TW202229411A - Polyimide precursor and polyimide resin composition wherein the polyimide precursor includes a structural unit represented by a specific general formula which is partially imidized - Google Patents

Abstract

The present invention provides a composition including a polyimide precursor (PAI) having imide groups in one part, and a polyimide film obtained by heating the same, the composition has excellent results of various evaluations when being compared to the use of unpurified siloxane compounds. A resin composition of the present invention includes a polyimide precursor and a compound represented by the following general formula (3), wherein the polyimide precursor includes a structural unit represented by a specific general formula which is partially imidized. The total amount of compound in the following general formula (3) in which n is 4, is more than 0 ppm and 120 ppm or less on the basis of the mass of the resin composition, or, in the following general formula (3) in which n is 5, the total amount of the compound is more than 0 ppm and 50 ppm or less on the basis of the mass of the resin composition.

Description

Polyimide precursor and polyimide resin composition

The present invention relates to a polyimide precursor resin composition, a polyimide resin composition, and a method for producing the same. Furthermore, the present invention relates to a method for producing a polyimide film, a display, a laminate, and a flexible device using the polyimide precursor resin composition and the polyimide resin composition.

Polyimide resins are insoluble and infusible super heat-resistant resins with excellent properties such as thermal oxidation resistance, heat resistance, radiation resistance, low temperature resistance, and chemical resistance. Therefore, polyimide resins are used in a wide range of fields including electronic materials. Examples of applications of polyimide resins in the field of electronic materials include insulating coatings, insulating films, semiconductors, and electrode protection films for thin film transistor liquid crystal displays (TFT-LCDs). Recently, taking advantage of the light weight and flexibility of the polyimide film, it has been studied to use the polyimide film as a flexible substrate to replace the glass substrate previously used in the field of display materials.

For example, Patent Document 1 describes a resin precursor (weight-average molecular weight: 30,000 to 90,000) having a siloxane unit polymerized from bis(diaminodiphenyl) sulfide (hereinafter also referred to as DAS). According to Patent Document 1, the polyimide obtained by curing the precursor has low residual stress with a support such as glass, excellent chemical resistance, and the oxygen concentration during the curing step has an effect on the yellowness ( YI value) and total light transmittance are less affected. Patent Document 2 describes a resin precursor which is polymerized from 2,2'-bis(trifluoromethyl)benzidine (hereinafter also referred to as TFMB) and has a siloxane unit. According to Patent Document 2, the polyimide film obtained by curing the precursor has a specific glass transition temperature, low residual stress with the inorganic film, and excellent mechanical properties and thermal stability. [Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2014/148441 [Patent Document 2] International Publication No. 2014/098235 [Patent Document 3] Japanese Patent Laid-Open No. 2016-029126 [Patent Document 4] Japanese Patent Laid-Open No. 2006-028533 [Patent Document 5] Japanese Patent Laid-Open No. 2002-012666 [Patent Document 6] International Publication No. 2019/208587 [Patent Document 7] Japanese Patent Laid-Open No. 2019-203117 [Patent Document 8] Japanese Patent Laid-Open No. 9-263636 [Patent Document 9] International Publication No. 2020/138360 [Non-patent literature]

[Non-Patent Document 1] Homepage of Shin-Etsu Chemical Co., Ltd., "Q&A", "About Silicone Grease-Oil Compounds", [online], [Searched on November 26, 2020], Internet Road ＜URL: https://www.silicone.jp/contact/qa/qa103.shtml＞

[Problems to be Solved by Invention]

Patent Documents 1 and 2 use siloxane-containing compounds as monomers of polyimide precursors, and such siloxane-containing compounds contain low molecular weight cyclic siloxanes (hereinafter also referred to as low molecular weight cyclic siloxanes). ). Since this low molecular weight cyclosiloxane is volatile, it can be seen that outgassing may be generated, thereby causing the contact failure of the manufacturing apparatus in the process. For example, see Non-Patent Document 1.

Patent documents 3 to 5 can be exemplified as prior art documents related to reducing the polyimide precursor of the low-molecular-weight cyclic siloxane by purification. According to Patent Document 3, after adding a siloxane-containing compound to acetone, centrifugation and decantation are performed to remove low-molecular-weight cyclic siloxane, the obtained polyimide is transparent, and outgassing is generated. less. According to Patent Documents 4 and 5, the siloxane-containing compound is removed by stripping the siloxane-containing compound under specific conditions, or dissolving the siloxane-containing compound in 2-butanone and reprecipitating it with methanol. After purification, the adhesion of the obtained polyimide was improved.

The present inventors synthesize a polyimide precursor and a polyimide using the siloxane-containing compounds purified by the same purification methods as those described in the above-mentioned Patent Documents 3 to 5, and use these to produce polyimide imine film. As a result, it was found that the storage stability of the resin composition, the repulsion of the coating film, and the in-plane uniformity of the retardation (Rth) of the polyimide resin film when the resin composition was repeatedly frozen and stored at room temperature Each evaluation is insufficient. Therefore, an object of the present invention is to provide a composition comprising a polyimide precursor (PAI) having an imide group in a part, and a polyimide film obtained by heating the composition, the composition and When compared with the case of the unpurified siloxane compound, the excellent results of each of the above evaluations can be taken into account. [Technical means to solve problems]

{式中，P ₁表示二價有機基，P ₂表示四價有機基，p表示正整數}， [化2]

{式中，P ₈表示二價有機基，P ₉表示四價有機基，q表示正整數}， [化3]

{式中，P ₃及P ₄分別獨立地為碳數1～5之一價脂肪族烴、或碳數6～10之一價芳香族基，r為1～200之整數}， [化4]

{式中，n為2以上之整數}。 [2] 如項目1所記載之樹脂組合物，其中上述通式(3)中n為4之化合物之總量，以上述樹脂組合物之質量為基準，超過0 ppm且為70 ppm以下，或者， 上述通式(3)中n為5之化合物之總量，以上述樹脂組合物之質量為基準，超過0 ppm且為30 ppm以下。 [3] 如項目2所記載之樹脂組合物，其中上述通式(3)中n為4之化合物之總量，以上述樹脂組合物之質量為基準，超過0 ppm且為30 ppm以下，或者， 上述通式(3)中n為5之化合物之總量，以上述樹脂組合物之質量為基準，超過0 ppm且為15 ppm以下。 [4] 一種樹脂組合物，其含有 聚醯亞胺前驅體及下述通式(3)所表示之化合物， 上述聚醯亞胺前驅體包含下述通式(1-1)及(1-2)所表示之結構單元、及下述通式(2)所表示之結構單元，且部分醯亞胺化， 上述樹脂組合物係藉由以下方法而製造，該方法包括 使含有下述通式(4)所表示之含矽化合物及下述通式(3)所表示之化合物之原料組合物與四羧酸二酐及二胺進行縮聚反應，使其醯亞胺化而獲得聚醯亞胺後，進而與四羧酸二酐及二胺進行縮聚反應，藉此提供部分醯亞胺化之聚醯亞胺前驅體之步驟，或者，與四羧酸二酐及二胺進行縮聚反應，使其醯亞胺化而獲得聚醯亞胺後，進而使含有下述通式(4)所表示之含矽化合物及下述通式(3)所表示之化合物之原料組合物與四羧酸二酐及二胺進行縮聚反應，藉此提供部分醯亞胺化之聚醯亞胺前驅體之步驟， 上述原料組合物所含的下述通式(3)中n為4之化合物之總量，以下述通式(3)及(4)所表示之含矽化合物之合計質量為基準，超過0 ppm且為1300 ppm以下，或者， 上述原料組合物所含的下述通式(3)中n為5之化合物之總量，以上述通式(3)及(4)之含矽化合物之合計質量為基準，超過0 ppm且為500 ppm以下， [化5]

{式中，P ₁表示二價有機基，P ₂表示四價有機基，p表示正整數}， [化6]

{式中，P ₈表示二價有機基，P ₉表示四價有機基，q表示正整數}， [化7]

{式中，P ₃及P ₄分別獨立地為碳數1～5之一價脂肪族烴、或碳數6～10之一價芳香族基，r為1～200之整數}， [化8]

{式中，n為2以上之整數}， [化9]

{式中，R ₁分別獨立地為單鍵或碳數1～10之二價有機基，R ₂及R ₃分別獨立地為碳數1～10之一價有機基，至少一者為碳數1～5之一價脂肪族烴基，R ₄及R ₅分別獨立地為碳數1～10之一價有機基，至少一者為碳數6～10之一價芳香族基，R ₆及R ₇分別獨立地為碳數1～10之一價有機基，L ₁及L ₂分別獨立地為胺基、酸酐基、異氰酸基、羧基、酸酯基、醯鹵基、羥基、環氧基、或巰基，i為1～200之整數，j及k分別獨立地為0～200之整數，0≦j/(i＋j＋k)≦0.50}。 [5] 如項目4所記載之樹脂組合物，其中上述原料組合物所含的上述通式(3)中n為4之化合物之總量，以上述通式(3)及(4)所表示之含矽化合物之合計質量為基準，超過0 ppm且為800 ppm以下，或者， 上述原料組合物所含的上述通式(3)中n為5之化合物之總量，以上述通式(3)及(4)之含矽化合物之合計質量為基準，超過0 ppm且為300 ppm以下。 [6] 如項目4所記載之樹脂組合物，其中上述原料組合物所含的上述通式(3)中n為4之化合物之總量，以上述通式(3)及(4)所表示之含矽化合物之合計質量為基準，超過0 ppm且為30 ppm以下，或者， 上述原料組合物所含的上述通式(3)中n為5之化合物之總量，以上述通式(3)及(4)之含矽化合物之合計質量為基準，超過0 ppm且為15 ppm以下。 [7] 一種樹脂組合物，其含有 聚醯亞胺前驅體及下述通式(3)所表示之化合物， 上述聚醯亞胺前驅體包含下述通式(1-1)及(1-2)所表示之結構單元、及下述通式(2)所表示之結構單元，且部分醯亞胺化， 下述通式(3)中n為3以上8以下之化合物之總量，以上述樹脂組合物之質量為基準，超過0 ppm且為150 ppm以下， [化10]

{式中，P ₁表示二價有機基，P ₂表示四價有機基，p表示正整數}， [化11]

{式中，P ₈表示二價有機基，P ₉表示四價有機基，q表示正整數}， [化12]

{式中，P ₃及P ₄分別獨立地為碳數1～5之一價脂肪族烴、或碳數6～10之一價芳香族基，r為1～200之整數}， [化13]

{式中，n為2以上之整數}。 [8] 一種樹脂組合物，其含有 聚醯亞胺前驅體及下述通式(3)所表示之化合物， 上述聚醯亞胺前驅體包含下述通式(1-1)及(1-2)所表示之結構單元、及下述通式(2)所表示之結構單元，且部分醯亞胺化， 下述通式(3)中n為3以上8以下之化合物之總量，以上述樹脂組合物之非溶劑成分之質量為基準，超過0 ppm且為900 ppm以下， [化14]

{式中，P ₁表示二價有機基，P ₂表示四價有機基，p表示正整數}， [化15]

{式中，P ₈表示二價有機基，P ₉表示四價有機基，q表示正整數}， [化16]

{式中，P ₃及P ₄分別獨立地為碳數1～5之一價脂肪族烴、或碳數6～10之一價芳香族基，r為1～200之整數}， [化17]

{式中，n為2以上之整數}。 [9] 一種樹脂組合物，其含有 聚醯亞胺前驅體及下述通式(3)所表示之化合物， 上述聚醯亞胺前驅體包含下述通式(1-1)及(1-2)所表示之結構單元、及下述通式(2)所表示之結構單元，且部分醯亞胺化， 上述樹脂組合物係藉由以下方法而製造，該方法包括 使含有下述通式(4)所表示之含矽化合物及下述通式(3)所表示之化合物之原料組合物與四羧酸二酐及二胺進行縮聚反應，使其醯亞胺化而獲得聚醯亞胺後，進而與四羧酸二酐及二胺進行縮聚反應，藉此提供部分醯亞胺化之聚醯亞胺前驅體之步驟，或者，與四羧酸二酐及二胺進行縮聚反應，使其醯亞胺化而獲得聚醯亞胺後，進而使含有下述通式(4)所表示之含矽化合物及下述通式(3)所表示之化合物之原料組合物與四羧酸二酐及二胺進行縮聚反應，藉此提供部分醯亞胺化之聚醯亞胺前驅體之步驟， 上述原料組合物所含的下述通式(3)中n為3以上8以下之化合物之總量，以下述通式(3)及(4)所表示之含矽化合物之合計質量為基準，超過0 ppm且為4500 ppm以下， [化18]

{式中，P ₁表示二價有機基，P ₂表示四價有機基，p表示正整數}， [化19]

{式中，P ₈表示二價有機基，P ₉表示四價有機基，q表示正整數}， [化20]

{式中，P ₃及P ₄分別獨立地為碳數1～5之一價脂肪族烴、或碳數6～10之一價芳香族基，r為1～200之整數}， [化21]

{式中，n為2以上之整數}， [化22]

{式中，R ₁分別獨立地為單鍵或碳數1～10之二價有機基，R ₂及R ₃分別獨立地為碳數1～10之一價有機基，至少一者為碳數1～5之一價脂肪族烴基，R ₄及R ₅分別獨立地為碳數1～10之一價有機基，至少一者為碳數6～10之一價芳香族基，R ₆及R ₇分別獨立地為碳數1～10之一價有機基，L ₁及L ₂分別獨立地為胺基、酸酐基、異氰酸基、羧基、酸酯基、醯鹵基、羥基、環氧基、或巰基，i為1～200之整數，j及k分別獨立地為0～200之整數，0≦j/(i＋j＋k)≦0.50}。 [10] 如項目1至9中任一項所記載之樹脂組合物，其中p及q滿足20≦q/(p＋q)×100≦80。 [11] 如項目4至6及9中任一項所記載之樹脂組合物，其中上述通式(4)所表示之含矽化合物之L ₁及L ₂分別獨立地選自由胺基、酸酐基、環氧基、羥基、及巰基所組成之群。 [12] 如項目4至6及9中任一項所記載之樹脂組合物，其中上述通式(4)所表示之含矽化合物之L ₁及L ₂係胺基。 [13] 如項目4至6及9中任一項所記載之樹脂組合物，其中上述通式(4)所表示之含矽化合物之官能基當量為800以上。 [14] 如項目4至6、9及11至13中任一項所記載之樹脂組合物，其中上述四羧酸二酐係選自由均苯四甲酸二酐(PMDA)、3,3',4,4'-聯苯四羧酸二酐(BPDA)、9,9-雙(3,4-二羧基苯基)茀二酸酐(BPAF)、4,4'-氧二鄰苯二甲酸酐(ODPA)、1,2,4,5-環己烷四羧酸二酐(HPMDA)、及1,2,3,4-環丁烷四羧酸二酐(CBDA)、對伸苯基雙(偏苯三酸酐)(TAHQ)所組成之群中之至少一種。 [15] 如項目4至6、9及11至14中任一項所記載之樹脂組合物，其中上述二胺係選自由4,4'-二胺基二苯基碸(4,4'-DAS)、3,3'-雙(二胺基二苯基)碸(3,3'-DAS)、9,9-雙(4-胺基苯基)茀(BAFL)、二胺基雙(三氟甲基)聯苯(TFMB)、2,2'-雙[4-(4-胺基苯氧基)苯基]丙烷(BAPP)、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷(HFBAPP)、1,3-雙(胺基甲基)環己烷(BAC)所組成之群中之至少一種。 [16] 如項目1至15中任一項所記載之樹脂組合物，其中使上述樹脂組合物硬化所得之聚醯亞胺樹脂膜係用於可撓性基板。 [17] 如項目1至15中任一項所記載之樹脂組合物，其中使上述樹脂組合物硬化所得之聚醯亞胺樹脂膜係用於可撓性顯示器。 [18] 一種樹脂組合物之製造方法，其包括使含有下述通式(4)所表示之含矽化合物及下述通式(3)所表示之化合物之原料組合物與四羧酸二酐及二胺進行縮聚反應，使其醯亞胺化而獲得聚醯亞胺後，進而與四羧酸二酐及二胺進行縮聚反應，藉此提供部分醯亞胺化之聚醯亞胺前驅體之步驟，或者，與四羧酸二酐及二胺進行縮聚反應，使其醯亞胺化而獲得聚醯亞胺後，進而使含有下述通式(4)所表示之含矽化合物及下述通式(3)所表示之化合物之原料組合物與四羧酸二酐及二胺進行縮聚反應，藉此提供部分醯亞胺化之聚醯亞胺前驅體之步驟， 上述樹脂組合物可包含下述通式(4)所表示之含矽化合物、及下述通式(3)所表示之化合物，上述原料組合物所含的下述通式(3)中n為4之化合物之總量，以下述通式(3)及(4)所表示之含矽化合物之合計質量為基準，超過0 ppm且為1300 ppm以下，或者， 上述原料組合物所含的下述通式(3)中n為5之化合物之總量，以上述通式(3)及(4)之含矽化合物之合計質量為基準，超過0 ppm且為500 ppm以下， [化23]

{式中，n為2以上之整數}， [化24]

{式中，R ₁分別獨立地為單鍵或碳數1～10之二價有機基，R ₂及R ₃分別獨立地為碳數1～10之一價有機基，至少一者為碳數1～5之一價脂肪族烴基，R ₄及R ₅分別獨立地為碳數1～10之一價有機基，至少一者為碳數6～10之一價芳香族基，R ₆及R ₇分別獨立地為碳數1～10之一價有機基，L ₁及L ₂分別獨立地為胺基、酸酐基、異氰酸基、羧基、酸酯基、醯鹵基、羥基、環氧基、或巰基，i為1～200之整數，j及k分別獨立地為0～200之整數，0≦j/(i＋j＋k)≦0.50}。 [19] 如項目18所記載之樹脂組合物之製造方法，其中上述原料組合物所含的上述通式(3)中n為4之化合物之總量，以上述通式(3)及(4)所表示之含矽化合物之合計質量為基準，超過0 ppm且為800 ppm以下，或者， 上述原料組合物所含的上述通式(3)中n為6之化合物之總量，以上述通式(3)及(4)之含矽化合物之合計質量為基準，超過0 ppm且為300 ppm以下。 [20] 一種樹脂組合物之製造方法，其包括使含有下述通式(4)所表示之含矽化合物及下述通式(3)所表示之化合物之原料組合物與四羧酸二酐及二胺進行縮聚反應，使其醯亞胺化而獲得聚醯亞胺後，進而與四羧酸二酐及二胺進行縮聚反應，藉此提供部分醯亞胺化之於一部分中具有醯亞胺基之聚醯亞胺前驅體之步驟，或者，與四羧酸二酐及二胺進行縮聚反應，使其醯亞胺化而獲得聚醯亞胺後，進而使含有下述通式(4)所表示之含矽化合物及下述通式(3)所表示之化合物之原料組合物與四羧酸二酐及二胺進行縮聚反應，藉此提供部分醯亞胺化之聚醯亞胺前驅體之步驟， 上述樹脂組合物可包含下述通式(4)所表示之含矽化合物、及下述通式(3)所表示之化合物，上述原料組合物所含的下述通式(3)中n為3以上8以下之化合物之總量，以下述通式(3)及(4)所表示之含矽化合物之合計質量為基準，超過0 ppm且為4500 ppm以下， [化25]

{式中，n為2以上之整數}， [化26]

{式中，R ₁分別獨立地為單鍵或碳數1～10之二價有機基，R ₂及R ₃分別獨立地為碳數1～10之一價有機基，至少一者為碳數1～5之一價脂肪族烴基，R ₄及R ₅分別獨立地為碳數1～10之一價有機基，至少一者為碳數6～10之一價芳香族基，R ₆及R ₇分別獨立地為碳數1～10之一價有機基，L ₁及L ₂分別獨立地為胺基、酸酐基、異氰酸基、羧基、酸酯基、醯鹵基、羥基、環氧基、或巰基，i為1～200之整數，j及k分別獨立地為0～200之整數，0≦j/(i＋j＋k)≦0.50}。 [21] 如項目18至20中任一項所記載之樹脂組合物之製造方法，其中上述通式(4)所表示之含矽化合物之官能基當量為800以上。 [22] 一種樹脂組合物之製造方法，其包括使含有下述通式(4)所表示之含矽化合物及下述通式(3)所表示之化合物之原料組合物與四羧酸二酐及二胺進行縮聚反應，使其醯亞胺化而獲得聚醯亞胺後，進而與四羧酸二酐及二胺進行縮聚反應，藉此提供部分醯亞胺化之聚醯亞胺前驅體之步驟，或者，與四羧酸二酐及二胺進行縮聚反應，使其醯亞胺化而獲得聚醯亞胺後，進而使含有下述通式(4)所表示之含矽化合物及下述通式(3)所表示之化合物之原料組合物與四羧酸二酐及二胺進行縮聚反應，藉此使上述聚醯亞胺前驅體部分醯亞胺化而提供部分醯亞胺化之聚醯亞胺前驅體之步驟， 上述樹脂組合物可包含下述通式(4)所表示之含矽化合物、及下述通式(3)所表示之化合物，上述樹脂組合物之製造方法包括以下述通式(4)及(3)之含矽化合物之合計質量為基準降低下述通式(3)中n為5之化合物之總量、或n為6之化合物之總量、或n為7之化合物之總量之步驟， 上述降低之步驟包括於150～300℃、300 Pa以下對上述組合物進行2～12小時之處理， [化27]

{式中，n為2以上之整數}， [化28]

