WO2021241763A1

WO2021241763A1 - Resin composition

Info

Publication number: WO2021241763A1
Application number: PCT/JP2021/020567
Authority: WO
Inventors: 友裕頼末; 昌樹米谷; 隆行金田; 隆志岩田
Original assignee: 旭化成株式会社
Priority date: 2020-05-28
Filing date: 2021-05-28
Publication date: 2021-12-02
Also published as: CN115667368A; JPWO2021241763A1; KR20220158818A; TW202330733A; TW202204474A

Abstract

Provided is a resin composition that includes a polyimide precursor and/or a polyimide resin and that satisfies (A) or (B) below: (A) A polyimide structural unit includes a divalent organic group P₅ and a tetravalent organic group P₆, P₅ or P₆ includes a structural unit derived from a silicon-containing compound represented by formula (10), and the resin composition contains 25 mass% or less of silicon-containing compounds in terms of the total mass of resin; (B) a resin structural unit includes a divalent organic group P₁ and a tetravalent organic group P₂, P₁ includes a structural unit derived from a compound represented by formula (3), and P₁ or P₂ includes a structural unit derived from a silicon-containing compound represented by formula (5). [In the formulas, each symbol is as defined in the specification.]

Description

Resin composition

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 polyimide resins in the field of electronic materials include insulating coating materials, insulating films, semiconductors, electrode protective films for thin film transistor liquid crystal displays (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, as a monomer, 3,5-diaminobenzamide (hereinafter, also referred to as DABA) and the following structural formula:

A polyimide film obtained by synthesizing a polyimide using the above compound (hereinafter, also referred to as CpODA) and another compound, adding a cross-linking agent to the obtained polyimide varnish, applying the mixture, and drying 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 CpODA as an acid dianhydride. Is described.

Japanese Patent No. 651640 International Publication No. 2019/211972

The polyimide film described in Patent Document 1 is used as a gas separation membrane 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 CpODA, a silicon-containing compound, etc. as a monomer, and found that the varnish required in the varnish manufacturing process. It was found that the polyimide film obtained by applying and heating the polyimide varnish has insufficient properties (tensile elongation, etc.) required for display applications. On the other hand, the present inventors have DABA, 3,3'-diaminodiphenyl sulfone (33DAS), 4,4'-diaminodiphenyl sulfone (44DAS), 9,9-bis (4-aminophenyl) fluorene (BAFL) and the like. Diamine, acid dianhydrides such as CpODA, 4,4'-oxydiphthalic anhydride (ODPA), 9,9-bis (3,4-dicarboxyphenyl) fluorene diacid anhydride (BPAF), and others. It has been found that the polyimide obtained by using the silicon-containing compound of the above 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.

The above problem can be solved by the following technical means.

[First aspect]
<1>
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 containing a resin of a structural unit represented by.
Wherein _{P 5} or _{P 6} is represented by 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 the silicon-containing compound represented by, and contains 25% by mass or less of the silicon-containing compound based on the total mass of the resin.
Resin composition.
<2>
The following general formulas (6) and (7):

{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 imidization ratio of the resin is 50% or more.
Resin composition.
<3>
The resin composition according to item 1, wherein the resin has an imidization ratio of 50% or more.
<4>
The following general formulas (6) and (7):

{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 (a) or (b) below.
(A) The P ₃ and / or P ₅ is the following general formula (8):

In comprising a structural unit derived from a compound represented; or (b) the P ₄ and / or P ₆ is represented by the following general formula (9):

Includes structural units derived from the compounds represented by;
A resin composition that satisfies any of the above.
<5>
The following general formulas (6) and (7):

{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 a structural unit derived from the silicon-containing compound represented by, and the P ₃ and / or P ₅ are independent of each other.
3,3'-Diaminodiphenyl sulfone (33DAS),
4,4'-Diaminodiphenyl sulfone (44DAS), or 9,9-bis (4-aminophenyl) fluorene (BAFL)
A resin composition containing at least one structural unit derived from each of the above compounds.
<6>
The following general formulas (6) and (7):

{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 a structural unit derived from the silicon-containing compound represented by, and the P ₃ and / or P ₅ are independent of each other.
2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ether (6FODA)
A resin composition containing at least one structural unit derived from.
<7>
The following general formulas (6) and (7):

{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. , Each independently is an amino group, i is an integer of 1 to 200, and j and k are independently integers of 0 to 200, with 0 ≦ j / (i + j + k) ≦ 0.50. be. }
Containing a structural unit derived from in the silicon-containing compound represented, and A (wt%): Of the diamine that constitutes the P ₅ in the general formula (7), the proportion of the general formula (10) B (wt%): of the diamine that constitutes the _{P 3} in the general formula (6), when the ratio of the general formula (10), B-a is greater than 0 and less than 60,
Resin composition.
<8>
The diamine
The following general formula (8):

Compound represented by,
3,3'-Diaminodiphenyl sulfone (33DAS),
4,4'-Diaminodiphenyl sulfone (44DAS), and 9,9-bis (4-aminophenyl) fluorene (BAFL)
The resin composition according to item 7, which is at least one compound selected from the above.
<9>
In Formula (6) and / or the general formula (7), _{P 4} and / or _{P 6} are each independently, 4,4'-oxydiphthalic anhydride (ODPA), or 9,9-bis ( 3,4-Dicarboxyphenyl) The resin composition according to any one of claims 1 to 8, which comprises at least one structural unit derived from each compound of fluorene diacid anhydride (BPAF).
<10>
The resin composition according to any one of items 1 to 9, wherein the silicon-containing compound represented by the general formula (10) has a functional group equivalent of 800 or more.
<11>
The P ₅ contains a structural unit derived from the compound represented by the general formula (10), and the L ₁ _{and L 2} in the general formula (10) are independently amino groups.
The resin composition according to any one of items 1 to 10.
<12>
The compound represented by the general formula (8) is more than 50 mol% when the total diamine (excluding the compound represented by the general formula (10)) is 100 mol%, whichever of items 4 and 9 to 11. The resin composition according to item 1.
<13>
Wherein _{P 3} or _{P 5} are each independently, the following formula:

