).

<Analysis of low molecular cyclic siloxane concentration (composition standard / solid content standard)>
(1) Outline A calibration curve for quantifying the amount of cyclic siloxane was prepared. The calibration curve was prepared according to the method to be described later, using a standard sample (manufactured by Tokyo Chemical Industry Co., Ltd.) of n = 4 cyclic siloxane (hereinafter also referred to as D4 body) of the general formula (4).
The amount of low molecular cyclic siloxane contained in the resin composition was measured by heating the resin composition in a pyrolyzer at 150 ° C. and 200 ° C. for 30 minutes and analyzing the resulting volatile components by GC / MS. Using the calibration curve prepared in advance, the peak area of each obtained compound was converted into the D4 concentration.
The GC / MS measurement was performed using the following device.
Pyrolyzer: Py-3030iD (Frontier Lab)
GC system: 7890B (Agilent Technology)
MSD: 5977A (Agilent Technology)
Column: UA-1 (inner diameter 0.25 mm, length 15 m, liquid phase thickness 0.25 μm) (Frontier Lab)
All the GC / MS measurements were performed under the following measurement conditions.
Column temperature: Hold at 40 ° C for 5 minutes, raise at 20 ° C / minute, hold at 320 ° C for 11 minutes, total 30 minutes Inlet temperature: 320 ° C
Injection method: split method (split ratio 1/20)
Interface temperature: 320 ℃
Ion source temperature: 230 ℃
Ionization method: Electron ionization method (EI)
Measurement method: SCAN method (m / z 10-800)

(2) Preparation of calibration curve A sample (manufactured by Tokyo Chemical Industry Co., Ltd.) of n = 4 compound of general formula (4) (hereinafter, also referred to as D4 body) was measured in a 10 mL volumetric flask, and chloroform was used as a solvent. A sample having a concentration of D4 bodies of 0.1 mg / mL and a sample having a concentration of 0.01 mg / mL were prepared.
A sampler for liquid sample was attached to a pyrolyzer set to 400 ° C., 1 μL of the sample having the adjusted concentration was measured with a microsyringe and injected into the pyrolyzer. While heating the pyrolyzer to 400 ° C., the column was immersed in liquid nitrogen to trap volatile components in the column. One minute after the end of heating, the column was taken out of the liquid nitrogen, and GC / MS measurement was performed. The slope of the D4 body calibration curve was determined from the concentration of the D4 body and the obtained peak area.
The retention time of cyclic siloxane in the GC / MS measurement using the apparatus and measurement conditions used is as shown in Table 1 below. The same applies to the subsequent GC / MS measurement.

  Dn (n = 3 to 8) in Table 1 above is a cyclic siloxane corresponding to n = 3 to 8 in the general formula (4). Dimethyl m diphenyl 1 and Dmφ (m = 3 to 5) in Table 1 above are cyclic siloxanes corresponding to m = 3 to 5 in the general formula (3).

(3) Analysis of Concentration of Low Molecular Cyclic Siloxane of General Formulas (3) and (4) in Resin Composition The concentration of the phenyl side chain of the general formula (3) contained in the resin composition depends on the resin composition. It was measured by heating to 200 ° C. and performing GC / MS measurement of the generated volatile component. The concentration of the methyl side chain of the general formula (4) was measured by heating the resin composition to 150 ° C. and performing GC / MS measurement of the generated volatile component. The concentration of each compound was calculated from the peak area of the measurement result of the volatile component of the resin composition. If the peak of each compound does not overlap with other compounds, the peak area obtained from the total ion chromatogram (TIC) was used. When overlapping with other compounds, the peak area obtained from the mass chromatogram (MS) at m / z = 281 was used.

A. Analysis of Low Molecular Cyclic Siloxane Concentration of General Formula (3) (Phenyl Side Chain) in Resin Composition A pyrolyzer heating furnace (He atmosphere) set at 200 ° C. contains the resin composition weighed at about 1 mg. The sample cup was placed and heated at 200 ° C. for 30 minutes. The generated volatile components were measured by analyzing by GC / MS. Using the calibration curve prepared in advance, the peak area of each obtained compound was converted into the D4 concentration. The amount of low molecular cyclic siloxane of the general formula (3) was calculated according to the following formula.
Dmφ (μg / g) = {Dmφ (GC-Area)} / {D4 slope of the calibration curve} / {mass of the weighed resin composition (mg)} × 1000
M in the formula corresponds to the carbon number m in the general formula (3), and m is an integer of 3 or more.