{式中，R ₁分別獨立地為單鍵或碳數1～10之二價有機基，R ₂及R ₃分別獨立地為碳數1～10之一價有機基，至少一者為碳數1～5之一價脂肪族烴基，R ₄及R ₅分別獨立地為碳數1～10之一價有機基，至少一者為碳數6～10之一價芳香族基，R ₆及R ₇分別獨立地為碳數1～10之一價有機基，L ₁及L ₂分別獨立地為胺基、酸酐基、異氰酸基、羧基、酸酯基、醯鹵基、羥基、環氧基、或巰基，i為1～200之整數，j及k分別獨立地為0～200之整數，0≦j/(i＋j＋k)≦0.50}。 [23] 如項目18至22中任一項所記載之方法，其中上述通式(4)所表示之含矽化合物之L ₁及L ₂分別獨立地選自由胺基、酸酐基、環氧基、羥基、及巰基所組成之群。 [24] 如項目18至22中任一項所記載之方法，其中上述通式(4)所表示之含矽化合物之L ₁及L ₂係胺基。 [25] 如項目18至24中任一項所記載之方法，其中上述四羧酸二酐係選自由均苯四甲酸二酐(PMDA)、3,3',4,4'-聯苯四羧酸二酐(BPDA)、9,9-雙(3,4-二羧基苯基)茀二酸酐(BPAF)、4,4'-氧二鄰苯二甲酸酐(ODPA)、1,2,4,5-環己烷四羧酸二酐(HPMDA)、及1,2,3,4-環丁烷四羧酸二酐(CBDA)所組成之群中之至少一種。 [26] 如項目18至25中任一項所記載之方法，其中上述二胺係選自由4,4'-二胺基二苯基碸(4,4'-DAS)、3,3'-雙(二胺基二苯基)碸(3,3'-DAS)、9,9-雙(4-胺基苯基)茀(BAFL)、2,2'-二甲基聯苯胺(mTB)、對苯二胺(PDA)、二胺基雙(三氟甲基)聯苯(TFMB)、2,2'-雙[4-(4-胺基苯氧基)苯基]丙烷(BAPP)、4,4'-二胺基二苯醚(ODA)、及1,4-環己烷二胺(CHDA)所組成之群中之至少一種。 [27] 一種聚醯亞胺膜之製造方法，其包括： 於支持體之表面上塗佈如項目1至17中任一項所記載之樹脂組合物之塗佈步驟、 對上述樹脂組合物進行加熱而形成聚醯亞胺樹脂膜之膜形成步驟、及 將上述聚醯亞胺樹脂膜自上述支持體剝離之剝離步驟。 [28] 如項目27所記載之聚醯亞胺膜之製造方法，其於上述剝離步驟之前，包括自上述支持體側對上述樹脂組合物照射雷射之照射步驟。 [29] 一種顯示器之製造方法，其包括： 於支持體之表面上塗佈如項目1至17中任一項所記載之樹脂組合物之塗佈步驟、 對上述樹脂組合物進行加熱而形成聚醯亞胺樹脂膜之膜形成步驟、 於上述聚醯亞胺樹脂膜上形成元件之元件形成步驟、及 將形成有上述元件之上述聚醯亞胺樹脂膜自上述支持體剝離之剝離步驟。 [30] 一種積層體之製造方法，其包括： 於支持體之表面上塗佈如項目1至17中任一項所記載之樹脂組合物之塗佈步驟、 對上述樹脂組合物進行加熱而形成聚醯亞胺樹脂膜之膜形成步驟、及 於上述聚醯亞胺樹脂膜上形成元件之元件形成步驟。 [31] 如項目30所記載之積層體之製造方法，其進而包括將形成有上述元件之上述聚醯亞胺樹脂膜自上述支持體剝離之步驟。 [32] 一種可撓性裝置之製造方法，其包括藉由如項目30或31所記載之方法製造積層體之步驟。 [33] 一種聚醯亞胺膜，其係如項目1至17中任一項所記載之樹脂組合物之硬化物。 [34] 一種樹脂組合物，其含有聚醯亞胺前驅體，上述聚醯亞胺前驅體包含下述通式(1-1)及(1-2)所表示之結構單元，且部分醯亞胺化， [化29]

{式中，P ₁表示二價有機基，P ₂表示四價有機基，p表示正整數}， [化30]

{式中，P ₈表示二價有機基，P ₉表示四價有機基，q表示正整數}， P ₉係來源於9,9-雙(3,4-二羧基苯基)茀二酸酐(BPAF)、或對伸苯基雙(偏苯三酸酐)(TAHQ)之基。 [35] 一種樹脂組合物，其含有聚醯亞胺前驅體，上述聚醯亞胺前驅體包含下述通式(1-1)及(1-2)所表示之結構單元，且部分醯亞胺化， [化31]

{式中，P ₁表示二價有機基，P ₂表示四價有機基，p表示正整數}， [化32]

{式中，P ₈表示二價有機基，P ₉表示四價有機基，q表示正整數}， P ₈係來源於選自4,4'-二胺基二苯基碸(4,4'-DAS)、3,3'-雙(二胺基二苯基)碸(3,3'-DAS)、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷(HFBAPP)、對伸苯基雙(偏苯三酸酐)(TAHQ)之任一者之1種以上之化合物之基。 [發明之效果] As a result of intensive research by the present inventors, it was found that some compounds of the general formula (3) were not sufficiently reduced in the case of using the purification method described in the above-mentioned prior art document. Then, it was found that by further purifying the silicon-containing compound to reduce a part of the compound of the general formula (3) to a specific amount, and using it as a raw material, the obtained PAI with a specific structure can solve the above-mentioned problems. The following [1] to [35] give examples of embodiments of the present invention. [1] A resin composition comprising a polyimide precursor and a compound represented by the following general formula (3), wherein the polyimide precursor comprises the following general formulas (1-1) and (1- 2) The structural unit represented by the following general formula (2) and the structural unit represented by the following general formula (2), and the partial imidization, the total amount of compounds in the following general formula (3) where n is 4, is combined with the above resins Based on the mass of the resin composition, it exceeds 0 ppm and is less than 120 ppm, or the total amount of the compounds in the following general formula (3) where n is 5 is more than 0 ppm and is 50 ppm based on the mass of the above resin composition. Below ppm, [Chemical 1]

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

{In the formula, P ₈ represents a divalent organic group, P ₉ represents a tetravalent organic group, and q represents a positive integer}, [Chem. 3]

{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 r is an integer of 1 to 200}, [Chem. 4 ]

{In the formula, n is an integer of 2 or more}. [2] The resin composition according to item 1, wherein the total amount of the compounds of the general formula (3) where n is 4 is more than 0 ppm and 70 ppm or less based on the mass of the resin composition, or , the total amount of the compound in which n is 5 in the above general formula (3), based on the mass of the above resin composition, exceeds 0 ppm and is 30 ppm or less. [3] The resin composition according to item 2, wherein the total amount of the compounds in the general formula (3) where n is 4 is more than 0 ppm and 30 ppm or less based on the mass of the resin composition, or , the total amount of the compounds in which n is 5 in the above general formula (3), based on the mass of the above resin composition, exceeds 0 ppm and is 15 ppm or less. [4] A resin composition comprising a polyimide precursor and a compound represented by the following general formula (3), wherein the polyimide precursor comprises the following general formulas (1-1) and (1- 2) The structural unit represented by the following general formula (2) and the structural unit represented by the following general formula (2) are partially imidized, and the above-mentioned resin composition is produced by the following method, which comprises making the following general formula The raw material composition of the silicon-containing compound represented by (4) and the compound represented by the following general formula (3) is subjected to a polycondensation reaction with tetracarboxylic dianhydride and diamine to imidize to obtain polyimide Then, it is further subjected to a polycondensation reaction with tetracarboxylic dianhydride and diamine, thereby providing a partially imidized polyimide precursor, or a polycondensation reaction with tetracarboxylic dianhydride and diamine to make After its imidization to obtain polyimide, a raw material composition containing a silicon-containing compound represented by the following general formula (4) and a compound represented by the following general formula (3) and a tetracarboxylic acid di Anhydride and diamine are subjected to a polycondensation reaction, thereby providing a step of partially imidized polyimide precursor, the total amount of compounds in the following general formula (3) contained in the above-mentioned raw material composition where n is 4, Based on the total mass of the silicon-containing compounds represented by the following general formulas (3) and (4), it exceeds 0 ppm and is 1300 ppm or less, or, n in the following general formula (3) contained in the raw material composition The total amount of the compound of 5, based on the total mass of the silicon-containing compounds of the above general formulas (3) and (4), exceeds 0 ppm and is not more than 500 ppm, [Chemical 5]

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer}, [Chem. 6]

{In the formula, P ₈ represents a divalent organic group, P ₉ represents a tetravalent organic group, and q represents a positive integer}, [Chem. 7]

{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 r is an integer of 1 to 200}, [Chem. 8 ]

{In the formula, n is an integer of 2 or more}, [Formula 9]

{In the formula, R ₁ is each independently a single bond or a divalent organic group with 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group with 1 to 10 carbon atoms, and at least one of them is a carbon number 1 to 5 monovalent aliphatic hydrocarbon groups, R ₄ and R ₅ are independently a monovalent organic group with 1 to 10 carbon atoms, at least one of them is a monovalent aromatic group with 6 to 10 carbon atoms, R ₆ and R ₇ are independently a monovalent organic group with 1 to 10 carbon atoms, L ₁ and L ₂ are independently an amine group, an acid anhydride group, an isocyanate group, a carboxyl group, an ester group, an halide group, a hydroxyl group, an epoxy group group or mercapto group, i is an integer of 1 to 200, j and k are each independently an integer of 0 to 200, 0≦j/(i+j+k)≦0.50}. [5] The resin composition according to item 4, wherein the total amount of the compounds in which n is 4 in the above-mentioned general formula (3) contained in the above-mentioned raw material composition is represented by the above-mentioned general formulas (3) and (4) The total mass of the silicon-containing compounds is more than 0 ppm and not more than 800 ppm based on the total mass of the above-mentioned raw material composition, or the total amount of the compounds of the above-mentioned general formula (3) contained in the above-mentioned general formula (3) is 5, according to the above-mentioned general formula (3). ) and (4) are based on the total mass of the silicon-containing compounds, exceeding 0 ppm and not more than 300 ppm. [6] The resin composition according to item 4, wherein the total amount of the compounds in which n is 4 in the above-mentioned general formula (3) contained in the above-mentioned raw material composition is represented by the above-mentioned general formulas (3) and (4) The total mass of the silicon-containing compounds is more than 0 ppm and not more than 30 ppm based on the total mass of the above-mentioned raw material composition, or the total amount of the compounds of the above-mentioned general formula (3) contained in the above-mentioned general formula (3) is 5, according to the above-mentioned general formula (3). ) and (4), the total mass of the silicon-containing compounds is more than 0 ppm and not more than 15 ppm. [7] A resin composition comprising a polyimide precursor and a compound represented by the following general formula (3), wherein the polyimide precursor comprises the following general formulas (1-1) and (1- 2) The structural unit represented by the following general formula (2) and the structural unit represented by the following general formula (2) are partially imidized, and n in the following general formula (3) is the total amount of compounds of 3 or more and 8 or less, with The mass of the above-mentioned resin composition is the standard, and it exceeds 0 ppm and is not more than 150 ppm, [Chemical 10]

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer}, [Chem. 11]

{In the formula, P ₈ represents a divalent organic group, P ₉ represents a tetravalent organic group, and q represents a positive integer}, [Chem. 12]

{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 r is an integer of 1 to 200}, [Chem. 13 ]

{In the formula, n is an integer of 2 or more}. [8] A resin composition comprising a polyimide precursor and a compound represented by the following general formula (3), wherein the polyimide precursor comprises the following general formulas (1-1) and (1- 2) The structural unit represented by the following general formula (2) and the structural unit represented by the following general formula (2) are partially imidized, and n in the following general formula (3) is the total amount of compounds of 3 or more and 8 or less, with Based on the mass of the non-solvent component of the above resin composition, it exceeds 0 ppm and is not more than 900 ppm, [Chemical 14]

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer}, [Chem. 15]

{In the formula, P ₈ represents a divalent organic group, P ₉ represents a tetravalent organic group, and q represents a positive integer}, [Chem. 16]

{wherein, 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 r is an integer of 1 to 200}, [Chem. 17 ]

{In the formula, n is an integer of 2 or more}. [9] A resin composition comprising a polyimide precursor and a compound represented by the following general formula (3), wherein the polyimide precursor comprises the following general formulas (1-1) and (1- 2) The structural unit represented by the following general formula (2) and the structural unit represented by the following general formula (2) are partially imidized, and the above-mentioned resin composition is produced by the following method, which comprises making the following general formula The raw material composition of the silicon-containing compound represented by (4) and the compound represented by the following general formula (3) is subjected to a polycondensation reaction with tetracarboxylic dianhydride and diamine to imidize to obtain polyimide Then, it is further subjected to a polycondensation reaction with tetracarboxylic dianhydride and diamine, thereby providing a partially imidized polyimide precursor, or a polycondensation reaction with tetracarboxylic dianhydride and diamine to make After its imidization to obtain polyimide, a raw material composition containing a silicon-containing compound represented by the following general formula (4) and a compound represented by the following general formula (3) and a tetracarboxylic acid di Anhydride and diamine are subjected to polycondensation reaction, thereby providing a step of partially imidized polyimide precursor, wherein n in the following general formula (3) contained in the above-mentioned raw material composition is one of the compounds of 3 or more and 8 or less. The total amount, based on the total mass of the silicon-containing compounds represented by the following general formulas (3) and (4), exceeds 0 ppm and is not more than 4500 ppm, [Chemical 18]

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer}, [Chem. 19]

{In the formula, P ₈ represents a divalent organic group, P ₉ represents a tetravalent organic group, and q represents a positive integer}, [Chem. 20]

{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 r is an integer of 1 to 200}, [Chem. 21 ]

{In the formula, n is an integer of 2 or more}, [Formula 22]

{In the formula, R ₁ is each independently a single bond or a divalent organic group with 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group with 1 to 10 carbon atoms, and at least one of them is a carbon number 1 to 5 monovalent aliphatic hydrocarbon groups, R ₄ and R ₅ are independently a monovalent organic group with 1 to 10 carbon atoms, at least one of them is a monovalent aromatic group with 6 to 10 carbon atoms, R ₆ and R ₇ are independently a monovalent organic group with 1 to 10 carbon atoms, L ₁ and L ₂ are independently an amine group, an acid anhydride group, an isocyanate group, a carboxyl group, an ester group, an halide group, a hydroxyl group, an epoxy group group or mercapto group, i is an integer of 1 to 200, j and k are each independently an integer of 0 to 200, 0≦j/(i+j+k)≦0.50}. [10] The resin composition according to any one of items 1 to 9, wherein p and q satisfy 20≦q/(p+q)×100≦80. [11] The resin composition as described in any one of items 4 to 6 and 9, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (4) are independently selected from amine groups, acid anhydride groups , epoxy group, hydroxyl group, and thiol group. [12] The resin composition according to any one of items 4 to 6 and 9, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (4) are amine groups. [13] The resin composition according to any one of items 4 to 6 and 9, wherein the functional group equivalent of the silicon-containing compound represented by the general formula (4) is 800 or more. [14] The resin composition as described in any one of items 4 to 6, 9 and 11 to 13, wherein above-mentioned tetracarboxylic dianhydride is selected from pyromellitic dianhydride (PMDA), 3,3', 4,4'-Biphenyltetracarboxylic dianhydride (BPDA), 9,9-bis(3,4-dicarboxyphenyl)perylene dianhydride (BPAF), 4,4'-oxydiphthalic anhydride (ODPA), 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA), and 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), p-phenylene bis At least one of the group consisting of (trimellitic anhydride) (TAHQ). [15] The resin composition as described in any one of items 4 to 6, 9 and 11 to 14, wherein the above-mentioned diamine is selected from 4,4'-diaminodiphenylene (4,4'- DAS), 3,3'-bis(diaminodiphenyl) benzene (3,3'-DAS), 9,9-bis(4-aminophenyl) fluoride (BAFL), diaminobis( Trifluoromethyl)biphenyl (TFMB), 2,2'-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 2,2-bis[4-(4-amino) At least one of the group consisting of phenoxy)phenyl]hexafluoropropane (HFBAPP) and 1,3-bis(aminomethyl)cyclohexane (BAC). [16] The resin composition according to any one of items 1 to 15, wherein the polyimide resin film obtained by curing the resin composition is used for a flexible substrate. [17] The resin composition according to any one of items 1 to 15, wherein the polyimide resin film obtained by curing the above resin composition is used for a flexible display. [18] A method for producing a resin composition, comprising: a raw material composition containing a silicon-containing compound represented by the following general formula (4) and a compound represented by the following general formula (3) and tetracarboxylic dianhydride and diamine for polycondensation reaction to obtain polyimide after imidization, and then polycondensation reaction with tetracarboxylic dianhydride and diamine to provide partially imidized polyimide precursor or, after polycondensation reaction with tetracarboxylic dianhydride and diamine to imidize to obtain polyimide, and then a silicon-containing compound represented by the following general formula (4) and the following The raw material composition of the compound represented by the general formula (3) is subjected to a polycondensation reaction with tetracarboxylic dianhydride and diamine to provide a partially imidized polyimide precursor. The above resin composition can be Including the silicon-containing compound represented by the following general formula (4) and the compound represented by the following general formula (3), the total of the compounds of the following general formula (3) contained in the above-mentioned raw material composition where n is 4 The amount, based on the total mass of the silicon-containing compounds represented by the following general formulas (3) and (4), exceeds 0 ppm and is 1300 ppm or less, or, the following general formula (3) contained in the above-mentioned raw material composition The total amount of the compounds in which n is 5, based on the total mass of the silicon-containing compounds of the above general formulas (3) and (4), exceeds 0 ppm and is not more than 500 ppm, [Chemical 23]

{In the formula, n is an integer of 2 or more}, [Formula 24]

{In the formula, R ₁ is each independently a single bond or a divalent organic group with 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group with 1 to 10 carbon atoms, and at least one of them is a carbon number 1 to 5 monovalent aliphatic hydrocarbon groups, R ₄ and R ₅ are independently a monovalent organic group with 1 to 10 carbon atoms, at least one of them is a monovalent aromatic group with 6 to 10 carbon atoms, R ₆ and R ₇ are independently a monovalent organic group with 1 to 10 carbon atoms, L ₁ and L ₂ are independently an amine group, an acid anhydride group, an isocyanate group, a carboxyl group, an ester group, an halide group, a hydroxyl group, an epoxy group group or mercapto group, i is an integer of 1 to 200, j and k are each independently an integer of 0 to 200, 0≦j/(i+j+k)≦0.50}. [19] The method for producing a resin composition as described in item 18, wherein the total amount of the compounds in the above-mentioned general formula (3) contained in the above-mentioned raw material composition where n is 4 is equal to the above-mentioned general formulas (3) and (4) ), the total mass of the silicon-containing compounds represented by ) exceeds 0 ppm and is less than or equal to 800 ppm, or the total amount of the compounds in the above-mentioned general formula (3) contained in the above-mentioned raw material composition where n is 6 is 6. The total mass of the silicon-containing compounds of the formulae (3) and (4) is more than 0 ppm and 300 ppm or less. [20] A method for producing a resin composition, comprising: a raw material composition containing a silicon-containing compound represented by the following general formula (4) and a compound represented by the following general formula (3) and tetracarboxylic dianhydride and diamine to carry out a polycondensation reaction, make it imidized to obtain polyimide, and then carry out a polycondensation reaction with tetracarboxylic dianhydride and diamine, thereby providing partial imidization with imide in a part. The step of amine-based polyimide precursor, or, after polycondensation reaction with tetracarboxylic dianhydride and diamine, the imidization is carried out to obtain polyimide, and then the polyimide containing the following general formula (4 ) and the raw material composition of the compound represented by the following general formula (3) are subjected to a polycondensation reaction with tetracarboxylic dianhydride and diamine, thereby providing a partially imidized polyimide precursor In the step of forming, the resin composition may include a silicon-containing compound represented by the following general formula (4) and a compound represented by the following general formula (3), and the following general formula (3) contained in the raw material composition. ), the total amount of compounds in which n is 3 or more and 8 or less, based on the total mass of the silicon-containing compounds represented by the following general formulas (3) and (4), exceeds 0 ppm and is 4500 ppm or less, [Chem. 25]

{where n is an integer greater than or equal to 2}, [Formula 26]

{In the formula, R ₁ is each independently a single bond or a divalent organic group with 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group with 1 to 10 carbon atoms, and at least one of them is a carbon number 1 to 5 monovalent aliphatic hydrocarbon groups, R ₄ and R ₅ are independently a monovalent organic group with 1 to 10 carbon atoms, at least one of them is a monovalent aromatic group with 6 to 10 carbon atoms, R ₆ and R ₇ are independently a monovalent organic group with 1 to 10 carbon atoms, L ₁ and L ₂ are independently an amine group, an acid anhydride group, an isocyanate group, a carboxyl group, an ester group, an halide group, a hydroxyl group, an epoxy group group or mercapto group, i is an integer of 1 to 200, j and k are each independently an integer of 0 to 200, 0≦j/(i+j+k)≦0.50}. [21] The method for producing a resin composition according to any one of items 18 to 20, wherein the functional group equivalent of the silicon-containing compound represented by the general formula (4) is 800 or more. [22] A method for producing a resin composition, comprising: a raw material composition containing a silicon-containing compound represented by the following general formula (4) and a compound represented by the following general formula (3) and tetracarboxylic dianhydride and diamine for polycondensation reaction to obtain polyimide after imidization, and then polycondensation reaction with tetracarboxylic dianhydride and diamine to provide partially imidized polyimide precursor or, after polycondensation reaction with tetracarboxylic dianhydride and diamine to imidize to obtain polyimide, and then a silicon-containing compound represented by the following general formula (4) and the following The raw material composition of the compound represented by the general formula (3) is subjected to a polycondensation reaction with tetracarboxylic dianhydride and diamine, whereby the above-mentioned polyimide precursor is partially imidized to provide a partially imidized In the step of the polyimide precursor, the resin composition may include a silicon-containing compound represented by the following general formula (4) and a compound represented by the following general formula (3). The manufacturing method of the resin composition includes: Based on the total mass of the silicon-containing compounds of the following general formulas (4) and (3), reduce the total amount of the compounds of the following general formula (3) where n is 5, or the total amount of the compounds where n is 6, or n The step of reducing the total amount of the compound as 7, the step of reducing the above-mentioned composition comprises subjecting the above-mentioned composition to a treatment at 150-300°C and below 300 Pa for 2-12 hours, [Chem. 27]