The resin composition according to any one of items 1 to 12, which comprises a structural unit derived from the compound represented by (BisAM).
<14>
Wherein _{P 4} or _{P 6} are each independently, 4,4 '- (hexafluoro isopropylidene) diphthalic anhydride, the following formula:

Compound represented by (BzDA), or the following formula:

The resin composition according to any one of items 1 to 13, which comprises a structural unit derived from the compound represented by (BNBDA).
<15>
The resin composition according to any one of items 1 to 14, wherein the polyimide resin film obtained by heating the resin is used for a flexible substrate.
<16>
The resin composition according to any one of items 1 to 15, wherein the polyimide resin film obtained by curing the resin is used for a flexible display.
<17>
Diamine or acid dianhydride and 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. }
After polycondensation reaction of the silicon-containing compound represented by
It comprises polycondensing reaction with other compounds to provide a resin composition containing a polyimide precursor and a resin containing polyimide.
The silicon-containing compound is contained in an amount of 25% by mass or less based on the total mass of the resin.
A method for producing a resin composition.
<18>
Diamine or acid dianhydride and 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. }
After polycondensation reaction of the silicon-containing compound represented by
It comprises polycondensing reaction with other compounds to provide a resin composition containing a polyimide precursor and a resin containing polyimide.
The imidization rate of the resin is 50% or more.
A method for producing a resin composition.
<19>
The following general formula (8):

The compound represented by, or the following general formula (9):

The compound represented by the following and 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. }
After polycondensation reaction of the silicon-containing compound represented by (1) and other compounds to obtain polyimide,
A method for producing a resin composition, which comprises subjecting a resin composition containing a polyimide precursor and a polyimide by polycondensation reaction with other compounds.
<20>
3,3'-Diaminodiphenyl sulfone (33DAS),
4,4'-Diaminodiphenyl sulfone (44DAS), and 9,9-bis (4-aminophenyl) fluorene (BAFL)
With at least one compound selected from
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. }
After polycondensation reaction of the silicon-containing compound represented by (1) and other compounds to obtain polyimide,
A method for producing a resin composition, which comprises subjecting a resin composition containing a polyimide precursor and a polyimide by polycondensation reaction with other compounds.
<21>
At least one compound selected from 4,4'-oxydiphthalic anhydride (ODPA) and 9,9-bis (3,4-dicarboxyphenyl) fluorene diic acid anhydride (BPAF), and 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. }
After polycondensation reaction of the silicon-containing compound represented by (1) and other compounds to obtain polyimide,
A method for producing a resin composition, which comprises subjecting a resin composition containing a polyimide precursor and a polyimide by polycondensation reaction with other compounds.
<22>
A coating step of applying the resin composition according to any one of items 1 to 16 or the resin composition obtained by the method according to any one of items 17 to 21 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.
<23>
The method for producing a polyimide resin film according to item 22, further comprising an irradiation step of irradiating the resin composition with a laser from the support side prior to the peeling step.
<24>
A coating step of applying the resin composition according to any one of items 1 to 16 or the resin composition obtained by the method according to any one of items 17 to 21 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.
<25>
A coating step of applying the resin composition according to any one of items 1 to 16 or the resin composition obtained by the method according to any one of items 17 to 21 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.
<26>
The method for producing a laminate according to item 25, further comprising a step of peeling the polyimide resin film on which the element is formed from the support.
<27>
A method for manufacturing a flexible device, which comprises manufacturing the laminate by the method according to item 25 or 26.

[Second aspect]
<28>
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 resin composition containing a resin of a structural unit represented by.
The P ₁ is the following general formula (3):

Containing a structural unit derived from in the compound represented by, and the P ₁ The P ₂ is 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. , Each independently is an amino group, i is an integer of 1 to 200, j and k are each independently an integer of 0 to 200, and 0 ≦ j / (i + j + k) ≦ 0.50. Yes, and the functional group equivalent is 800 or more. }
Containing structural units derived from silicon-containing compounds represented by
Resin composition.
<29>
The above P ₂ is the following general formula (4):

28. The resin composition according to item 28, which comprises a structural unit derived from the compound represented by.
<30>
The following general formulas (6) and (7):

{In the formula, P ₃ represents a divalent organic group, P ₄ represents a tetravalent organic group, p represents a positive integer, and P ₃ represents a 2,2'-bis (tri). Fluoromethyl) -4,4'-diaminodiphenyl ether (6FODA) is not included. }

{In the formula, P ₅ indicates a divalent organic group, P ₆ indicates a tetravalent organic group, q indicates a positive integer, and P ₅ indicates a 2,2'-bis (tri). Fluoromethyl) -4,4'-diaminodiphenyl ether (6FODA) is not included. }
A resin composition containing a resin of 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. , Each independently is an amino group, i is an integer of 1 to 200, and j and k are independently integers of 0 to 200, with 0 ≦ j / (i + j + k) ≦ 0.50. be. }
Containing structural units derived from silicon-containing compounds represented by
Resin composition.
<31>
The following general formulas (6) and (7):

{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. , Each independently is an amino group, i is an integer of 1 to 200, and j and k are independently integers of 0 to 200, with 0 ≦ j / (i + j + k) ≦ 0.50. be. }
It contains a structural unit derived from a silicon-containing compound represented by (a) or (b) below.
(A) The P ₃ and / or P ₅ is the following general formula (8):

Includes structural units derived from the compounds represented by;
A resin composition that satisfies any of the above.
<32>
The following general formulas (6) and (7):