B. Analysis of Concentration of Low-Molecular Cyclic Siloxane of General Formula (4) (Methyl Side Chain) in Resin Composition Sample containing about 1 mg of resin composition in a pyrolyzer heating furnace (He atmosphere) set at 150 ° C. The cup was put and it heated at 150 degreeC for 30 minutes. The generated volatile components were measured by analyzing by GC / MS. Using the calibration curve prepared in advance, the peak area of each obtained compound was converted into the D4 concentration.
Dn (μg / g) = {Dn (GC-Area)} / {D4 slope of the calibration curve} / {mass of the weighed resin composition (mg)} × 1000
In the formula, n corresponds to the carbon number n of the general formula (4), and n is an integer of 3 or more.

(5) Analysis of Concentration of Low Molecular Cyclic Siloxane of General Formulas (3) and (4) in Solid Content Included in Resin Composition Low Molecular Cyclic Siloxane of General Formulas (3) and (4) Contained in Solid Content The analysis of the concentration was calculated from the concentration of the low molecular cyclic siloxane of the general formulas (3) and (4) in the resin composition described above. That is, the total mass of the monomers used in the polyimide precursors of Examples and Comparative Examples is defined as the mass of the solid content contained in the resin composition, and the concentration of the cyclic siloxanes of the general formulas (3) and (4) in the resin composition. The concentration of the cyclic siloxanes of the formulas (3) and (4) in the solid content was calculated from the total mass and the total mass. The mass of the solid content contained in the resin composition is, as described above, the mass of the solvent is obtained by GC analysis of the resin composition, and the mass of the solvent is subtracted from the mass of the resin composition, or the resin composition is heated. Then, the solvent can be volatilized and removed, the mass of the solvent can be determined, and the mass of the solvent can be subtracted from the mass of the resin composition.

<Analysis of Concentration of Low-Molecular Cyclic Siloxane Contained in Raw Material Composition (Based on Silicon-Containing Compound)>
(Overview)
Analysis of low molecular weight cyclic siloxane concentrations includes silicon-containing compounds (general formulas (3), (4) and (5)) dissolved in acetone (containing n-tetradecane as an internal standard). .) Solution was analyzed by GC. From the obtained peak area of each compound, the concentration of each compound was determined based on the peak area of n-tetradecane according to the method described below.
The GC measurement was performed using the following device.
GC system: 7890A (Agilent Technology)
Column: J & W Scientific Durabond DB-5MS (MEGABORE inner diameter 0.53 mm, length 30 m, liquid phase thickness 1.0 μm)
All the GC measurements were performed under the following measurement conditions.
Column temperature: 50 ° C, temperature rise at 10 ° C / min, hold at 280 ° C for 17 minutes, total 40 minutes Inlet temperature: 270 ° C
Carrier gas: He
Injection method: split method (split ratio 1/10)
Detector: FID (300 ℃)

(Calculation of the amount of low molecular weight cyclic siloxane)
The amount of low molecular cyclic siloxane of the general formula (3) was calculated according to the following formula.
Dmφ (μm / g) = {total amount of compounds of general formula (3) (μg)} / {total mass of compounds of general formulas (3-1), (3-2), (4) and (5) ( g)} = {Dmφ (GC-Area)} / {n-tetradecane (GC-Area) × GC-Area Factor} × 20 × 100
M in the formula corresponds to the carbon number m in the general formula (3), and m is an integer of 3 or more.
The GC-Area Factor in the formula was calculated according to the following formula.
GC-Area Factor = molecular weight / carbon number

The amount of low molecular cyclic siloxane of the general formula (4) was calculated according to the following formula.
Dn (μg / g) = {total amount (μg) of compounds of general formula (4)} / {total mass of compounds of general formulas (3-1), (3-2), (4) and (5) ( g)} = {Dn (GC-Area)} / {n-tetradecane (GC-Area) × GC-Area Factor} × 20 × 100
In the formula, n corresponds to the carbon number n of the general formula (4), and n is an integer of 3 or more.
The GC-Area Factor in the formula was calculated according to the following formula.
GC-Area Factor = molecular weight / carbon number

  The retention time (minutes) of the cyclic siloxane in the GC measurement using the apparatus used and the above measurement conditions is as shown in Table 2 below. The same applies to the subsequent GC measurements.