{In the formula, n is an integer of 2 or more}, [Formula 28]

{In the formula, R ₁ is each independently a single bond or a divalent organic group with 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group with 1 to 10 carbon atoms, and at least one of them is a carbon number 1 to 5 monovalent aliphatic hydrocarbon groups, R ₄ and R ₅ are independently a monovalent organic group with 1 to 10 carbon atoms, at least one of them is a monovalent aromatic group with 6 to 10 carbon atoms, R ₆ and R ₇ are independently a monovalent organic group with 1 to 10 carbon atoms, L ₁ and L ₂ are independently an amine group, an acid anhydride group, an isocyanate group, a carboxyl group, an ester group, an halide group, a hydroxyl group, an epoxy group group or mercapto group, i is an integer of 1 to 200, j and k are each independently an integer of 0 to 200, 0≦j/(i+j+k)≦0.50}. [23] The method according to any one of items 18 to 22, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (4) are independently selected from amine groups, acid anhydride groups, epoxy groups , hydroxyl, and sulfhydryl groups. [24] The method according to any one of items 18 to 22, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (4) are amine groups. [25] The method as described in any one of items 18 to 24, wherein the above-mentioned tetracarboxylic dianhydride is selected from pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetrakis Carboxylic dianhydride (BPDA), 9,9-bis(3,4-dicarboxyphenyl)perylene dianhydride (BPAF), 4,4'-oxydiphthalic anhydride (ODPA), 1,2, At least one of the group consisting of 4,5-cyclohexanetetracarboxylic dianhydride (HPMDA) and 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA). [26] The method according to any one of items 18 to 25, wherein the above-mentioned diamine is selected from Bis(diaminodiphenyl) sulfone (3,3'-DAS), 9,9-bis(4-aminophenyl) fluoride (BAFL), 2,2'-dimethylbenzidine (mTB) , p-phenylenediamine (PDA), diaminobis(trifluoromethyl)biphenyl (TFMB), 2,2'-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) , at least one of the group consisting of 4,4'-diaminodiphenyl ether (ODA) and 1,4-cyclohexanediamine (CHDA). [27] A manufacturing method of a polyimide film, comprising: on the surface of the support, coating the coating step of the resin composition as described in any one of items 1 to 17, carrying out the above-mentioned resin composition A film forming step of heating to form a polyimide resin film, and a peeling step of peeling off the polyimide resin film from the support. [28] The method for producing a polyimide film according to item 27, comprising an irradiation step of irradiating the resin composition with a laser from the support side before the peeling step. [29] A manufacturing method of a display, comprising: on the surface of the support, coating the coating step of the resin composition as described in any one of items 1 to 17, heating the above-mentioned resin composition to form a polymer The film forming step of the imide resin film, the element forming step of forming the element on the polyimide resin film, and the peeling step of peeling the polyimide resin film with the element formed thereon from the support. [30] A manufacturing method of a laminate, comprising: on the surface of the support, coating the coating step of the resin composition as described in any one of items 1 to 17, heating the above-mentioned resin composition to form A film forming step of a polyimide resin film, and an element forming step of forming an element on the above-mentioned polyimide resin film. [31] The method for producing a laminate according to item 30, further comprising the step of peeling off the polyimide resin film on which the element is formed from the support. [32] A method of manufacturing a flexible device, comprising the step of manufacturing a laminate by the method as described in item 30 or 31. [33] A polyimide film, which is a cured product of the resin composition according to any one of items 1 to 17. [34] A resin composition comprising a polyimide precursor, the polyimide precursor comprising the structural units represented by the following general formulae (1-1) and (1-2), and a portion of the polyimide precursor Amination, [Chem. 29]

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer}, [Chem. 30]

{in the formula, P ₈ represents a divalent organic group, P ₉ represents a tetravalent organic group, and q represents a positive integer}, P ₉ is derived from 9,9-bis(3,4-dicarboxyphenyl) sulfonic anhydride ( BPAF), or p-phenylene bis(trimellitic anhydride) (TAHQ). [35] A resin composition comprising a polyimide precursor, the polyimide precursor comprising the structural units represented by the following general formulae (1-1) and (1-2), and a portion of the polyimide precursor Amination, [Chemical 31]

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer}, [Chem. 32]

{in the formula, P ₈ represents a divalent organic group, P ₉ represents a tetravalent organic group, and q represents a positive integer}, P ₈ is derived from the group consisting of 4,4'-diaminodiphenyl group (4,4' -DAS), 3,3'-bis(diaminodiphenyl) bis(3,3'-DAS), 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoro Propane (HFBAPP) and p-phenylene bis(trimellitic anhydride) (TAHQ) as the base of one or more compounds. [Effect of invention]

According to the present invention, by using a silicon-containing compound with a specific structure, performing specific purification conditions, and using the silicon-containing compound to form a polyimide precursor (PAI) structure having an imide group in a part, a polyimide precursor (PAI) structure can be provided. A resin composition and a polyimide film that can simultaneously evaluate the storage stability of the resin composition, the repulsion of the coating film, and the in-plane uniformity of the retardation (Rth) of the polyimide resin film. Furthermore, the above description should not be construed as revealing all the embodiments of the present invention and all the advantages of the present invention. Further embodiments of the present invention and advantages thereof will become apparent with reference to the following description.

Hereinafter, an exemplary embodiment of the present invention (hereinafter abbreviated as "this embodiment") will be described in detail. The present invention is not limited to the present embodiment, and can be implemented with various modifications within the scope of the gist. In the specification of the present application, the upper limit value and the lower limit value of each numerical range can be combined arbitrarily.

<resin composition> <polyimide precursor and polyimide> Structural units of general formula (1-1) and (1-2) The resin composition of this embodiment may contain a polyimide precursor (hereinafter also referred to as PAI), and the polyimide precursor includes a structural unit represented by the following general formula (1-1), and the following general formula The structural unit represented by the formula (1-2) is partially imidized.

{式中，P ₁表示二價有機基，P ₂表示四價有機基，p表示正整數} [化34]

{式中，P ₈表示二價有機基，P ₉表示四價有機基，q表示正整數} 如此，藉由具有聚醯亞胺前驅體結構與聚醯亞胺結構兩者，可兼顧各者之長處。具體而言，聚醯亞胺前驅體之情形時，溶劑溶解性、塗膜相斥等優異；聚醯亞胺之情形時，組合物之黏度穩定性、於低溫、室溫下保存組合物之情形時之保存穩定性等優異，因此較佳。 [Chemical 33]

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer} [Chem. 34]

{In the formula, P ₈ represents a divalent organic group, P ₉ represents a tetravalent organic group, and q represents a positive integer} In this way, by having both a polyimide precursor structure and a polyimide structure, both of them can be taken into account. the advantages. Specifically, in the case of the polyimide precursor, the solvent solubility and film repulsion are excellent; in the case of polyimide, the viscosity stability of the composition, the stability of the composition stored at low temperature and room temperature, etc. are excellent. In this case, the storage stability and the like are excellent, so it is preferable.

Among them, the P ₂ group and the P ₉ group are acid anhydride residues, and these may be the same or different. In addition, the P ₁ group and the P ₈ group are diamine residues, and these may be the same or different.

The ratio of the polyimide structure, that is, the value of q/(p+q)×100 is preferably more than 0 and 80 or less, more preferably 20 or more and 80 or less. If the ratio of the polyimide structure is within this range, the storage stability of the resin composition, the evaluation of the repulsion of the coating film, and the evaluation of the in-plane uniformity of the Rth of the polyimide film can be taken into consideration.

The larger the ratio of the polyimide structure (the smaller the ratio of the polyimide precursor structure), the better the storage stability of the composition described below, and thus the better. The reason for this is not clear, but it is believed that the reason is that, especially when the resin composition is stored at room temperature, the polyimide precursor structure is more easily decomposed into monomers (acids) than the polyimide structure. dianhydride, diamine).

On the other hand, the larger the ratio of the polyimide precursor structure (the smaller the ratio of the polyimide structure), the better the repulsion evaluation of the coating film described below is, so it is preferable. The reason is not clear, but it is believed that the reason is that although the resin composition is coated on the glass substrate, there are hydroxyl groups on the surface of the glass substrate. The affinity is high, so the mutual evaluation is good.

Acid dianhydride As the acid dianhydride containing the P ₂ group or P ₉ group of the general formulae (1-1) and (1-2), pyromellitic dianhydride (PMDA), 3,3',4 ,4'-biphenyltetracarboxylic dianhydride (BPDA), 2,2',3,3'-biphenyltetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic acid Formic anhydride, 5-(2,5-dioxytetrahydro-3-furyl)-3-methyl-cyclohexene-1,2 dicarboxylic acid anhydride, 1,2,3,4-benzenetetracarboxylic acid Dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 3,3',4, 4'-diphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylene-4,4'-diphthalic dianhydride , 2,2-propylene-4,4'-diphthalic dianhydride, 1,2-ethylidene-4,4'-diphthalic dianhydride, 1,3-trimethylene -4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'- Diphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, p-phenylene bis(trimellitic anhydride), thio-4,4'-diphthalic dianhydride, sulfonyl -4,4'-Diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)phthalic anhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene Dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl]phthalic anhydride , 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]phthalic anhydride, 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 - Naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic acid dianhydride, and 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)perylene dianhydride (BPAF), bicyclohexyl-3,3', 4,4'-tetracarboxylic dianhydride (CpODA), 4,4'-oxydiphthalic anhydride (ODPA), 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA), And 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), etc.

The acid dianhydride is preferably selected from pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 9,9-bis(3,4-bis Carboxyphenyl) perylene dianhydride (BPAF), 4,4'-oxydiphthalic anhydride (ODPA), 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA), p-phenylene At least one of the group consisting of bis(trimellitic anhydride) (TAHQ) and 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA).

The acid dianhydride may be used alone or in combination of two or more. Among these, from the viewpoints of mechanical properties of the polyimide film, optical properties such as lower retardation in the thickness direction (Rth) and lower YI value, and higher glass transition temperature, 9 is preferred ,9-bis(3,4-dicarboxyphenyl) perylene dianhydride (BPAF), pyromellitic dianhydride (PMDA), p-phenylene bis(trimellitic anhydride) (TAHQ) and biphenyl tetracarboxylic dianhydride (BPDA). Polyimide precursor having structure represented by general formula (1-1), and copolymer of polyimide-based tetracarboxylic dianhydride and diamine having structure represented by general formula (1-2) , and the tetracarboxylic dianhydride more preferably contains 9,9-bis(3,4-dicarboxyphenyl)perylene dianhydride (BPAF).

Based on the lower Rth and YI values of the polyimide film, and the higher glass transition temperature, 9,9-bis(3,4-dicarboxyphenyl)perylenedi The acid anhydride (BPAF) is preferably 60 mol % or more, more preferably 80 mol % or more, and still more preferably 100 mol %.

Diamine As the diamine containing the P ₁ group or the P ₈ group of the general formulae (1-1) and (1-2), diaminodiphenyl sulfone (for example, 4,4'-diaminodiphenyl) can be exemplified. Phenylene, 3,3'-diaminodiphenyl), p-phenylenediamine (PDA), m-phenylenediamine, 2,2'-dimethylbenzidine (mTB), 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'-diamine benzophenone, 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)benzene Oxy)phenyl]diphenyl, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-amine) phenoxy)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-aminopropyldimethylsilyl)benzene, 9,9-bis(4-aminophenyl)fluoride (BAFL), 2,2-bis[4-(4 -Aminophenoxy)phenyl]hexafluoropropane (HFBAPP), p-phenylene bis(trimellitic anhydride) (TAHQ), etc.

The diamine is preferably selected from the group consisting of 4,4'-diaminodiphenylene (4,4'-DAS), 3,3'-bis-diaminodiphenylene (3,3'-DAS), At least one of the group consisting of 9,9-bis(4-aminophenyl) fluoride (BAFL) and 1,4-cyclohexanediamine (CHDA).

As the diamine, it is preferable to contain diaminodiphenyl bismuth, for example, 4,4'-diaminodiphenyl bismuth (4,4'-DAS), and/or 3,3'-diaminodiphenyl Phenylidene (3,3'-DAS).

From the viewpoint of in-plane uniformity in the thickness direction Rth of the obtained polyimide resin film, the diamine is more preferably selected from 4,4'-diaminodiphenylene (4,4'-DAS) At least one of the group consisting of 3,3'-diaminodiphenyl sulfone (3,3'-DAS) and 9,9-bis(4-aminophenyl) fluoride (BAFL).

The content of diaminodiphenyl sulfone in all diamines may be 50 mol% or more, or 70 mol% or more, or 90 mol% or more, or 95 mol% or more. The higher the amount of diaminodiphenyl sulfide, the lower the YI value of the polyimide film, and the higher the glass transition temperature can be obtained, which is therefore preferred. As a diaminodiphenyl selenium, from the viewpoint of lowering the YI value, 4,4'-diamino diphenyl selenium is particularly preferred.

A diamine may be used individually by 1 type, and may be used in combination of 2 or more types. It is preferable to copolymerize the diaminodiphenyl sulfone with other diamines. As other diamines to be copolymerized with diaminodiphenylene, from the viewpoint of higher heat resistance and lower YI value of the polyimide film, diamide-based diamines are preferred. Benzenes, more preferably, diaminobis(trifluoromethyl)biphenyl (TFMB). From the viewpoint of the lower YI value of the polyimide film, the content of diamine-based bis(trifluoromethyl)biphenyl (TFMB) in all diamines is preferably above 20 mol%, more preferably is more than 30 mol%. From the viewpoint of designing the diamine to include other favorable diamines such as diaminodiphenyl sulfone, the content of TFMB in the total diamine is preferably 80 mol % or less, more preferably 70 mol % ear % below.

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

{式中，P ₃及P ₄分別獨立地為碳數1～5之一價脂肪族烴、或碳數6～10之一價芳香族基，r為1～200之整數，P ₃及P ₄較佳為分別獨立地為碳數1～5之一價脂肪族烴，更佳為碳數1～3之一價脂肪族烴，進而較佳為甲基} [Chemical 35]

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

From the viewpoint of reducing the residual stress of the polyimide film generated between the support and the support, the lower limit of the ratio of the structural moieties represented by the general formula (2) is the mass of the polyimide precursor or polyimide. On the basis, it is preferably 5 mass % or more, more preferably 6 mass % or more, and still more preferably 7 mass % or more. From the viewpoint of transparency and heat resistance of the polyimide film, the upper limit of the ratio of the structural site represented by the general formula (2) is based on the mass of the polyimide precursor or polyimide, and is higher than Preferably it is 40 mass % or less, More preferably, it is 30 mass % or less, More preferably, it is 25 mass % or less. In the above-mentioned general formula (2), r is an integer of 1 to 200, and is preferably an integer of 3 to 200 from the viewpoint of the heat resistance of the obtained polyimide.

The polyimide precursor and the polyimide can have the structure of the general formula (2) at any position in the molecule. The structure of the general formula (2) is preferably a structure derived from a silicon-containing compound represented by the following general formula (4).

From the viewpoint of good evaluation of the storage stability of the following resin composition, P ₃ and P ₄ of the general formula (2) are more preferably an aliphatic group (specifically a methyl group) than an aromatic group (specifically a phenyl group). base). The reason for this is not clear, but it is presumed that when the composition is stored at room temperature, the polyimide precursor structure may be decomposed into various monomers, and the silicon-containing monomer obtained by the decomposition is a compound having a phenyl group. Aggregation is easier than that of a compound having a methyl group, and as a result, the storage stability is deteriorated.

Dicarboxylic acid As the acid component for forming the polyimide precursor and polyimide of the present embodiment, other than acid dianhydrides (for example, tetracarboxylic dianhydrides exemplified above) may be used within the range that does not impair their performance. Dicarboxylic acids are used. That is, the polyimide precursor of the present invention may be a polyimide precursor, and the polyimide may be a polyimide. Various properties such as mechanical elongation, glass transition temperature Tg, YI value, etc. of the polyimide film obtained from such a polyimide precursor or polyimide are good. As a dicarboxylic acid used, the dicarboxylic acid which has an aromatic ring and an alicyclic dicarboxylic acid are mentioned. Particularly preferred is 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. The number of carbons mentioned here also includes the number of carbons contained in the carboxyl group. Among these, the dicarboxylic acid which has an aromatic ring is 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'-sulfonic acid bisbenzoic 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'-biphenyl dicarboxylic acid, 3,3'-dimethyl-4,4'-biphenyl dicarboxylic acid, 2,2'-dimethyl-3,3'-biphenyl dicarboxylic acid, 9,9-bis(4-(4-carboxyphenoxy)phenyl) fluoride, 9,9-bis(4-(3-carboxyphenoxy)phenyl) fluoride, 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)-para-terphenyl, 4,4'-bis(4-carboxyphenoxy)-para-terphenyl, 3,4'-bis(4-carboxyphenoxy)-para-terphenyl Benzene, 3,3'-bis(4-carboxyphenoxy)-terphenyl, 3,4'-bis(4-carboxyphenoxy)-terphenyl, 3,3'-bis(4- Carboxyphenoxy)-m-terphenyl, 4,4'-bis(3-carboxyphenoxy)-para-terphenyl, 4,4'-bis(3-carboxyphenoxy)-m-terphenyl, 3,4'-bis(3-carboxyphenoxy)-terphenyl, 3,3'-bis(3-carboxyphenoxy)-terphenyl, 3,4'-bis(3-carboxyphenoxy) base)-meta-triphenyl, 3,3'-bis(3-carboxyphenoxy)-meta-triphenyl, 1,1-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4,4'-benzophenonedicarboxylic acid, 1,3-phenylene diacetic acid, 1,4-phenylene diacetic acid, etc.; and International Publication No. 2005 5-aminoisophthalic acid derivatives and the like described in No. /068535. When these dicarboxylic acids are actually copolymerized with a polymer, they may be used in the form of a thiochloride body, an active ester body, or the like derived from thionine chlorine or the like.

The polyimide precursor and polyimide in the resin composition of this embodiment can also be described as a copolymer containing a silicon-containing compound, a tetracarboxylic dianhydride, and a diamine as monomer units. In this case, the silicon-containing compound may include compounds of the following general formula (4), general formula (3) and/or general formula (5). The silicon-containing compound can be synthesized using the technical knowledge at the time of filing, or a commercially available product can be used. The synthesized silicon-containing compound or commercially available silicon-containing compound can be used as a polyimide precursor and a polyimide monomer unit after the following purification treatment.

{式中，R ₁分別獨立地為單鍵或碳數1～10之二價有機基，R ₂及R ₃分別獨立地為碳數1～10之一價有機基，至少一者為碳數1～5之一價脂肪族烴基，R ₄及R ₅分別獨立地為碳數1～10之一價有機基，至少一者為碳數6～10之一價芳香族基，R ₆及R ₇分別獨立地為碳數1～10之一價有機基，L ₁及L ₂分別獨立地為胺基、酸酐基、異氰酸基、羧基、酸酯基、醯鹵基、羥基、環氧基、或巰基，i為1～200之整數，j及k分別獨立地為0～200之整數，0≦j/(i＋j＋k)≦0.50} [Chemical 36]

{In the formula, R ₁ is each independently a single bond or a divalent organic group with 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group with 1 to 10 carbon atoms, and at least one of them is a carbon number 1 to 5 monovalent aliphatic hydrocarbon groups, R ₄ and R ₅ are independently a monovalent organic group with 1 to 10 carbon atoms, at least one of them is a monovalent aromatic group with 6 to 10 carbon atoms, R ₆ and R ₇ are independently a monovalent organic group with 1 to 10 carbon atoms, L ₁ and L ₂ are independently an amine group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an halide group, a hydroxyl group, an epoxy group group, or mercapto group, i is an integer of 1 to 200, j and k are each independently an integer of 0 to 200, 0≦j/(i+j+k)≦0.50}

L ₁ and L ₂ of the silicon-containing compound represented by the general formula (4) are not limited, but are preferably independently an amine group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an halide group, hydroxyl, epoxy, or mercapto. From the viewpoint of the molecular weight of the obtained polyimide precursor and polyimide, L ₁ and L ₂ are preferably selected from the group consisting of amine group, acid anhydride group, epoxy group, hydroxyl group, and mercapto group, More preferably, it is an amine group.