{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. , Each independently is an amino group, i is an integer of 1 to 200, and j and k are independently integers of 0 to 200, with 0 ≦ j / (i + j + k) ≦ 0.50. be. }
Containing a structural unit derived from in the silicon-containing compound represented, and the P ₃ and / or P ₅ is
3,3'-diaminodiphenyl sulfone (33DAS), or 4,4'-diaminodiphenyl sulfone (44DAS)
A resin composition containing at least one structural unit derived from each of the above compounds.
<33>
The following general formulas (6) and (7):

{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. , Each independently is an amino group, i is an integer of 1 to 200, and j and k are independently integers of 0 to 200, with 0 ≦ j / (i + j + k) ≦ 0.50. be. }
Containing a structural unit derived from in the silicon-containing compound represented, and the P ₃ and / or P ₅ is
9,9-Bis (4-aminophenyl) fluorene (BAFL), or the following general formula:

Compound (BisAM)
A resin composition containing at least one structural unit derived from each of the above compounds.
<34>
The following general formulas (6) and (7):

{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. , Each independently is an amino group, i is an integer of 1 to 200, and j and k are independently integers of 0 to 200, with 0 ≦ j / (i + j + k) ≦ 0.50. be. }
In comprising a structural unit derived from silicon-containing compound represented, and the P ₄ and / or P ₆ is
4,4'-Oxydiphthalic anhydride (ODPA),
4,4'-(Hexafluoroisopropylidene) diphthalic acid anhydride (6FDA),
9,9-Bis (3,4-dicarboxyphenyl) fluorene diic acid anhydride (BPAF),
The following general formula:

Compound (BzDA); or the following general formula:

Compound (BNBDA);
A resin composition containing at least one structural unit derived from each of the above compounds.
<35>
The P ₃ contains a structural unit derived from the compound represented by the general formula (10).
The resin composition according to any one of items 30 to 34, wherein the silicon-containing compound represented by the general formula (10) has a functional group equivalent of 800 or more.
<36>
The P ₃ contains a structural unit derived from the compound represented by the general formula (10), and the L ₁ _{and L 2} in the general formula (10) are independently amino groups.
The resin composition according to any one of items 30 to 35.
<37>
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 28, 29 and 31.
<38>
The resin composition according to any one of items 28 to 37, wherein the polyimide resin film obtained by heating the resin is used for a flexible substrate.
<39>
The resin composition according to any one of items 28 to 38, wherein the polyimide resin film obtained by curing the resin is used for a flexible display.
<40> The following general formula (3):

Compound represented by,
3,3'-Diaminodiphenyl sulfone (33DAS), and 4,4'-diaminodiphenyl sulfone (44DAS),
With at least one diamine selected from,
Acid dianhydride and
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. , Each independently is an amino group, i is an integer of 1 to 200, and j and k are independently integers of 0 to 200, with 0 ≦ j / (i + j + k) ≦ 0.50. be. }
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 polyimide precursor and / or a polyimide.
<41>
After polycondensation reaction of diamine (however, 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ether (6FODA) is not contained) and acid dianhydride 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. , Each independently is an amino group, i is an integer of 1 to 200, and j and k are independently integers of 0 to 200, with 0 ≦ j / (i + j + k) ≦ 0.50. be. }
A method for producing a resin composition, which comprises subjecting a silicon-containing compound represented by (1) to a polycondensation reaction with another compound to provide a resin composition containing a polyimide precursor and a polyimide.
<42>
The following general formula (3):

Compound represented by,
3,3'-Diaminodiphenyl sulfone (33AS), and 4,4'-diaminodiphenyl sulfone (44DAS),
With at least one diamine selected from,
Acid dianhydride and
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 s 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. , Each independently is an amino group, i is an integer of 1 to 200, and j and k are independently integers of 0 to 200, with 0 ≦ j / (i + j + k) ≦ 0.50. be. }
A method for producing a resin composition, which comprises subjecting a silicon-containing compound represented by (1) to a polycondensation reaction with another compound to provide a resin composition containing a polyimide precursor and a polyimide.
<43>
A coating step of applying the resin composition according to any one of items 28 to 39 or the resin composition obtained by the method according to any one of items 40 to 42 on 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.
<44>
The method for producing a polyimide resin film according to item 43, which comprises an irradiation step of irradiating the resin composition with a laser from the support side prior to the peeling step.
<45>
A coating step of applying the resin composition according to any one of items 28 to 39 or the resin composition obtained by the method according to any one of items 40 to 42 on 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.
<46>
A coating step of applying the resin composition according to any one of items 28 to 39 or the resin composition obtained by the method according to any one of items 40 to 42 on 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.
<47>
The method for producing a laminate according to item 46, further comprising a step of peeling the polyimide resin film on which the element is formed from the support.
<48>
A method for manufacturing a flexible device, which comprises manufacturing the laminate by the method according to item 46 or 47.

According to the present invention, firstly, it is possible to provide a polyimide precursor or a polyimide resin composition having excellent properties required for display applications by using DABA, CpODA, other silicon-containing compounds and the like as monomers.
According to the present invention, secondly, using DABA, a silicon-containing compound and other compounds as a monomer, or using DABA and a silicon-containing compound and other compounds as a monomer, 3,3'-diamino Using diphenyl sulfone (33DAS) and / or 4,4'-diaminodiphenyl sulfone (44DAS), a silicon-containing compound and other compounds as monomers, a polyimide precursor or polyimide resin composition having excellent properties required for display applications. Can provide things.
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, an exemplary embodiment 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.

