JP2022082450A - Resin composition - Google Patents

Abstract

To provide a polyimide film that excels in both of the properties required for the production process of a polyimide precursor and/or a polyimide-containing resin composition and other properties required for displays, and a resin composition for forming the same.SOLUTION: Constitutional units of a polyimide precursor and/or a polyimide include a divalent organic group P1 and a tetravalent organic group P2, each of which includes a constitutional unit derived from a compound represented by any of general formulae (3), (4), (5), (12).SELECTED DRAWING: Figure 1

Description

The present invention relates to a polyimide precursor / polyimide-containing resin composition and a polyimide film. The present invention further relates to a method for producing a polyimide precursor / polyimide-containing resin composition, and a method for producing a polyimide film, a display, a laminate, and a flexible device.

The polyimide resin is an insoluble and infusible super heat resistant resin, and has excellent properties such as heat 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 the polyimide resin in the field of electronic materials include an insulating coating material, an insulating film, a semiconductor, an electrode protective film of a thin film transistor liquid crystal display (TFT-LCD), and the like. Recently, taking advantage of the lightness and flexibility of the polyimide film, adoption as a flexible substrate is being considered in place of the glass substrate conventionally used in the field of display materials.

Patent Document 1 describes 3,5-diaminobenzamide (hereinafter, also referred to as DABA) and pyromellitic acid anhydride (hereinafter, also referred to as PMDA) or 4,4'-(hexafluoroisopropylidene) diphthal as monomers. A polyimide obtained by synthesizing a polyimide using an acid anhydride (hereinafter, also referred to as 6FDA) and a silicon-containing compound having a specific structure, adding a cross-linking agent to the obtained polyimide varnish, applying and drying the polyimide. The film is described. Further, Patent Document 1 also describes that this film has excellent gas separation performance.

Patent Document 2 is a transparent polyimide film obtained by applying and drying a polyimide varnish using DABA, TFMB (2,2'-bis (trifluoromethyl) benzidine) as a diamine and PMDA, 6FDA as an acid dianhydride. Is described.

Japanese Unexamined Patent Publication No. 2020-084067 Chinese Patent No. 111205645

The polyimide film described in Patent Document 1 is used as a paint such as a coating agent and an adhesive, and has not been studied as an optical material.

Further, the present inventors synthesized a polyimide varnish in the same manner as described in Patent Document 2 using DABA, TFMB and PMDA, 6FDA as monomers, and obtained the polyimide varnish by applying and heating the polyimide varnish. It has been found that the polyimide film has insufficient properties (for example, tensile elongation, residual stress, etc.) required for display applications. On the other hand, the present inventors have found that a polyimide obtained by using DABA, PMDA and / or 6FDA and a specific amount of a silicon-containing compound or the like as a monomer has excellent properties required for display applications.

Therefore, the present invention has been made in view of the above circumstances, and has both the characteristics required for the manufacturing process of the polyimide precursor and / or the polyimide-containing resin composition and other characteristics required for display applications. It is an object of the present invention to provide an excellent polyimide film and a resin composition for forming the same.

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

｛式中、Ｐ_１は、２価の有機基を示し、Ｐ_２は、４価の有機基を示し、ｐは、かつ正の整数を示す。｝
で表される構造単位を含む、ポリイミド前駆体又はポリイミドを含む、樹脂組成物であって、
前記Ｐ_１は、下記一般式（３）：

で表される化合物に由来する構成単位を含み、かつ
前記Ｐ_１又Ｐ_２は、下記一般式（５）：

｛式中、Ｒ_１は、それぞれ独立に、単結合又は炭素数１～１０の二価の有機基であり、Ｒ_２及びＲ_３は、それぞれ独立に、炭素数１～１０の一価の有機基であり、少なくとも一つは炭素数１～５の一価の脂肪族炭化水素基であり、Ｒ_４及びＲ_５は、それぞれ独立に、炭素数１～１０の一価の有機基であり、少なくとも一つは炭素数６～１０の一価の芳香族基であり、Ｒ_６及びＲ_７は、それぞれ独立に、炭素数１～１０の一価の有機基であり、Ｌ_１及びＬ_２は、それぞれ独立に、アミノ基、酸無水物基、イソシアネート基、カルボキシル基、酸エステル基、酸ハライド基、ヒドロキシ基、エポキシ基、又はメルカプト基であり、ｉは、１～２００の整数であり、ｊ及びｋは、それぞれ独立に、０～２００の整数であり、０≦ｊ／（ｉ＋ｊ＋ｋ）≦０．５０であり、かつ官能基当量が８００以上である。｝
で表されるケイ素含有化合物に由来する構成単位を含み、かつ
下記（ア）及び（イ）：
（ア）前記Ｐ_２は、下記一般式（４）：

で表される化合物に由来する構成単位を含む；
（イ）前記Ｐ_２は、下記一般式（１２）：

で表される化合物に由来する構成単位を含む；
を満たし、
そして前記ケイ素含有化合物が、
全ジアミンを１００ｍｏｌ％としたとき、２０ｍｏｌ％以下、または、
全酸二無水物を１００ｍｏｌ％としたとき、２０ｍｏｌ％以下
である、樹脂組成物。
［２］
前記Ｌ_１及びＬ_２が、それぞれ独立に、アミノ基である、項目１に記載の樹脂組成物。
［３］
下記一般式（６）及び（７）：

｛式中、Ｐ_３は、２価の有機基を示し、Ｐ_４は、４価の有機基を示し、かつｐは、正の整数を示す。｝

｛式中、Ｐ_５は、２価の有機基を示し、Ｐ_６は、４価の有機基を示し、かつｑは、正の整数を示す。｝
で表される構造単位を含む、ポリイミド前駆体及びポリイミドを含む、樹脂組成物であって、
前記Ｐ_３又はＰ_４が、下記一般式（１０）：

｛式中、Ｒ_１は、それぞれ独立に、単結合又は炭素数１～１０の二価の有機基であり、Ｒ_２及びＲ_３は、それぞれ独立に、炭素数１～１０の一価の有機基であり、少なくとも一つは炭素数１～５の一価の脂肪族炭化水素基であり、Ｒ_４及びＲ_５は、それぞれ独立に、炭素数１～１０の一価の有機基であり、少なくとも一つは炭素数６～１０の一価の芳香族基であり、Ｒ_６及びＲ_７は、それぞれ独立に、炭素数１～１０の一価の有機基であり、Ｌ_１及びＬ_２は、それぞれ独立に、アミノ基、酸無水物基、イソシアネート基、カルボキシル基、酸エステル基、酸ハライド基、ヒドロキシ基、エポキシ基、又はメルカプト基であり、ｉは、１～２００の整数であり、ｊ及びｋは、それぞれ独立に、０～２００の整数であり、０≦ｊ／（ｉ＋ｊ＋ｋ）≦０．５０である。｝
で表されるケイ素含有化合物に由来する構成単位を含み、かつ
前記Ｐ_３及び／又はＰ_５は、下記一般式（８）：

で表される化合物に由来する構成単位を含み、かつ
下記（ウ）及び（エ）：
（ウ）前記Ｐ_４及び／又はＰ_６は、下記一般式（９）：

で表される化合物に由来する構成単位を含む；
（エ）前記Ｐ_４及び／又はＰ_６は、下記一般式（１３）：

で表される化合物に由来する構成単位を含む；
を満たす、樹脂組成物。
［４］
前記ケイ素含有化合物が、
全ジアミンを１００ｍｏｌ％としたとき、２０ｍｏｌ％以下、または、
全酸二無水物を１００ｍｏｌ％としたとき、２０ｍｏｌ％以下
である、項目３に記載の樹脂組成物。
［５］
前記Ｌ_１及びＬ_２が、それぞれ独立に、アミノ基である、項目３又は４に記載の樹脂組成物。
［６］
前記Ｐ_１，Ｐ_３，Ｐ_５が、ＴＦＭＢ（２，２’－ビス（トリフルオロメチル）ベンジジン）に由来する基を含まない、項目１～５のいずれか一項に記載の樹脂組成物。
［７］
前記一般式（３）又は（８）で表される化合物が、全ジアミン（前記一般式（５）又は（１０）で表される化合物を除く）を１００ｍｏｌ％としたとき、５０ｍｏｌ％より多い、項目１～６のいずれか一項に記載の樹脂組成物。
［８］
前記ポリイミド前駆体又は前記ポリイミドを加熱して得られるポリイミド樹脂膜が、フレキシブル基板に用いられる、項目１～７のいずれか一項に記載の樹脂組成物。
［９］
前記ポリイミド前駆体を硬化して得られるポリイミド樹脂膜が、フレキシブルディスプレイに用いられる、項目１～８のいずれか一項に記載の樹脂組成物。
［１０］
下記一般式（３）：

で表される化合物と、
下記一般式（４）：

で表される化合物及び、
下記一般式（１２）：

で表される化合物と、
下記一般式（５）：

｛式中、Ｒ_１は、それぞれ独立に、単結合又は炭素数１～１０の二価の有機基であり、Ｒ_２及びＲ_３は、それぞれ独立に、炭素数１～１０の一価の有機基であり、少なくとも一つは炭素数１～５の一価の脂肪族炭化水素基であり、Ｒ_４及びＲ_５は、それぞれ独立に、炭素数１～１０の一価の有機基であり、少なくとも一つは炭素数６～１０の一価の芳香族基であり、Ｒ_６及びＲ_７は、それぞれ独立に、炭素数１～１０の一価の有機基であり、Ｌ_１及びＬ_２は、それぞれ独立に、アミノ基、酸無水物基、イソシアネート基、カルボキシル基、酸エステル基、酸ハライド基、ヒドロキシ基、エポキシ基、又はメルカプト基であり、ｉは、１～２００の整数であり、ｊ及びｋは、それぞれ独立に、０～２００の整数であり、０≦ｊ／（ｉ＋ｊ＋ｋ）≦０．５０である。｝
で表されるケイ素含有化合物と、その他の化合物とを重縮合反応させてポリイミド前駆体及び／又はポリイミドを提供することを含む、樹脂組成物の製造方法。
［１１］
下記一般式（３）：

で表される化合物と、
下記一般式（４）：

で表される化合物及び、
下記一般式（１２）：

で表される化合物と、
その他の化合物とを重縮合反応させてポリイミドを得た後、
下記一般式（５）：

｛式中、Ｒ_１は、それぞれ独立に、単結合又は炭素数１～１０の二価の有機基であり、Ｒ_２及びＲ_３は、それぞれ独立に、炭素数１～１０の一価の有機基であり、少なくとも一つは炭素数１～５の一価の脂肪族炭化水素基であり、Ｒ_４及びＲ_５は、それぞれ独立に、炭素数１～１０の一価の有機基であり、少なくとも一つは炭素数６～１０の一価の芳香族基であり、Ｒ_６及びＲ_７は、それぞれ独立に、炭素数１～１０の一価の有機基であり、Ｌ_１及びＬ_２は、それぞれ独立に、アミノ基、酸無水物基、イソシアネート基、カルボキシル基、酸エステル基、酸ハライド基、ヒドロキシ基、エポキシ基、又はメルカプト基であり、ｉは、１～２００の整数であり、ｊ及びｋは、それぞれ独立に、０～２００の整数であり、０≦ｊ／（ｉ＋ｊ＋ｋ）≦０．５０である。｝
で表されるケイ素含有化合物と、その他の化合物とを重縮合反応させて、ポリイミド前駆体及びポリイミドを含む樹脂組成物を提供することを含む、樹脂組成物の製造方法。
［１２］
支持体の表面上に、項目１～９のいずれか一項に記載の樹脂組成物、又は項目１０若しくは１１に記載の方法により得られた樹脂組成物を塗布する塗布工程と、
該樹脂組成物を加熱してポリイミド樹脂膜を形成する膜形成工程と、
該ポリイミド樹脂膜を該支持体から剥離する剥離工程と、
を含む、ポリイミド樹脂膜の製造方法。
［１３］
前記剥離工程に先立って、前記支持体側から前記樹脂組成物にレーザーを照射する照射工程を含む、項目１２に記載のポリイミド樹脂膜の製造方法。
［１４］
支持体の表面上に、項目１～９のいずれか一項に記載の樹脂組成物、又は項目１０若しくは１１に記載の方法により得られた樹脂組成物を塗布する塗布工程と、
該樹脂組成物を加熱してポリイミド樹脂膜を形成する膜形成工程と、
該ポリイミド樹脂膜上に素子を形成する素子形成工程と、
該素子が形成された該ポリイミド樹脂膜を該支持体から剥離する剥離工程と、
を含む、ディスプレイの製造方法。
［１５］
支持体の表面上に、項目１～９のいずれか一項に記載の樹脂組成物、又は項目１０若しくは１１に記載の方法により得られた樹脂組成物を塗布する塗布工程と、
該樹脂組成物を加熱してポリイミド樹脂膜を形成する膜形成工程と、
該ポリイミド樹脂膜上に素子を形成する素子形成工程と、
を含む、積層体の製造方法。
［１６］
前記素子が形成された前記ポリイミド樹脂膜を前記支持体から剥離する工程をさらに含む、項目１５に記載の積層体の製造方法。
［１７］
項目１５又は１６に記載の方法により積層体を製造することを含む、フレキシブルデバイスの製造方法。 The above problems can be solved by the following technical means.
[1]
The following general formula (1) or (2):

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

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer. }
A polyimide precursor or a resin composition containing a polyimide, which comprises a structural unit represented by.
The P ₁ is the following general formula (3):

It contains a structural unit derived from the compound represented by the above, and the P1 or P2 is the following general _formula ( ₅ ) :.