From the viewpoints of heat resistance (glass transition temperature) and residual stress of the obtained polyimide film, the functional group equivalent of the silicon-containing compound represented by the general formula (4) is preferably 800 or more, more preferably 1500 or more. The functional group equivalent refers to the molecular weight of the silicon-containing compound per 1 mol of the functional group (unit: g/mol). As a functional group, an amine group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an halide group, a hydroxyl group, an epoxy group, and a mercapto group are mentioned. The functional group equivalent can be measured by the method described in the Examples. When the functional group equivalent of the silicon-containing compound is 800 or more, the silicone region increases and the stress is relaxed, so that the residual stress of the polyimide film is reduced.

In the general formula (4), 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, ethylidene, n-propylidene, isopropylidene, n-butylene, second-butylene, and third-butylene Alkyl, n-pentyl extended, neopentyl extended, n-hexyl extended, n-heptyl extended, n-octyl extended, n-nonyl extended, and n-decenyl extended straight chain or branched alkyl group; and cyclo extended propyl group, ring extended Cycloalkylene such as butyl, cyclopentylene, cyclohexylene, cycloheptide, and cyclooctyl. The divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferably at least one selected from the group consisting of ethylidene, n-propylidene, and isopropylidene.

In the general formula (4), R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one of them is a monovalent aliphatic hydrocarbon group having 1 to 5 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 a C1-C10 monovalent organic group, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, Linear or branched alkyl groups such as neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; and cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cycloalkyl groups such as cyclooctyl, and aromatic groups such as phenyl, tolyl, xylyl, α-naphthyl, and β-naphthyl. 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 a C1-C5 monovalent aliphatic hydrocarbon group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group can be mentioned. , and linear or branched alkyl groups such as neopentyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, and cyclopentyl. 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, and more preferably methyl.

In the general formula (4), R ₄ and R ₅ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one of them 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 a C1-C10 monovalent organic group, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, Linear or branched alkyl groups such as neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; and cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cycloalkyl groups such as cyclooctyl, and aromatic groups such as phenyl, tolyl, xylyl, α-naphthyl, and β-naphthyl. Examples of the monovalent aromatic group having 6 to 10 carbon atoms include phenyl, tolyl, xylyl, α-naphthyl, and β-naphthyl, preferably phenyl, tolyl, or Xylyl.

In the general formula (4), R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and a part thereof may be 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, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, Linear or branched alkyl groups such as sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; and cyclopropyl , cycloalkyl groups such as cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, and aromatic groups such as phenyl, tolyl, xylyl, α-naphthyl, and β-naphthyl. The monovalent organic group having 1 to 10 carbon atoms is preferably at least one selected from the group consisting of a methyl group, an ethyl group, and a phenyl group. 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, and hexyl. Alkenyl, cyclohexenyl, heptenyl, octenyl, nonenyl, decenyl, ethynyl, propynyl, butynyl, pentynyl, and hexynyl, and the like. The unsaturated aliphatic hydrocarbon group having 3 to 10 carbon atoms is preferably at least one selected from the group consisting of vinyl groups, allyl groups, and 3-butenyl groups.

In the general formula (4), a part or all of the hydrogen atoms of R ₁ to R ₇ may be substituted with substituents such as halogen atoms such as F, Cl, and Br, or may be unsubstituted.

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

The silicon-containing compound of the general formula (4) is preferably a silicon-containing diamine from the viewpoints of types of monomers, cost, and molecular weights of the obtained polyimide precursor and polyimide. As the silicon-containing diamine, for example, a diamine (poly)siloxane represented by the following formula (6) is preferable.

{式中，P ₅分別獨立地表示二價烴基，可相同亦可不同，P ₃及P ₄與通式(2)中定義者相同，l表示1～200之整數} [Chemical 37]

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

As a preferable structure of _P3 and P4 in the said general formula ( ₂ ), a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, etc. are mentioned. Among these, a methyl group is preferable. In the above general formula (6), l is an integer of 1 to 200, and from the viewpoint of the heat resistance of the polyimide obtained, it is preferably an integer of 3 to 200.

The preferable range of the functional group equivalent of the compound represented by the general formula (6) is the same as that of the silicon-containing compound represented by the above-mentioned general formula (4), preferably 800 or more, more preferably 1500 or more.

The copolymerization ratio of the silicon-containing diamine is preferably 0.5 to 30 mass %, more preferably 1.0 to 25 mass %, and still more preferably 1.5 mass % relative to the total mass of the polyimide precursor or polyimide % to 20% by mass. When the silicon-containing diamine is 0.5 mass % or more, the residual stress generated between the silicon-containing diamine and the support can be effectively reduced. When the silicon-containing diamine is less than 30% by mass, the obtained polyimide film has good transparency (especially low haze), based on the realization of higher total light transmittance and higher glass transition It is preferable from the viewpoint of temperature.

The silicon-containing compound used as a polyimide precursor and a monomer for polyimide is as described above, and can be synthesized using the technical common sense at the time of application, or a commercially available product can be used. As a commercial item, double-terminated amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.: X22-1660B-3 (functional group equivalent 2200), X22-9409 (functional group equivalent 670)), Two-terminated acid anhydride-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.: X22-168-P5-B (functional group equivalent: 2100)), two-terminated epoxy group-modified methylphenyl silicone oil ( Shin-Etsu Chemical Co., Ltd.: X22-2000 (functional group equivalent 620)), two-terminated amino group-modified dimethyl silicone (Shin-Etsu Chemical Co., Ltd.: PAM-E (functional group equivalent 130), X22-161A (functional group equivalent) Equivalent 800), X22-161B (functional group equivalent 1500), KF8012 (functional group equivalent 2200), manufactured by Toray Dow Corning: BY16-853U (functional group equivalent 450), manufactured by JNC Corporation: SILAPLANE FM3311 (number average molecular weight 1000)) , Two-terminated epoxy group-modified dimethyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd.: X-22-163A (functional group equivalent 1750)), two-terminated alicyclic epoxy group-modified dimethyl silicone ( Shin-Etsu Chemical Co., Ltd.: X-22-169B (functional group equivalent: 1700)), two-terminated hydroxyl-modified dimethyl silicone (Shin-Etsu Chemical Co., Ltd.: KF-6000), two-terminated mercapto-modified dimethyl silicone Ketone (manufactured by Shin-Etsu Chemical Co., Ltd.: X-22-167B (functional group equivalent: 1700)), double-terminated acid anhydride-modified dimethyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd.: X-22-168A (functional group equivalent: 1000)), etc. . Among these, from the viewpoints of price, improvement in chemical resistance, and improvement in Tg, the double-terminated amine-modified dimethyl silicone oil is preferred.

weight average molecular weight In this embodiment, from the viewpoint of reducing the YI value of the polyimide film, the weight average molecular weight of the polyimide precursor and the polyimide is preferably 50,000 or more, more preferably 60,000 or more. From the viewpoint of reducing the haze of the polyimide film, the weight average molecular weight of the polyimide precursor and the polyimide is preferably 150,000 or less, more preferably 120,000 or less. The ideal weight average molecular weight of the polyimide precursor and the polyimide can be determined according to the desired application, the type of the polyimide precursor and the polyimide, the non-solvent content of the resin composition, and the resin composition. The substance may differ depending on the kind of solvent and the like which may be contained.

{式中，P ₆及P ₇分別獨立地為碳數1～5之一價脂肪族烴基、或碳數6～10之芳香族基，且m為2以上之整數} <Cyclic siloxane> The resin composition of this embodiment may contain a cyclic siloxane represented by the following general formula (5), the silicon-containing compound (polyimide precursor) used in the resin composition of this embodiment The monomer used in the polycondensation reaction of the monomer) may include the silicon-containing compound represented by the general formula (3) and the silicon-containing compound represented by the general formula (4). [Chemical 38]

{In the formula, P ₆ and P ₇ are each independently a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an aromatic group having 6 to 10 carbon atoms, and m is an integer of 2 or more}

{式中，n為2以上之整數} The resin composition of the present embodiment contains the compound represented by the cyclosiloxane represented by the following general formula (3) among the compounds of the general formula (5) at a specific ratio. [Chemical 39]

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

In the general formula (3), the total amount of the compounds in which n is 4 is based on the mass of the resin composition, preferably more than 0 ppm and 120 ppm or less, more preferably more than 0 ppm and 70 ppm or less, and more preferably more than 0 ppm and 50 ppm or less, more preferably more than 0 ppm and 40 ppm or less, particularly preferably more than 0 ppm and 30 ppm or less. Alternatively, or in addition to this, the total amount of the compounds in which n is 5 in the general formula (3), based on the mass of the resin composition, preferably exceeds 0 ppm and is 50 ppm or less, more preferably exceeds 0 ppm and is 30 ppm ppm or less, more preferably more than 0 ppm and 20 ppm or less, still more preferably more than 0 ppm and 15 ppm or less. In the general formula (3), the total amount of the compound in which n is 6 is based on the mass of the resin composition, preferably more than 0 ppm and 70 ppm or less, more preferably more than 0 ppm and 60 ppm or less, and more preferably more than 0 ppm and 50 ppm or less, and more preferably more than 0 ppm and 40 ppm or less. The total amount of the compounds in which n is 7 in the general formula (3), based on the mass of the resin composition, is preferably more than 0 ppm and 80 ppm or less, more preferably more than 0 ppm and 70 ppm or less, and more preferably more than 0 ppm and 60 ppm or less, and more preferably more than 0 ppm and 50 ppm or less. If the total amount of the compound represented by the general formula (3) is within the above range, the defects of the polyimide resin film obtained from the resin composition are reduced, and the YI value is further reduced, which is preferable.

In the case of taking the mass of the non-solvent component in the resin composition as the basis, the total amount of the compound in which n is 4 in the general formula (3) is preferably more than 0 ppm and 500 ppm or less, more preferably more than 0 ppm and 500 ppm or less. 400 ppm or less, more preferably more than 0 ppm and 300 ppm or less, still more preferably more than 0 ppm and 10 ppm or less. On the basis of the mass of the non-solvent component in the resin composition, the total amount of the compound in which n is 5 in the general formula (3) is preferably more than 0 ppm and 200 ppm or less, more preferably more than 0 ppm and 200 ppm or less. 100 ppm or less, more preferably more than 0 ppm and 50 ppm or less, still more preferably more than 0 ppm and 5 ppm or less. In the case of taking the mass of the non-solvent component in the resin composition as the basis, the total amount of the compound in which n is 6 in the general formula (3) is preferably more than 0 ppm and 450 ppm or less, more preferably more than 0 ppm and is 300 ppm or less, more preferably more than 0 ppm and 250 ppm or less, still more preferably more than 0 ppm and 230 ppm or less. In the case of taking the mass of the non-solvent component in the resin composition as the basis, the total amount of the compound in which n is 7 in the general formula (3) is preferably more than 0 ppm and 500 ppm or less, more preferably more than 0 ppm and 500 ppm or less. 400 ppm or less, more preferably more than 0 ppm and 300 ppm or less, still more preferably more than 0 ppm and 250 ppm or less. When the total amount of the compound represented by the general formula (3) is within the above range, the defects of the polyimide resin film obtained from the resin composition are reduced, the in-plane uniformity of Rth is good, and the YI value is further reduced , so it is better.

When based on the total mass of the silicon-containing compounds represented by the above general formulas (3) and (4), the total amount of the compounds in which n is 4 in the general formula (3) is preferably more than 0 ppm and is 1300 ppm Below, more preferably more than 0 ppm and 800 ppm or less, still more preferably more than 0 ppm and 500 ppm or less, still more preferably more than 0 ppm and 30 ppm or less. When based on the total mass of the silicon-containing compounds represented by the above general formulas (3) and (4), the total amount of the compounds in which n is 5 in the general formula (3) preferably exceeds 0 ppm and is 500 ppm Below, more preferably more than 0 ppm and 300 ppm or less, still more preferably more than 0 ppm and 100 ppm or less, still more preferably more than 0 ppm and 15 ppm or less. When based on the total mass of the silicon-containing compounds represented by the above general formulas (3) and (4), the total amount of the compounds in which n is 6 in the general formula (3) is preferably more than 0 ppm and is 2000 ppm Below, more preferably more than 0 ppm and 1000 ppm or less, still more preferably more than 0 ppm and 500 ppm or less, still more preferably more than 0 ppm and 20 ppm or less. When based on the total mass of the silicon-containing compounds represented by the above general formulas (3) and (4), the total amount of the compounds in which n is 7 in the general formula (3) preferably exceeds 0 ppm and is 2200 ppm Below, more preferably more than 0 ppm and 1100 ppm or less, still more preferably more than 0 ppm and 600 ppm or less, still more preferably more than 0 ppm and 10 ppm or less. When the total amount of the compound represented by the general formula (3) is within the above range, the defects of the polyimide resin film obtained from the resin composition are reduced, the in-plane uniformity of Rth is good, and the YI value is further reduced , so it is better.

In the case of taking the mass of the resin composition as the basis, the total amount of the compounds in the general formula (3) in which n is 3 or more and 8 or less is preferably more than 0 ppm and 150 ppm or less, more preferably more than 0 ppm and 130 ppm or less, more preferably more than 0 ppm and 100 ppm or less. When taking the mass of the non-solvent component in the resin composition as a reference, the total amount of the compounds in the general formula (3) where n is 3 or more and 8 or less is preferably more than 0 ppm and 900 ppm or less, more preferably more than 0 ppm. ppm and 800 ppm or less, more preferably more than 0 ppm and 700 ppm or less. When based on the total mass of the silicon-containing compounds represented by the above general formulas (3) and (4), the total amount of the compounds in which n is 3 or more and 8 or less in the general formula (3) is preferably more than 0 ppm and It is 4500 ppm or less, more preferably more than 0 ppm and 4000 ppm or less, and still more preferably more than 0 ppm and 3000 ppm or less. When the total amount of the compound represented by the general formula (3) is within the above range, the defects of the polyimide resin film obtained from the resin composition are reduced, the in-plane uniformity of Rth is good, and the YI value is further reduced , so it is better.

Conventionally, in order to achieve the purpose of reducing outgassing from the obtained polyimide resin film, etc., in the cyclosiloxane of the general formula (3), in particular, the amount of the compound in which n is 4 or less (Patent Documents 3 to 5, etc.) ). However, in the case of the method for reducing the cyclosiloxane of the prior art, it was found that the reduction in the amount of the compound in which n is 7 or less in the cyclosiloxane of the general formula (3) was insufficient. In addition, it was found that the in-plane uniformity of Rth of the obtained polyimide resin film can be further improved when the compound in which n is 5 or more and 7 or less in the compound of the general formula (3) is in a specific amount. The detailed mechanism of these is not clear, but the inventors etc. presume as follows. The manufacturing method of the polyimide resin film typically includes: coating the composition comprising the polyimide precursor composition/polyimide resin on a support such as a glass substrate, and in an oven, for example, in a reduced The step of removing the solvent by heating at 100°C for 30 minutes under pressure (solvent removal step); and, heating at a higher temperature such as 400°C for 1 hour, thereby carrying out imidization (or removing the solvent), The step of forming a polyimide resin film. In the case where n of the compound of the general formula (3) (methyl side chain cyclosiloxane) is 3 or more and 8 or less, the boiling point under normal pressure does not reach 400°C, and in the above-mentioned imidization step (for example, at 400°C) During heating at °C for 1 hour), the compound was volatilized and removed. On the other hand, when the temperature of the solvent removal step is lower than the imidization step, and when n of the compound of the general formula (3) is 3 or more and 8 or less, the compound is volatilized and removed in the solvent removal step. However, in the compound of general formula (3), especially when the amount of the compound whose n is 3 or more and 8 or less is large, it is presumed that traces of volatilization remain, resulting in deterioration of Rth of the polyimide resin film. In addition, in the case of distillation above 250°C as the previous purification method, the temperature is relatively high, so the silicon-containing compound decomposed during cooling is cyclized again. In the compound of the general formula (3), n is 4 and 5 in the compound. volume increase. As a result, it is estimated that the defects on the polyimide resin film increased. In view of these problems, the inventors found that, by performing purification treatment (reduced pressure distillation) on the compound comprising the general formula (3) and (4) under specific conditions, in particular, n of the general formula (3) is 4 and The amount of the compound of 5 is adjusted to a specific amount, or the total amount of the compound of the general formula (3) whose n is 3 or more and 8 or less is adjusted to a specific amount, so that the in-plane uniformity of Rth of the polyimide resin film can be improved. .

Furthermore, as a method for adjusting the amount of the compounds in which n of the general formula (3) is 4 and 5 to a specific amount, or the total amount of the compounds in which n in the general formula (3) is 3 or more and 8 or less is adjusted to a specific amount. , in addition to the purification treatment (decompression distillation) under the above-mentioned specific conditions, the step of partial imidization of the polyimide precursor can also be used in the synthesis of the resin composition of the present invention. As a specific example of the partial imidization step, in the synthesis of the resin of the present invention, a step of heating a solution containing a polyimide precursor to 160° C. or higher (thermal imidization). This step can also be used to adjust the amount of the compounds in which n of the general formula (3) is 4 and 5 to a specific amount.

Among the compounds in which n is 3 or more and 8 or less in the general formula (3), it is also preferable to reduce the amount of the compound in which n is 3 or more and 7 or less, and the amount of the compound in which n is 3 or 4. That is, based on the mass of the non-solvent component of the resin composition, the total amount of compounds in which n is 3 in the general formula (3) is d3 (ppm), and the total amount of compounds where n is 4 is d4 (ppm) ), when the total amount of compounds where n is 5 is d5 (ppm), the total amount of compounds where n is 6 is d6 (ppm), and the total amount of compounds where n is 7 is d7 (ppm), d3+d4+d5+d6+d7 It is preferably more than 0 ppm and less than 2000 ppm. Furthermore, d3+d4 is preferably more than 0 ppm and 10 ppm or less. In general formula (3), it is preferable from the viewpoint of defect evaluation of the obtained polyimide film that the amount of the compound in which n is 3 or more and 7 or less exceeds 0 ppm and is less than 2000 ppm. In addition, if the amount of the compounds in which n is 3 and 4 in the general formula (3) exceeds 0 ppm and is less than 10 ppm, based on the use of the purified polyimide precursor of the silicon-containing compound, the use of the unpurified It is preferable from the viewpoint of in-plane uniformity of Rth of the polyimide film obtained from the polyimide precursor of the silicon compound.

<Solvent> The resin composition typically contains a solvent. As the solvent, preferably the polyimide precursor and the polyimide have good solubility and can appropriately control the solution viscosity of the resin composition. 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), a compound represented by the general formula (4), and the like are preferred. Specific examples of the solvent composition include N-methyl-2-pyrrolidone (NMP) alone, or a combination of N-methyl-2-pyrrolidone (NMP) and γ-butyrolactone (GBL). mixed solvent, etc. The mass ratio of NMP and GBL can be, for example, NMP:GBL (mass ratio)=10:90˜90:10.

<Additional components> The resin composition of the present embodiment may further contain additional components in addition to the polyimide precursor, polyimide, cyclosiloxane, and solvent. As an additional component, a surfactant, an alkoxysilane compound, etc. are mentioned, for example.

Surfactant By adding a surfactant to the resin composition of the present embodiment, the coatability of the resin composition can be improved. Specifically, the generation of streaks on the coating film can be prevented. As such a surfactant, a silicone type surfactant, a fluorine type surfactant, a nonionic surfactant other than these, etc. are mentioned, for example. 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 Dow Corning Toray Silicone); SILWET L-77, L-7001, FZ-2105, FZ-2120, FZ-2154, FZ-2164, FZ-2166, L-7604 (trade name, manufactured by Nippon Unicar); DBE-814, DBE-224, DBE-621, CMS-626, CMS -222, KF-352A, KF-354L, KF-355A, KF-6020, DBE-821, DBE-712(Gelest), BYK-307, BYK-310, BYK-378, BYK-333 (trade name, BYK -Chemie Japan); Glaanol (trade name, manufactured by Kyeisha Chemical Co., Ltd.), and the like. Examples of fluorine-based surfactants include: Megafac F171, F173, R-08 (manufactured by Dainippon Ink Chemical Co., Ltd., trade name); Fluorad FC4430, FC4432 (Sumitomo 3M Co., Ltd., trade name) Wait. As a nonionic surfactant other than these, a polyoxyethylene lauryl ether, a polyoxyethylene stearyl ether, a polyoxyethylene oleyl ether, a polyoxyethylene octyl phenol ether, etc. are mentioned, for example.

Among these surfactants, silicone-based surfactants and fluorine-based surfactants are preferred from the viewpoint of the coatability (coating streak suppression) of the resin composition, which reduces the amount of oxygen in the curing step. From the viewpoint of the influence of the concentration on the YI value and the total light transmittance, a silicone-based surfactant is preferred. When a surfactant is used, its compounding amount is preferably 0.001-5 parts by mass, more preferably 0.01-3 parts by mass, relative to 100 parts by mass of the polyimide precursor in the resin composition.

Alkoxysilane compounds When the polyimide film obtained from the resin composition of the present embodiment is used for a flexible substrate or the like, from the viewpoint of obtaining good adhesion between the support and the polyimide film in the manufacturing process , the resin composition may contain 0.01 to 20 parts by mass of the alkoxysilane compound relative to 100 parts by mass of the polyimide precursor. When the content of the alkoxysilane compound with respect to 100 parts by mass of the polyimide precursor is 0.01 part by mass or more, good adhesion between the support and the polyimide film can be obtained. Moreover, from the viewpoint of the storage stability of the resin composition, the content of the alkoxysilane compound is preferably 20 parts by mass or less. 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 still more preferably 0.1 to 8 parts by mass with respect to 100 parts by mass of the polyimide precursor. By using the alkoxysilane compound, in addition to the above-mentioned improvement of the adhesion, the coatability of the resin composition is also improved (stripe unevenness is suppressed), and the effect of the oxygen concentration during curing on the YI value of the polyimide film is also improved. can be reduced.