  Dn (n = 3 to 8) in Table 2 above is a cyclic siloxane corresponding to n in the general formula (4). Further, Dmφ (m = 3 to 5) in Table 2 is a cyclic siloxane corresponding to m in the general formula (3).

(Analysis of low molecular cyclic siloxane concentration)
The analysis of the low molecular cyclic siloxane concentration of the general formulas (3) and (4) contained in the silicon-containing compound was performed by the following procedure. 0.1 g of the silicon-containing compound was dissolved in 10 mL of acetone (containing 20 μg / mL of n-tetradecane as an internal standard substance), and the mixture was left standing for 16 hours. The solution left to stand was measured by 1 μL with a microsyringe and introduced into the GC for measurement. In the obtained chromatogram, the peak area of each low-molecular cyclic siloxane and n-tetradecane was calculated by the software attached to GC, and the low-molecular cyclic siloxane concentration was calculated by the above-described calculation formula.

<Foreign matter count evaluation of polyimide resin film>
In this evaluation, after a large amount of polyimide precursor was dried and cured using an oven, and when a polyimide resin film was manufactured in the same oven, the amount of foreign matter attached to the surface of the polyimide resin film was evaluated.
The resin compositions of Examples and Comparative Examples were applied to a 200 mm square non-alkali glass substrate (hereinafter also referred to as a glass substrate) so that the film thickness after curing would be 10 μm to form a coating film. A slit coater (TN25000, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used for coating. At this time, a resin composition formed on 50 glass substrates was prepared for each resin composition. One of the glass substrates having a coating film of the resin composition was dried in an oven (KLO-30NH, manufactured by Koyo Thermo System) under a nitrogen atmosphere (oxygen concentration of 300 ppm or less) at 100 ° C. for 30 minutes to remove the solvent. Removed. Then, under a nitrogen atmosphere (oxygen concentration of 300 ppm or less), heating was performed at 350 ° C. for 1 hour to form a polyimide resin film on the glass substrate. The size and the number of foreign matters were counted using a microscope (VHX-6000, manufactured by Keyence Corporation) in the range of the central 50 mm square of the obtained 200 mm square polyimide resin film.
The observation conditions are as follows.
Lens: 100 times threshold: Auto Then, the number of foreign matters having a major axis of 50 μm or more and less than 1000 μm was evaluated according to the following criteria.
The number of foreign matters is 10 or more and less than 50: A (good)
The number of foreign substances is 50 or more and less than 100: B (possible)
100 or more foreign substances: C (not possible)
When the observed foreign matter was subjected to EDS analysis (elemental analysis) using a scanning electron microscope (JSM-IT500HR, manufactured by JEOL Ltd.), C, Si, O elements and the like were observed, and N element was not observed. . From this result, it is presumed that the foreign matter is a low-molecular cyclic siloxane that is volatilized during vacuum drying and is attached to the inner wall of the dryer and dropped or attached.
When evaluating different types of resin compositions, the oven was baked at 600 ° C. for 5 hours or more before evaluation.

<Evaluation of difference in YI value>
In this evaluation, the polyimide precursor obtained using the purified silicon compound and the polyimide precursor obtained using the unpurified silicon compound were each cured to obtain the YI value of the polyimide resin film. The difference was evaluated.
The resin compositions of Examples and Comparative Examples were applied to a 200 mm square non-alkali glass substrate (hereinafter also referred to as a glass substrate) so that the film thickness after curing would be 10 μm to form a coating film. The coating was performed using a slit coater (TN25000, Tokyo Ohka Kogyo). One of the glass substrates having a coating film of the obtained resin composition was dried in an oven (KLO-30NH, Koyo Thermo System) at 100 ° C. for 30 minutes under a nitrogen atmosphere (oxygen concentration of 300 ppm or less). The solvent was removed. Then, in a nitrogen atmosphere (oxygen concentration of 300 ppm or less), it was heated at 400 ° C. for 1 hour to form a polyimide resin film on the glass substrate.
Using the obtained polyimide resin film, the YI value was measured using Nippon Denshoku Industries Co., Ltd. (Spectrophotometer: SE600). A D65 light source was used as a light source. The difference in YI value was obtained from the following formula.
(Difference in YI value) = (YI value of polyimide resin film obtained by curing polyimide precursor obtained by using unpurified silicon compound)-(Polyimide precursor obtained by using purified silicon compound) (YI value of cured polyimide resin film)
In obtaining the difference in YI value, the curing of the polyimide precursor obtained by using the unpurified silicon compound and the curing of the polyimide precursor obtained by using the purified silicon compound are the same. Instrumentation was eliminated by heating in a batch of ovens.