[First aspect]
<< Resin composition >>
<Resin / Polyimide precursor / Polyimide>
The resin composition of the present embodiment has the following general formulas (6) and (7):

{In the formula, P ₅ represents a divalent organic group, P ₆ represents a tetravalent organic group, and q represents a positive integer. }
In comprising a structural unit of the resin represented, in part may also include imidized polyimide precursor, P ₅ or P ₆ is represented by 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. }
Includes a structural unit derived from a silicon-containing compound represented by. In the case of such a partially imidized polyimide precursor, the viscosity stability of the composition is superior to that of the total polyimide precursor, and the polyimide (polyimide precursor) is synthesized as compared with the total polyimide. Excellent in terms of ease.

The ratio of the silicon group-containing compound is 25% by mass or less based on the total mass of the resin. The ratio of the silicon-containing compound in the total resin is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less, from the viewpoint of viscosity storage stability and filterability of the varnish. As described above, the mechanism by which the smaller the ratio of the silicon-containing compound in the resin is, the better the viscosity storage stability and the filterability of the varnish is unclear, but it is considered that the aggregation of the dissociated silicon group-containing compound is correlated. Be done.

On the other hand, the ratio of the silicon group-containing compound is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass or more, from the viewpoint of the residual stress of the obtained polyimide film.

The appropriate ratio of the silicon-containing compound in the total resin varies depending on the type and ratio of the diamine monomer and acid dianhydride monomer used, and the residual stress of the polyimide film, the viscosity storage stability of the varnish, the filterability, etc. are mutually considered. Then you need to decide.

The imidization rate of the resin is 50% or more. The imidization ratio of the resin is preferably 60% or more, more preferably 70% or more, further preferably 80% or more, and particularly preferably 90% or more from the viewpoint of viscosity storage stability of the varnish. As described above, the mechanism by which the viscosity storage stability of the varnish is better as the imidization ratio is larger is not clear, but it is considered that there is a correlation with the occurrence of decomposition polymerization of the amide portion during the storage of the varnish.

On the other hand, the imidization rate of the resin is preferably 90% or less, more preferably 80% or less, still more preferably 70% or less, from the viewpoint of hygroscopic white turbidity of the varnish. As described above, the mechanism by which the hygroscopic white turbidity of the varnish is less likely to occur as the imidization ratio is smaller is not clear, but it is considered to have a correlation with the solvent solubility of the polyimide / polyamide.

The appropriate imidization ratio of the resin varies depending on the type and ratio of the diamine monomer and acid dianhydride monomer used, and it is necessary to determine the appropriate imidization ratio in consideration of the viscosity storage stability of the varnish, the moisture absorption and cloudiness of the varnish, and the like. ..

The difference between the imide unit and the amide unit in the ratio of the silicon-containing compound in the diamine monomer of the resin is larger than 0 and 60 or less. The difference between the imide unit and the amide unit in the ratio of the silicon-containing compound in the diamine monomer of the resin can be obtained from the following formula.
A: Silicon-containing compound ratio (% by mass) in diamine of imide unit = silicon-containing compound used in imidization step / total mass of diamine monomer (including silicon-containing compound) used in imidization step * 100
B: Silicon-containing compound ratio (% by mass) in diamine of the amide unit = total mass of silicon-containing compound used in the imidization step / diamine monomer (including silicon-containing compound) used in the amidation step * 100
Here, A is "among the general formula in (7) of the diamine constituting the _{P 5,} the ratio (mass%) of the general formula (10)" and can turn also. Further, B can be rephrased as "the ratio (mass%) of the general formula (10) to the diamines constituting _{P 3} in the general formula (6)".
Then, the difference between the imide unit and the amide unit in the ratio of the silicon-containing compound in the diamine becomes BA by using the above A and B.

The difference between the imide unit and the amide unit in the proportion of the silicon-containing compound in the diamine monomer is the difference between the imide unit and the amide unit in the partially imidized polyimide precursor (polyamide-imide) resin having a structure derived from the silicon-containing compound. It can be said that the larger the ratio of the silicon-containing compound is, the more the imide unit has a structure derived from the silicon-containing compound. The larger this value, the better the residual stress of the polyimide film, and the smaller this value, the better the foaming property, the filterability, and the haze (turbidity) of the polyimide film. When this value is in the above range, it is preferable because each property such as foaming property of varnish, filterability, residual stress of polyimide film, and Haze (degree of turbidity) can be compatible with each other.

Among them, the diamine used for the resin is
The following general formula (8):

Compound;
3,3'-Diaminodiphenyl sulfone (33DAS);
4,4'-Diaminodiphenyl sulfone (44DAS); and 9,9-bis (4-aminophenyl) fluorene (BAFL)
When it is at least one compound selected from the above, it is preferable because the characteristics of the varnish / polyimide are further improved.

Further, the resin composition according to another embodiment of the present invention has the following general formulas (6) and (7):

{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.
P ₅ or _{P 6} is represented by 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 can contain a structural unit derived from a silicon-containing compound represented by, and can satisfy any of the following (a) or (b):
(A) The P ₃ and / or P ₅ is the following general formula (8):

Includes building blocks derived from the compound represented by.

The diamine resin composition has the following general formula (8):

Compound;
3,3'-Diaminodiphenyl sulfone (33DAS);
4,4'-Diaminodiphenyl sulfone (44DAS);
9,9-bis (4-aminophenyl) fluorene (BAFL); or 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ether (6FODA)
Contains at least one building block selected from each diamine compound of. Among the diamine compounds represented by the general formula (8), 3,5-diaminobenzoic acid (DABA) is preferable from the viewpoint of transparency of the polyimide film and YI. It is preferable to use at least one selected from DABA, 33DAS, 44DAS, BAFL, and 6FODA as the diamine compound because the mechanical properties of the polyimide film can be improved (particularly the tensile elongation) and the heat resistance can be improved. ..

_{The content of DABA in the total diamine (including the compound in which L 1} and L ₂ are amino groups in (10) of the above general formula) is more than 50 mol%, more than 55 mol%, or more than 70 mol%, or 90. It may be 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.