{In the formula, R ₁ is an independently single-bonded or divalent organic group having 1 to 10 carbon atoms, and R ₂ and R ₃ are independently monovalent organic groups having 1 to 10 carbon atoms. It is a group, at least one is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, and R ₄ and R ₅ are independently monovalent organic groups having 1 to 10 carbon atoms, respectively. At least one is a monovalent aromatic group having 6 to 10 carbon atoms, R ₆ and R ₇ are independently monovalent organic groups having 1 to 10 carbon atoms, and L ₁ and L ₂ are independent groups. Independently, each is an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid halide group, a hydroxy group, an epoxy group, or a mercapto group, and i is an integer of 1 to 200. j and k are independently integers of 0 to 200, 0 ≦ j / (i + j + k) ≦ 0.50, and the functional group equivalent is 800 or more. }
It contains a structural unit derived from a silicon-containing compound represented by, and the following (a) and (b):
(A) The P ₂ is the following general formula (4):

Includes structural units derived from the compounds represented by;
(A) The P ₂ is the following general formula (12):

Includes structural units derived from the compounds represented by;
The filling,
And the silicon-containing compound
When the total diamine is 100 mol%, it is 20 mol% or less, or
A resin composition having a total acid dianhydride of 20 mol% or less when the total acid dianhydride is 100 mol%.
[2]
The resin composition according to item 1, wherein L ₁ and L ₂ are independently amino groups.
[3]
The following general formulas (6) and (7):

{In the formula, P ₃ represents a divalent organic group, P ₄ represents a tetravalent organic group, and p represents a positive integer. }

{In the formula, P ₅ represents a divalent organic group, P ₆ represents a tetravalent organic group, and q represents a positive integer. }
A resin composition comprising a polyimide precursor and a polyimide, which comprises a structural unit represented by.
The above P ₃ or P ₄ is the following general formula (10):

{In the formula, R ₁ is an independently single-bonded or divalent organic group having 1 to 10 carbon atoms, and R ₂ and R ₃ are independently monovalent organic groups having 1 to 10 carbon atoms. It is a group, at least one is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, and R ₄ and R ₅ are independently monovalent organic groups having 1 to 10 carbon atoms, respectively. At least one is a monovalent aromatic group having 6 to 10 carbon atoms, R ₆ and R ₇ are independently monovalent organic groups having 1 to 10 carbon atoms, and L ₁ and L ₂ are independent groups. Independently, each is an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid halide group, a hydroxy group, an epoxy group, or a mercapto group, and i is an integer of 1 to 200. j and k are independently integers of 0 to 200, and 0 ≦ j / (i + j + k) ≦ 0.50. }
It contains a structural unit derived from a silicon-containing compound represented by, and the P ₃ and / or P ₅ is the following general formula (8) :.

It contains a structural unit derived from the compound represented by, and the following (c) and (d):
(C) The _P4 and / or _P6 is expressed by the following general formula (9):

Includes structural units derived from the compounds represented by;
(D) The above _P4 and / or _P6 is expressed by the following general formula (13):

Includes structural units derived from the compounds represented by;
A resin composition that meets the requirements.
[4]
The silicon-containing compound
When the total diamine is 100 mol%, it is 20 mol% or less, or
The resin composition according to item 3, wherein the total acid dianhydride is 20 mol% or less when the total acid dianhydride is 100 mol%.
[5]
The resin composition according to item 3 or 4, wherein L ₁ and L ₂ are independently amino groups.
[6]
The resin composition according to any one of items 1 to 5, wherein P ₁ , P ₃ , and P ₅ do not contain a group derived from TFMB (2,2'-bis (trifluoromethyl) benzidine).
[7]
The compound represented by the general formula (3) or (8) is more than 50 mol% when the total diamine (excluding the compound represented by the general formula (5) or (10)) is 100 mol%. The resin composition according to any one of items 1 to 6.
[8]
The resin composition according to any one of items 1 to 7, wherein the polyimide precursor or the polyimide resin film obtained by heating the polyimide is used for a flexible substrate.
[9]
The resin composition according to any one of items 1 to 8, wherein the polyimide resin film obtained by curing the polyimide precursor is used for a flexible display.
[10]
The following general formula (3):

And the compound represented by
The following general formula (4):

Compounds represented by and
The following general formula (12):

And the compound represented by
The following general formula (5):

{In the formula, R ₁ is an independently single-bonded or divalent organic group having 1 to 10 carbon atoms, and R ₂ and R ₃ are independently monovalent organic groups having 1 to 10 carbon atoms. It is a group, at least one is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, and R ₄ and R ₅ are independently monovalent organic groups having 1 to 10 carbon atoms, respectively. At least one is a monovalent aromatic group having 6 to 10 carbon atoms, R ₆ and R ₇ are independently monovalent organic groups having 1 to 10 carbon atoms, and L ₁ and L ₂ are independent groups. Independently, each is an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid halide group, a hydroxy group, an epoxy group, or a mercapto group, and i is an integer of 1 to 200. j and k are independently integers of 0 to 200, and 0 ≦ j / (i + j + k) ≦ 0.50. }
A method for producing a resin composition, which comprises subjecting a silicon-containing compound represented by (1) and another compound to a polycondensation reaction to provide a polyimide precursor and / or a polyimide.
[11]
The following general formula (3):

And the compound represented by
The following general formula (4):

Compounds represented by and
The following general formula (12):

And the compound represented by
After polycondensation reaction with other compounds to obtain polyimide,
The following general formula (5):

{In the formula, R ₁ is an independently single-bonded or divalent organic group having 1 to 10 carbon atoms, and R ₂ and R ₃ are independently monovalent organic groups having 1 to 10 carbon atoms. It is a group, at least one is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, and R ₄ and R ₅ are independently monovalent organic groups having 1 to 10 carbon atoms, respectively. At least one is a monovalent aromatic group having 6 to 10 carbon atoms, R ₆ and R ₇ are independently monovalent organic groups having 1 to 10 carbon atoms, and L ₁ and L ₂ are independent groups. Independently, each is an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid halide group, a hydroxy group, an epoxy group, or a mercapto group, and i is an integer of 1 to 200. j and k are independently integers of 0 to 200, and 0 ≦ j / (i + j + k) ≦ 0.50. }
A method for producing a resin composition, which comprises subjecting a silicon-containing compound represented by (1) to a polycondensation reaction of another compound to provide a resin composition containing a polyimide precursor and a polyimide.
[12]
A coating step of applying the resin composition according to any one of items 1 to 9 or the resin composition obtained by the method according to item 10 or 11 onto the surface of the support.
A film forming step of heating the resin composition to form a polyimide resin film,
A peeling step of peeling the polyimide resin film from the support,
A method for producing a polyimide resin film, including.
[13]
The method for producing a polyimide resin film according to item 12, further comprising an irradiation step of irradiating the resin composition with a laser from the support side prior to the peeling step.
[14]
A coating step of applying the resin composition according to any one of items 1 to 9 or the resin composition obtained by the method according to item 10 or 11 onto the surface of the support.
A film forming step of heating the resin composition to form a polyimide resin film,
An element forming step of forming an element on the polyimide resin film and
A peeling step of peeling the polyimide resin film on which the element is formed from the support,
How to make a display, including.
[15]
A coating step of applying the resin composition according to any one of items 1 to 9 or the resin composition obtained by the method according to item 10 or 11 onto the surface of the support.
A film forming step of heating the resin composition to form a polyimide resin film,
An element forming step of forming an element on the polyimide resin film and
A method for manufacturing a laminate, including.
[16]
The method for producing a laminate according to item 15, further comprising a step of peeling the polyimide resin film on which the element is formed from the support.
[17]
A method for manufacturing a flexible device, which comprises manufacturing a laminate by the method according to item 15 or 16.

According to the present invention, it is possible to provide a polyimide precursor or a polyimide resin composition having excellent properties required for display applications by using DABA, PMDA, 6FDA, and a specific amount of a silicon-containing compound as monomers.
It should be noted that the above description shall not be deemed to disclose all the embodiments of the present invention and all the advantages relating to the present invention. Further embodiments of the present invention and their advantages will become apparent with reference to the following description.

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

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

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

｛式中、Ｐ_１は、２価の有機基を示し、Ｐ_２は、４価の有機基を示し、かつｐは、正の整数を示す。｝
で表される構造を含むポリイミド前駆体（以下、全ポリイミド前駆体ともいう）又はポリイミド（以下、全ポリイミドともいう）を含み、Ｐ_１は、下記一般式（３）：

で表される化合物に由来する構成単位を含み、
Ｐ_１又Ｐ_２は、下記一般式（５）：

｛式中、Ｒ_１は、それぞれ独立に、単結合又は炭素数１～１０の二価の有機基であり、Ｒ_２及びＲ_３は、それぞれ独立に、炭素数１～１０の一価の有機基であり、少なくとも一つは炭素数１～５の一価の脂肪族炭化水素基であり、Ｒ_４及びＲ_５は、それぞれ独立に、炭素数１～１０の一価の有機基であり、少なくとも一つは炭素数６～１０の一価の芳香族基であり、Ｒ_６及びＲ_７は、それぞれ独立に、炭素数１～１０の一価の有機基であり、Ｌ_１及びＬ_２は、それぞれ独立に、アミノ基、酸無水物基、イソシアネート基、カルボキシル基、酸エステル基、酸ハライド基、ヒドロキシ基、エポキシ基、又はメルカプト基であり、ｉは、１～２００の整数であり、ｊ及びｋは、それぞれ独立に、０～２００の整数であり、０≦ｊ／（ｉ＋ｊ＋ｋ）≦０．５０であり、かつ官能基当量が８０００以上である｝
で表されるケイ素含有化合物に由来する構成単位を含み、
そして、下記（ア）及び（イ）：
（ア）前記Ｐ_２は、下記一般式（４）：

で表される化合物に由来する構成単位を含む；
（イ）前記Ｐ_２は、下記一般式（１２）：

で表される化合物に由来する構成単位を含む；
を満たす。 << Resin composition >>
<Polyimide precursor / Polyimide>
The resin composition of this embodiment is
The following general formula (1) or (2):

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

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer. }
A polyimide precursor containing a structure represented by (hereinafter, also referred to as a total polyimide precursor) or a polyimide (hereinafter, also referred to as a total polyimide) is included, and P ₁ is the following general formula (3) :.