Examples of the alkoxysilane compound include 3-ureidopropyltriethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, 3-glycidoxysilane γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltripropoxysilane, γ-aminopropyltributoxysilane, γ-aminoethyltrimethoxysilane Ethoxysilane, gamma-aminoethyltripropoxysilane, gamma-aminoethyltributoxysilane, gamma-aminobutyltriethoxysilane, gamma-aminobutyltrimethoxysilane Silane, gamma-aminobutyltripropoxysilane, gamma-aminobutyltributoxysilane, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, dimethoxysilane Phenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and alkoxy groups represented by the following structures, respectively Silane compounds, etc. An alkoxysilane compound may be used individually by 1 type, and may be used in combination of 2 or more types.

[Chemical 40]

<<Manufacturing method of resin composition>> The manufacturing method of the resin composition of this embodiment is not specifically limited, For example, the following method can be used.

<Purification of Silicon-Containing Compound> The polyimide precursor contained in the resin composition of the present 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 reduce the amount of the compound of the general formula (3). Method for total amount of compound. Alternatively, the resin composition can also be purified after the polycondensation reaction to reduce the total amount of the compound of the general formula (3).

As a method of purifying the silicon-containing compound, for example, a method of blowing an inert gas such as nitrogen gas into the silicon-containing compound in an arbitrary container, and performing stripping can be exemplified. The stripping temperature is preferably 150°C or higher and 300°C or lower, more preferably 200°C or higher and 300°C or lower, and still more preferably 230°C or higher and 300°C or lower. The vapor pressure of stripping is preferably as low as possible, 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, and more preferably 6 hours or more and 10 hours or less. By adjusting to the above-mentioned conditions, the compound of the general formula (3) can be efficiently removed, and the total amount of the general formulae (3) and (4) can be controlled within a preferable range.

<Polyimide Precursor and Synthesis of Polyimide> The partially imidized polyimide precursor can be obtained by containing the silicon-containing compound represented by the general formula (4) and the compound represented by the general formula (3). The raw material composition of the compound shown is subjected to a polycondensation reaction with tetracarboxylic dianhydride and diamine, imidized to obtain a polyimide, and further synthesized by polycondensation reaction with tetracarboxylic dianhydride and diamine. Alternatively, the partially imidized polyimide can be prepared by mixing a raw material composition containing the silicon-containing compound represented by the general formula (4) and the compound represented by the general formula (3) with tetracarboxylic dianhydride and dicarboxylic acid After the polyimide precursor is obtained by polycondensation reaction of amine, the polyimide precursor is partially imidized and synthesized. The silicon-containing compound is preferably the purified one described above. In a preferred form, the polycondensation component includes acid dianhydride, diamine, and a silicon-containing compound. The polycondensation reaction is preferably carried out in a suitable solvent. Specifically, for example, after dissolving a predetermined amount of a diamine component and a silicon-containing compound in a solvent, a predetermined amount of an acid dianhydride is added to the obtained diamine solution, and a method of stirring is exemplified.

From the viewpoint of the high molecular weight of the obtained polyimide precursor and polyimide resin, and the slot coating characteristics of the resin composition, the acid dianhydride and diamine in the synthesis of the polyimide precursor The molar ratio is preferably in the range of acid dianhydride:diamine=100:90～100:110 (with respect to 1 mol part of acid dianhydride, diamine is 0.90～1.10 mol part), and more preferably Within the range of 100:95 to 100:105 (0.95 to 1.05 mol of diamine relative to 1 mol of acid dianhydride).

The molecular weight of the polyimide precursor and polyimide can be adjusted by the type of acid dianhydride, diamine and silicon-containing compound, the molar ratio of acid dianhydride and diamine, the addition of end-capping agent, and the reaction conditions. controlled by adjustment, etc. The closer the molar ratio of the acid dianhydride component and 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 and the polyimide can be achieved.

High-purity products are recommended for acid dianhydride components and diamine components. The purity is preferably 98% by mass or more, more preferably 99% by mass or more, and still more preferably 99.5% by mass or more. High purification can also be achieved by reducing the water content in the acid dianhydride component and the diamine component. In the case of using a plurality of acid dianhydride components and/or a plurality of diamine components, it is preferable that the whole acid dianhydride component and the whole diamine component have the above-mentioned purity, and it is more preferable that all kinds of acid dianhydrides are used. The components and the diamine component have the above-mentioned purity, respectively.

{式中，R ₁₂＝甲基所表示之Equamide M100(商品名：出光興產公司製造)，及R ₁₂＝正丁基所表示之Equamide B100(商品名：出光興產公司製造)}；γ-丁內酯、γ-戊內酯等內酯系溶劑；六甲基磷醯胺、六甲基膦三醯胺等含磷系醯胺系溶劑；二甲基碸、二甲基亞碸、環丁碸等含硫系溶劑；環己酮、甲基環己酮等酮系溶劑；甲基吡啶、吡啶等三級胺系溶劑；乙酸(2-甲氧基-1-甲基乙基)酯、乙酸3-甲氧基-3-甲基-1-丁酯、二乙二醇單丁醚乙酸酯等酯系溶劑等。作為酚系溶劑，例如，可例舉苯酚、鄰甲酚、間甲酚、對甲酚、2,3-二甲苯酚、2,4-二甲苯酚、2,5-二甲苯酚、2,6-二甲苯酚、3,4-二甲苯酚、3,5-二甲苯酚等。作為醚及二醇系溶劑，例如，可例舉1,2-二甲氧基乙烷、雙(2-甲氧基乙基)醚、1,2-雙(2-甲氧基乙氧基)乙烷、雙[2-(2-甲氧基乙氧基)乙基]醚、四氫呋喃、1,4-二㗁烷、二丙二醇甲醚乙酸酯、二丙二醇二甲醚、丙二醇單甲醚、丙二醇單甲醚乙酸酯等。該等溶劑可單獨使用，亦可兩種以上混合使用。 The solvent for the reaction is not particularly limited, and may dissolve the acid dianhydride component and the diamine component, as well as the polyimide precursor and polyimide produced, and may obtain a high-molecular-weight polymer. As such a solvent, an aprotic solvent, a phenol type solvent, an ether, a glycol type solvent, etc. are mentioned, for example. As the aprotic solvent, for example, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N-methylcaprolactamide, 1,3-dimethylimidazolidinone, tetramethylurea, N,N-dimethylisobutylamide, dimethylacetamide, 1 , 3-dimethyl-2-imidazolidinone, and an amide-based solvent of the following general formula (7):

{wherein, R ₁₂ = Equamide M100 represented by methyl group (trade name: manufactured by Idemitsu Kosan Co., Ltd.), and R ₁₂ = Equamide B100 represented by n-butyl group (trade name: manufactured by Idemitsu Kosan Co., Ltd.)}; γ -Lactone-based solvents such as butyrolactone and γ-valerolactone; phosphorus-containing amide-based solvents such as hexamethylphosphine, hexamethylphosphine triamide, etc.; Sulfur-containing solvents such as cyclobutane; ketone solvents such as cyclohexanone and methylcyclohexanone; tertiary amine solvents such as picoline and pyridine; acetic acid (2-methoxy-1-methylethyl) esters, 3-methoxy-3-methyl-1-butyl acetate, ester-based solvents such as diethylene glycol monobutyl ether acetate, and the like. Examples of the phenol-based solvent include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,5-xylenol, 6-xylenol, 3,4-xylenol, 3,5-xylenol, etc. Examples of ether and glycol-based 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, dipropylene glycol methyl ether acetate, dipropylene glycol dimethyl ether, propylene glycol monomethyl ether ether, propylene glycol monomethyl ether acetate, etc. These solvents may be used alone or in combination of two or more.

The boiling point of the polyimide precursor and the solvent used in the synthesis of the polyimide under normal pressure is preferably 60-300°C, more preferably 140-280°C, and still more preferably 170-270°C. Since the boiling point of the solvent is lower than 300°C, the drying step is shorter. If the boiling point of the solvent is 60°C or higher, the surface roughness of the resin film and the incorporation of air bubbles in the resin film are less likely to occur during the drying step, and a more uniform film can be obtained. From the viewpoint of solubility and reduction of edge abnormality during coating, it is particularly preferable to use a solvent having a boiling point of 170 to 270°C and/or a vapor pressure of 250 Pa or less at 20°C. More specifically, it is preferably 1 selected from the group consisting of N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), and a compound represented by the general formula (7). more than one species.

In order for the polycondensation reaction to proceed favorably, the water content in the solvent is preferably, for example, 3,000 mass ppm or less. In the resin composition of the present embodiment, the content of molecules having a molecular weight of less than 1,000 is preferably less than 5% by mass. The reason for the presence of molecules with a molecular weight of less than 1,000 in the resin composition is related to the water content of the solvent or raw material (acid dianhydride, diamine) used in the synthesis. That is, the reason is that the acid anhydride group of a part of acid dianhydride monomers is hydrolyzed into a carboxyl group by moisture, and the molecular weight is not high, but remains in a low molecular weight state. Therefore, the water content of the solvent used in the above-mentioned polycondensation reaction is preferably as small as possible. 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 water content contained in the raw material is preferably 3,000 mass ppm or less, and more preferably 1,000 mass ppm or less.

The moisture content of the solvent is related to the grade of the solvent used (dehydration grade, general-purpose grade, etc.), the solvent container (bottle, 18 L can, cylinder, etc.), the storage state of the solvent (whether the rare gas is loaded, etc.), from opening to use time (use immediately after opening, or use after a period of time after opening, etc.). The moisture content of the solvent is also related to the replacement of the rare gas in the reactor before the synthesis, and the presence or absence of the rare gas circulation during the synthesis process. Therefore, when synthesizing polyimide precursors, it is recommended to use high-purity products as raw materials, use solvents with less water content, and take measures to prevent water from the environment from mixing into the system before and during the reaction.

When dissolving each polycondensation component in a solvent, it may heat as needed. From the viewpoint of obtaining a polyimide precursor with a high degree of polymerization, the reaction temperature during the synthesis of the polyimide precursor is preferably 0°C to 120°C, 40°C to 100°C, or 60°C The polymerization time at -100°C is preferably 1 hour to 100 hours, or 2 hours to 10 hours. By setting the polymerization time to 1 hour or more, the degree of polymerization of the polyimide precursor is uniform, and by setting the polymerization time to 100 hours or less, a polyimide precursor with a high degree of polymerization can be obtained.

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

The polyimide precursor of this embodiment can be partially imidized (partially imidized). By partially imidizing the polyimide precursor, the viscosity stability during storage of the resin composition can be improved. From the viewpoint of maintaining a balance between the solubility of the polyimide precursor in the resin composition and the storage stability of the solution, the imidization rate in this case is preferably 5% or more, more preferably 8% Above, preferably 80% or less, more preferably 70% or less, still more preferably 50% or less. This partial imidization is obtained by heating and dehydrating a polyimide precursor. The heating can be performed at a temperature of preferably 120°C to 200°C, more preferably 150°C to 180°C, preferably for 15 minutes to 20 hours, more preferably 30 minutes to 10 hours.

N,N-dimethylformamide dimethyl acetal or N,N-dimethylformamide diethyl acetal can be added to the polyamide acid obtained by the above reaction and heated, A part or all of the carboxylic acid esterified in this way is used as the polyimide precursor of the present embodiment. By esterification, the viscosity stability during storage can be improved. These ester-modified polyamic acids can also be obtained by the following methods, even if the above-mentioned acid dianhydride component is 1 equivalent of monohydric alcohol with respect to the acid anhydride group, thionine chloride, dicyclohexylcarbodiimide After the dehydration condensing agent reacts in sequence, a condensation reaction occurs with the diamine component.

<Synthesis of polyimide> As a more preferable form, the polyimide varnish can be prepared by dissolving the acid dianhydride component and the diamine component in a solvent such as an organic solvent and adding an azeotropic solvent such as toluene. The water generated during amination is removed to the outside of the system to prepare a polyimide solution (also called polyimide varnish) containing polyimide and a solvent. The conditions during the reaction are not particularly limited. For example, the reaction temperature is 0°C to 180°C, and the reaction time is 3 hours to 72 hours. In order to sufficiently advance the reaction with the molybdenum group-containing diamines, the reaction is preferably heated at 180° C. for about 12 hours. In addition, during the reaction, an inert gas atmosphere such as argon or nitrogen is preferable.

<Adjustment of the resin composition> When the solvent used for synthesizing the polyimide precursor or polyimide is the same as the solvent contained in the resin composition, the synthesized polyimide precursor solution can be directly used Or a polyimide solution is used as the resin composition of this embodiment. It is also possible to add one or more other solvents and additional components to the polyimide precursor or polyimide solution within the temperature range of room temperature (25°C) to 80°C as required, and stir and mix. This adjusts the resin composition. The stirring and mixing can be carried out using appropriate devices such as a Sany motor (manufactured by Shinto Chemical Co., Ltd.) equipped with stirring blades, an autorotation revolution mixer, and the like. The resin composition may be heated to 40°C to 100°C as needed.

On the other hand, when the solvent used in synthesizing the polyimide precursor or polyimide is different from the solvent contained in the resin composition, it can be removed by appropriate methods such as reprecipitation and solvent distillation. The synthesized polyimide precursor solution or the solvent in the polyimide solution is removed, and the polyimide precursor or polyimide is isolated. Next, in the temperature range of room temperature (25°C) to 80°C, the required solvent and additional components used as needed can be added to the polyimide precursor or polyimide obtained by isolation, and Stirring and mixing are performed, thereby preparing a resin composition.

In the case of a resin composition comprising a polyimide precursor, after preparing the resin composition as described above, the resin composition may be heated, for example, at 130° C. to 200° C. for, for example, 5 minutes to 2 hours, thereby causing a portion of the resin composition to be heated. The polyimide precursor is dehydrated imidized (partial imidized) to such an extent that the polymer does not precipitate. By controlling the heating temperature and heating time, the imidization rate can be controlled. By partially imidizing the polyimide precursor, the viscosity stability during storage of the resin composition can be improved.

From the viewpoint of slot coating 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 still more preferably 3,000 to 20,000 mPa·s. Specifically, it is preferably 500 mPa·s or more, more preferably 1,000 mPa·s or more, and still more preferably 3,000 mPa·s or more, from the viewpoint of less leakage from the slit nozzle. From the viewpoint that the slit nozzle is not easily clogged, it is preferably 100,000 mPa·s or less, more preferably 50,000 mPa·s or less, and still more preferably 20,000 mPa·s or less.

From the viewpoint of easy stirring during synthesis, the solution viscosity of the polyimide precursor or the resin composition during the synthesis of polyimide is preferably 200,000 mPa·s or less. Among them, although the solution has a high viscosity during synthesis, by adding a solvent and stirring after the completion of the reaction, a resin composition with a good viscosity for handling can be obtained. The solution viscosity of the resin composition of the present embodiment is a value measured at 23° C. using an E-type viscometer (eg, VISCONICE HD, manufactured by Toki Sangyo).

From the viewpoint of viscosity stability when the resin composition is stored, 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 still more preferably 2,000 mass ppm or less, More preferably, it is 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, and particularly preferably 100 mass ppm or less.

<<Polyimide film and method for producing the same>> The method for producing the polyimide film of the present embodiment will be described below. Examples of the first production method include a coating step including coating (casting) a solution of a polyimide precursor on a support, and drying and imide by heating the coated solution. The manufacturing method of the polyimide film of the film-forming step of forming the polyimide resin film (referred to as the manufacturing method 1). The production method 1 may include any peeling step of peeling off the polyimide resin film from the support to obtain the polyimide film. As the second production method, a coating step including coating (casting) a polyimide solution (polyimide varnish) on a support, and heating and drying the coated solution can be exemplified. The manufacturing method of the polyimide film of the film forming step of forming the polyimide resin film (as manufacturing method 2-1). The production method 1 may include any peeling step of peeling off the polyimide resin film from the support to obtain the polyimide film. In addition, since the second production method forms a film from a previously imidized polyimide solution, it is also possible to produce a polyimide film ( as production method 2-2).

<Coating step> In the coating step, the resin composition of this embodiment is coated on the surface of the support. The support is not particularly limited as long as it has heat resistance to the heating temperature in the subsequent film forming step (heating step), and good peelability in the peeling step. As a support, for example, a glass substrate such as an alkali-free glass substrate; a silicon wafer; PET (polyethylene terephthalate, polyethylene terephthalate), OPP (oriented polypropylene, extended polypropylene), polypara Ethylene phthalate, polyethylene naphthalate, polycarbonate, polyimide, polyimide, polyetherimide, polyetheretherketone, polyetheroxane, polyphenylene Resin substrates such as dust and polyphenylene sulfide; metal substrates such as stainless steel, alumina, copper, nickel, etc.

In the case of forming a thin-film polyimide molded body, for example, a glass substrate, a silicon wafer, etc. are preferable, and in the case of forming a thick-film-shaped polyimide molded body or a sheet-like polyimide molded body, it is more preferable. Preferred are, for example, a support including PET (polyethylene terephthalate), OPP (extended polypropylene), and the like.

As a coating method, generally, a knife coater, an air knife coater, a roll coater, a spin coater, a flow coater, a die coater, and a bar coater may be mentioned. and other coating methods; coating methods such as spin coating, spray coating, dip coating, etc.; printing technologies represented by screen printing and gravure printing, etc. In the resin composition of this embodiment, coating by slit coating is preferable. The coating thickness should be appropriately adjusted according to the required thickness of the resin film and the content of the polyimide precursor in the resin composition, preferably about 1 μm to 1,000 μm. The temperature in the coating step may be room temperature, and in order to reduce the viscosity and improve the workability, the resin composition may be heated to, for example, 40°C to 80°C.

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

<Film forming step> Next, a film forming step (heating step) is performed. In the case of the polyimide precursor solution, the heating step is to remove the organic solvent contained in the above-mentioned coating film, and carry out the imidization reaction of the polyimide precursor in the coating film to obtain the polyimide Steps of resin film. Moreover, in the case of a polyimide solution, the heating step is a step of removing the organic solvent contained in the above-mentioned coating film to obtain a polyimide resin film. This heating step can be performed using, for example, an inert gas oven, a hot plate, a box drier, a conveyor belt drier, or the like. This step and the drying step may be performed simultaneously, or the two steps may be performed sequentially.

The heating step can be carried out in an air atmosphere, and is preferably inert from the viewpoints of safety, good transparency, lower thickness direction Rth and lower YI value of the obtained polyimide film. carried out under a gas atmosphere. As an inert gas, nitrogen gas, an argon gas, etc. are mentioned, for example. In the case of the polyimide precursor solution, the heating temperature can be appropriately set according to the type of the polyimide precursor and the type of the solvent in the resin composition, preferably 250°C to 550°C, more preferably 300°C ℃～450℃. When the heating temperature is 250°C or higher, imidization proceeds well, and when the heating temperature is 550°C or lower, the resulting polyimide film can be prevented from deteriorating transparency and heat resistance. In the case of a polyimide solution, the heating temperature can be appropriately set according to the type of polyimide and the type of solvent in the resin composition, and is preferably 50°C to 450°C. The heating time is preferably about 6 minutes to 10 hours.

In the present embodiment, in the case of the polyimide precursor solution, the oxygen concentration in the surrounding atmosphere of the heating step is preferably 2,000 mass from the viewpoint of the transparency and YI value of the obtained polyimide film ppm or less, more preferably 100 mass ppm or less, still more preferably 10 mass ppm or less. By heating in an atmosphere with an oxygen concentration of 2,000 mass ppm or less, the YI value of the obtained polyimide film can be made 30 or less.

<Peeling step> In the peeling step, the polyimide resin film on the support can be cooled to, for example, room temperature (25°C) to about 50°C, and then peeled off. As this peeling step, the following forms (1)-(4) are mentioned, for example.

(1) After the structure comprising the polyimide resin film/support is fabricated by the above method, a laser is irradiated from the support side of the structure to ablate the interface between the support and the polyimide resin film, The method of peeling off the polyimide resin thereby. As the kind of laser, a solid (YAG (Yttrium Aluminum Garnet, yttrium aluminum garnet)) laser, a gas (UV (ultraviolet, ultraviolet) excimer) laser, etc. are mentioned. It is preferable to use a spectrum having a wavelength of 308 nm or the like (refer to Japanese Patent Application Laid-Open No. 2007-512568, Japanese Patent Application Laid-Open No. 2012-511173, etc.). (2) Before applying the resin composition to the support, a release layer is formed on the support, and then a structure comprising a polyimide resin film/release layer/support is obtained, thereby releasing the polyimide resin film method. Examples of the release layer include Parylene (registered trademark, manufactured by Nippon Parylene Contract Co., Ltd.) and tungsten oxide, and release agents such as vegetable oil-based, silicone-based, fluorine-based, and alkyd-based mold release agents can be used (see Japanese Patent Laid-Open No. 2010-067957 ). No., Japanese Patent Laid-Open No. 2013-179306, etc.). This method (2) can be used in combination with the laser irradiation of the method (1).

(3) A method of obtaining a polyimide resin film by etching the metal with an etchant after obtaining a structure comprising a polyimide resin film/support using an etchable metal substrate as a support. As the metal, for example, copper (specifically, for example, electrolytic copper foil "DFF" manufactured by Mitsui Metal Mining Co., Ltd.), aluminum, and 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 the structure comprising the polyimide resin film/support by the above method, the adhesive film is attached to the surface of the polyimide resin film, and the adhesive film/polyimide resin film is separated from the support, A method of separating the polyimide resin film from the adhesive film thereafter.