<< Purification method of silicon-containing compound >>
The silicon-containing compounds described in Examples and Comparative Examples described later were treated by the following purification method to reduce the amount of low-molecular cyclic siloxane contained. The concentration of the low-molecular cyclic siloxane after purification was analyzed by the above method.
<Purification A>
10 kg of a silicon-containing compound was placed in a flask, and stripping was performed at a temperature of 160 ° C. and a pressure of 270 Pa for 8 hours while blowing nitrogen gas.
<Purification B-1>
1 kg of a silicon-containing compound was placed in a flask, and stripping was performed at a temperature of 200 ° C. and a pressure of 200 Pa for 8 hours while blowing a nitrogen gas.
<Purification B-2>
10 kg of a silicon-containing compound was placed in a flask, and stripping was performed at a temperature of 200 ° C. and a pressure of 200 Pa for 8 hours while blowing a nitrogen gas.
<Purification C> According to the synthesis example of amino-terminal modified silicone oil (purified product) described in JP-A-2016-029126 1000 g of acetone was added to 100 g of a silicon-containing compound, and the mixture was stirred at room temperature for 30 minutes. Centrifugation was performed at 2500 rpm for 15 minutes with a centrifuge to separate acetone and silicone oil, and then acetone was removed by decantation. After repeating this operation three times, acetone was distilled off by an evaporator to obtain a purified silicon-containing compound.
<Purification D> Based on Purification Example 1 described in JP 2006-028533 A 500 g of a silicon-containing compound was placed in a flask, and stripping was performed at a temperature of 250 ° C. and a pressure of 1330 Pa for 8 hours while blowing a nitrogen gas.
<Purification E> Based on Purification Example 2 described in JP 2006-028533 A 100 g of a silicon-containing compound was put into 300 g of 2-butanone and uniformly dissolved. This solution was slowly poured into methanol with stirring to perform reprecipitation. The above reprecipitation was repeated a total of 3 times and then dried to obtain a purified silicon-containing compound.

<< Example 1 >>
As described in Table 2, the silicon-containing compound (1) (in the general formula (1), L ₁ and L ₂ are amino groups, R ₁ is —CH ₂ CH ₂ CH ₂ —, and R ₂ and R _{3 are} , R ₆ and R ₇ are methyl groups, R ₄ and R ₅ are phenyl groups, and j / (i + j + k) = 0.15, and the number average molecular weight is 4,400). While introducing nitrogen gas into a 3 L separable flask equipped with a stir bar, NMP (332 g) as a solvent, 4,4′-DAS (14.2 g) as a diamine, TFMB (37.8 g), and a purified silicon-containing compound (1) (10.56 g) was added with stirring, followed by PMDA (21.8 g) as an acid dianhydride. The molar ratio of acid dianhydride and diamine was 100: 97. The mixture was stirred at room temperature for 48 hours to obtain a transparent NMP solution of polyamic acid (hereinafter, also referred to as varnish). The obtained varnish was stored in a freezer (setting -20 ° C, the same applies below), and thawed before use for evaluation.

<< Examples 2-32 and Comparative Examples 17-19 >>
Example 1 was carried out in the same manner as in Example 1 except that the types and amounts of the solvent, the acid dianhydride, the diamine and the silicon-containing compound were changed to those described in Tables 2 and 3.
The types of silicon-containing compounds in Table 3 are as follows.
Silicon-containing compound (2): In the general formula (1), L ₁ and L ₂ are amino groups, R ₁ is —CH ₂ CH ₂ CH ₂ —, and R ₂ , R ₃ , R ₆ , and R ₇ are methyl. Group, R ₄ and R ₅ are phenyl groups, j / (i + j + k) = 0.15, and the number average molecular weight is 1340. Silicon-containing compound (3): In the general formula (1), L ₁ and L ₂ are An acid anhydride group, R ₁ is —CH ₂ CH ₂ CH ₂ —, R ₂ , R ₃ , R ₆ and R ₇ are methyl groups, R ₄ and R ₅ are phenyl groups, and j / (i + j + k) = 0. 0.15 and a compound having a number average molecular weight of 4,200 Silicon-containing compound (4): In the general formula (1), L ₁ and L ₂ are epoxy groups, R ₁ is —CH ₂ CH ₂ CH ₂ —, and R _{2 is , R 3, R 6, R} 7 is a methyl _group, R 4, _{R 5} is a phenyl group, A /(Itasujtasuk)=0.15, compounds having a number average molecular weight 1240