Containing structural units derived from the compound represented by
P ₁ or P ₂ is the following general formula (5):

{In the formula, R ₁ is an independently single-bonded or divalent organic group having 1 to 10 carbon atoms, and R ₂ and R ₃ are independently monovalent organic groups having 1 to 10 carbon atoms. It is a group, at least one is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, and R ₄ and R ₅ are independently monovalent organic groups having 1 to 10 carbon atoms, respectively. At least one is a monovalent aromatic group having 6 to 10 carbon atoms, R ₆ and R ₇ are independently monovalent organic groups having 1 to 10 carbon atoms, and L ₁ and L ₂ are independent groups. Independently, each is an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid halide group, a hydroxy group, an epoxy group, or a mercapto group, and i is an integer of 1 to 200. j and k are independently integers from 0 to 200, 0 ≦ j / (i + j + k) ≦ 0.50, and the functional group equivalent is 8000 or more}.
Containing structural units derived from silicon-containing compounds represented by
And the following (a) and (b):
(A) The P ₂ is the following general formula (4):

Includes structural units derived from the compounds represented by;
(A) The P ₂ is the following general formula (12):

Includes structural units derived from the compounds represented by;
Meet.

In the resin composition, the silicon-containing compound represented by the general formula (5) is:
When the total diamine is 100 mol%, it is 20 mol% or less; or
When the total acid dianhydride is 100 mol%, it is 20 mol% or less. When the silicon-containing compound is in the above range, it is preferable from the viewpoint of the filterability of the obtained polyimide precursor or the polyimide resin composition. From the viewpoint of further improving the filterability, the silicon-containing compound is 20.0 mol% or less, 19.0 mol% or less, 18 when the total diamine or total acid dianhydride in the resin composition is 100 mol%. It is more preferably 9.0 mol% or less, 17.0 mol% or less, 16.0 mol% or less, 15.0 mol% or less, or 14.0 mol% or less. The silicon-containing compound can exceed 0 mol% when the total diamine or total acid dianhydride of the resin composition is 100 mol%.

The polyimide precursor in the present embodiment may have a structure represented by the above formula (1) as well as a structure represented by the above formula (2). The content ratio of the structure represented by the formula (2) in the polyimide precursor is preferably 5% by mass or more and 40% by mass or less based on the mass of the polyimide precursor. It is preferable that the polyimide precursor contains the structure represented by the formula (2) within this numerical range because it is possible to achieve both low residual stress and high transparency and heat resistance in the obtained polyimide film. The content ratio of the structure represented by the formula (2) may be 6% by mass or more, 7% by mass or more, and 30% by mass or less, or 25% by mass or less, based on the mass of the polyimide precursor. May be.

The polyimide can be obtained by thermally imidizing a polyimide precursor and can also be chemically imidized. Thermal imidization is preferable from the viewpoint of transparency of the obtained polyimide film.

Further, the polyimide resin composition is preferable as compared with the polyimide precursor resin composition from the viewpoint of the viscosity stability of the composition.

｛式中、Ｐ_３は、２価の有機基を示し、Ｐ_４は、４価の有機基を示し、かつｐは、正の整数を示す。｝

｛式中、Ｐ_５は、２価の有機基を示し、Ｐ_６は、４価の有機基を示し、かつｑは、正の整数を示す。｝
で表される構造単位を含む、一部がイミド化されたポリイミド前駆体を含むこともでき、
前記Ｐ_３又はＰ_４が、下記一般式（１０）：

｛式中、Ｒ_１は、それぞれ独立に、単結合又は炭素数１～１０の二価の有機基であり、Ｒ_２及びＲ_３は、それぞれ独立に、炭素数１～１０の一価の有機基であり、少なくとも一つは炭素数１～５の一価の脂肪族炭化水素基であり、Ｒ_４及びＲ_５は、それぞれ独立に、炭素数１～１０の一価の有機基であり、少なくとも一つは炭素数６～１０の一価の芳香族基であり、Ｒ_６及びＲ_７は、それぞれ独立に、炭素数１～１０の一価の有機基であり、Ｌ_１及びＬ_２は、それぞれ独立に、アミノ基、酸無水物基、イソシアネート基、カルボキシル基、酸エステル基、酸ハライド基、ヒドロキシ基、エポキシ基、又はメルカプト基であり、ｉは、１～２００の整数であり、ｊ及びｋは、それぞれ独立に、０～２００の整数であり、０≦ｊ／（ｉ＋ｊ＋ｋ）≦０．５０である。｝
で表されるケイ素含有化合物に由来する構成単位を含み、
前記Ｐ_３及び／又はＰ_５は、下記一般式（８）：

で表される化合物に由来する構成単位を含むこともでき、
下記（ウ）及び（エ）：
（ウ）前記Ｐ_４及び／又はＰ_６は、下記一般式（９）：

で表される化合物に由来する構成単位を含む；
（エ）前記Ｐ_４及び／又はＰ_６は、下記一般式（１３）：

で表される化合物に由来する構成単位を含む；
を満たす。このような一部がイミド化されたポリイミド前駆体の場合、前述の全ポリイミド前駆体と比較して、組成物の粘度安定性に優れ、前述の全ポリイミドと比較すると、ポリイミド（ポリイミド前駆体）の合成のし易さの観点で優れる。 Further, the resin composition according to another embodiment of the present invention has the following general formulas (6) and (7):

{In the formula, P ₃ represents a divalent organic group, P ₄ represents a tetravalent organic group, and p represents a positive integer. }

{In the formula, P ₅ represents a divalent organic group, P ₆ represents a tetravalent organic group, and q represents a positive integer. }
It can also contain a partially imidized polyimide precursor, including structural units represented by.
The above P ₃ or P ₄ is the following general formula (10):

{In the formula, R ₁ is an independently single-bonded or divalent organic group having 1 to 10 carbon atoms, and R ₂ and R ₃ are independently monovalent organic groups having 1 to 10 carbon atoms. It is a group, at least one is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, and R ₄ and R ₅ are independently monovalent organic groups having 1 to 10 carbon atoms, respectively. At least one is a monovalent aromatic group having 6 to 10 carbon atoms, R ₆ and R ₇ are independently monovalent organic groups having 1 to 10 carbon atoms, and L ₁ and L ₂ are independent groups. Independently, each is an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid halide group, a hydroxy group, an epoxy group, or a mercapto group, and i is an integer of 1 to 200. j and k are independently integers of 0 to 200, and 0 ≦ j / (i + j + k) ≦ 0.50. }
Containing structural units derived from silicon-containing compounds represented by
The above P ₃ and / or P ₅ is expressed by the following general formula (8):

It can also contain structural units derived from the compounds represented by
The following (c) and (d):
(C) The _P4 and / or _P6 is expressed by the following general formula (9):

Includes structural units derived from the compounds represented by;
(D) The above _P4 and / or _P6 is expressed by the following general formula (13):

Includes structural units derived from the compounds represented by;
Meet. In the case of such a partially imidized polyimide precursor, the viscosity stability of the composition is excellent as compared with the above-mentioned all polyimide precursor, and compared with the above-mentioned all polyimide, the polyimide (polyimide precursor) It is excellent in terms of ease of synthesis.

From the viewpoint of the filterability of the obtained polyimide precursor or the polyimide resin composition, in the resin composition, the silicon-containing compound represented by the general formula (10) is:
When the total diamine is 100 mol%, it is 20 mol% or less; or
When the total acid dianhydride is 100 mol%, it is preferably 20 mol% or less. From the viewpoint of further improving the filterability, the silicon-containing compound is 20.0 mol% or less, 19.0 mol% or less, 18 when the total diamine or total acid dianhydride in the resin composition is 100 mol%. It is more preferably 9.0 mol% or less, 17.0 mol% or less, 16.0 mol% or less, 15.0 mol% or less, or 14.0 mol% or less. The silicon-containing compound can exceed 0 mol% when the total diamine or total acid dianhydride of the resin composition is 100 mol%.

The resin composition is represented by the general formula (3) or (8) from the viewpoint of being excellent in both the characteristics required for the manufacturing process of the polyimide precursor and / or the polyimide-containing resin composition and the characteristics required for the display application. The amount of the compound is preferably more than 50 mol% when the total diamine (excluding the compound represented by the general formula (5) or (10)) is 100 mol%.

で表されるジアミン化合物に由来する構成単位を含む。一般式（３）で表されるジアミン化合物の中でも、ポリイミドフィルムの透明性、ＹＩの観点から、３，５－ジアミノ安息香酸（ＤＡＢＡ）が好ましい。この構造単位を有すると、得られるポリイミドフィルムの機械特性（特に引張伸度）が向上し、耐熱性を向上することができるため好ましい。このような特性が向上する理由は明確ではないが、カルボキシル基の作用によって、分子間相互作用が働いているためと考えられる。 (Diamine)
The resin composition has the following general formula (3):

Contains structural units derived from the diamine compound represented by. Among the diamine compounds represented by the general formula (3), 3,5-diaminobenzoic acid (DABA) is preferable from the viewpoint of transparency of the polyimide film and YI. Having this structural unit is preferable because the mechanical properties (particularly the tensile elongation) of the obtained polyimide film can be improved and the heat resistance can be improved. The reason for the improvement of such properties is not clear, but it is considered that the intramolecular interaction is working due to the action of the carboxyl group.

The content of DABA in the total diamine (including the compound in which L ₁ and L ₂ are amino groups in the above general formulas (5) and (10)) is more than 50 mol%, more than 55 mol%, or more than 70 mol%. , Or 90 mol% or more, or 95 mol% or more. The larger the amount of DABA, the larger the tensile elongation of the polyimide film, which is preferable.

If desired, the resin composition may contain a diamine other than the diamine compound represented by the general formula (3). Examples of the diamine other than the general formula (3) include diaminodiphenyl sulfone (for example, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone), 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'-diamino Biphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-Diaminodiphenylmethane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4 -(4-Aminophenoxy) phenyl] sulfone, 4,4-bis (4-aminophenoxy) biphenyl, 4,4-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether , Bis [4- (3-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 9,10-bis (4-amino) Phenyl) 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, 1,4-bis (3-aminopropyldimethylsilyl) benzene, 9,9-bis (4-aminophenyl) fluorene (BAFL) ), 1,3-Bis [1- (4-aminophenyl) -1-methylethyl] benzene] (BiSAM) and the like.

Diamines other than the general formula (3) are 4,4'-diaminodiphenyl sulfone (4,4'-DAS), 9,9-bis (4-aminophenyl) fluorene (BAFL), 1,3-bis [1. -(4-Aminophenyl) -1-methylethyl] benzene] (BiSAM), and preferably at least one selected from the group consisting of 1,4-cyclohexanediamine (CHDA).

From the viewpoint of heat resistance and mechanical strength of the obtained polyimide resin film, diamines other than the general formula (3) are 9,9-bis (4-aminophenyl) fluorene (BAFL) and 1,3-bis [1- ( It is more preferably at least one selected from the group consisting of 4-aminophenyl) -1-methylethyl] benzene] (BiSAM).
Here, it is preferable that the resin composition does not contain TFMB (2,2'-bis (trifluoromethyl) benzidine) other than the diamine compound represented by the general formula (3). When at least one of P ₁ , P ₃ , and P ₅ in the general formulas (1), (2), (6) or (7) contains a group derived from TFMB, the viscosity stability and filterability of the resin composition are high. This is because it tends to get worse.

で表される化合物（ＰＭＤＡともいう）に由来する構成単位を含む。この構造単位を有すると、得られるポリイミドフィルムの耐熱性、及び／又は機械特性（例えば、伸度、残留応力、他の機械的性質など）を向上することができるため好ましい。 (Acid dianhydride)
The resin composition has the following general formula (4):

It contains a structural unit derived from a compound represented by (also referred to as PMDA). Having this structural unit is preferable because it can improve the heat resistance and / or mechanical properties (for example, elongation, residual stress, other mechanical properties, etc.) of the obtained polyimide film.

The content of PMDA in the total acid dianhydride (where L ₁ and L ₂ include the compound having an acid anhydride group in the above general formulas (5) and (10)) is 50 mol% or more, 60 mol% or more, Or it may be 70 mol% or more, 90 mol% or more, or 95 mol% or more. The larger the amount of PMDA, the better the heat resistance and mechanical properties of the polyimide film, which is preferable.