Among these peeling methods, the method (1) or (2) is preferable from the viewpoints of the difference in refractive index, YI value, and elongation between the front and back surfaces of the obtained polyimide resin film. From the viewpoint of the difference in refractive index between the front and back surfaces of the obtained polyimide resin film, the method (1) is more preferably an irradiation step of irradiating a laser from the support side before the peeling step. Furthermore, in the method (3), when copper is used as a support, the YI value of the polyimide resin film tends to increase and the elongation tends to decrease. The reason is due to the influence of copper ions.

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

<Yellowness (YI value)> From the viewpoint of obtaining good optical properties, the YI value of the polyimide film obtained from the resin composition of the present embodiment with a film thickness of 10 μm is preferably 20 or less, more preferably 18 or less, more preferably 16 or less, particularly preferably 14 or less, particularly preferably 13 or less, particularly preferably 10 or less, and particularly preferably 7 or less. The YI value varies according to the monomer skeleton of the polyimide precursor. If the monomer skeleton is the same, the larger the weight-average molecular weight of the polyimide precursor, the smaller the YI value tends to be.

The YI value is influenced by, for example, the amine value of the silicon-containing compound used. If the amine value is higher, the YI value tends to be larger, and if the amine value is smaller, the YI value also tends to decrease. However, as for the use of the purified silicon-containing compound, that is, the polyimide precursor whose total amount of the compounds represented by the general formula (3) is within the above range, the difference between the use of the unpurified silicon-containing compound having the same amine value is Compared with the polyimide precursor, the YI value of the obtained polyimide resin film tends to be lower. The mechanism thereof is not clear, but the inventors etc. presume as follows. That is, in the case of the previous purification method, the acyclic low-molecular-weight diamine used for the production of the polyimide precursor remains, and when the polyimide is hardened, it decomposes to generate free radicals, resulting in an increase in the YI value. cause of large (variation). By reducing the amount of the cyclosiloxane represented by the general formula (3), not only the cyclosiloxane represented by the general formula (3) is removed during purification, but the diamine component having an increased amine value is more easily Volatile low molecular weight diamines are also removed. Therefore, according to this embodiment, it is estimated that the YI value of the polyimide resin film of the polyimide precursor of which the total amount of the compound represented by the general formula (3) is reduced is further improved. In the case of the previous purification method, it is difficult to reduce the acyclic low-molecular-weight diamine, so even if purification is performed, the degree of improvement of the YI value of the polyimide resin film is lower than that of the present embodiment.

<<Application of Polyimide Film>> The polyimide film obtained by curing the resin composition of this embodiment can be applied to, for example, a semiconductor insulating film, a thin film transistor liquid crystal display (TFT-LCD) insulating film, and an electrode protection film, It can also be used as a transparent substrate for display devices such as liquid crystal displays, organic electroluminescence displays, field emission displays, and electronic paper. In particular, the polyimide film obtained by curing the resin composition of this embodiment can be used in the manufacture of flexible devices, and is suitable for flexible substrates, flexible displays, thin film transistor (TFT) substrates, and color filters. Optical film substrate, touch panel substrate, transparent conductive film (ITO, Indium Thin Oxide) substrate, etc. Examples of flexible devices to which the polyimide film of the present embodiment can be applied include: TFT devices for flexible displays, flexible solar cells, flexible touch panels, flexible lighting, flexible Flexible batteries, flexible printed substrates, flexible color filters, surface housing lenses for smart phones, etc.

The step of forming a TFT on a flexible substrate using a polyimide film is typically performed in a wide temperature range of 150°C to 650°C. Specifically, in the case of fabricating TFT devices using amorphous silicon, a process temperature of 250° C. to 350° C. is generally required. The polyimide film of this embodiment needs to be able to withstand this temperature. The polymer structure with the glass transition temperature above the process temperature and the onset temperature of thermal decomposition is appropriately selected.

In the case of fabricating TFT devices using metal oxide semiconductors (IGZO (indium gallium zinc oxide, indium gallium zinc oxide), etc.), a process temperature of 320°C to 400°C is generally required, and the polyimide film of this embodiment requires To be able to withstand this temperature, it is necessary to properly select a polymer structure having a glass transition temperature above the maximum temperature of the TFT fabrication process and a thermal decomposition initiation temperature.

In the case of fabricating TFT devices using low temperature polysilicon (LTPS), a process temperature of 380°C to 520°C is generally required. The polyimide film of this embodiment needs to be able to withstand this temperature. Therefore, it is necessary to appropriately select a TFT fabrication process. The glass transition temperature above the maximum temperature of the process and the polymer structure of the onset temperature of thermal decomposition. On the other hand, due to these thermal histories, the optical properties of polyimide films (especially light transmittance, Rth and YI values) decrease with exposure to high temperature processes. However, the polyimide obtained from the polyimide precursor of this embodiment has good optical properties despite the thermal history.

Hereinafter, the manufacturing method of the display and the laminated body which are application examples of the polyimide film of this embodiment is demonstrated.

<Manufacturing method of display> The manufacturing method of the display of the present embodiment includes a coating step of coating the resin composition of the present embodiment on the surface of the support, heating the resin composition to form a polyimide resin film The film forming step, the element forming step of forming the element on the polyimide resin film, and the peeling step of peeling the polyimide resin film with the element formed thereon from the support. The display may be a flexible display.

Manufacturing example of flexible organic EL display FIG. 1 is a schematic view showing a structure of an upper part of 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 part 25 of FIG. 1 is demonstrated. For example, the organic EL element 250a that emits red light, the organic EL element 250b that emits green light, and the organic EL element 250c that emits blue light are arranged in a matrix as a unit, and are delimited by partition walls (barriers) 251. The light-emitting region of each organic EL element. Each organic EL element includes 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 representing a CVD (Chemical Vapor Deposition) multilayer film (multi-barrier layer) comprising silicon nitride (SiN) or silicon oxide (SiO), a plurality of layers for driving organic EL are arranged The element TFT 256 (selected from low temperature polysilicon (LTPS) or metal oxide semiconductor (IGZO, etc.)), an interlayer insulating film 258 with contact holes 257 , and a lower electrode 259 are included. The organic EL elements are 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 steps of the flexible organic EL display include the steps of forming a polyimide film on the glass substrate support, manufacturing the above-mentioned organic EL substrate shown in FIG. The combined assembly step and the peeling step of peeling off the organic EL display fabricated on the polyimide film from the glass substrate support. A well-known manufacturing process can be applied to the organic EL substrate manufacturing process, the sealing substrate manufacturing process, and the assembling process. An example is given below, but it is not limited to this. The peeling step is the same as the peeling step of the above-mentioned polyimide film.

For example, referring to FIG. 1 , first, a polyimide film is formed on a glass substrate support by the above method, and a polyimide film containing silicon nitride (SiN) and silicon oxide (SiO) is formed on the upper part by a CVD method or a sputtering method. The multi-barrier layer of the multi-layer structure (the lower substrate 2a in FIG. 1 ) uses a photoresist or the like on the upper part to form a metal wiring layer for driving the TFT. An active buffer layer such as SiO is formed on the upper part by CVD method, and TFT devices such as metal oxide semiconductor (IGZO) or low temperature polysilicon (LTPS) are formed on the upper part (TFT256 in FIG. 1 ). After the TFT substrate for a flexible display is produced, an interlayer insulating film 258 having contact holes 257 is formed using a photosensitive acrylic resin or the like. An ITO film is formed by sputtering or the like, and the lower electrode 259 is formed so as to be paired with the TFT.

Next, after forming the partition wall (barrier wall) 251 with photosensitive polyimide or the like, in each space divided by the partition wall, the hole transport layer 253 and the light emitting layer 254 are formed. The upper electrode (cathode) 255 is formed so as to cover the light-emitting layer 254 and the partition (barrier) 251 . Thereafter, using a refined pure metal mask or the like as a mask, the organic EL material emitting red light (corresponding to the organic EL element 250a emitting red light in FIG. The EL material (corresponding to the organic EL element 250b emitting green light in FIG. 1) and the organic EL material emitting blue light (corresponding to the organic EL element 250c emitting blue light in FIG. EL substrate. The organic EL substrate is sealed with a sealing film or the like (sealing substrate 2b in FIG. 1 ), and the upper part of the polyimide substrate is peeled off from the glass substrate support by a known peeling method such as laser peeling. Top emission flexible organic EL display. When the polyimide of this embodiment is used, a see-through flexible organic EL display can be produced. The flexible organic EL display of bottom emission type can be produced by a known method.

Manufacturing example of flexible liquid crystal display A flexible liquid crystal display can be fabricated using the polyimide film of this embodiment. As a specific production method, the above method can be used to form a polyimide film on a glass substrate support, and the above method can be used to produce a TFT substrate including, for example, amorphous silicon, metal oxide semiconductor (IGZO, etc.), and low temperature polysilicon. In addition, according to the coating step and the film forming step of the present embodiment, a polyimide film is formed on the glass substrate support, and a color filter glass having a polyimide film is produced by using a color photoresist according to a known method. substrate (CF substrate). On one of the TFT substrate and the CF substrate, by screen printing, a sealing material including thermosetting epoxy resin, etc., is coated into a frame-like pattern lacking the portion of the liquid crystal injection port, and the other substrate is arranged with the liquid crystal. The thickness of the layer is equal to the diameter of spherical spacers comprising plastic or silicon dioxide.

Next, the TFT substrate and the CF substrate are bonded together, and the sealing material is cured. Then, the 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, thereby forming a liquid crystal layer. Finally, the glass substrate on the CF side and the glass substrate on the TFT side are peeled off at the interface between the polyimide film and the glass substrate by a laser lift-off method, whereby a flexible liquid crystal display can be produced.

<Manufacturing method of laminated body> The manufacturing method of the laminated body of the present embodiment includes a coating step of coating the resin composition of the present embodiment on the surface of the support, heating the resin composition to form a polyimide A film forming step of a resin film, and an element forming step of forming an element on the above-mentioned polyimide resin film.

As an element in a laminated body, what was exemplified in the manufacture of the above-mentioned flexible device can be mentioned. As a support, for example, a glass substrate can be used. The preferable specific steps of the coating step and the film forming step are the same as those described in the above-mentioned manufacturing method of the polyimide film. In the element forming step, the element is formed on the polyimide resin film as the flexible substrate formed on the support. Thereafter, the polyimide resin film and the element are peeled off from the support in any peeling step, whereby a flexible substrate can be obtained. [Example]

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

"Measurement and Evaluation Method" <Non-solvent component> The total mass of the monomers used in the polyimide precursor can be used as the mass of the non-solvent component contained in the resin composition. Alternatively, the mass of the non-solvent component can be obtained by subjecting the resin composition to gas chromatography (hereinafter also referred to as GC) analysis to obtain the mass of the solvent, and subtracting the mass of the solvent from the mass of the resin composition. As the conditions of GC, the following conditions can be mentioned. Apparatus: Gas chromatograph (manufactured by Agilent, gas chromatograph 6890N) Injection port temperature: 280℃ Injection volume: 1 μL Oven temperature: After holding at 50°C for 1 minute, the temperature was raised to 350°C at a temperature increase rate of 20°C/min, and held 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℃

<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. Using NMP (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatography, 24.8 mmol/L lithium bromide monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.5%) and 63.2 mmol/L phosphoric acid were added immediately before the measurement. (manufactured by Wako Pure Chemical Industries, Ltd., for high-performance liquid chromatography) and dissolved therein) as a solvent. A calibration curve for calculating the weight average molecular weight was prepared using standard polystyrene (manufactured by Tosoh Corporation). Column: Shodex KD-806M (manufactured by Showa Denko Co., Ltd.) Flow rate: 1.0 mL/min Column temperature: 40℃ Pump: PU-2080Plus (manufactured by JASCO) Detectors: RI-2031Plus (RI: Differential Refractometer, manufactured by JASCO) and UV-2075Plus (UV-VIS: UV-Vis Absorptometer, manufactured by JASCO)

<Functional group equivalent> The functional group equivalent is as described below, and is measured in accordance with existing standards and the like. The functional group equivalent of the amine group is measured according to JIS K 7237. The functional group equivalent of an epoxy group is measured according to JIS K 7236. The functional group equivalent of a hydroxyl group is measured according to JIS K 0070. For other functional groups, the molecular weight of the silicon-containing compound per mole of functional group was also determined by titration.

<Analysis of Cyclosiloxane Concentration> Analysis of Cyclosiloxane Concentration of General Formula (3) in Resin Composition Containing Polyimide Precursor and Silicon-Containing Compound (General Formula (3)) As shown below, quantification was performed by GC (gas chromatography analysis) (refer to the following analysis of cyclosiloxane concentration (based on silicon-containing compounds)).

<Analysis of cyclosiloxane concentration (based on composition, based on non-solvent components)> (1) Outline A calibration curve was drawn for quantifying the amount of cyclosiloxane. The calibration curve was drawn according to the following method using a sample (manufactured by Tokyo Chemical Industry Co., Ltd.) of a cyclosiloxane having n=4 of the general formula (3) (hereinafter also referred to as D4 form). The amount of cyclosiloxane contained in the resin composition was determined by heating the resin composition at 150° C. for 30 minutes in a pyrolyzer, and analyzing the generated volatile components by GC/MS. Using a pre-drawn calibration curve, the obtained peak area of each compound was converted into D4 body concentration. The GC/MS measurement was performed using the following apparatus. Pyrolyzer: Py-3030iD (Frontier Laboratories) GC system: 7890B (Agilent Technologies) MSD (Mass Selective Detector): 5977A (Agilent Technologies) Column: UA-1 (inner diameter 0.25 mm, length 15 m, liquid phase thickness 0.25 μm) (Frontier Laboratories) The GC/MS measurements were all carried out under the following measurement conditions. Column temperature: hold at 40°C for 5 minutes, raise the temperature at 20°C/min, hold at 320°C for 11 minutes, a total of 30 minutes Injection port temperature: 320℃ Injection method: split method (split ratio 1/20) Interface temperature: 320℃ Ion source temperature: 230℃ Ionization method: Electron ionization method (EI) Measurement method: Scanning method (m/z 10-800)

(2) Drawing of calibration curve Measure a sample of the compound of the general formula (3) with n=4 (hereinafter also referred to as D4 body) (manufactured by Tokyo Chemical Industry Co., Ltd.) in a 10 mL volumetric flask, using chloroform as a solvent to prepare D4 body at a concentration of 0.1 mg /mL sample, and 0.01 mg/mL sample. A liquid sample sampler was installed in a pyrolyzer set at 400° C., 1 μL of the above-mentioned sample whose concentration was adjusted was measured with a micro syringe, and injected into the pyrolyzer. During the heating of the pyrolyzer to 400°C, the column was immersed in liquid nitrogen, and the volatile components were trapped in the column. One minute after the completion of heating, the column was taken out from the liquid nitrogen, and GC/MS measurement was performed. From the concentration of D4 body and the obtained peak area, the slope of the D4 body calibration curve was calculated. The retention time of the cyclosiloxane in the GC/MS measurement using the apparatus and measurement conditions used is shown in Table 1 below. The same is true for the following GC/MS measurement.

[Table 1] Table 1 Compound name Hold time (minutes) D3 3:08 D4 7:35 D5 9:12 D6 10:30 D7 11:37 D8 12:30

Dn (n=3-8) in the above-mentioned Table 1 is a cyclosiloxane corresponding to n=3-8 of the above-mentioned general formula (3).

(3) Analysis of the cyclosiloxane concentration of the general formula (3) in the resin composition The concentration of the compound of the general formula (3) contained in the resin composition was measured by heating the resin composition to 150° C. and performing GC/MS measurement on the generated volatile components. From the peak area of the measurement result of the volatile content of the resin composition, the concentration of each compound was calculated. When the peak of each compound overlapped with other compounds, the peak area obtained from the total ion chromatogram (TIC) was used. When the peak of each compound overlapped with other compounds, the peak area obtained from the mass chromatogram (MS) of m/z=281 was used.

In the heating furnace (He atmosphere) of the pyrolyzer set at 150°C, a sample cup containing about 1 mg of the resin composition was placed, and heated at 150°C for 30 minutes. The resulting volatile components were analyzed by GC/MS to measure. Using a pre-drawn calibration curve, the obtained peak area of each compound was converted into D4 body concentration. Dn(μg/g)={Dn(GC-Area)}/{Slope of D4-body calibration curve}/{Weighed mass of resin composition (mg)}×1000 In the formula, n corresponds to the carbon number n of the general formula (3), and n is an integer of 3 or more.

<Analysis of Cyclosiloxane Concentration in Raw Material Composition (Based on Silicon-Containing Compounds)> (Summary) The cyclosiloxane concentration was analyzed by GC on the solution of the silicon-containing compound (containing the silicon-containing compound of the general formula (3)) dissolved in acetone (including n-tetradecane as an internal standard substance), by means of GC. This is measured. From the peak area of each compound obtained, the concentration of each compound was determined based on the peak area of n-tetradecane according to the following method. The GC measurement was performed using the following apparatus. GC system: 7890A (Agilent Technologies) Column: J&W Scientific Durabond DB-5MS (MEGABORE, inner diameter 0.53 mm, length 30 m, liquid thickness 1.0 μm) The GC measurements were all carried out under the following measurement conditions. Column temperature: Raised at 50°C at 10°C/min, held at 280°C for 17 minutes, for a total of 40 minutes Injection port temperature: 270℃ Carrier gas: He Injection method: split method (split ratio 1/10) Detector: FID (flame ionization detector, hydrogen flame ionization detector) (300 ℃)

(Calculation of the amount of cyclosiloxane) The amount of cyclosiloxane represented by the general formula (3) was calculated according to the following formula. Dn (μg/g)={Total amount of compounds of general formula (3) (μg)}/{Total mass of compounds of general formulas (3) and (4) (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 (3), and n is an integer of 3 or more. The GC-Area Factor in the formula is calculated according to the following formula. GC-Area Factor = molecular weight/carbon number

The retention time (min) of the cyclosiloxane in the GC measurement using the apparatus used and the above-mentioned measurement conditions is shown in Table 2 below. The same is true for the following GC measurement.

[Table 2] Table 2 Compound name Hold time (minutes) D3 3.8 D4 6.1 D5 8.4 D6 10.7 D7 12.8 D8 14.6 n-tetradecane 12.2

Dn (n=3-8) in the above-mentioned Table 2 is a cyclosiloxane corresponding to n of the above-mentioned general formula (3).

(Analysis of Cyclosiloxane Concentration) The analysis of the cyclosiloxane concentration of the general formula (3) contained in the silicon-containing compound was carried out according to 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 left to stand for 16 hours. 1 μL of the left solution was measured with a microsyringe, introduced into the GC, and measured. In the obtained chromatogram, the peak area of each cyclosiloxane and n-tetradecane was calculated using the software attached to the GC, and the cyclosiloxane concentration was obtained by the calculation formula shown above.