Examples of diamines other than the general formula (8) include p-phenylenediamine (PDA), m-phenylenediamine, 2,2'-dimethylbenzidine (mTB), 4,4'-diaminodiphenylsulfide, and 3,4'-diamino. Diphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diamino Benzophenone, 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-amino) Benzene) benzene, 1,3-bis (4-aminophenyl) benzene, 9,10-bis (4-aminophenyl) anthracene, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4) -Aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl) propane, 2,2-bis [4- (4-aminophenoxy) phenyl) hexafluoropropane, and 1,4 -Bis (3-aminopropyldimethylsilyl) benzene, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene] (BiSAM) and the like can be mentioned.

Diamines other than the general formula (8) consist of a group consisting of 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene] (BisAM) and 1,4-cyclohexanediamine (CHDA). It is preferably at least one selected.

The acid dianhydride resin composition has the following general formula (9):

Compound represented by (also referred to as CpODA),
4,4'-Oxydiphthalic anhydride (ODPA) or 9,9-bis (3,4-dicarboxyphenyl) fluorene diic acid anhydride (BPAF)
Contains at least one building block selected from each acid dianhydride compound of. Having these structural units is preferable because the transparency, YI, and heat resistance of the obtained polyimide film can be improved.

_{The content of CpODA, ODPA, and BPAF in the total acid dianhydride (where L 1} and L ₂ include the compound having an acid anhydride group in the above general formula (10)) is 50 mol% or more and 60 mol% or more. , Or 70 mol% or more, 90 mol% or more, or 95 mol% or more. A larger amount of CpODA, ODPA, and BPAF is preferable because the transparency of the polyimide film is improved.

Examples of the acid dianhydride other than the general formula (9) include pyromellitic acid dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), 2,2',. 3,3'-Biphenyltetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 5- (2,5-dioxotetrahydro-3-franyl) -3- Methyl-cyclohexene-1,2 dicarboxylic acid anhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2' , 3,3'-benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, methylene-4,4'-diphthalic acid dianhydride, 1,1- Ethiliden-4,4'-diphthalic acid dianhydride, 2,2-propylidene-4,4'-diphthalic acid dianhydride, 1,2-ethylene-4,4'-diphthalic acid dianhydride, 1,3 -Trimethylene-4,4'-diphthalic acid dianhydride, 1,4-tetramethylene-4,4'-diphthalic acid dianhydride, 1,5-pentamethylene-4,4'-diphthalic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, p-phenylenebis (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-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6 7-Naphthalenetetracarboxylic 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 -Anthracene tetracarboxylic acid dianhydride and 1,2,7,8-phenanthrentetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride (HPMDA), and 1,2, 3,4-Cyclobutanetetracarboxylic acid dianhydride (CBDA), structure:

Compound (BzDA); structure below:

(BNBDA) and the like.

The acid dianhydride other than the above general formula (9) may be at least one selected from the group consisting of BzDA, BNBDA, 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA). preferable. The acid dianhydride may be used alone or in combination of two or more.

<Silicon-containing compound>
The polyimide precursor in the present embodiment may have a structure represented by the above formula (6) as well as a structure represented by the above formula (7). The content ratio of the structure derived from the silicon-containing compound 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 a structure derived from a silicon-containing compound 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 derived from the silicon-containing compound may be 6% by mass or more, 7% by mass or more, or 30% by mass or less, or 25% by mass or less, based on the mass of the polyimide precursor. You may.

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 the tetracarboxylic dianhydride and the diamine.

Such a silicon-containing compound is, for example, the following formula (10) :.

{In the formula,
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 an organic group containing a hydrogen group.
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 and j are independently integers from 1 to 200, respectively.
k is an integer from 0 to 200, and
The relationship of 0.05 ≦ j / (i + j + k) ≦ 0.50 is satisfied. } Can be mentioned.

_{R 1} in the formula (10) 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 (10) 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 (10) 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, monovalent organic groups having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group and n-pentyl. 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 (10) are independently monovalent organic groups having 1 to 10 carbon atoms, and at least one is an organic group having an unsaturated aliphatic hydrocarbon group. The monovalent organic group having 1 to 10 carbon atoms may be linear, cyclic or branched. 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 (10) may be substituted with a substituent such as a halogen atom such as F, Cl, Br, etc., or may be unsubstituted.

_{L 1} and L ₂ in the formula (10) 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 (10) 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 increases and stress is relaxed.
The functional group equivalent can be measured according to existing standards and the like.

I in the formula (10) 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, preferably an integer of 0 to 50, more preferably an integer of 0 to 20, and even more preferably an integer of 0 to 50.

It is preferable that the polyimide in the resin composition has a structure derived from the formula (10) 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.

[Second aspect]
<< Resin composition >>
<Resin / 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. }
It contains the resin of the structural unit represented by, and may also contain a polyimide precursor (hereinafter, also referred to as a total polyimide precursor) or a polyimide (hereinafter, also referred to as a total polyimide), and P ₁ is the following general formula (3). :

Containing a structural unit derived from the compound represented by, and optionally, P ₂ is the following general formula (4) :.

It can contain a structural unit derived from the compound represented by.
Further, P ₁ or P ₂ is expressed 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. 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. , Each independently is an amino group, i is an integer of 1 to 200, j and k are each independently an integer of 0 to 200, and 0 ≦ j / (i + j + k) ≦ 0.50. Yes, and the functional group equivalent is 8000 or more}
Includes a structural unit derived from a silicon-containing compound represented by.

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.

{In the formula, P ₃ represents a divalent organic group, P ₄ represents a tetravalent organic group, p represents a positive integer, and P ₃ represents a 2,2'-bis (tri). Does not contain fluoromethyl) -4,4'-diaminodiphenyl ether (6FODA) or structural units derived from it. }

{In the formula, P ₅ indicates a divalent organic group, P ₆ indicates a tetravalent organic group, q indicates a positive integer, and P ₅ indicates a 2,2'-bis (tri). Does not contain fluoromethyl) -4,4'-diaminodiphenyl ether (6FODA) or structural units derived from it. }
In a structural unit represented by the part it can also include imidized polyimide precursor, P ₃ and / or P ₅ is represented by the following general formula (8):

It can also contain a structural unit derived from the compound represented by.