で表される化合物に由来する（６ＦＤＡともいう）に由来する構成単位を含む。この構造単位を有すると、得られるポリイミドフィルムの透明性（例えば、透過率、ＹＩ等）を向上することができるため好ましい。また、一般式（１）、（２）、（６）又は（７）においてＰ_２、Ｐ_４、又はＰ_６が、前記一般式（４）及び（１２）に由来する構成単位を有すると、得られるポリイミドフィルムの耐熱性、機械特性、透明性を両立できるため、さらに好ましい。 The resin composition, together with the general formula (4), has the following general formula (12):

It contains a structural unit derived from the compound represented by (also referred to as 6FDA). Having this structural unit is preferable because the transparency (for example, transmittance, YI, etc.) of the obtained polyimide film can be improved. Further, when P ₂ , P ₄ , or P ₆ in the general formulas (1), (2), (6) or (7) has a structural unit derived from the general formulas (4) and (12), It is more preferable because the obtained polyimide film can have both heat resistance, mechanical properties, and transparency.

The content of 6FDA in the total acid dianhydride (where L ₁ and L ₂ include the compound having an acid anhydride group in the above general formulas (5) and (10)) is 50 mol% or more, 60 mol% or more, Or it may be 70 mol% or more, 90 mol% or more, or 95 mol% or more. A larger amount of 6FDA is preferable because the transparency of the polyimide film is improved.

の化合物（ＢｚＤＡ）；下記構造：

の化合物（ＢＮＢＤＡ）等が挙げられる。 If desired, the resin composition may contain an acid dianhydride other than the compounds represented by the general formulas (4) and (12). Examples of the acid dianhydride other than the general formulas (4) and (12) include 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), 2,2', 3,3'-biphenyl. Tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-franyl) -3-methyl-cyclohexene-1,2 dicarboxylic acid anhydride, 1,2,3,4-benzenetetracarboxylic dianhydride Anhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2', 3,3'-benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenyl Sulfontetracarboxylic dianhydride, methylene-4,4'-diphthalic acid dianhydride, 1,1-ethylidene-4,4'-diphthalic acid dianhydride, 2,2-propyridene-4,4'-diphthalide Acid dianhydride, 1,2-ethylene-4,4'-diphthalic acid dianhydride, 1,3-trimethylethylene-4,4'-diphthalic acid dianhydride, 1,4-tetramethylene-4,4' -Diphthalic acid dianhydride, 1,5-pentamethylene-4,4'-diphthalic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, p-phenylenebis (trimeritate acid anhydride), thio-4 , 4'-diphthalic acid dianhydride, sulfonyl-4,4'-diphthalic acid dianhydride, 1,3-bis (3,4-dicarboxyphenyl) benzene dianhydride, 1,3-bis (3, 4-Dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,3-bis [2- (3,4-dicarboxyphenyl) -2- Propyl] benzene dianhydride, 1,4-bis [2- (3,4-dicarboxyphenyl) -2-propyl] benzene dianhydride, bis [3- (3,4-dicarboxyphenoxy) phenyl] methane Dianhydride, bis [4- (3,4-dicarboxyphenoxy) phenyl] methane dianhydride, 2,2-bis [3- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2, 2-Bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, bis (3,4-dicarboxyphenoxy) dimethylsilane dianhydride, 1,3-bis (3,4-dicarboxy) Phenyl) -1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride , 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 3,4 , 9,10-Perylenetetracarboxylic acid dianhydride, 2,3,6,7-anthracentetracarboxylic acid dianhydride, and 1,2,7,8-phenanthrentetracarboxylic acid dianhydride, 9,9- Bis (3,4-dicarboxyphenyl) fluorene diacid anhydride (BPAF), 4,4'-oxydiphthalic acid anhydride (ODPA), 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride (HPMDA) , And 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride (CBDA), the following structure:

Compound (BzDA); structure below:

(BNBDA) and the like.

Acid dianhydrides other than the above general formulas (4) and (12) are 4,4'-oxydiphthalic acid anhydride (ODPA) and 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride. It is preferably at least one selected from the group consisting of (BPAF), BzDA, BNBDA, and 1,2,4,5-cyclohexanetetracarboxylic acid anhydride (HPMDA). The acid dianhydride may be used alone or in combination of two or more.

<Silicon-containing compound>

The polyimide / polyimide precursor in this embodiment has a structure derived from a silicon-containing compound. Therefore, the silicon-containing compound used in the synthesis of the polyimide precursor in the present embodiment may be a compound having a reactive group capable of cocondensing with at least one of tetracarboxylic acid dianhydride and diamine.

｛式中、
Ｒ_１は、それぞれ独立に、単結合又は炭素数１～１０の２価の有機基であり、
Ｒ_２及びＲ_３は、それぞれ独立に、炭素数１～１０の１価の有機基であって、Ｒ_２及びＲ_３のうちの少なくとも１つは、炭素数１～５の１価の脂肪族炭化水素基であり、
Ｒ_４及びＲ_５は、それぞれ独立に、炭素数１～１０の１価の有機基であって、Ｒ_４及びＲ_５のうちの少なくとも１つは、炭素数６～１０の１価の芳香族基であり、
Ｒ_６及びＲ_７は、それぞれ独立に、炭素数１～１０の１価の有機基であって、Ｒ_６及びＲ_７のうちの少なくとも１つは、炭素数２～１０の不飽和脂肪族炭化水素基を含む有機基であることが好ましく、
Ｌ_１及びＬ_２は、それぞれ独立に、酸無水物構造を含む１価の有機基、アミノ基、イソシアネート基、カルボキシル基、アルコキシカルボニル基、ハロゲン化カルボニル基、ヒドロキシ基、エポキシ基、又はメルカプト基であり、
ｉは、１～２００の整数であり、
ｊ及びｋは、それぞれ独立に０～２００の整数であり、ｊは、１～２００の整数であることが好ましく、そして、
０≦ｊ／（ｉ＋ｊ＋ｋ）≦０．５０であり、０．０５≦ｊ／（ｉ＋ｊ＋ｋ）≦０．５０の関係を満たすことが好ましい。｝で表される化合物が挙げられる。 Such a silicon-containing compound may be, for example, the following formulas (5) and (10) (hereinafter, also simply referred to as (5)):

{In the ceremony,
R ₁ is an independently single-bonded or divalent organic group having 1 to 10 carbon atoms.
R ₂ and R ₃ are independently monovalent organic groups having 1 to 10 carbon atoms, and at least one of R ₂ and R ₃ is a monovalent aliphatic group having 1 to 5 carbon atoms. It is a hydrocarbon group and
R ₄ and R ₅ are independently monovalent organic groups having 1 to 10 carbon atoms, and at least one of R ₄ and R ₅ is a monovalent aromatic group having 6 to 10 carbon atoms. Is the basis and
R ₆ and R ₇ are independently monovalent organic groups having 1 to 10 carbon atoms, and at least one of R ₆ and R ₇ is an unsaturated aliphatic hydrocarbon having 2 to 10 carbon atoms. It is preferably an organic group containing a hydrogen group, preferably
L ₁ and L ₂ are each independently a monovalent organic group containing an acid anhydride structure, an amino group, an isocyanate group, a carboxyl group, an alkoxycarbonyl group, a halogenated carbonyl group, a hydroxy group, an epoxy group, or a mercapto group. And
i is an integer from 1 to 200,
j and k are each independently an integer of 0 to 200, preferably an integer of 1 to 200, and
It is preferable that 0 ≦ j / (i + j + k) ≦ 0.50 and the relationship of 0.05 ≦ j / (i + j + k) ≦ 0.50 is satisfied. } Can be mentioned.

R ₁ in the formula (5) is a single bond or a divalent organic group having 1 to 10 carbon atoms, respectively. 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 a methylene group, an ethylene group, an n-propylene group, an i-propylene group, an n-butylene group, an s-butylene group and a t-butylene group. Linear or branched alkylene groups such as n-pentylene group, neopentylene group, n-hexylene group, n-heptylene group, n-octylene group, n-nonylene group, n-decylene group; cyclopropylene group, cyclobutylene group, Examples thereof include a cycloalkylene group such as a cyclopentylene group, a cyclohexylene group, a cycloheptylene group and a cyclooctylene group. The divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferably at least one selected from the group consisting of an ethylene group, an n-propylene group and an i-propylene group.

R ₂ and R ₃ in the formula (5) are independently monovalent organic groups having 1 to 10 carbon atoms, and at least one 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, the monovalent organic group having 1 to 10 carbon atoms includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, a t-butyl group, and an n-pentyl group. , Neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and other linear or branched alkyl groups; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group. , Cycloalkyl group such as cycloheptyl group, cyclooctyl group; aromatic group such as phenyl group, tolyl group, xsilyl group, α-naphthyl group, β-naphthyl group and the like.
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, the monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, and a t-butyl group. Linear or branched alkyl groups such as n-pentyl group and neopentyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group and cyclopentyl group can be mentioned. The monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferably at least one selected from the group consisting of a methyl group, an ethyl group, and an n-propyl group.

R ₄ and R ₅ in the formula (5) are independently monovalent organic groups having 1 to 10 carbon atoms, and at least one is a monovalent aromatic group having 6 to 10 carbon atoms. The monovalent organic group having 1 to 10 carbon atoms may be linear, cyclic or branched, and may be saturated or unsaturated. For example, the monovalent organic group having 1 to 10 carbon atoms includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, a t-butyl group and an n-pentyl group. Linear or branched alkyl group such as group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl. Cycloalkyl groups such as groups, cycloheptyl groups and cyclooctyl groups; aromatic groups such as phenyl group, trill group, xylyl group, α-naphthyl group and β-naphthyl group can be mentioned. Examples of the monovalent aromatic group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, a xsilyl group, an α-naphthyl group, a β-naphthyl group and the like, and may be a phenyl group, a tolyl group, or a xsilyl group. It is preferable to have.

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

A part or all of the hydrogen atoms of R ₁ to R ₇ in the formula (5) may be substituted with a substituent such as a halogen atom such as F, Cl, Br or the like, or may be unsubstituted.

｛上記式中、「＊」は、結合手を表す。｝で表される、２，５－ジオキソテトラヒドロフラン－３－イル基が挙げられる。これらの中でもアミノ基、酸無水物基が好ましく、樹脂組成物の粘度安定性の観点から、アミノ基がより好ましい。
アルコキシカルボニル基におけるアルコキシル基は、炭素数１～６のアルコキシル基であってよく、例えば、メトキシル基、エトキシル基、ｎ－プロポキシル基、ｉ－プロポキシル基、ｎ－ブトキシル基、ｉ－ブトキシル基、ｔ－ブトキシル基等であってよい。
ハロゲン化カルボニル基におけるハロゲン原子は、フッ素原子以外のハロゲン原子が好ましく、より好ましくは、塩素原子又はヨウ素原子である。 L ₁ and L ₂ in the formula (5) are each independently a monovalent organic group (also referred to as an acid anhydride group) containing an acid anhydride structure, an amino group, an isocyanate group, a carboxyl group, an alkoxycarbonyl group, and the like. It is a halogenated carbonyl group, a hydroxy group, an epoxy group, or a mercapto group.
Examples of the monovalent organic group containing an acid anhydride structure include the following formula:

{In the above formula, "*" represents a bond. }, Examples thereof include a 2,5-dioxotetrahydrofuran-3-yl group. Among these, an amino group and an acid anhydride group are preferable, and an amino group is more preferable from the viewpoint of viscosity stability of the resin composition.
The alkoxyl group in the alkoxycarbonyl group may be an alkoxyl group having 1 to 6 carbon atoms, for example, a methoxyl group, an ethoxyl group, an n-propoxyl group, an i-propoxyl group, an n-butoxyl group, or an i-butoxyl group. , T-butoxyl group and the like.
The halogen atom in the halogenated carbonyl group is preferably a halogen atom other than a fluorine atom, and more preferably a chlorine atom or an iodine atom.

The functional group equivalent of the silicon-containing compound represented by the formula (5) is preferably 800 or more, more preferably 1000 or more, still more preferably 1500 or more, from the viewpoint of the filterability of the resin composition. On the other hand, when the functional group equivalent is 500 or less, the filterability may deteriorate. Here, the functional group equivalent is the molecular weight of the silicon-containing compound per 1 mol of the functional group (unit: g / mol). The functional group equivalent can be measured by a known method. Further, when the functional group equivalent of the silicon-containing compound is 800 or more, the residual stress of the polyimide film under the nitrogen atmosphere is small, which is preferable. The reason for this is considered to be that when the functional group equivalent is equal to or more than a specific value, the silicone domain is increased and stress is relaxed.
The functional group equivalent can be measured according to existing standards and the like.