<Storage stability evaluation of resin composition> The resin composition is usually stored in a freezer, but before being delivered to a customer for actual use, the freezer storage and room temperature storage are repeated. The storage stability of the resin composition in such a state was evaluated as follows. The obtained resin compositions of Examples and Comparative Examples were stored in a refrigerator at -20° C. for more than one day. The sample was placed in an environment of 23°C and 50% humidity for 24 hours. Next, it was stored again in the refrigerator of -20 degreeC for 24 hours. Then, it was placed in an environment of 23° C. and a humidity of 50% again for 24 hours. After that, the samples were repeatedly stored for 24 hours in a refrigerator at -20° C. for 24 hours, and left in an environment of 23° C. and a humidity of 50% for 24 hours, and the obtained samples were evaluated according to the following criteria. A: According to the visual observation of the resin composition, it was confirmed that no abnormality such as turbidity and viscosity increase occurred (excellent) B: The occurrence of turbidity was confirmed by visual observation of the resin composition, but an increase in viscosity was not observed (good) C: Based on the visual observation of the resin composition, it was confirmed that turbidity was generated, and an increase in viscosity was observed (unfavorable)

<Repulsion evaluation of coating film> For an alkali-free glass substrate of 300 mm in length x 350 mm in width x 0.5 mm in thickness (hereinafter also referred to as "glass substrate" or just "substrate"), the distance from the end of the glass substrate The resin compositions of Examples and Comparative Examples were applied to an area of 5 mm inward so that the film thickness after curing was 10 μm. The coating system used a slot coater (LC-R300G, manufactured by SCREEN Finetech Solutions). The obtained glass substrate with a coating film was used to remove the solvent under the conditions of 80° C., 100 Pa, and 30 minutes using a vacuum dryer (manufactured by Tokyo Oka Industry Co., Ltd.) to obtain a length of 290 mm × width of 340 mm × thickness of 10 μm. The glass substrate with the resin composition coating film. The edge part (coating start, side part, and coating end) of the coating film was observed with a laser microscope, and the length of the repelling part was measured. Five substrates were coated under the same conditions, and the average value of the lengths of the repelling portions was obtained, and evaluated according to the following criteria. A: The length of the repelling part of the coating film is less than 10 mm (excellent) B: The length of the repelling portion of the coating film is 10 mm or more and less than 30 mm (good) C: The length of the repulsive part of the coating film is 30 mm or more (not good)

<In-plane uniformity of retardation (Rth) of polyimide resin film> For an alkali-free glass substrate of 300 mm in length x 350 mm in width x 0.5 mm in thickness (hereinafter also referred to as "glass substrate" or simply "substrate") ”), in an area 5 mm inward from the end of the glass substrate, the resin compositions of Examples and Comparative Examples were coated so that the film thickness after curing was 10 μm. The coating system used a slot coater (LC-R300G, manufactured by SCREEN Finetech Solutions). The obtained glass substrate with a coating film was used to remove the solvent under the conditions of 80° C., 100 Pa, and 30 minutes using a vacuum dryer (manufactured by Tokyo Oka Industry Co., Ltd.) to obtain a length of 290 mm × width of 340 mm × thickness of 10 μm. The glass substrate with the resin composition coating film. At this time, 10 compositions formed on the glass substrate of the same composition were continuously processed. In addition, when the treatment of another composition is performed, it is used after drying in a vacuum dryer at 600° C. for 5 hours or more. The obtained glass substrate with the resin composition coating film was heated at 400° C. for 1 hour under a nitrogen atmosphere (oxygen concentration of 300 ppm or less) in an oven (INH-9N1, manufactured by Koyo Thermo Systems Co., Ltd.) A polyimide resin film is formed thereon. Using the produced polyimide resin film, the in-plane uniformity of Rth was evaluated. For 4 positions spaced 80 mm apart from the end of the polyimide resin film in the longitudinal (290 mm wide) direction and 25 mm inward from the end of the polyimide resin film, the distance in the lateral (340 mm wide) direction from the polyimide resin film 50 mm inward from the end of the film, the thickness is measured using a retardation birefringence measuring device (KOBRA-WR, manufactured by Oji Scientific Instruments Co., Ltd.) at 4 measuring points with an interval of 80 mm and a total of 16 measuring points (4×4). Direction Rth (converted to 10 μm). From this result, the range of ±3 sigma was calculated, and the Rth in-plane uniformity of the PI (Polyimide) precursor coating film was evaluated according to the following criteria. A: In-plane uniformity (±3 sigma) less than 10 (excellent) B: In-plane uniformity (±3 sigma) is 10 or more and less than 20 (good) C: In-plane uniformity (±3 sigma) is 20 or more (poor)

"Method of Purification of Silicon-Containing Compounds" The silicon-containing compounds described in the following examples and comparative examples were treated by the following purification methods, so that the cyclosiloxane contained therein was reduced. The concentration of the purified cyclosiloxane was analyzed by the method described above. <Purified A> 10 kg of the silicon-containing compound was put into the flask, nitrogen gas was blown, and stripping was performed at a temperature of 200° C. and a pressure of 200 Pa for 8 hours. <Purified B> 10 kg of the silicon-containing compound was put into the flask, nitrogen gas was blown, and stripping was performed at a temperature of 160° C. and a pressure of 270 Pa for 8 hours. <Purified C> According to the synthesis example of the two-terminated amino group-modified silicone oil (purified product) described in Japanese Patent Laid-Open No. 2016-029126 1000 g of acetone was added to 100 g of the silicon-containing compound, and the mixture was stirred at room temperature for 30 minutes. Centrifugation was performed at 2500 rpm for 15 minutes using a centrifuge to separate the acetone from the silicone oil, and then the acetone was removed by decantation. After repeating this operation three times, the acetone was distilled off with an evaporator to obtain a purified silicon-containing compound. <Purification D> According to the purification example 1 described in Japanese Patent Laid-Open No. 2006-028533 500 g of the silicon-containing compound was put into the flask, nitrogen gas was blown, and stripping was performed at a temperature of 250° C. and a pressure of 1330 Pa for 2 hours. <Purification E> According to Purification Example 2 described in Japanese Patent Laid-Open No. 2006-028533 100 g of the silicon-containing compound was put into 300 g of 2-butanone and dissolved uniformly. This solution was slowly thrown into methanol while stirring, and reprecipitation was performed. After repeating the above reprecipitation three times in total, drying was performed to obtain a purified silicon-containing compound. <Purified F> 10 kg of the silicon-containing compound was put into the flask, nitrogen gas was blown, and stripping was performed at a temperature of 150° C. and a pressure of 300 Pa for 2 hours.

<<Example 1>> Nitrogen gas was introduced into a separable flask with a stirring bar equipped with a Dean-Stark tube and a reflux tube at the top, and as described in Tables 1 and 2, NMP was added as a solvent while stirring. (307 g), toluene (31 g), 44DAS as diamine (7.1 g), silicon-containing compound (1) (9.94 g) after purification treatment A (L ₁ and L ₂ in general formula (4) are amines group (-NH ₂ ), R ₁ is trimethylene (-CH ₂ CH ₂ CH ₂ -), R ₂ , R ₃ are methyl groups, j, k are 0, the functional group equivalent is 1500 compounds), and then in BPAF (22.9 g) was added as the acid dianhydride at room temperature. Then, it heated up to 160 degreeC of internal temperature, and it heated and refluxed at 160 degreeC for 1 hour, and carried out imidization. After the imidization was completed, the temperature was raised to 180° C., toluene was extracted, and the reaction was continued. After 12 hours of reaction, the oil bath was removed and the temperature was returned to room temperature. Next, 44DAS (7.6 g) as a diamine and PMDA (10.9 g) as an acid dianhydride were added while stirring. Then, the mixture was stirred at room temperature for 48 hours to obtain a partially imidized polyimide precursor (PAI). The obtained varnish was stored in a freezer (set to -20°C, and the same applies hereinafter), and was thawed for use during evaluation.

<<Examples 2 to 15>> The types and amounts of the solvent, acid dianhydride, diamine, silicon-containing compound, and purification conditions of the silicon-containing compound in Example 1 were changed to those described in Tables 3 and 4, except that, It carried out similarly to Example 1. The types of silicon-containing compounds in the table are as follows. Silicon-containing compound (2): in the general formula (4), L ₁ and L ₂ are acid anhydride groups, R ₁ is trimethylene (-CH ₂ CH ₂ CH ₂ -), R ₂ and R ₃ are methyl groups, j, Compounds where k is 0 and the functional group equivalent is 800. Silicon-containing compound (3): In general formula (4), L ₁ and L ₂ are amino groups (-NH ₂ ), and R ₁ is trimethylene (-CH ₂ CH ₂ ). CH ₂ -), R ₂ and R ₃ are phenyl groups, j and k are 0, and the functional group equivalent is 2200. Silicon-containing compound (4): In the general formula (4), L ₁ and L ₂ are amino groups (- NH ₂ ), R ₁ is trimethylene (-CH ₂ CH ₂ CH ₂ -), R ₂ and R ₃ are phenyl, j and k are 0, and the functional group equivalent is 670. Silicon-containing compound (5): In the general formula (4), L ₁ and L ₂ are amino groups (-NH ₂ ), R ₁ is trimethylene (-CH ₂ CH ₂ CH ₂ -), R ₂ and R ₃ are methyl groups, and j and k are 0. Compounds with functional group equivalent of 800

<<Comparative Example 1>> Nitrogen gas was introduced into a separable flask with a stirring bar equipped with a Dean-Stark tube and a reflux tube at the upper part, and as described in Tables 1 and 2, NMP ( 307 g), toluene (31 g), 44DAS as a diamine (7.6 g), followed by addition of PMDA (10.9 g) as an acid dianhydride at room temperature. Then, it heated up to 160 degreeC of internal temperature, and it heated and refluxed at 160 degreeC for 1 hour, and carried out imidization. After the imidization was completed, the temperature was raised to 180° C., toluene was extracted, and the reaction was continued. After 12 hours of reaction, the oil bath was removed and the temperature was returned to room temperature. Next, 44DAS (7.1 g) as a diamine, an untreated silicon-containing compound (1) (9.94 g) (in the general formula (4), L ₁ and L ₂ are amine groups (—NH ₂ ), R ₁ is trimethylene (-CH ₂ CH ₂ CH ₂ -), R ₂ and R ₃ are methyl groups, j and k are 0, and the functional group equivalent is 1500), BPAF (22.9 g) as acid dianhydride ). Then, the mixture was stirred at room temperature for 48 hours to obtain a partially imidized polyimide precursor (PAI). The obtained varnish was stored in a freezer (set to -20°C, and the same applies hereinafter), and was thawed for use during evaluation.

"Comparative Example 2" Nitrogen gas was introduced into a separable flask equipped with a thermometer and a stirring bar, and as described in Table 3, NMP (158 g), toluene (16 g), and diamine were added as solvents while stirring. 44DAS (7.1 g) and the silicon-containing compound (1) (9.94 g) treated with purification D were stirred at room temperature for 12 hours to obtain a polyamide acid solution. To this polyamic acid solution, 90 g of NMP and 13.45 g of pyridine as an imidization catalyst were added and completely dispersed, then 17.33 g of acetic anhydride was added, and the mixture was stirred at 80° C. for 4 hours. While stirring the solution cooled to room temperature, a solution obtained by mixing 110 g of 2-propanol (hereinafter referred to as "IPA") and 20 g of NMP was added dropwise at a rate of 2 to 3 drops/sec to make the polymer. Imide precipitation. Furthermore, 375 g of IPA was added, and after stirring for about 30 minutes, suction filtration was performed using a Kiriyama funnel. The obtained solid was washed with IPA, and the washing operation was repeated 5 times, then dried in a vacuum oven set at 120° C. for 8 hours, and dissolved with NMP to obtain a polyimide with a solid content of 25%. (PI) in NMP. The obtained varnish was stored in a freezer (set to -20°C, and the same applies hereinafter), and was thawed for use during evaluation.

"Comparative Example 3" The type and amount of solvent, acid dianhydride, diamine, silicon-containing compound, and purification conditions of silicon-containing compound in Comparative Example 2 were changed to those described in Tables 3 and 4. Example 2 was carried out in the same manner.

"Comparative Example 4" According to Japanese Patent Laid-Open No. 9-263636, the types and amounts of the solvent, acid dianhydride, diamine, silicon-containing compound, and purification conditions of the silicon-containing compound in Comparative Example 2 were changed to those in Tables 3 and 4. The description was carried out in the same manner as in Comparative Example 2 except that (according to Japanese Patent Laid-Open No. 9-263636, the mole % of the silicon-containing compound in the total diamine was 1.9 mol % or less than 2 mol %).

"Comparative Example 5" Nitrogen gas was introduced into a 3 L separable flask with a stirring bar, and while stirring, NMP (313 g) as a solvent, 44DAS (11.6 g) as a diamine, and treated C were added Purified silicon-containing compound (1) (10.56 g), followed by addition of BPAF (36.7 g) as acid dianhydride. The mixture was stirred at room temperature for 48 hours to obtain an NMP solution of polyamide acid (PAA) (hereinafter also referred to as varnish). The obtained varnish was stored in a freezer (set to -20°C, and the same applies hereinafter), and was thawed for use during evaluation.

"Comparative Example 6" In Comparative Example 5, the types and amounts of the solvent, acid dianhydride, diamine, silicon-containing compound, and purification conditions of the silicon-containing compound were changed to those described in Tables 3 and 4. Example 5 was carried out in the same manner.

"Comparative Example 7" In a 300 mL four-necked flask, set a thermometer and a stirring bar with a stirring blade. Next, under a dry air flow, 109 g of NMP was charged, and the temperature was raised to 60°C. After the temperature was raised, stirring was performed, 14.9 g of CHDA and 2.68 g of the silicon-containing compound (4) treated with purified D were added, and the mixture was washed with 20 g of NMP. After confirming that CHDA was dissolved, 32.1 g of BPDA and 15.6 g of BSAA were added, and washed with 20 g of NMP. After 4 hours, it was allowed to cool to obtain an NMP solution of polyimide precursor (PAA).

"Comparative Example 8" Into a 500 mL five-neck round-bottomed flask equipped with a half-moon-shaped stirring blade made of stainless steel, a nitrogen introduction tube, a Dean-Stark tube with a cooling tube, a thermometer, and a glass end cap, put into 6FODA 20.2 g of NMP and 113 g of NMP were stirred at 200 rpm at a temperature of 70° C. in the system under a nitrogen atmosphere to obtain a solution. To this solution, after adding 19.2 g of CpODA and 20 g of NMP at one time, 0.302 g of TEA (triethylamine) as an imidization catalyst was added, and heated with a heating mantle for about 20 minutes. The temperature in the reaction system rose to 190°C. The components removed by distillation were collected, the rotational speed was adjusted so as to correspond to the increase in viscosity, and the temperature in the reaction system was maintained at 190° C., and reflux was performed for 1 hour. Then, 50 g of NMP was added, and the temperature in the reaction system was cooled to 50 degreeC, and the solution containing the oligomer which has an imide repeating structural unit was obtained. To the obtained solution, 40 g of s-BPDA (3,3',4,4'-Biphenyl tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride), and NMP were added at one time. 8 g, stirred at 50 °C for 5 hours. Then, after adding 107.143 g of NMPs and performing homogenization, the mixed liquid obtained by dissolving 9.19 g of the silicon-containing compound (3) in 10 g of NMPs was injected|thrown-in, and it stirred for about 1 hour. Then, NMP was added and it was made to homogenize so that the solid content concentration might become about 15 mass %, and the NMP solution of the partially imidized polyimide precursor (PAI) was obtained.

Abbreviations in Examples and Comparative Examples are as follows. <Acid dianhydride> BPAF: 9,9-bis(3,4-dicarboxyphenyl)perylene anhydride PMDA: pyromellitic dianhydride CpODA: nor𦯉alkane-2-spiro-α-cyclopentanone-α'-spiro-2''-nor𦯉alkane-5,5'',6,6''-tetracarboxylic dianhydride BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride BSAA: 2,2'-bis[(dicarboxyphenoxy)phenyl]propanedianhydride ODPA: 4,4'-Oxydiphthalic anhydride ＜Diamine＞ 44DAS: 4,4'-bis(diaminodiphenyl) bismuth 33DAS: 3,3'-bis(diaminodiphenyl) bismuth CHDA: 1,4-cyclohexanediamine 6FODA: 2,2'bis(trifluoromethyl)-4,4'diaminodiphenyl ether HFBAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane BAC: 1,3-bis(aminomethyl)cyclohexane

[table 3] table 3. imide unit amide unit Acid dianhydride 1 Diamine 1 Silicon containing compounds Acid dianhydride 2 Diamine 2 Acid dianhydride 2 Silicon containing compounds type mmol Mass (g) type mmol Mass (g) type functional group equivalent mmol Mass (g) type mmol Mass (g) type mmol Mass (g) type mmol Mass (g) type functional group equivalent mmol Mass (g) Example 1 BPAF 50.0 22.9 44DAS 46.7 7.1 (1) 1500 3.3 9.94 PMDA 50.0 10.9 44DAS 50.0 7.6 Example 2 BPAF 20.0 9.2 44DAS 17.2 2.6 (1) 1500 2.8 8.48 PMDA 80.0 17.4 44DAS 80.0 12.2 Example 3 BPAF 80.0 36.7 44DAS 76.2 11.6 (1) 1500 3.8 11.40 PMDA 20.0 4.4 44DAS 20.0 3.0 Example 4 BPAF 50.0 22.9 44DAS 46.7 7.1 (1) 1500 3.3 9.94 PMDA 50.0 10.9 44DAS 50.0 7.6 Example 5 PMDA 50.0 10.9 44DAS 50.0 7.6 BPAF 50.0 22.9 44DAS 46.7 7.1 (1) 1500 3.3 9.94 Example 6 PMDA 20.0 4.4 44DAS 20.0 3.0 BPAF 80.0 36.7 44DAS 76.2 11.6 (1) 1500 3.8 11.40 Example 7 PMDA 80.0 17.4 44DAS 80.0 12.2 BPAF 20.0 9.2 44DAS 17.2 2.6 (1) 1500 2.8 8.48 Example 8 BPAF 50.0 22.9 33DAS 46.7 7.1 (1) 1500 3.3 9.94 PMDA 50.0 10.9 33DAS 50.0 7.6 Example 9 BPAF 45.2 20.7 44DAS 50.0 7.6 (2) 1000 4.8 9.59 PMDA 50.0 10.9 44DAS 50.0 7.6 Example 10 CpODA 50.0 19.2 44DAS 46.9 7.1 (1) 1500 3.1 9.19 PMDA 50.0 10.9 44DAS 50.0 7.6 Example 11 TAHQ 50.0 22.9 44DAS 46.7 7.1 (1) 1500 3.3 9.94 PMDA 50.0 10.9 44DAS 50.0 7.6 Example 12 BPAF 50.0 22.9 HFBAPP 44.4 23.0 (1) 1500 5.7 16.95 PMDA 50.0 10.9 HFBAPP 50.0 25.9 Example 13 BPAF 50.0 22.9 BAC 46.8 6.6 (1) 1500 3.3 9.75 PMDA 50.0 10.9 BAC 50.0 7.1 Example 14 ODPA 90.0 41.3 33DAS/44DAS 43.8/43.8 6.7/6.7 (4) 800 2.4 3.82 ODPA 10.0 2.2 33DAS/44DAS 5.0/5.0 0.8/0.8 Example 15 BPAF 50.0 22.9 44DAS 46.7 7.1 (1) 1500 3.3 9.94 PMDA 50.0 10.9 44DAS 50.0 7.6 Comparative Example 1 PMDA 50.0 10.9 44DAS 50.0 7.6 BPAF 50.0 22.9 44DAS 46.7 7.1 (1) 1500 3.3 9.94 Comparative Example 2 BPAF 50.0 22.9 44DAS 46.7 7.1 (1) 1500 3.3 9.94 Comparative Example 3 BPAF 50.0 22.9 44DAS 46.7 7.1 (1) 1500 3.3 9.94 Comparative Example 4 BPAF 50.0 22.9 44DAS 48.1 7.3 (1) 1500 1.9 5.70 Comparative Example 5 BPAF 80.0 36.7 44DAS 76.2 11.6 (1) 1500 3.8 11.40 Comparative Example 6 BPAF 80.0 36.7 44DAS 76.2 11.6 (1) 1500 3.8 11.40 Comparative Example 7 BPDA 70.0 32.1 CHDA 98.0 14.9 BSAA 30.0 15.6 (4) 670 2.0 2.68 Comparative Example 8 CpODA 60.0 19.2 6FODA 60.0 20.2 BPDA 40.0 10.9 6FODA 38.3 7.6 (3) 2200 1.7 9.19

[Table 4] Table 4. Silicon containing compounds polymer structure q/(p＋q)×100 solvent Cyclosiloxane concentration [ppm] (based on resin composition) Cyclosiloxane concentration [ppm] Storage stability of the composition Coating Film Repulsion Evaluation In-plane uniformity of Rth P ₃ , P ₄ base Purification (Based on silicon-containing compounds) (%) type Mass (g) Compounds with n=4 Compounds with n=5 Compounds with n=6 Compounds with n=7 Compounds with n=4 Compounds with n=5 Compounds with n=6 Compounds with n=7 Example 1 Me Purified A PAI 50.0 NMP 307 12 5 twenty three twenty one 291 102 743 815 A B A Example 2 Me Purified A PAI 20.0 NMP 262 14 6 19 20 291 102 743 815 A B A Example 3 Me Purified A PAI 80.0 NMP 352 13 6 twenty one twenty three 291 102 743 815 A B A Example 4 Me Purified B PAI 50.0 NMP 307 56 twenty three 54 60 1281 483 1943 2125 A B A Example 5 Me Purified A PAI 50.0 NMP 307 16 7 twenty three twenty one 291 102 743 815 A A A Example 6 Me Purified A PAI 20.0 NMP 352 13 8 twenty three 19 291 102 743 815 A B A Example 7 Me Purified A PAI 80.0 NMP 262 twenty four 6 28 30 775 134 981 1070 A B A Example 8 Me Purified A PAI 50.0 NMP 307 twenty four 5 25 27 775 134 981 1070 A A A Example 9 Me Purified A PAI 50.0 NMP 296 12 5 twenty three twenty one 291 102 743 815 A B A Example 10 Me Purified A PAI 50.0 NMP 284 twenty four 6 30 33 775 134 981 1070 A B A Example 11 Me Purified A PAI 50.0 NMP 307 14 6 19 20 291 102 743 815 A B A Example 12 Me Purified A PAI 50.0 NMP 523 12 5 twenty three twenty one 291 102 743 815 A B A Example 13 Me Purified A PAI 50.0 NMP 301 13 8 twenty three 19 291 102 743 815 A B A Example 14 Me Purified A PAI 90.0 NMP 321 14 9 25 twenty two 773 121 750 820 A A A Example 15 Me Purified F PAI 50.0 NMP 255 120 45 104 82 1621 815 2218 2542 B B B Comparative Example 1 Me not purified PAI 50.0 NMP 307 143 94 124 139 4671 2642 4821 3891 C B C Comparative Example 2 Me handle D PI 100.0 NMP 158 143 96 73 77 2065 1508 1623 1725 B C B Comparative Example 3 Me handle E PI 100.0 NMP 158 150 111 356 215 2229 4119 10254 5641 B C C Comparative Example 4 Me not purified PI 100.0 NMP 159 124 72 113 123 5481 2531 5104 4124 B C C Comparative Example 5 Me process C PAA 0.0 NMP 313 112 86 334 193 2967 4643 11651 6723 C A C Comparative Example 6 Ph Purified A PAA 0.0 NMP 313 twenty one 7 30 31 731 142 862 902 C A B Comparative Example 7 Ph handle D PAA 15.0 NMP 261 96 61 49 55 1984 1262 1871 1980 C B B Comparative Example 8 Ph not purified PAI 60.0 NMP 380 twenty four 6 30 33 775 134 981 1070 C B A

2a: lower substrate 2b: Seal the substrate 25: Organic EL Structure Department 250a: Organic EL elements that emit red light 250b: Organic EL element that emits green light 250c: Organic EL element that emits blue light 251: Partition (barrier) 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

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

2a: lower substrate

2b: Seal the substrate

25: Organic EL Structure Department

250a: Organic EL elements that emit red light

250b: Organic EL element that emits green light

250c: Organic EL element that emits blue light

251: Partition (barrier)