<< Comparative Example 1 >>
As described in Table 3, NMP (319 g) as a solvent, 4,4′-DAS (14.3 g) as a diamine, and TFMB (12.3 g) as a solvent were introduced into a 3 L separable flask equipped with a stirring rod while introducing nitrogen gas. ), A crude silicon-containing compound (in the general formula (1), L ₁ and L ₂ are amino groups, R ₁ is —CH ₂ CH ₂ CH ₂ —, and R ₂ , R ₃ , R ₆ , and R _{7 are} Is a methyl group, R ₄ and R ₅ are phenyl groups, j is 15, and i + j + k is 10, and the compound having a number average molecular weight of 4400) (5.72 g) is added with stirring, followed by PMDA (as a dianhydride). 15.3 g) was added. The molar ratio of acid dianhydride and diamine was 100: 97. Next, the mixture was stirred at room temperature for 48 hours to obtain a transparent NMP solution of polyamic acid (hereinafter, also referred to as varnish). The obtained varnish was stored in a freezer (setting -20 ° C, the same applies below), and thawed before use for evaluation.

<< Comparative Examples 2 to 16 >>
Comparative Example 1 was carried out in the same manner as Comparative Example 1 except that the kinds and amounts of the solvent, acid dianhydride, diamine and silicon-containing compound were changed to those listed in Table 3.

  With respect to the resin compositions of Examples and Comparative Examples, low molecular cyclic siloxane concentrations based on resin composition, based on solid content, and based on silicon-containing compound; molecular weight of polyimide precursor; foreign matter count evaluation; and difference in YI value were evaluated. .. The results are shown in Tables 5 and 6. In Tables 5 and 6, "compound of formula (3)" corresponds to compound of general formula (3), m is 3 to 5, and "compound of formula (4)" is compound of general formula (4). And n is 3-8.

2a Lower substrate 2b Encapsulation substrate 25 Organic EL structure part 250a Organic EL element emitting red light 250b Organic EL element emitting green light 250c Organic EL element emitting blue light 251 Partition (bank)
252 Lower electrode (anode)
253 Hole transport layer 254 Light emitting layer 255 Upper electrode (cathode)
256 TFT
257 Contact hole 258 Interlayer insulating film 259 Lower electrode 261 Hollow part

Claims (34)

A polyimide precursor containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2);
At least one compound of the following general formula (3-1) or (3-2), wherein m is an integer of 3 or more;
A resin composition, optionally comprising a compound represented by the following general formula (4):
Whether the total amount of compounds in which m is an integer of 3 or more in the following general formula (3-1) or (3-2) is more than 0 ppm and 1,100 ppm or less based on the mass of the resin composition, Alternatively,
In the following general formula (3-1) or (3-2), the total amount of the compound in which m is an integer of 3 or more and the compound in which n is an integer of 3 or more in the following general formula (4) is the above resin. Greater than 0 ppm and less than or equal to 1,300 ppm, based on the weight of the composition,
Resin composition.

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer. }

{In the formula, P ₃ and P ₄ are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms, and q is 1 to It is an integer of 200. }

{In the formula, m is an integer of 1 or more. }

{In the formula, n is an integer of 2 or more. }   The total amount of compounds in which m is an integer of 3 or more in the general formula (3-1) or (3-2) is more than 0 ppm and 300 ppm or less based on the mass of the resin composition. The resin composition according to. A polyimide precursor containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2);
At least one compound in which m is 3 or 4 in the following general formula (3-1) or (3-2);
A resin composition, optionally comprising a compound represented by the following general formula (4):
In the following general formula (3-1) or (3-2), the total amount of compounds in which m is 3 is more than 0 ppm and 650 ppm or less based on the mass of the resin composition, or
In the following general formula (3-1) or (3-2), the total amount of compounds in which m is 4 is more than 0 ppm and 350 ppm or less based on the mass of the resin composition,
Resin composition.