I in the formula (5) is an integer of 1 to 200, preferably an integer of 2 to 100, more preferably an integer of 4 to 80, and even more preferably an integer of 8 to 40. j and k are independently integers of 0 to 200, j may be an integer of 1 to 200, and j and k are preferably integers of 0 to 50, more preferably integers of 0 to 20, and further. It is preferably an integer of 0 to 50.

It is preferable that the polyimide in the resin composition has a structure derived from the formula (5) because the residual stress measured in the nitrogen atmosphere of the polyimide film is good (small). The reason for measuring in a nitrogen atmosphere is that when an inorganic film such as SiO, SiN is formed on a polyimide film in the display process, it may be exposed to the nitrogen atmosphere, and the residual stress in the nitrogen atmosphere is small. This is because it is required.

｛式中、Ｐ_５は、それぞれ独立に、二価の炭化水素基を示し、同一でも異なっていてもよく、Ｐ_３及びＰ_４は、一般式（５）において定義したＲ_２、Ｒ_３と同様であり、ｌは、１～２００の整数を表す。｝
で表されるジアミノ（ポリ）シロキサンが好ましい。 From the viewpoint of the type of monomer, cost, and the molecular weight of the obtained polyimide precursor, the silicon-containing compound of the general formulas (5) and (10) is preferably a silicon-containing diamine. Examples of the silicon-containing diamine include the following formula (11):

{In the formula, P ₅ independently represents a divalent hydrocarbon group and may be the same or different, and P ₃ and P ₄ are R ₂ and R ₃ defined in the general formula (5). Similarly, l represents an integer from 1 to 200. }
The diamino (poly) siloxane represented by is preferable.

Preferred structures of _P3 and _P4 in the general formula (11) include a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group and the like. Of these, the methyl group is preferable.

L in the general formula (11) is an integer of 1 to 200, and is an integer of 3 to 200 from the viewpoint of the heat resistance of the polyimide obtained by using the silicon-containing diamine represented by the formula (11). Is preferable.

The preferable range of the functional group equivalent of the compound represented by the general formula (11) is the same as that of the silicon-containing compound represented by the general formula (5) described above.

The copolymerization ratio of the silicon-containing diamine is preferably 0.5 to 30% by mass, more preferably 1.0% by mass to 25% by mass, and further preferably 1.5 with respect to the total mass of the polyimide precursor / polyimide. It is from% by mass to 20% by mass. When the silicon-containing diamine is 0.5% by 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 30% by mass or less, the transparency (particularly low HAZE) of the obtained polyimide film is good, which is preferable from the viewpoint of achieving high total light transmittance and high glass transition temperature.

As described above, the silicon-containing compound as the monomer used in the polyimide precursor / polyimide may be synthesized by using the common general technical knowledge at the time of filing, or a commercially available product may be used. Commercially available products include both-terminal 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)), both-terminal acid anhydride-modified methylphenyl. Silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-168-P5-B (functional group equivalent 2100)), both-ended epoxy-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-2000 (functional group equivalent 620)), both ends Amino-modified dimethyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd .: PAM-E (functional group equivalent 130), X22-161A (functional group equivalent 800), X22-161B (functional group equivalent 1500), KF8012 (functional group equivalent 2200), Toledau Made by Corning: BY16-853U (functional group equivalent 450), JNC: Silaplane FM3311 (number average molecular weight 1000)), both-ended epoxy-modified dimethyl silicone (made by Shin-Etsu Chemical Co., Ltd .: X-22-163A (functional group equivalent 1750) ), Both-ended alicyclic epoxy-modified dimethyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd .: X-22-169B (functional group equivalent 1700)), both-ended hydroxy group-modified dimethyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd .: KF-6000), both ends Mercapto-modified dimethyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd .: X-22-167B (functional group equivalent 1700)), bi-terminal acid anhydride-modified dimethyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd .: X-22-168A (functional group equivalent 1000)), etc. Among these, both-terminal amine-modified dimethyl silicone oil is preferable from the viewpoint of price, improvement of chemical resistance, and improvement of Tg.

<solvent>
The resin composition typically contains a solvent. As the solvent, those having good solubility of the polyimide / polyimide precursor and capable of appropriately controlling the solution viscosity of the resin composition are preferable, and the reaction solvent of the polyimide precursor can be used as the solvent of the composition. Among them, N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), the following Equamid M100, Equamid B100 and the like are preferable. Specific examples of the solvent composition include N-methyl-2-pyrrolidone (NMP) alone, or a mixed solvent of N-methyl-2-pyrrolidone (NMP) and γ-butyrolactone (GBL). The mass ratio of NMP to GBL may be, for example, NMP: GBL (mass ratio) = 10: 90 to 90:10.

<Additional ingredients>
The resin composition of the present embodiment may further contain additional components in addition to the polyimide / polyimide precursor, small molecule cyclic siloxane, and solvent. Additional components include, for example, surfactants, alkoxysilane compounds and the like.

(Surfactant)
By adding a surfactant to the resin composition of the present embodiment, the coatability of the resin composition can be improved. Specifically, it is possible to prevent the occurrence of streaks in the coating film.

Examples of such a surfactant include silicone-based surfactants, fluorine-based surfactants, and nonionic surfactants other than these. Examples of the silicone-based surfactant include organosiloxane polymers KF-640, 642, 643, KP341, X-70-092, X-70-093 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.); SH-28PA, SH. -190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (trade name, manufactured by Toray Dow Corning Silicone Co., Ltd.); SILWET L-77, L-7001, FZ-2105, FZ -2120, FZ-214, FZ-2164, FZ-2166, L-7604 (trade name, manufactured by Nippon Unicar Co., Ltd.); DBE-814, DBE-224, DBE-621, CMS-626, CMS-222, KF- 352A, KF-354L, KF-355A, KF-6020, DBE-821, DBE-712 (Gelest), BYK-307, BYK-310, BYK-378, BYK-333 (trade name, manufactured by Big Chemie Japan); Granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and the like can be mentioned. Examples of the fluorine-based surfactant include Megafuck F171, F173, R-08 (manufactured by Dainippon Ink and Chemicals, Inc., trade name); Florard FC4430, FC4432 (Sumitomo 3M Ltd., trade name) and the like. .. Examples of the nonionic surfactant other than these include polyoxyethylene uralyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether and the like.

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

(Alkoxysilane compound)
When the polyimide film obtained from the resin composition of the present embodiment is used for a flexible substrate or the like, the resin composition is 100 parts by mass of the polyimide precursor from the viewpoint of obtaining good adhesion between the support and the polyimide film in the manufacturing process. On the other hand, 0.01 to 20 parts by mass of the alkoxysilane compound can be contained. When the content of the alkoxysilane compound with respect to 100 parts by mass of the polyimide precursor is 0.01 parts by mass or more, good adhesion between the support and the polyimide film can be obtained. Further, it is preferable that the content of the alkoxysilane compound is 20 parts by mass or less from the viewpoint of storage stability of the resin composition. The content of the alkoxysilane compound is preferably 0.02 to 15 parts by mass, more preferably 0.05 to 10 parts by mass, and further preferably 0.1 to 8 parts by mass with respect to 100 parts by mass of the polyimide precursor. be. By using the alkoxysilane compound, in addition to the above-mentioned improvement of the adhesiveness, the coatability of the resin composition is improved (sujimura suppression), and the influence of the oxygen concentration at the time of curing on the YI value of the polyimide film is reduced. You can also do it.

のそれぞれで表されるアルコキシシラン化合物等を挙げることができる。アルコキシシラン化合物は、一種を単独で用いても二種以上を組み合わせて使用してもよい。 Examples of the alkoxysilane compound include 3-ureidopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane. γ-Aminopropyltripropoxysilane, γ-aminopropyltributoxysilane, γ-aminoethyltriethoxysilane, γ-aminoethyltripropoxysilane, γ-aminoethyltributoxysilane, γ-aminobutyltriethoxysilane, γ- Aminobutyltrimethoxysilane, γ-aminobutyltripropoxysilane, γ-aminobutyltributoxysilane, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy (p-tolyl) silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenyl Silane, dimethoxydi-p-tolylsilane, triphenylsilanol, and the following structures:

Examples thereof include an alkoxysilane compound represented by each of the above. The alkoxysilane compound may be used alone or in combination of two or more.

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

<Purification of silicon-containing compounds>
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 for reducing the total amount of the cyclic silicon-containing compound contained in the resin composition of the present embodiment, for example, the silicon-containing compound is purified before the polycondensation reaction to obtain the total amount of the cyclic silicon-containing compound. Is mentioned. Alternatively, after the polycondensation reaction, the resin composition may be purified to reduce the total amount of cyclic silicon-containing compounds.

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

<Synthesis of polyimide / polyimide precursor>
The polyimide precursor of the present embodiment can be synthesized by subjecting a polycondensation component containing an acid dianhydride, a diamine, and a silicon-containing compound to a polycondensation reaction. In connection with the synthesis of polyimide / polyimide precursor, for example, one of the following steps:
-The compound represented by the general formula (3) described above, the compound represented by the general formulas (4) and (12), the silicon-containing compound represented by the general formula (5), and other compounds. A step of polycondensing a compound with a compound to provide a polyimide precursor and / or a polyimide;
-The compound represented by the general formula (3) and other compounds described above, and the compounds represented by the general formulas (4) and (12) and other compounds are subjected to a polycondensation reaction to obtain a polyimide. After that, a step of subjecting the silicon-containing compound represented by the general formula (5) described above to a polycondensation reaction with another compound to provide a polyimide precursor; or-diamine and acid described above. (2) A step of subjecting a polyimide to a polyimide by subjecting it to a polycondensation reaction with an anhydride, and then subjecting the silicon-containing compound represented by the general formula (5) to a polycondensation reaction of another compound to provide a polyimide precursor;
A method for producing a resin composition containing the above is provided. Further, it is preferable to use the above-mentioned purified compound as the silicon-containing compound. In a preferred embodiment, the polycondensation component comprises an acid dianhydride, a diamine, and a silicon-containing compound. The polycondensation reaction is preferably carried out in a suitable solvent. Specific examples thereof include a method in which a predetermined amount of a diamine component and a silicon-containing compound are dissolved in a solvent, a predetermined amount of acid dianhydride is added to the obtained diamine solution, and the mixture is stirred.

The molar ratio of acid dianhydride to diamine when synthesizing the polyimide / polyimide precursor is determined from the viewpoint of increasing the molecular weight of the polyimide precursor resin and the slit coating characteristics of the resin composition: acid dianhydride: diamine = 100. The range is preferably 90 to 100: 110 (0.90 to 1.10 parts of diamine with respect to 1 mol of acid dianhydride), and 100: 95 to 100: 105 (with respect to 1 mol of acid dianhydride). The range of diamine 0.95 to 1.05 mol part) is more preferable.

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

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

The solvent for the reaction is not particularly limited as long as it can dissolve the acid dianhydride component and the diamine component, and the resulting polyimide / polyimide precursor, and can obtain a high molecular weight polymer. Examples of such a solvent include an aprotic solvent, a phenol-based solvent, an ether and a glycol-based solvent, and the like.

｛式中、Ｒ_１２＝メチル基で表されるエクアミドＭ１００（商品名：ＫＪケミカルズ社製）、及び、Ｒ_１２＝ｎ－ブチル基で表されるエクアミドＢ１００（商品名：ＫＪケミカルズ社製）｝；γ－ブチロラクトン、γ－バレロラクトン等のラクトン系溶媒；ヘキサメチルホスホリックアミド、ヘキサメチルホスフィントリアミド等の含リン系アミド系溶媒；ジメチルスルホン、ジメチルスルホキシド、スルホラン等の含硫黄系溶媒；シクロヘキサノン、メチルシクロヘキサノン等のケトン系溶媒；ピコリン、ピリジン等の３級アミン系溶媒；酢酸（２－メトキシ－１－メチルエチル）等のエステル系溶媒等が挙げられる。 Examples of the aprotic solvent include N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N-methylcaprolactam, 1,3-dimethyl. Imidazolidinone, tetramethylurea, and amide solvents of the following general formula:

{In the formula, R ₁₂ = Equamid M100 represented by a methyl group (trade name: manufactured by KJ Chemicals) and R ₁₂ = Equamid B100 represented by an n-butyl group (trade name: manufactured by KJ Chemicals)} Lactone-based solvents such as γ-butyrolactone and γ-valerolactone; phosphorus-containing amide-based solvents such as hexamethylphosphoric amide and hexamethylphosphintriamide; sulfur-containing solvents such as dimethylsulfone, dimethylsulfoxide and sulfolane; cyclohexanone , A ketone solvent such as methylcyclohexanone; a tertiary amine solvent such as picolin and pyridine; an ester solvent such as acetic acid (2-methoxy-1-methylethyl) and the like.