Further, P ₃ and / or P ₅ are
3,3'-diaminodiphenyl sulfone (33DAS); or 4,4'-diaminodiphenyl sulfone (44DAS)
It can contain at least one structural unit derived from each compound of.

Further, P ₃ and / or P ₅ are
9,9-Bis (4-aminophenyl) fluorene (BAFL); or the following general formula:

Compound (BisAM)
It can contain at least one structural unit derived from each compound of.

Among these, from the viewpoint of the elongation and mechanical properties of the polyimide film, the compound of the following general formula (8), 3,3'-diaminodiphenyl sulfone (33DAS) and / or 4,4'-diaminodiphenyl sulfone ( 44DAS) is preferred. On the other hand, the _{use of 6FODA for P 3} and / or P ₅ is not preferable from the viewpoint of viscosity stability of the varnish, filterability, and foreign matter generated during imidization.

P ₄ and / or _{P 6} is represented by the following general formula (9):

It can also contain a structural unit derived from the compound represented by.

Moreover, _{P 4} and / or _{P 6} is
4,4'-Oxydiphthalic anhydride (ODPA);
4,4'-(Hexafluoroisopropylidene) diphthalic acid anhydride (6FDA);
9,9-Bis (3,4-dicarboxyphenyl) fluorene diic acid anhydride (BPAF); the following general formula:

Compound (BzDA); and the following general formula:

Compound (BNBDA);
Can contain at least one structural unit derived from the compound of.

Among these, the compound of the general formula (9), ODPA, is preferable from the viewpoint of viscosity stability of the varnish, filterability, and transparency of the polyimide film.

Further, in one embodiment, _{P 3} or _{P 4} is represented by 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 from 0 to 200, 0 ≦ j / (i + j + k) ≦ 0.50, and the functional group equivalent is 8000 or more}.
Includes a structural unit derived from a silicon-containing compound represented by.

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.

Further, in the general formula (10), L ₁ and L ₂ are independently amino group, acid anhydride group, isocyanate group, carboxyl group, acid ester group, acid halide group, hydroxy group, epoxy group or mercapto. It is a group, and among them, an amino group is preferable from the viewpoint of resin properties or film properties.

The diamine 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 of the obtained polyimide film can be improved (particularly the tensile elongation) 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 70 mol%. It may be 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.

The resin composition also contains structural units derived from 33 DAS and / or 44 DAS. For 33DAS and 44DAS, it is preferable to use a mixture of 33DAS and 44DAS from the viewpoint of achieving both the thickness direction Rth (retaration) of the polyimide film and the mechanical properties.

The total content of 33 DAS and / or 44 DAS 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% and more than 55 mol%. , Or 70 mol% or more, 90 mol% or more, or 95 mol% or more. A larger amount of 33 DAS and / or 44 DAS is preferable because the mechanical strength of the polyimide film is improved.

Examples of diamines other than the general formula (3) include p-phenylenediamine (PDA), m-phenylenediamine, 2,2'-dimethylbenzidine (mTB), 4,4'-diaminodiphenylsulfide, and 3,4'-diamino. Diphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diamino Benzophenone, 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-amino) Benzene) benzene, 1,3-bis (4-aminophenyl) benzene, 9,10-bis (4-aminophenyl) anthracene, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4) -Aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl) propane, 2,2-bis [4- (4-aminophenoxy) phenyl) hexafluoropropane, and 1,4 -Bis (3-aminopropyldimethylsilyl) benzene, 9,9-bis (4-aminophenyl) fluorene (BAFL), 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene] (BiSAM) and the like.

Among these, 9,9-bis (4-aminophenyl) fluorene (BAFL), 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene] (BiSAM), and 1,4 -Preferably at least one selected from the group consisting of cyclohexanediamine (CHDA).

From the viewpoint of heat resistance and mechanical strength of the obtained polyimide resin film, diamines other than the general formula (3) 33DAS and / or 44DAS are 9,9-bis (4-aminophenyl) fluorene (BAFL), 1,3-. More preferably, it is at least one selected from the group consisting of bis [1- (4-aminophenyl) -1-methylethyl] benzene] (BiSAM).

The acid dianhydride resin composition has the following general formula (4):

It contains a structural unit derived from a compound represented by (also referred to as CpODA). Having this structural unit is preferable because it can improve the transparency, YI, and heat resistance of the obtained polyimide film.

_{The content of CpODA in total acid anhydride (including compounds in which L 1} and L ₂ are acid anhydride groups in the above general formulas (5) and (10)) is 50 mol% or more and 60 mol% or more. , Or 70 mol% or more, 90 mol% or more, or 95 mol% or more. The larger the amount of CpODA, the better the transparency of the polyimide film, which is preferable.

Also. The resin composition contains a structural unit derived from ODPA. Having this structural unit is preferable because it can improve the viscosity stability of the varnish, the filterability, and the transparency of the obtained polyimide film.

_{The content of ODPA in total acid anhydride (including compounds in which L 1} and L ₂ are acid anhydride groups in the above general formulas (5) and (10)) is 50 mol% or more and 60 mol% or more. , Or 70 mol% or more, 90 mol% or more, or 95 mol% or more. The larger the amount of ODPA, the better the transparency of the polyimide film, which is preferable.