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 (35)

A resin composition comprising a polyimide precursor and a compound represented by the following general formula (3), the polyimide precursor comprising the following general formulas (1-1) and (1-2) The structural unit represented by the following general formula (2) and the structural unit represented by the following general formula (2) are partially imidized, and the total amount of the compounds in which n is 4 in the following general formula (3) is based on the mass of the above resin composition As a basis, it exceeds 0 ppm and is not more than 120 ppm, or, the total amount of compounds in the following general formula (3) where n is 5 is more than 0 ppm and is not more than 50 ppm, based on the mass of the above resin composition, [hua 1]

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

{In the formula, P ₈ represents a divalent organic group, P ₉ represents a tetravalent organic group, and q represents a positive integer}, [Chem. 3]

{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 r is an integer of 1 to 200}, [Chem. 4 ]

{In the formula, n is an integer of 2 or more}. The resin composition according to claim 1, wherein the total amount of the compounds in the general formula (3) where n is 4, based on the mass of the resin composition, exceeds 0 ppm and is less than 70 ppm, or, The total amount of the compound in which n is 5 in the above-mentioned general formula (3) is more than 0 ppm and 30 ppm or less based on the mass of the above-mentioned resin composition. The resin composition according to claim 2, wherein the total amount of the compounds in the general formula (3) where n is 4 is more than 0 ppm and less than 30 ppm based on the mass of the above resin composition, or, The total amount of the compound in which n is 5 in the above-mentioned general formula (3) is more than 0 ppm and 15 ppm or less based on the mass of the above-mentioned resin composition. A resin composition comprising a polyimide precursor and a compound represented by the following general formula (3), the polyimide precursor comprising the following general formulas (1-1) and (1-2) The structural unit represented by the following general formula (2) and the structural unit represented by the following general formula (2) are partially imidized, and the above-mentioned resin composition is produced by the following method comprising making the following general formula (4) The raw material composition of the represented silicon-containing compound and the compound represented by the following general formula (3) is subjected to a polycondensation reaction with tetracarboxylic dianhydride and diamine to imidize to obtain polyimide, and then further The step of polycondensation reaction with tetracarboxylic dianhydride and diamine, thereby providing a partially imidized polyimide precursor, or, polycondensation reaction with tetracarboxylic dianhydride and diamine to make it imide After amination to obtain a polyimide, a raw material composition containing a silicon-containing compound represented by the following general formula (4) and a compound represented by the following general formula (3) was further mixed with tetracarboxylic dianhydride and dicarboxylic acid dianhydride. In the step of conducting a polycondensation reaction of amines, thereby providing a partially imidized polyimide precursor, the total amount of the compounds of the following general formula (3) contained in the above-mentioned raw material composition, where n is 4, is calculated by the following general formula: The total mass of the silicon-containing compounds represented by the formulae (3) and (4) is more than 0 ppm and 1300 ppm or less, or, in the following general formula (3) contained in the raw material composition, n is 5 The total amount of compounds, based on the total mass of the silicon-containing compounds of the above general formulas (3) and (4), exceeds 0 ppm and is not more than 500 ppm, [Chem. 5]

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer}, [Chem. 6]

{In the formula, P ₈ represents a divalent organic group, P ₉ represents a tetravalent organic group, and q represents a positive integer}, [Chem. 7]

{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 r is an integer of 1 to 200}, [Chem. 8 ]

{where n is an integer greater than or equal to 2}, [Formula 9]

{In the formula, R ₁ is each independently a single bond or a divalent organic group with 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group with 1 to 10 carbon atoms, and at least one of them is a carbon number 1 to 5 monovalent aliphatic hydrocarbon groups, R ₄ and R ₅ are independently a monovalent organic group with 1 to 10 carbon atoms, at least one of them is a monovalent aromatic group with 6 to 10 carbon atoms, R ₆ and R ₇ are independently a monovalent organic group with 1 to 10 carbon atoms, L ₁ and L ₂ are independently an amine group, an acid anhydride group, an isocyanate group, a carboxyl group, an ester group, an halide group, a hydroxyl group, an epoxy group group or mercapto group, i is an integer of 1 to 200, j and k are each independently an integer of 0 to 200, 0≦j/(i+j+k)≦0.50}. The resin composition according to claim 4, wherein the total amount of the compounds in which n is 4 in the above-mentioned general formula (3) contained in the above-mentioned raw material composition is the silicon-containing compound represented by the above-mentioned general formulas (3) and (4) The total mass is based on 0 ppm and 800 ppm or less, or, The total amount of the compounds in which n is 5 in the above-mentioned general formula (3) contained in the above-mentioned raw material composition, based on the total mass of the silicon-containing compounds in the above-mentioned general formulas (3) and (4), exceeds 0 ppm and is 300 ppm or less. The resin composition according to claim 4, wherein the total amount of the compounds in which n is 4 in the above-mentioned general formula (3) contained in the above-mentioned raw material composition is the silicon-containing compound represented by the above-mentioned general formulas (3) and (4) The total mass is based on 0 ppm and 30 ppm or less, or, The total amount of the compounds in which n is 5 in the above-mentioned general formula (3) contained in the above-mentioned raw material composition, based on the total mass of the silicon-containing compounds in the above-mentioned general formulas (3) and (4), exceeds 0 ppm and is 15 ppm or less. A resin composition comprising a polyimide precursor and a compound represented by the following general formula (3), the polyimide precursor comprising the following general formulas (1-1) and (1-2) The structural unit represented by the following general formula (2) and the structural unit represented by the following general formula (2), which are partially imidized, and the total amount of compounds in which n is 3 or more and 8 or less in the following general formula (3), are combined with the above resins Based on the mass of the material, if it exceeds 0 ppm and is below 150 ppm, [Chem. 10]

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer}, [Chem. 11]

{In the formula, P ₈ represents a divalent organic group, P ₉ represents a tetravalent organic group, and q represents a positive integer}, [Chem. 12]

{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 r is an integer of 1 to 200}, [Chem. 13 ]

{In the formula, n is an integer of 2 or more}. A resin composition comprising a polyimide precursor and a compound represented by the following general formula (3), the polyimide precursor comprising the following general formulas (1-1) and (1-2) The structural unit represented by the following general formula (2) and the structural unit represented by the following general formula (2), which are partially imidized, and the total amount of compounds in which n is 3 or more and 8 or less in the following general formula (3), are combined with the above resins Based on the mass of the non-solvent component of the material, more than 0 ppm and less than 900 ppm, [Chem. 14]

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer}, [Chem. 15]

{In the formula, P ₈ represents a divalent organic group, P ₉ represents a tetravalent organic group, and q represents a positive integer}, [Chem. 16]

{wherein, 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 r is an integer of 1 to 200}, [Chem. 17 ]

{In the formula, n is an integer of 2 or more}. A resin composition comprising a polyimide precursor and a compound represented by the following general formula (3), the polyimide precursor comprising the following general formulas (1-1) and (1-2) The structural unit represented by the following general formula (2) and the structural unit represented by the following general formula (2) are partially imidized, and the above-mentioned resin composition is produced by the following method comprising making the following general formula (4) The raw material composition of the represented silicon-containing compound and the compound represented by the following general formula (3) is subjected to a polycondensation reaction with tetracarboxylic dianhydride and diamine to imidize to obtain polyimide, and then further The step of polycondensation reaction with tetracarboxylic dianhydride and diamine, thereby providing a partially imidized polyimide precursor, or, polycondensation reaction with tetracarboxylic dianhydride and diamine to make it imide After amination to obtain a polyimide, a raw material composition containing a silicon-containing compound represented by the following general formula (4) and a compound represented by the following general formula (3) was further mixed with tetracarboxylic dianhydride and dicarboxylic acid dianhydride. A step of performing a polycondensation reaction of amines, thereby providing a partially imidized polyimide precursor, wherein n in the following general formula (3) contained in the above-mentioned raw material composition is the total amount of compounds of 3 or more and 8 or less, Based on the total mass of the silicon-containing compounds represented by the following general formulas (3) and (4), if it exceeds 0 ppm and is not more than 4500 ppm, [Chemical 18]

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer}, [Chem. 19]

{In the formula, P ₈ represents a divalent organic group, P ₉ represents a tetravalent organic group, and q represents a positive integer}, [Chem. 20]

{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 r is an integer of 1 to 200}, [Chem. 21 ]

{In the formula, n is an integer of 2 or more}, [Formula 22]

{In the formula, R ₁ is each independently a single bond or a divalent organic group with 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group with 1 to 10 carbon atoms, and at least one of them is a carbon number 1 to 5 monovalent aliphatic hydrocarbon groups, R ₄ and R ₅ are independently a monovalent organic group with 1 to 10 carbon atoms, at least one of them is a monovalent aromatic group with 6 to 10 carbon atoms, R ₆ and R ₇ are independently a monovalent organic group with 1 to 10 carbon atoms, L ₁ and L ₂ are independently an amine group, an acid anhydride group, an isocyanate group, a carboxyl group, an ester group, an halide group, a hydroxyl group, an epoxy group group or mercapto group, i is an integer of 1 to 200, j and k are each independently an integer of 0 to 200, 0≦j/(i+j+k)≦0.50}. The resin composition according to any one of claims 1 to 9, wherein p and q satisfy 20≦q/(p+q)×100≦80. The resin composition according to any one of claims 4 to 6 and 9, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (4) are independently selected from amine groups, acid anhydride groups, epoxy groups , hydroxyl, and sulfhydryl groups. The resin composition according to any one of claims 4 to 6 and 9, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (4) are amine groups. The resin composition according to any one of claims 4 to 6 and 9, wherein the functional group equivalent of the silicon-containing compound represented by the general formula (4) is 800 or more. The resin composition according to any one of claims 4 to 6, 9 and 11 to 13, wherein the above-mentioned tetracarboxylic dianhydride is selected from pyromellitic dianhydride (PMDA), 3,3', 4,4' - Biphenyltetracarboxylic dianhydride (BPDA), 9,9-bis(3,4-dicarboxyphenyl)perylene anhydride (BPAF), 4,4'-oxydiphthalic anhydride (ODPA), 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA), and 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), p-phenylene bis(trimellitic anhydride) ( At least one of the group consisting of TAHQ). The resin composition according to any one of claims 4 to 6, 9 and 11 to 14, wherein the above-mentioned diamine is selected from 4,4'-diaminodiphenylene (4,4'-DAS), 3 ,3'-bis(diaminodiphenyl) bismuth (3,3'-DAS), 9,9-bis(4-aminophenyl) fluoride (BAFL), diaminobis(trifluoromethyl) ) biphenyl (TFMB), 2,2'-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 2,2-bis[4-(4-aminophenoxy) At least one of the group consisting of phenyl]hexafluoropropane (HFBAPP) and 1,3-bis(aminomethyl)cyclohexane (BAC). The resin composition according to any one of claims 1 to 15, wherein the polyimide resin film obtained by curing the above resin composition is used for a flexible substrate. The resin composition according to any one of claims 1 to 15, wherein the polyimide resin film obtained by curing the above resin composition is used for a flexible display. A method for producing a resin composition, comprising: a raw material composition containing a silicon-containing compound represented by the following general formula (4) and a compound represented by the following general formula (3), tetracarboxylic dianhydride and diamine Carry out a polycondensation reaction, make it imidized to obtain polyimide, and then carry out a polycondensation reaction with tetracarboxylic dianhydride and diamine, thereby providing the step of partially imidized polyimide precursor, Alternatively, polyimide is obtained by polycondensation reaction with tetracarboxylic dianhydride and diamine to imidize, and then a silicon-containing compound represented by the following general formula (4) and the following general formula are contained (3) The step of performing a polycondensation reaction of the raw material composition of the represented compound with tetracarboxylic dianhydride and diamine, thereby providing a partially imidized polyimide precursor, the resin composition may include the following The silicon-containing compound represented by the general formula (4) and the compound represented by the following general formula (3), and the total amount of the compound in which n is 4 in the following general formula (3) contained in the raw material composition, the following The total mass of the silicon-containing compounds represented by the general formulae (3) and (4) is more than 0 ppm and not more than 1300 ppm, or, in the following general formula (3) contained in the raw material composition, n is The total amount of the compounds of 5, based on the total mass of the silicon-containing compounds of the above general formulas (3) and (4), exceeds 0 ppm and is not more than 500 ppm, [Chemical 23]

{where, n is an integer of 2 or more}, [Formula 24]

{In the formula, R ₁ is each independently a single bond or a divalent organic group with 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group with 1 to 10 carbon atoms, and at least one of them is a carbon number 1 to 5 monovalent aliphatic hydrocarbon groups, R ₄ and R ₅ are independently a monovalent organic group with 1 to 10 carbon atoms, at least one of them is a monovalent aromatic group with 6 to 10 carbon atoms, R ₆ and R ₇ are independently a monovalent organic group with 1 to 10 carbon atoms, L ₁ and L ₂ are independently an amine group, an acid anhydride group, an isocyanate group, a carboxyl group, an ester group, an halide group, a hydroxyl group, an epoxy group group or mercapto group, i is an integer of 1 to 200, j and k are each independently an integer of 0 to 200, 0≦j/(i+j+k)≦0.50}. The method for producing a resin composition according to claim 18, wherein the total amount of the compounds in which n is 4 in the above-mentioned general formula (3) contained in the above-mentioned raw material composition is represented by the above-mentioned general formulas (3) and (4) Based on the total mass of silicon-containing compounds, it exceeds 0 ppm and is not more than 800 ppm, or, The total amount of the compounds in which n is 6 in the above-mentioned general formula (3) contained in the above-mentioned raw material composition, based on the total mass of the silicon-containing compounds in the above-mentioned general formulas (3) and (4), exceeds 0 ppm and is 300 ppm or less. A method for producing a resin composition, comprising: a raw material composition containing a silicon-containing compound represented by the following general formula (4) and a compound represented by the following general formula (3), tetracarboxylic dianhydride and diamine After polycondensation reaction is carried out, it is imidized to obtain polyimide, and then polyimide is carried out with tetracarboxylic dianhydride and diamine to provide partially imidized polyimide with imide group in part. The step of the polyimide precursor, or, after polycondensation reaction with tetracarboxylic dianhydride and diamine to imidize the polyimide to obtain polyimide, further containing the following general formula (4) The raw material composition of the silicon-containing compound and the compound represented by the following general formula (3) is subjected to a polycondensation reaction with tetracarboxylic dianhydride and diamine, thereby providing a step of partially imidized polyimide precursor , the resin composition may include a silicon-containing compound represented by the following general formula (4) and a compound represented by the following general formula (3), and n in the following general formula (3) contained in the raw material composition The total amount of compounds of 3 or more and 8 or less, based on the total mass of the silicon-containing compounds represented by the following general formulas (3) and (4), exceeds 0 ppm and is 4500 ppm or less, [Chemical 25]

{where n is an integer greater than or equal to 2}, [Formula 26]

{In the formula, R ₁ is each independently a single bond or a divalent organic group with 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group with 1 to 10 carbon atoms, and at least one of them is a carbon number 1 to 5 monovalent aliphatic hydrocarbon groups, R ₄ and R ₅ are independently a monovalent organic group with 1 to 10 carbon atoms, at least one of them is a monovalent aromatic group with 6 to 10 carbon atoms, R ₆ and R ₇ are independently a monovalent organic group with 1 to 10 carbon atoms, L ₁ and L ₂ are independently an amine group, an acid anhydride group, an isocyanate group, a carboxyl group, an ester group, an halide group, a hydroxyl group, an epoxy group group or mercapto group, i is an integer of 1 to 200, j and k are each independently an integer of 0 to 200, 0≦j/(i+j+k)≦0.50}. The method for producing a resin composition according to any one of claims 18 to 20, wherein the functional group equivalent of the silicon-containing compound represented by the general formula (4) is 800 or more. A method for producing a resin composition, comprising: a raw material composition containing a silicon-containing compound represented by the following general formula (4) and a compound represented by the following general formula (3), tetracarboxylic dianhydride and diamine Carry out a polycondensation reaction, make it imidized to obtain polyimide, and then carry out a polycondensation reaction with tetracarboxylic dianhydride and diamine, thereby providing the step of partially imidized polyimide precursor, Alternatively, polyimide is obtained by polycondensation reaction with tetracarboxylic dianhydride and diamine to imidize, and then a silicon-containing compound represented by the following general formula (4) and the following general formula are contained The raw material composition of the compound represented by (3) is subjected to a polycondensation reaction with tetracarboxylic dianhydride and diamine, whereby the above-mentioned polyimide precursor is partially imidized to provide a partially imidized polyimide In the step of amine precursor, the resin composition may include a silicon-containing compound represented by the following general formula (4) and a compound represented by the following general formula (3). The manufacturing method of the resin composition includes the following general formula. Based on the total mass of the silicon-containing compounds of formulas (4) and (3), reduce the total amount of compounds in the following general formula (3) where n is 5, or the total amount of compounds where n is 6, or n is 7 In the step of reducing the total amount of the compound, the above-mentioned step of reducing includes treating the above-mentioned composition for 2-12 hours at 150-300°C and below 300 Pa, [Chemical 27]

{where, n is an integer of 2 or more}, [Formula 28]

{In the formula, R ₁ is each independently a single bond or a divalent organic group with 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group with 1 to 10 carbon atoms, and at least one of them is a carbon number 1 to 5 monovalent aliphatic hydrocarbon groups, R ₄ and R ₅ are independently a monovalent organic group with 1 to 10 carbon atoms, at least one of them is a monovalent aromatic group with 6 to 10 carbon atoms, R ₆ and R ₇ are independently a monovalent organic group with 1 to 10 carbon atoms, L ₁ and L ₂ are independently an amine group, an acid anhydride group, an isocyanate group, a carboxyl group, an ester group, an halide group, a hydroxyl group, an epoxy group group or mercapto group, i is an integer of 1 to 200, j and k are each independently an integer of 0 to 200, 0≦j/(i+j+k)≦0.50}. The method according to any one of claims 18 to 22, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (4) are independently selected from amine groups, acid anhydride groups, epoxy groups, hydroxyl groups, and A group of sulfhydryl groups. The method according to any one of claims 18 to 22, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (4) are amino groups. The method according to any one of claims 18 to 24, wherein the above-mentioned tetracarboxylic dianhydride is selected from the group consisting of pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 9,9-bis(3,4-dicarboxyphenyl)perylene anhydride (BPAF), 4,4'-oxydiphthalic anhydride (ODPA), 1,2,4,5- At least one of the group consisting of cyclohexanetetracarboxylic dianhydride (HPMDA) and 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA). The method according to any one of claims 18 to 25, wherein the above-mentioned diamine is selected from the group consisting of 4,4'-diaminodiphenylene (4,4'-DAS), 3,3'-bis(diamine) (3,3'-DAS), 9,9-bis(4-aminophenyl) fluoride (BAFL), 2,2'-dimethylbenzidine (mTB), terephthalic acid Amine (PDA), Diaminobis(trifluoromethyl)biphenyl (TFMB), 2,2'-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 4,4 At least one of the group consisting of '-diaminodiphenyl ether (ODA) and 1,4-cyclohexanediamine (CHDA). A manufacturing method of a polyimide film, comprising: The coating step of coating the resin composition according to any one of claims 1 to 17 on the surface of the support, A film forming step of heating the above resin composition to form a polyimide resin film, and The peeling step of peeling the above-mentioned polyimide resin film from the above-mentioned support. The method for producing a polyimide film according to claim 27, comprising an irradiation step of irradiating the resin composition with a laser from the support side before the peeling step. A method of manufacturing a display, comprising: The coating step of coating the resin composition according to any one of claims 1 to 17 on the surface of the support, A film forming step of heating the above resin composition to form a polyimide resin film, an element forming step of forming an element on the above-mentioned polyimide resin film, and A peeling step of peeling off the above-mentioned polyimide resin film on which the above-mentioned element is formed from the above-mentioned support. A method for manufacturing a laminate, comprising: The coating step of coating the resin composition according to any one of claims 1 to 17 on the surface of the support, A film forming step of heating the above resin composition to form a polyimide resin film, and The element forming step of forming elements on the above-mentioned polyimide resin film. The manufacturing method of the laminated body of Claim 30 which further comprises the process of peeling the said polyimide resin film on which the said element was formed from the said support body. A method of manufacturing a flexible device, comprising the step of manufacturing a laminate by the method of claim 30 or 31. A polyimide film, which is a cured product of the resin composition according to any one of claims 1 to 17. A resin composition comprising a polyimide precursor, the polyimide precursor comprising structural units represented by the following general formulae (1-1) and (1-2), and partially imidized, [Chemical 29]

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer}, [Chem. 30]

{in the formula, P ₈ represents a divalent organic group, P ₉ represents a tetravalent organic group, and q represents a positive integer}, P ₉ is derived from 9,9-bis(3,4-dicarboxyphenyl) sulfonic anhydride ( BPAF), or p-phenylene bis(trimellitic anhydride) (TAHQ). A resin composition comprising a polyimide precursor, the polyimide precursor comprising structural units represented by the following general formulae (1-1) and (1-2), and partially imidized, [Chemical 31]

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer}, [Chem. 32]

{in the formula, P ₈ represents a divalent organic group, P ₉ represents a tetravalent organic group, and q represents a positive integer}, P ₈ is derived from the group consisting of 4,4'-diaminodiphenyl group (4,4' -DAS), 3,3'-bis(diaminodiphenyl) bis(3,3'-DAS), 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoro Propane (HFBAPP) and p-phenylene bis(trimellitic anhydride) (TAHQ) as the base of one or more compounds.

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