Examples of the phenolic solvent include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3, Examples thereof include 4-xylenol and 3,5-xylenol.

Examples of the ether and glycol-based solvent include 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, and bis [2- (2-methoxyethoxy) ethyl. ] Ether, tetrahydrofuran, 1,4-dioxane and the like can be mentioned.

These solvents may be used alone or in combination of two or more.

The boiling point of the solvent used for the synthesis of the polyimide / polyimide precursor at normal pressure is preferably 60 to 300 ° C, more preferably 140 to 280 ° C, still more preferably 170 to 270 ° C. Since the boiling point of the solvent is lower than 300 ° C., the drying step is shortened. When the boiling point of the solvent is 60 ° C. or higher, roughening of the surface of the resin film, mixing of air bubbles in the resin film, and the like are less likely to occur during the drying step, and a more uniform film can be obtained. In particular, it is preferable to use a solvent having a boiling point of 170 to 270 ° C. and / or a vapor pressure of 250 Pa or less at 20 ° C. from the viewpoint of solubility and reduction of edge abnormality during coating. More specifically, one or more selected from the group consisting of N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), and a compound represented by the general formula (6) is preferable.

The water content in the solvent is preferably, for example, 3,000 mass ppm or less in order to allow the polycondensation reaction to proceed satisfactorily. 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. It is considered that the reason why the molecule having a molecular weight of less than 1,000 is present in the resin composition is that the water content of the solvent and the raw material (acid dianhydride, diamine) used at the time of synthesis is involved. That is, it is considered that the acid anhydride group of some acid anhydride monomers is hydrolyzed by water to become a carboxyl group and remains in a low molecular weight state without increasing the molecular weight. Therefore, it is preferable that the water content of the solvent used for the above polycondensation reaction is small. The water content of the solvent is preferably 3,000 mass ppm or less, more preferably 1,000 mass ppm or less. Similarly, the amount of water contained in the raw material is preferably 3,000 mass ppm or less, and more preferably 1,000 mass ppm or less.

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

When dissolving each polycondensation component in a solvent, it may be heated if necessary. From the viewpoint of obtaining a polyimide precursor having a high degree of polymerization, the reaction temperature at the time of synthesizing the polyimide precursor may be preferably 0 ° C to 120 ° C, 40 ° C to 100 ° C, or 60 to 100 ° C, and the polymerization time may be set. Is preferably 1 to 100 hours, or 2 to 10 hours. When the polymerization time is 1 hour or more, a polyimide precursor having a uniform degree of polymerization can be obtained, and when the polymerization time is 100 hours or less, a polyimide precursor having a high degree of polymerization can be obtained.

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

The polyimide precursor in the present embodiment may be partially imidized (partially imidized). By partially imidizing the polyimide precursor, the viscosity stability when the resin composition is stored can be improved. In this case, the imidization ratio is preferably 5% or more, more preferably 8% or more, and preferably 8% or more, from the viewpoint of balancing the solubility of the polyimide precursor in the resin composition and the storage stability of the solution. It is 80% or less, more preferably 70% or less, still more preferably 50% or less. This partial imidization is obtained by heating the polyimide precursor to dehydrate and ring closure. This heating can be carried out at a temperature of preferably 120 to 200 ° C., more preferably 150 to 185 ° C., still more preferably 150 to 180 ° C., preferably for 15 minutes to 20 hours, more preferably 30 minutes to 10 hours. ..

A part or all of the carboxylic acid is esterified by adding N, N-dimethylformamide dimethylacetal or N, N-dimethylformamide diethylacetal to the polyimide / polyimide precursor obtained by the above reaction and heating. May be used as the polyimide precursor of the present embodiment. Esterification can improve viscosity stability during storage. In these ester-modified polyamic acids, the above-mentioned acid dianhydride component is sequentially reacted with 1 equivalent of a monohydric alcohol with respect to the acid anhydride group and a dehydration condensing agent such as thionyl chloride and dicyclohexylcarbodiimide. It can also be obtained by a method of conducting a condensation reaction with a diamine component.

The polyimide / polyimide precursor obtained by the above reaction preferably does not contain a group derived from TFMB (2,2'-bis (trifluoromethyl) benzidine). When a group derived from TFMB is contained, for example, at least one of P ₁ , P ₃ , P ₅ in the above general formula (1), (2), (6) or (7) contains a group derived from TFMB. This is because the viscosity stability and the filterability of the resin composition containing the polyimide / polyimide precursor tend to deteriorate. From the viewpoint of viscosity stability and filterability of the resin composition, TFMB is not used as a raw material in the synthesis of the polyimide / polyimide precursor, for example, as a diamine raw material other than the diamine compound represented by the above general formula (3). It is preferable, or it is preferable to remove and purify the TFMB from the raw material.

<Synthesis of polyimide>
In a more preferable mode, in the polyimide varnish, the acid dianhydride component and the diamine component are dissolved in a solvent, for example, an organic solvent, a co-boiling solvent such as toluene is added, and water generated during imidization is removed from the system. By removing it, it can be produced as a polyimide solution (also referred to as polyimide varnish) containing a polyimide and a solvent. Here, the conditions at the time of reaction are not particularly limited, but for example, the reaction temperature is 0 ° C. to 180 ° C. and the reaction time is 3 to 72 hours. In order to sufficiently proceed with the reaction with the sulfone group-containing diamines, it is preferable to carry out a heating reaction at 180 ° C. for about 12 hours. Further, during the reaction, it is preferable that the atmosphere is an inert atmosphere such as argon or nitrogen.

<Preparation of resin composition>
When the solvent used when synthesizing the polyimide precursor and the solvent contained in the resin composition are the same, the synthesized polyimide / polyimide precursor solution can be used as it is as the resin composition. If necessary, a resin composition is prepared by adding one or more of a further solvent and an additional component to the polyimide precursor and stirring and mixing them in a temperature range of room temperature (25 ° C.) to 80 ° C. You may. This stirring and mixing can be performed by using an appropriate device such as a three-one motor (manufactured by Shinto Chemical Co., Ltd.) equipped with a stirring blade, a rotation / revolution mixer, and the like. If necessary, the resin composition may be heated to 40 ° C to 100 ° C.

On the other hand, if the solvent used when synthesizing the polyimide / polyimide precursor is different from the solvent contained in the resin composition, the solvent in the synthesized polyimide precursor solution is, for example, reprecipitated, distilled off, etc. The polyimide / polyimide precursor may be isolated by removing it by an appropriate method. Then, in the temperature range of room temperature (25 ° C.) to 80 ° C., a desired solvent and, if necessary, additional components are added to the isolated polyimide precursor, and the mixture is stirred and mixed to prepare a resin composition. You may.

After preparing the resin composition as described above, the resin composition is heated at, for example, 130 to 200 ° C. for, for example, 5 minutes to 2 hours to remove a part of the polyimide precursor to the extent that the polymer does not precipitate. Dehydration imidization may be carried out (partial imidization). The imidization rate can be controlled by controlling the heating temperature and the heating time. By partially imidizing the polyimide precursor, it is possible to improve the viscosity stability when the resin composition is stored.

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

If the solution viscosity of the resin composition during the synthesis of the polyimide / polyimide precursor is higher than 200,000 mPa · s, there may be a problem that stirring during the synthesis becomes difficult. However, even if the solution becomes highly viscous during synthesis, it is possible to obtain a resin composition having a viscosity that is easy to handle by adding a solvent and stirring after the reaction is completed. The solution viscosity of the resin composition in this embodiment is a value measured at 23 ° C. using an E-type viscometer (for example, VISCONICEHD, manufactured by Toki Sangyo).

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

The resin composition prepared by the above method preferably does not contain TFMB from the viewpoint of viscosity stability and filterability. From the same viewpoint, in the method for producing a resin composition according to the present embodiment, it is preferable not to use TFMB as a raw material, for example, as a diamine raw material other than the diamine compound represented by the general formula (3). It is preferable to remove and purify TFMB from the raw material.

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

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

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

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

<Arbitrary drying process>
The drying step may be performed after the coating step, or the drying step may be omitted and the process may be directly proceeded to the next film forming step (heating step). The drying step is performed for the purpose of removing the organic solvent in the resin composition. When performing the drying step, for example, an appropriate device such as a hot plate, a box-type dryer, or a conveyor-type dryer 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.

<Membrane formation process>
Subsequently, a film forming step (heating step) is performed. The heating step is a step of removing the organic solvent contained in the coating film and advancing the imidization reaction of the polyimide precursor in the coating film to obtain a polyimide resin film. This heating step can be performed using, for example, an apparatus such as an inert gas oven, a hot plate, a box-type dryer, and a conveyor-type dryer. This step may be carried out at the same time as the drying step, or both steps may be carried out sequentially.

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

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

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

(1) After producing a structure including a polyimide resin film / support 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. A method of peeling off the polyimide resin. Examples of the laser include a solid (YAG) laser and a gas (UV excimer) laser. It is preferable to use a spectrum having a wavelength of 308 nm or the like (see Japanese Patent Publication No. 2007-512568, Japanese Patent Publication No. 2012-511173, etc.).

(2) A method in which a release layer is formed on a support before the resin composition is applied to the support, and then a structure including a polyimide resin film / release layer / support is obtained and the polyimide resin film is peeled off. .. Examples of the release layer include parylene (registered trademark, manufactured by Japan Parylene GK) and tungsten oxide; and a release agent such as vegetable oil-based, silicone-based, fluorine-based, and alkyd-based may be used (Japanese Patent Laid-Open No. 2010-067957). No., Japanese Patent Application Laid-Open No. 2013-179306, etc.).
This method (2) and the laser irradiation of the method (1) may be used in combination.

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

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

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

<< Applications of polyimide film >>
The polyimide film obtained from the resin composition of the present embodiment can be used as, for example, a semiconductor insulating film, a thin film transistor liquid crystal display (TFT-LCD) insulating film, an electrode protective film, a liquid crystal display, an organic electroluminescence display, a field emission display, or the like. It can be applied as a transparent substrate of a display device such as electronic paper. In particular, the polyimide film obtained from the resin composition of the present embodiment is suitable as a substrate for a thin film transistor (TFT) substrate, a color filter substrate, a touch panel substrate, and a transparent conductive film (ITO, Indium Thin Oxide) in the manufacture of a flexible device. Can be used. Examples of the flexible device to which the polyimide film in this embodiment can be applied include a TFT device for a flexible display, a flexible solar cell, a flexible touch panel, a flexible lighting, a flexible battery, a flexible printed substrate, a flexible color filter, a surface cover lens for a smartphone, and the like. Can be mentioned.

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

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

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

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

<Manufacturing method of display>
The method for manufacturing the display of the present embodiment includes a coating step of applying the resin composition of the present embodiment on the surface of the support; and a film forming step of heating the resin composition to form a polyimide resin film. It includes an element forming step of forming an element on the polyimide resin film; and a peeling step of peeling the polyimide resin film on which the element is formed from the support.

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

The manufacturing process of the flexible organic EL display consists of a step of manufacturing a polyimide film on a glass substrate support and a step of manufacturing an organic EL substrate shown in FIG. 1 and a step of manufacturing a sealed substrate on the polyimide film. The assembly step of bonding and the peeling step of peeling the organic EL display produced on the polyimide film from the glass substrate support are included. A well-known manufacturing process can be applied to the organic EL substrate manufacturing process, the sealed substrate manufacturing process, and the assembling process. The following is an example, but the present invention is not limited to this. The peeling step is the same as the peeling step of the polyimide film described above.