Examples of the acid dianhydride other than the general formula (4) include pyromellitic acid dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), 2,2',. 3,3'-Biphenyltetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 5- (2,5-dioxotetrahydro-3-franyl) -3- Methyl-cyclohexene-1,2 dicarboxylic acid anhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2' , 3,3'-benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, methylene-4,4'-diphthalic acid dianhydride, 1,1- Ethiliden-4,4'-diphthalic acid dianhydride, 2,2-propylidene-4,4'-diphthalic acid dianhydride, 1,2-ethylene-4,4'-diphthalic acid dianhydride, 1,3 -Trimethylene-4,4'-diphthalic acid dianhydride, 1,4-tetramethylene-4,4'-diphthalic acid dianhydride, 1,5-pentamethylene-4,4'-diphthalic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, p-phenylenebis (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-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6 7-Naphthalenetetracarboxylic 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 -Anthracene tetracarboxylic acid dianhydride, and 1,2,7,8-phenanthrentetracarboxylic acid dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianohydride (BPAF), 4 , 4'-oxydiphthalic 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 formula (4) include 6FDA, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride (BPAF), BzDA, BNBDA, 1, 2, 4, 5 -Preferably at least one selected from the group consisting of cyclohexanetetracarboxylic dianhydride (HPMDA). The acid dianhydride may be used alone or in combination of two or more.

<Silicon-containing compound>
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 derived from the silicon-containing compound 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 a structure derived from a silicon-containing compound 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 derived from the silicon-containing compound may be 6% by mass or more, 7% by mass or more, or 30% by mass or less, or 25% by mass or less, based on the mass of the polyimide precursor. You may.

Such a silicon-containing compound is, for example, the following formula (5) :.

_{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, monovalent organic groups having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group and n-pentyl. 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 is an organic group having an unsaturated aliphatic hydrocarbon group. The monovalent organic group having 1 to 10 carbon atoms may be linear, cyclic or branched. 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.

_{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. Among them, as L ₁ and L ₂ , an amino group is preferable from the viewpoint of resin properties or film properties.

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 increases 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, preferably an integer of 0 to 50, more preferably an integer of 0 to 20, and even more 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.

[Components common to the first and second aspects and preferred embodiments]
The components common to the first aspect and the second aspect of the present invention, and preferred embodiments of the present invention will be described below. The components of the first aspect and the second aspect may be compatible or combined.

<Silicon-containing diamine>
From the viewpoint of the type of monomer, the cost, and the molecular weight of the obtained polyimide precursor, the silicon-containing compound of the general formula (5) or (10) described above 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, which may be the same or different, and P ₃ and P ₄ _{are R 2} defined in the general formula (5) or (10). , R ₃ and l represents an integer from 1 to 200. }
The diamino (poly) siloxane represented by is preferable.

The preferred structure of P ₃ and P ₄ in the general formula (11), a methyl group, an ethyl group, a propyl group, a butyl group, and 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 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 (10) 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 for 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 compound represented by the above general formula (9) according to the first aspect, and the above general formula (4) according to the second aspect. ) 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 this 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 surfactants 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); 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, more preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the polyimide precursor in the resin composition.

Aalkoxysilane 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 a polyimide precursor from the viewpoint of obtaining good adhesion between the support and the polyimide film in the manufacturing process. 0.01 to 20 parts by mass of the alkoxysilane compound can be contained with respect to 100 parts by mass. When the content of the alkoxysilane compound with respect to 100 parts by mass of the polyimide precursor is 0.01 parts by mass or more, good adhesion 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 adhesion, 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.

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 stripping vapor pressure is preferably as low as possible, more 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) 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 the polyimide / polyimide precursor according to the first aspect, for example, one of the following steps:
-The compound represented by the general formula (8) or the compound represented by the general formula (9) described above is subjected to a polycondensation reaction with the silicon-containing compound represented by the general formula (10) to form a polyimide. After obtaining, a step of polycondensing reaction with other compounds to provide a resin composition containing a polyimide precursor and polyimide;
-The diamine or acid dianhydride described above and the silicon-containing compound represented by the general formula (10) are polycondensed to obtain a polyimide, and then other compounds are polycondensed to obtain the polyimide. Provided is a method for producing a resin composition, which comprises a step of providing a resin composition containing a precursor and a polyimide.

In connection with the synthesis of the polyimide / polyimide precursor according to the second aspect, for example, one of the following steps:
-The compound represented by the general formula (3) described above, the compound represented by the general formula (4), the silicon-containing compound represented by the general formula (5), and other compounds are weighted. A step of subjecting a condensation reaction to provide a polyimide precursor or a resin composition containing a polyimide;
-After subjecting the compound represented by the general formula (3) and other compounds described above to a polycondensation reaction with the compound represented by the general formula (4) and other compounds to obtain polyimide, the above. A step of polycondensing the silicon-containing compound represented by the general formula (5) described in (5) with another compound to provide a resin composition containing a polyimide precursor and a polyimide; or-described above. After a polycondensation reaction of diamine and acid dianhydride to obtain a polyimide, a silicon-containing compound represented by the general formula (5) and another compound are subjected to a polycondensation reaction to contain a polyimide precursor and a polyimide. Step of providing the resin composition;
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 parts) 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 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 a high-molecular-weight polymer can be obtained. Examples of such a solvent include an aprotic solvent, a phenol-based solvent, an ether and a glycol-based solvent, and the like.

Examples of the aprotonic solvent include N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N-methylcaprolactam, 1,3-dimethyl. Imidazolidinone, tetramethylurea, and amide-based solvents of the following general formula:

{In the formula, R ₁₂ = Equamid M100 represented by a methyl group (trade name: manufactured by Idemitsu Kosan Co., Ltd.) and R ₁₂ = Equamid B100 represented by an n-butyl group (trade name: manufactured by Idemitsu Kosan Co., Ltd.)} 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, and further 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, it is selected from the group consisting of N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), and the compound represented by the general formula (6) according to the first and second embodiments. One or more are 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 dianhydride 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 (bin, 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 mass ratio of the additional polyimide / polyimide precursor is relative to the total amount of the 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.