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer. }

{In the formula, P ₃ and P ₄ are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms, and q is 1 to It is an integer of 200. }

{In the formula, m is an integer of 1 or more. }

{In the formula, n is an integer of 2 or more. } M among the polyimide precursor and the following general formula (3-1) or (3-2) containing the structural unit represented by the following general formula (1) and the structural unit represented by the following general formula (2). And at least one compound in which is an integer of 3 or more;
A resin composition, optionally comprising a compound represented by the following general formula (4):
In the following general formula (3-1) or (3-2), the total amount of compounds in which m is an integer of 3 or more is greater than 0 ppm and equal to or less than 7,500 ppm based on the mass of the solid content in the resin composition. Or
In the following general formula (3-1) or (3-2), the total amount of the compound in which m is an integer of 3 or more and the compound in which n is an integer of 3 or more in the following general formula (4) is A resin composition which is more than 0 ppm and not more than 8,600 ppm based on the mass of the solid content in the resin composition.

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer. }

{In the formula, P ₃ and P ₄ are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms, and q is 1 to It is an integer of 200. }

{In the formula, m is an integer of 1 or more. }

{In the formula, n is an integer of 2 or more. } A polyimide precursor containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2);
At least one compound in which m is 3 or 4 in the following general formula (3-1) or (3-2);
A resin composition, optionally comprising a compound represented by the following general formula (4):
Is the total amount of compounds in which m is 3 in the following general formula (3-1) or (3-2) is more than 0 ppm and not more than 4,500 ppm based on the mass of the solid content in the resin composition. , Or
In the following general formula (3-1) or (3-2), the total amount of compounds in which m is 4 is more than 0 ppm and 2,500 ppm or less based on the mass of the solid content in the resin composition,
Resin composition.

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer. }

{In the formula, P ₃ and P ₄ are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms, and q is 1 to It is an integer of 200. }

{In the formula, m is an integer of 1 or more. }

  The resin composition according to any one of claims 1, 2 and 4, wherein m is an integer of 3 to 5 in the compound represented by the general formula (3-1) or (3-2).   The resin composition according to any one of claims 1, 2 and 4, wherein in the compound represented by the general formula (4), n is an integer of 3 to 8.   The resin composition according to claim 1, wherein the polyimide resin film obtained by curing the polyimide precursor is used for a flexible substrate.   The resin composition according to claim 1, wherein the polyimide resin film obtained by curing the polyimide precursor is used in a flexible display. A polyimide precursor containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2);
At least one compound of the following general formula (3-1) or (3-2), wherein m is an integer of 3 or more;
A resin composition, optionally comprising a compound represented by the following general formula (4):
The resin composition is as follows:
A silicon-containing compound represented by the following general formula (5),
At least one of the compounds of the following general formula (3-1) or (3-2), wherein m is an integer of 3 or more,
Optionally prepared by a method comprising polycondensing a raw material composition containing a compound represented by the following general formula (4) with a tetracarboxylic dianhydride and a diamine to provide a polyimide precursor. ,
Among the following general formulas (3-1) and (3-2) contained in the raw material composition, the total amount of compounds in which m is an integer of 3 or more is the following general formulas (3-1) and (3-2). ), (4) and (5) based on the total mass of the silicon-containing compounds, more than 0ppm and 46,000ppm or less, or
A compound in which m is an integer of 3 or more in the following general formula (3-1) or (3-2) contained in the raw material composition, and n is an integer of 3 or more in the following general formula (4). The total amount with a certain compound is more than 0 ppm and not more than 47,000 ppm, based on the total mass of the silicon-containing compounds of the general formulas (3-1), (3-2), (4) and (5),
Resin composition.