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

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

Manufacturing Example of Flexible Liquid Crystal Display A flexible liquid crystal display can be manufactured using the polyimide film of the present embodiment. As a specific production method, a polyimide film is produced on a glass substrate support by the above method, and the above method is used, for example, composed of amorphous silicon, a metal oxide semiconductor (IGZO, etc.), and low-temperature polysilicon. A TFT substrate is manufactured. Separately, a polyimide film is produced on a glass substrate support according to the coating step and the film forming step of the present embodiment, and a color resist or the like is used according to a known method to provide a color filter glass substrate (CF substrate) with the polyimide film. ) Is prepared. A sealing material made of thermosetting epoxy resin or the like is applied to one of the TFT substrate and the CF substrate by screen printing to a frame-shaped pattern lacking the liquid crystal injection port portion, and the other substrate corresponds to the thickness of the liquid crystal layer. A spherical spacer made of plastic or silica is sprayed.

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

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

Examples of the element in the laminated body include those exemplifying the manufacture of a flexible device such as the above-mentioned flexible display. As the support, for example, a glass substrate can be used. The preferred specific procedure of the coating step and the film forming step is the same as that described with respect to the above-mentioned method for producing a polyimide film. In the element forming step, the above-mentioned element is formed on a polyimide resin film as a flexible substrate formed on a support. Then, optionally, the polyimide resin film and the element may be peeled from the support in the peeling step.

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

<< Measurement and evaluation method >>
<Weight average molecular weight>
The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) under the following conditions.
As solvents, NMP (Wako Pure Chemical Industries, Ltd., for high-speed liquid chromatograph, 24.8 mmol / L lithium bromide monohydrate (Wako Pure Chemical Industries, Ltd., purity 99.5%) immediately before measurement) and 63. .2 mmol / L phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd., for high-speed liquid chromatograph) was added and dissolved) was used. The calibration curve for calculating the weight average molecular weight was prepared using standard polystyrene (manufactured by Toso Co., Ltd.).
Column: Shodex KD-806M (manufactured by Showa Denko KK)
Flow velocity: 1.0 mL / min Column temperature: 40 ° C
Pump: PU-2080Plus (manufactured by JASCO)
Detector: RI-2031Plus (RI: differential refractometer, manufactured by JASCO) and UV-2075Plus (UV-VIS: ultraviolet-visible spectrophotometer, manufactured by JASCO)

<Evaluation of viscosity stability of composition (varnish)>
The resin compositions prepared in Examples and Comparative Examples were left to stand in an atmosphere of 23 ° C. and 50% RH for 24 hours, and the initial (0 day) viscosity of the resin composition was measured by a viscometer with a temperature controller (Toki). It was measured using VISCOMATER TVE-35H) manufactured by Sangyo Kikai. Then, the resin composition was left to stand in an atmosphere of 23 ° C. and 50% RH for 7 days, and the viscosity after 7 days was measured in the same manner as in the initial stage. Subsequently, the viscosity stability represented by the following formula was calculated.
Viscosity stability (% / day) = | (Initial viscosity (mPa · s))-(Viscosity after 7 days (mPa · s)) | / (Initial viscosity (mPa · s)) * 100/7 (day)
Viscosity stability was evaluated according to the following criteria.
A: Viscosity stability 1% / day or less "excellent"
B: Viscosity stability 1% / day over 3% / day or less "Good"
C: Viscosity stability 3% / day over 5% / day or less "OK"
D: Viscosity stability 5% / day over "OK"

<Evaluation of the filterability of the composition (varnish)>
The resin compositions prepared in Examples and Comparative Examples were pressure-filtered under an atmosphere of 23 ° C. and 50% RH at a pressure of 0.25 MPa using a polyethylene membrane filter having a basis weight of 0.2 μm. .. The mass of the filtered resin composition at this time was measured, and the filtration rate was calculated. The filterability was evaluated according to the following criteria.
A: Filtration speed 2000g / hr or more "excellent"
B: Filtration rate less than 2000 g / hr 1500 g / hr or more "Good"
C: Filtration rate less than 1500 g / hr 1000 g / hr or more "OK"
D: Filtration rate less than 1000 g / hr "impossible"

<Evaluation of tensile elongation of polyimide resin film>
As a support, a 6-inch silicon wafer substrate having an aluminum-deposited layer on its surface is used, and the resin compositions prepared in Examples and Comparative Examples are placed on the surface of the aluminum-deposited layer, and the thickness of the polyimide resin film is 10 μm. A coating film was formed by spin coating so as to be. After prebaking this coating film at 100 ° C. for 6 minutes, a vertical curing furnace (manufactured by Koyo Thermo System Co., Ltd., model name "VF-2000B") in which the oxygen concentration in the refrigerator was adjusted to 10 mass ppm or less was used. It was heated at 400 ° C. for 1 hour to form a polyimide film on the wafer. Subsequently, using a dicing saw (manufactured by Disco Co., Ltd., product name "DAD 3350"), a 3 mm wide cut was made in the obtained polyimide film, and then the wafer with the polyimide film was immersed in a dilute aqueous hydrochloric acid solution overnight. , The polyimide film piece was peeled off and dried to obtain a polyimide piece having a width of 3 mm. This was cut into a length of 50 mm to obtain a polyimide measurement sample having a width of 3 mm and a length of 50 mm. Using TENSILON (manufactured by Orientec Co., Ltd., model name "UTM-II-20"), the tensile elongation of the polyimide resin film was measured at a test speed of 40 mm / min and an initial load of 0.5 fs. The tensile elongation was evaluated according to the following criteria.
A: Tensile elongation exceeds 50% "excellent"
B: Tensile elongation is more than 40% and 50% or less "Good"
C: Tensile elongation is more than 30% and 40% or less "OK"
D: Tensile elongation is less than 30% "impossible"

<Evaluation of residual stress of polyimide resin film>
The resin compositions prepared in Examples and Comparative Examples were applied on a 6-inch silicon wafer having a thickness of 625 μm ± 25 μm for which the “warp amount” had been measured in advance by a spin coater, and prebaked at 100 ° C. for 7 minutes. After that, using a vertical curing furnace (manufactured by Koyo Lindbergh Co., Ltd., model name VF-2000B), the oxygen concentration in the refrigerator was adjusted to 10% by mass or less, and heat curing treatment was performed at 400 ° C. for 1 hour. After curing, a silicon wafer with a polyimide resin film having a thickness of 10 μm was produced.
The amount of warpage of this wafer was measured using a residual stress measuring device (model name FLX-2320 manufactured by Tencor), and the residual stress generated between the silicon wafer and the resin film was evaluated "under a nitrogen atmosphere". ..
A: Residual stress is less than 30 MPa "Good"
B: Residual stress is 30 MPa or more and less than 40 MPa "Yes"
C: Tensile elongation is 40 MPa or more "impossible"

<< Reference example 1 >>
As shown in Tables 1 and 2, NMP (128 g) as a solvent, DABA (13.6 g) as a diamine, and a silicon-containing compound (2) (2) while introducing nitrogen gas into a 3 L separable flask with a stirring rod. 7.3 g) was added with stirring, followed by PMDA (21.8 g) as acid dianhydride. The molar ratio of acid dianhydride: diamine was 100:98. The mixture was stirred at room temperature for 48 hours to obtain an NMP solution (hereinafter, also referred to as varnish) of a transparent polyimide precursor (functional group other than silicon-containing compound: amide group, functional group of silicon-containing compound: amide group). The obtained varnish was stored in a freezer (setting -20 ° C, the same applies hereinafter), and was thawed and used for evaluation.

<< Reference Example 2, Examples 3, 4 >>
In Reference Example 1, the same procedure as in Reference Example 1 was carried out, except that the types and amounts of the solvent, acid dianhydride, diamine, and silicon-containing compound were changed to those shown in Tables 1 and 2.

<< Reference example 5 >>
As shown in Tables 1 and 2, NMP (152 g), toluene (15 g), and diamine were used as solvents while introducing nitrogen gas into a separable flask with a stirring rod equipped with a Dean-Stark tube and a reflux tube at the top. DABA (11.9 g) and the silicon-containing compound (2) (16.9 g) were added with stirring, and then PMDA (21.8 g) as an acid dianhydride was added at room temperature. The molar ratio of acid dianhydride: diamine was 100:98. Then, the temperature was raised to an internal temperature of 160 ° C., and the mixture was heated under reflux at 160 ° C. for 1 hour to perform imidization. After the imidization was completed, the temperature was raised to 180 ° C., and the reaction was continued while extracting toluene. After the reaction for 12 hours, the oil bath was removed and the temperature was returned to room temperature to obtain an NMP solution of a polyimide resin (functional group other than silicon-containing compound: imide group, functional group of silicon-containing compound: imide group). The obtained varnish was stored in a freezer (setting -20 ° C, the same applies hereinafter), and was thawed and used for evaluation.

<< Reference Example 6, Examples 7, 8 >>
In Reference Example 5, the same procedure as in Reference Example 5 was carried out, except that the types and amounts of the solvent, acid dianhydride, diamine, and silicon-containing compound were changed to those shown in Tables 1 and 2.

<< Reference example 9 >>
As shown in Tables 1 and 2, NMP (131 g), toluene (13 g), and diamine were used as solvents while introducing nitrogen gas into a separable flask with a stirring rod equipped with a Dean-Stark tube and a reflux tube at the top. DABA (14.5 g) was added with stirring, and then PMDA (21.8 g) as an acid dianhydride was added at room temperature. Then, the temperature was raised to an internal temperature of 160 ° C., and the mixture was heated under reflux at 160 ° C. for 1 hour to perform imidization. After the imidization was completed, the temperature was raised to 180 ° C., and the reaction was continued while extracting toluene. After the reaction for 12 hours, the oil bath was removed and the temperature was returned to room temperature. Next, the silicon-containing compound (1) (7.4 g) was added with stirring. The molar ratio of acid dianhydride: diamine was 100:98. Then, the mixture was stirred at room temperature for 48 hours, and an NMP solution of a partially imidized polyimide precursor (functional group other than silicon-containing compound: amide group or imide group, functional group of silicon-containing compound: amide group) ( Hereinafter, it is also referred to as varnish).

<< Reference Example 10, Examples 11 and 12 >>
In Reference Example 9, the same procedure as in Reference Example 9 was carried out, except that the types and amounts of the solvent, acid dianhydride, diamine, and silicon-containing compound were changed to those shown in Tables 1 and 2.

<< Comparative Example 1 >>
A reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a gas introduction tube was charged with 77.5 parts of triethylene glycol dimethyl ether as a solvent and 3.8 parts of PMDA as a carboxylic acid dianhydride, and heated to 80 ° C. under a nitrogen atmosphere. The temperature was raised. Then, a solution prepared by mixing 45.4 parts of the silicon-containing compound (3), 0.8 parts of DABA, and 122.5 parts of triethylene glycol dimethyl ether as a solvent was added dropwise over 1 hour, followed by stirring for 1 hour.
Dean-Stark tube was attached to the reflux condenser of the reaction vessel, 20 parts of toluene and 5 parts of triethylamine were added, and the temperature was raised to 180 ° C. to confirm dehydration. After confirming that the same amount of water as the theoretical yield was produced, the mixture was allowed to cool to 50 ° C. Precipitation of the solid was confirmed by adding 1000 parts of methanol to another reaction vessel and dropping the reaction solution while stirring. The solid was separated by filtration, sprinkled with an appropriate amount of methanol for washing, and then dried in a vacuum oven at 80 ° C. to obtain a polyimide composition.

<< Comparative Example 2 >>
In Comparative Example 1, the same procedure as in Comparative Example 1 was carried out, except that the types and amounts of the solvent, acid dianhydride, diamine, and silicon-containing compound were changed to those shown in Tables 1 and 2.

<< Comparative Example 3 >>
At room temperature, 840 g of N, N-dimethylacetamide was added to the reactor and stirred rapidly until uniformly dispersed to form a reaction system. Under a 5 ° C. nitrogen gas atmosphere, 28.8 g of TFMB and 1.5 g of DABA were added to the system, and after dissolution, 40.0 g of 6FDA and 2.2 g of PMDA were added, and 24 hr. After the reaction was carried out, a polyamic acid solution was produced.

<< Comparative Example 4 >>
A 1 L three-necked flask was cooled to -15 ° C with an ice-methanol refrigerant, 123 ml of N-methylpyrrolidone, 10.9 g of PMDA and 22.2 g of 6FDA were added thereto, and the mixture was stirred under a nitrogen stream. , 3,5,6-Tetramethylphenylenediamine (also referred to as 4MPD) 28.8 g and DABA 1.5 g of N-methylpyrrolidone solution 84.0 ml were added dropwise over 30 minutes. After completion of the dropping, the reaction solution was stirred at 40 ° C. for 2.5 hours, and then 2.94 g (0.037 mol) of pyridine (manufactured by Wako Pure Chemical Industries, Ltd.) and 31.58 g of acetic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.). (0.31 mol) was added, and the mixture was further stirred at 80 ° C. for 3 hours to prepare a polyimide solution.

<< Comparative Example 5 >>
5.0 mmol of PMDA, 50.0 mmol of 6FDA, 44.0 mmol of BPDA, 10.0 mmol of DABA, and 90.0 mmol of TSN are placed in a separable flask equipped with a stirrer and a nitrogen gas introduction pipe together with 323 g of NMP. Then, nitrogen gas was circulated and both monomers were polymerized at 180 ° C. for 16 hours while stirring the reaction solution to produce a polyimide solution.

<< Comparative Example 6 >>
NMP (39.6 g) was charged into a 300 ml glass separable flask equipped with a stirrer equipped with a stainless stir bar and a nitrogen introduction tube, and TFMB (4.7 g) was added and stirred. PMDA (1.7 g) was added to this solution, and after stirring for 10 minutes or more, 6 FDA (3.5 g) was added and the mixture was stirred at room temperature for 12 hours. NMP was added to this solution (solid content concentration 25% by weight) to dilute it to a solid content concentration of 15% by weight, heated in an oil bath at 80 ° C. for 5 minutes, and then diluted to 10% by weight with diethylene glycol diethyl ether (a silicon compound (solid content concentration 25% by weight)). 3) (1.98 g) (20 parts by weight based on 100 parts by weight of the charged TFMB, PMDA, and 6FDA) was slowly added dropwise. After stirring for 30 minutes, the mixture was rapidly cooled with ice water to obtain a uniform and transparent polyamic acid solution.

<< Comparative Example 7 >>
DABA (2.1 g), diaminodiphenyl ether (9.3 g), 6FDA (26.1 g) in a four-necked flask equipped with a reflux nitrogen gas introduction tube, a cooler, a Dean-Stark aggregator filled with toluene and a stirrer. ), N, N-dimethylacetamide (112 g) and toluene (22.5 g) were added, and the mixture was heated under reflux in an oil bath at 190 ° C. for 12 hours. Then, toluene was distilled off under normal pressure to obtain a polyimide solution.

<< Explanation of abbreviations in Tables 1 and 2 >>
<Acid dianhydride>
PMDA: pyromellitic acid anhydride 6FDA: 4,4'-(hexafluoroisopropylidene) diphthalic acid anhydride BPDA: 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride

<Diamine>
DABA: 3,5-diaminobenzoic acid TFMB: diaminobis (trifluoromethyl) biphenyl 4MPD: 2,3,5,6-tetramethylphenylenediamine (
TSN: 3,7-diaminodimethyldiphenylene sulfone DAE: diaminodiphenyl ether

<Silicon-containing compound>
Silicon-containing compound (1): (in the general formulas (5) and (10), L ₁ and L ₂ are amino groups (-NH ₂ ) and R ₁ is a trimethylene group (-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).
Silicon-containing compound (2): (In the general formulas (5) and (10), L ₁ and L ₂ are amino groups (-NH ₂ ), and R ₁ is a trimethylene group (-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 430).
Silicon-containing compound (3): (in the general formulas (5) and (10), L ₁ and L ₂ are amino groups (-NH ₂ ) and R ₁ is a trimethylene group (-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 2200).
Silicon-containing compound (4): (In the general formulas (5) and (10), L ₁ and L ₂ are amino groups (-NH ₂ ), and R ₁ is a trimethylene group (-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 800).
Silicon-containing compound (5): (In the general formulas (5) and (10), L ₁ and L ₂ are acid anhydride groups (-CH (C = O) ₂ O), and R ₁ is a trimethylene group (-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 1000).

<solvent>
NMP: N-methylpyrrolidone MTM: Triethylene glycol dimethyl ether DMAc: N, N-dimethylacetamide <polymer>
PAA: Polyamic acid (polyimide precursor)
PI: Polyimide PAI: Polyamide-imide

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

Claims (17)

The following general formula (1) or (2):

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

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer. }
A polyimide precursor or a resin composition containing a polyimide, which comprises a structural unit represented by.
The P ₁ is the following general formula (3):

It contains a structural unit derived from the compound represented by the above, and the P1 or P2 is the following general _formula ( ₅ ) :.

{In the formula, R ₁ is an independently single-bonded or divalent organic group having 1 to 10 carbon atoms, and R ₂ and R ₃ are independently monovalent organic groups having 1 to 10 carbon atoms. It is a group, at least one is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, and R ₄ and R ₅ are independently monovalent organic groups having 1 to 10 carbon atoms, respectively. At least one is a monovalent aromatic group having 6 to 10 carbon atoms, R ₆ and R ₇ are independently monovalent organic groups having 1 to 10 carbon atoms, and L ₁ and L ₂ are independent groups. Independently, each is an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid halide group, a hydroxy group, an epoxy group, or a mercapto group, and i is an integer of 1 to 200. j and k are independently integers of 0 to 200, 0 ≦ j / (i + j + k) ≦ 0.50, and the functional group equivalent is 800 or more. }
It contains a structural unit derived from a silicon-containing compound represented by, and the following (a) and (b):
(A) The P ₂ is the following general formula (4):

Includes structural units derived from the compounds represented by;
(A) The P ₂ is the following general formula (12):

Includes structural units derived from the compounds represented by;
The filling,
And the silicon-containing compound
When the total diamine is 100 mol%, it is 20 mol% or less, or
A resin composition having a total acid dianhydride of 20 mol% or less when the total acid dianhydride is 100 mol%. The resin composition according to claim 1, wherein L ₁ and L ₂ are independently amino groups. The following general formulas (6) and (7):

{In the formula, P ₃ represents a divalent organic group, P ₄ represents a tetravalent organic group, and p represents a positive integer. }

{In the formula, P ₅ represents a divalent organic group, P ₆ represents a tetravalent organic group, and q represents a positive integer. }
A resin composition comprising a polyimide precursor and a polyimide, which comprises a structural unit represented by.
The above P ₃ or P ₄ is the following general formula (10):

{In the formula, R ₁ is an independently single-bonded or divalent organic group having 1 to 10 carbon atoms, and R ₂ and R ₃ are independently monovalent organic groups having 1 to 10 carbon atoms. It is a group, at least one is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, and R ₄ and R ₅ are independently monovalent organic groups having 1 to 10 carbon atoms, respectively. At least one is a monovalent aromatic group having 6 to 10 carbon atoms, R ₆ and R ₇ are independently monovalent organic groups having 1 to 10 carbon atoms, and L ₁ and L ₂ are independent groups. Independently, each is an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid halide group, a hydroxy group, an epoxy group, or a mercapto group, and i is an integer of 1 to 200. j and k are independently integers of 0 to 200, and 0 ≦ j / (i + j + k) ≦ 0.50. }
It contains a structural unit derived from a silicon-containing compound represented by, and the P ₃ and / or P ₅ is the following general formula (8) :.

It contains a structural unit derived from the compound represented by, and the following (c) and (d):
(C) The _P4 and / or _P6 is expressed by the following general formula (9):

Includes structural units derived from the compounds represented by;
(D) The above _P4 and / or _P6 is expressed by the following general formula (13):

Includes structural units derived from the compounds represented by;
A resin composition that meets the requirements. The silicon-containing compound
When the total diamine is 100 mol%, it is 20 mol% or less, or
The resin composition according to claim 3, wherein the total acid dianhydride is 20 mol% or less when the total acid dianhydride is 100 mol%. The resin composition according to claim 3 or 4, wherein L ₁ and L ₂ are independently amino groups. The resin composition according to any one of claims 1 to 5, wherein P ₁ , P ₃ , and P ₅ do not contain a group derived from TFMB (2,2'-bis (trifluoromethyl) benzidine). .. The compound represented by the general formula (3) or (8) is more than 50 mol% when the total diamine (excluding the compound represented by the general formula (5) or (10)) is 100 mol%. The resin composition according to any one of claims 1 to 6. The resin composition according to any one of claims 1 to 7, wherein the polyimide precursor or the polyimide resin film obtained by heating the polyimide is used for a flexible substrate. The resin composition according to any one of claims 1 to 8, wherein the polyimide resin film obtained by curing the polyimide precursor is used for a flexible display. The following general formula (3):

And the compound represented by
The following general formula (4):

Compounds represented by and
The following general formula (12):

And the compound represented by
The following general formula (5):

{In the formula, R ₁ is an independently single-bonded or divalent organic group having 1 to 10 carbon atoms, and R ₂ and R ₃ are independently monovalent organic groups having 1 to 10 carbon atoms. It is a group, at least one is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, and R ₄ and R ₅ are independently monovalent organic groups having 1 to 10 carbon atoms, respectively. At least one is a monovalent aromatic group having 6 to 10 carbon atoms, R ₆ and R ₇ are independently monovalent organic groups having 1 to 10 carbon atoms, and L ₁ and L ₂ are independent groups. Independently, each is an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid halide group, a hydroxy group, an epoxy group, or a mercapto group, and i is an integer of 1 to 200. j and k are independently integers of 0 to 200, and 0 ≦ j / (i + j + k) ≦ 0.50. }
A method for producing a resin composition, which comprises subjecting a silicon-containing compound represented by (1) and another compound to a polycondensation reaction to provide a polyimide precursor and / or a polyimide. The following general formula (3):

And the compound represented by
The following general formula (4):

Compounds represented by and
The following general formula (12):

And the compound represented by
After polycondensation reaction with other compounds to obtain polyimide,
The following general formula (5):

{In the formula, R ₁ is an independently single-bonded or divalent organic group having 1 to 10 carbon atoms, and R ₂ and R ₃ are independently monovalent organic groups having 1 to 10 carbon atoms. It is a group, at least one is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, and R ₄ and R ₅ are independently monovalent organic groups having 1 to 10 carbon atoms, respectively. At least one is a monovalent aromatic group having 6 to 10 carbon atoms, R ₆ and R ₇ are independently monovalent organic groups having 1 to 10 carbon atoms, and L ₁ and L ₂ are independent groups. Independently, each is an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid halide group, a hydroxy group, an epoxy group, or a mercapto group, and i is an integer of 1 to 200. j and k are independently integers of 0 to 200, and 0 ≦ j / (i + j + k) ≦ 0.50. }
A method for producing a resin composition, which comprises subjecting a silicon-containing compound represented by (1) to a polycondensation reaction of another compound to provide a resin composition containing a polyimide precursor and a polyimide. A coating step of applying the resin composition according to any one of claims 1 to 9 or the resin composition obtained by the method according to claim 10 or 11 onto the surface of the support.
A film forming step of heating the resin composition to form a polyimide resin film,
A peeling step of peeling the polyimide resin film from the support,
A method for producing a polyimide resin film, including. The method for producing a polyimide resin film according to claim 12, further comprising an irradiation step of irradiating the resin composition with a laser from the support side prior to the peeling step. A coating step of applying the resin composition according to any one of claims 1 to 9 or the resin composition obtained by the method according to claim 10 or 11 onto the surface of the support.
A film forming step of heating the resin composition to form a polyimide resin film,
An element forming step of forming an element on the polyimide resin film and
A peeling step of peeling the polyimide resin film on which the element is formed from the support,
How to make a display, including. A coating step of applying the resin composition according to any one of claims 1 to 9 or the resin composition obtained by the method according to claim 10 or 11 onto the surface of the support.
A film forming step of heating the resin composition to form a polyimide resin film,
An element forming step of forming an element on the polyimide resin film and
A method for manufacturing a laminate, including. The method for producing a laminate according to claim 15, further comprising a step of peeling the polyimide resin film on which the element is formed from the support. A method for manufacturing a flexible device, which comprises manufacturing a laminate by the method according to claim 15 or 16.

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