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer. }

{In the formula, P ₃ and P ₄ are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms, and q is 1 to It is an integer of 200. }

{In the formula, m is an integer of 1 or more. }

{In the formula, n is an integer of 2 or more. }

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, and R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms. At least one is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group having 1 to 10 carbon atoms, At least one is a monovalent aromatic group having 6 to 10 carbon atoms, R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one is an unsaturated fatty group. Is an organic group having a group hydrocarbon group, L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid halide group, a hydroxy group, an epoxy group, Or a mercapto group, and i and j are each independently an integer of 1 to 200. And a, k is an integer of 0 to 200, is 0.05 ≦ j / (i + j + k) ≦ 0.50. }   The resin composition according to claim 10, wherein m is an integer of 3 to 5 in the compound represented by the general formula (3-1) or (3-2).   The resin composition according to claim 10, wherein n is an integer of 3 to 8 in the compound represented by the general formula (4). A polyimide precursor containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2);
At least one compound in which m is 3 or 4 in the following general formula (3-1) or (3-2);
A resin composition, optionally comprising a compound represented by the following general formula (4):
The resin composition is as follows:
A silicon-containing compound represented by the following general formula (5),
At least one compound in which m is 3 or 4 in the following general formula (3-1) or (3-2),
Optionally prepared by a method comprising polycondensing a raw material composition containing a compound represented by the following general formula (4) with a tetracarboxylic dianhydride and a diamine to provide a polyimide precursor. ,
Of the following general formula (3-1) or (3-2) contained in the raw material composition, the total amount of compounds in which m is 3 is represented by the following general formula (3-1), (3-2), (3 4) and (5) based on the total mass of the silicon-containing compound, more than 0ppm and 25,000ppm or less, or
Of the following general formula (3-1) or (3-2) contained in the raw material composition, the total amount of compounds in which m is 4 is represented by the following general formula (3-1), (3-2), (3-2), 4) and (5) based on the total mass of the silicon-containing compound is more than 0ppm and 15,000ppm or less,
Resin composition.

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer. }

{In the formula, P ₃ and P ₄ are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms, and q is 1 to It is an integer of 200. }

{In the formula, m is an integer of 1 or more. }

{In the formula, n is an integer of 2 or more. }

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, and R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms. At least one is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group having 1 to 10 carbon atoms, At least one is a monovalent aromatic group having 6 to 10 carbon atoms, R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one is an unsaturated fatty group. Is an organic group having a group hydrocarbon group, L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid halide group, a hydroxy group, an epoxy group, Or a mercapto group, and i and j are each independently an integer of 1 to 200. And a, k is an integer of 0 to 200, is 0.05 ≦ j / (i + j + k) ≦ 0.50. } 14. The silicon-containing compound represented by the general formula (5), wherein L ₁ and L ₂ are each independently selected from the group consisting of an amino group, an acid anhydride group and an epoxy group. The resin composition according to any one of claims. The resin composition according to claim 10, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (5) are amino groups.   The compound represented by the said General formula (3-1) or (3-2) is a compound represented by the said General formula (3-1), Any one of Claims 10-15. Resin composition.   The tetracarboxylic dianhydride is pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic anhydride, cyclohexanetetracarboxylic dianhydride. The resin composition according to any one of claims 10 to 16, wherein the resin composition is at least one selected from the group consisting of a compound and cyclobutanetetracarboxylic dianhydride.   The diamine is 4,4′-diaminodiphenyl sulfone, m-tolidine, p-phenylenediamine, 2,2′-bis (trifluoromethyl) benzidine, and 2,2′-bis [4- (4-aminophenoxy). ) The resin composition according to any one of claims 10 to 17, which is at least one selected from the group consisting of phenyl] propane. A silicon-containing compound represented by the following general formula (5),
At least one of the compounds of the following general formula (3-1) or (3-2), wherein m is an integer of 3 or more,
A resin composition, which optionally comprises polycondensing a raw material composition containing a compound represented by the following general formula (4) with a tetracarboxylic dianhydride and a diamine to provide a polyimide precursor. The manufacturing method of
Among the following general formulas (3-1) and (3-2) contained in the raw material composition, the total amount of compounds in which m is an integer of 3 or more is the following general formulas (3-1) and (3-2). ), (4) and (5) based on the total mass of the silicon-containing compounds, more than 0ppm and 46,000ppm or less, or
A compound in which m is an integer of 3 or more in the following general formula (3-1) or (3-2) contained in the raw material composition, and n is an integer of 3 or more in the following general formula (4). The total amount with a certain compound is more than 0 ppm and not more than 47,000 ppm, based on the total mass of the silicon-containing compounds of the general formulas (3-1), (3-2), (4) and (5),
A method for producing a resin composition.

{In the formula, m is an integer of 1 or more. }

{In the formula, n is an integer of 2 or more. }

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, and R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms. At least one is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group having 1 to 10 carbon atoms, At least one is a monovalent aromatic group having 6 to 10 carbon atoms, R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one is an unsaturated fatty group. Is an organic group having a group hydrocarbon group, L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid halide group, a hydroxy group, an epoxy group, Or a mercapto group, and i and j are each independently an integer of 1 to 200. And a, k is an integer of 0 to 200, is 0.05 ≦ j / (i + j + k) ≦ 0.50. }   The method according to claim 19, wherein in the compound represented by the general formula (3-1) or (3-2), m is an integer of 3 to 5.   The method according to claim 19, wherein in the compound represented by the general formula (4), n is an integer of 3 to 8. A silicon-containing compound represented by the following general formula (5),
At least one compound in which m is 3 or 4 in the following general formula (3-1) or (3-2),
A resin composition, which optionally comprises polycondensing a raw material composition containing a compound represented by the following general formula (4) with a tetracarboxylic dianhydride and a diamine to provide a polyimide precursor. The manufacturing method of
Of the following general formula (3-1) or (3-2) contained in the raw material composition, the total amount of compounds in which m is 3 is represented by the following general formula (3-1), (3-2), (3 4) and (5) based on the total mass of the silicon-containing compound, more than 0ppm and 25,000ppm or less, or
Of the following general formula (3-1) or (3-2) contained in the raw material composition, the total amount of compounds in which m is 4 is represented by the following general formula (3-1), (3-2), (3-2), 4) and (5) based on the total mass of the silicon-containing compound is more than 0ppm and 15,000ppm or less,
A method for producing a resin composition.

{In the formula, m is an integer of 1 or more. }

{In the formula, n is an integer of 2 or more. }

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, and R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms. At least one is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group having 1 to 10 carbon atoms, At least one is a monovalent aromatic group having 6 to 10 carbon atoms, R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one is an unsaturated fatty group. Is an organic group having a group hydrocarbon group, L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid halide group, a hydroxy group, an epoxy group, Or a mercapto group, and i and j are each independently an integer of 1 to 200. And a, k is an integer of 0 to 200, is 0.05 ≦ j / (i + j + k) ≦ 0.50. } 23. The silicon-containing compound represented by the general formula (5), wherein L ₁ and L ₂ are each independently selected from the group consisting of an amino group, an acid anhydride group and an epoxy group. The method according to any one of claims. The method according to any one of claims 19 to 23, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (5) are amino groups.   25. The compound represented by the general formula (3-1) or (3-2) is the compound represented by the general formula (3-1), according to any one of claims 19 to 24. Method.   The tetracarboxylic dianhydride is pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic anhydride, cyclohexanetetracarboxylic dianhydride. 26. The method according to any one of claims 19 to 25, wherein the method is at least one selected from the group consisting of a compound and cyclobutanetetracarboxylic dianhydride.   The diamine is 4,4′-diaminodiphenyl sulfone, m-tolidine, p-phenylenediamine, 2,2′-bis (trifluoromethyl) benzidine, and 2,2′-bis [4- (4-aminophenoxy). ) Phenyl] propane, at least one selected from the group consisting of the method according to any one of claims 19 to 26. A coating step of coating the resin composition according to any one of claims 1 to 18 on the surface of a support,
A film forming step of heating the resin composition to form a polyimide resin film,
A peeling step of peeling the polyimide resin film from the support,
A method for producing a polyimide film, comprising:   The method for producing a polyimide film according to claim 28, comprising an irradiation step of irradiating the resin composition with a laser from the support side prior to the peeling step. A coating step of coating the resin composition according to any one of claims 1 to 18 on the surface of a support;
A film forming step of heating the resin composition to form a polyimide resin film,
An element forming step of forming an element on the polyimide resin film,
A peeling step of peeling the polyimide resin film on which the element is formed from the support,
A method of manufacturing a display, including: A coating step of coating the resin composition according to any one of claims 1 to 18 on the surface of a support;
A film forming step of heating the resin composition to form a polyimide resin film,
An element forming step of forming an element on the polyimide resin film,
The manufacturing method of a laminated body containing.   32. The method for manufacturing a laminate according to claim 31, further comprising a step of peeling the polyimide resin film having the element formed thereon from the support.   A method for manufacturing a flexible device, comprising manufacturing a laminate by the method according to claim 31 or 32.   A polyimide film, which is a cured product of the resin composition according to any one of claims 1 to 18.

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