A part of the polyimide precursor in the present embodiment may be 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 monovalent 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.

<Synthesis of polyimide>
In a more preferable mode, the polyimide varnish dissolves an acid dianhydride component and a diamine component in a solvent, for example, an organic solvent, adds a co-boiling solvent such as toluene, and removes water generated during imidization to the outside of the system. By removing it, it can be produced as a polyimide solution (also referred to as polyimide varnish) containing 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, when the solvent used when synthesizing the polyimide / polyimide precursor and the solvent contained in the resin composition are different, the solvent in the synthesized polyimide precursor solution is used, for example, reprecipitation, solvent distillation, 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.

<< 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 peelability 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 polyetheretherketone, polyethersulfone, polyphenylene sulfone, and polyphenylene sulfide; metal substrates such as stainless steel, alumina, copper, and nickel can be mentioned.

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 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 to 200 ° C, more preferably 100 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 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 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 the polyimide resin film / support by the above method, the interface between the support and the polyimide resin film is ablated by irradiating a laser from the support side of the structure. 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 LLC) and tungsten oxide; 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, and 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 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 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 fabrication 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 application example 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 manufacturing a polyimide film on a glass substrate support and manufacturing the organic EL substrate shown in FIG. 1 on the polyimide film, and manufacturing a sealed substrate. 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 the 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 exemplified in the manufacture of the above-mentioned flexible device. 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 the polyimide resin film as a flexible substrate formed on the 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.

[First aspect]
<< 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 (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph, 24.8 mmol / L lithium bromide monohydrate (manufactured by 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 performance 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 rate: 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 absorptiometer, 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 10 days, and the viscosity after 10 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 10 days (mPa · s)) | / (initial viscosity (mPa · s)) * 100/10 (day)
Viscosity stability was evaluated according to the following criteria.
A: Viscosity stability 2% / day or less "excellent"
B: Viscosity stability 4% / day over 7% / day or less "Good"
C: Viscosity stability 6% / day more than 10% / day or less "OK"
D: Viscosity stability 8% / day over "OK"

<Evaluation of the filterability of the composition (varnish)>
The resin compositions prepared in Examples and Comparative Examples were pressure-filtered at a pressure of 0.25 MPa at 23 ° C. and 50% RH using a polyethylene membrane filter having a size of 900 mmφ and a basis weight of 0.2 μm. Was done. 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 of 1700 g / hr or more "excellent"
B: Filtration rate less than 1700 g / hr 1500 g / hr or more "Good"
C: Filtration rate less than 1500 g / hr 500 g / hr or more "OK"
D: Filtration rate less than 500 g / hr "impossible"

<Evaluation of tensile elongation of polyimide resin film>
A 6-inch silicon wafer substrate having an aluminum-deposited layer on its surface was used as a support, and the resin compositions prepared in Examples and Comparative Examples were placed on the surface of the aluminum-deposited layer, and the thickness of the polyimide resin film was 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, a dicing saw (manufactured by Disco Co., Ltd., product name "DAD 3350") was used to make a 3 mm wide cut in the obtained polyimide film, and then the wafer with the polyimide film was immersed in a dilute hydrochloric acid aqueous 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 40% "excellent"
B: Tensile elongation is more than 30% and 40% or less "Good"
C: Tensile elongation is more than 20% and 30% or less "OK"
D: Tensile elongation is less than 20% "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 35 MPa "Good"
B: Residual stress is 35 MPa or more and less than 45 MPa "Yes"
C: Residual stress is 45 MPa or more "impossible"

<Ratio of silicon-containing compounds in all resins>
The ratio (mass%) of the silicon group-containing compound to the total mass of the total resin of the resin composition of Example / Comparative Example was calculated as follows.
Ratio of silicon group-containing compound (mass%) = mass of silicon group-containing compound (g) / total mass of each monomer (acid dianhydride monomer, diamine monomer, silicon group-containing compound) (g) * 100

The ratio of the silicon group-containing compound can be determined by the following method using a varnish.
An appropriate amount of water is added to the varnish, and the mixture is heat-treated at 80 ° C. for 3 days to depolymerize the depolymerization component into the acid component and the amine component to obtain an acid monomer and an amine monomer. Then, the solvent is distilled off to obtain a powder in which an acid monomer and an amine monomer are mixed, an acetonitrile solution is prepared, and high performance liquid chromatography mass spectrometry (LC / MS) measurement is performed. Then, the peak area of each monomer can be obtained and calculated from the peak area ratio.

<Imidization rate>
The imidization rate (%) of the resin of the example / comparative example was calculated as follows.
_{(When L 1} and L ₂ of the general formula (10) are amino groups)
Imidization rate (%) =
Total number of moles of diamine monomers in the imidization step (including compounds containing silicon containing amino groups _{L 1} and L _{2 in} the general formula (10)) _{/ {diamine monomers in the imidization step (L 1} and L in the general formula (10)) ₂ is the total number of moles of the amino group silicon-containing compound) + the total number of moles of the diamine monomer in the amidation step (where L ₁ and L ₂ of the general formula (10) include the amino group silicon-containing compound)} * 100

For example, in the case of Example I-1
Total number of moles of diamine monomer in the imidization step (including the silicon-containing compound in which _{L 1} and L _{2 of the general formula (10) are amino groups): 93.6 mmol}
Total number of moles of diamine monomer in the amidation step (including the silicon-containing compound in which _{L 1} and L _{2 of the general formula (10) are amino groups): 111.9 mmol}
The imidization rate is 83.7%.

_{(When L 1} and L ₂ of the general formula (10) are acid anhydride groups)
Imidization rate (%) =
_{Total number of moles of acid dianhydride monomer in the imidization step (where L 1} and L _{2 in} the general formula (10) include the silicon-containing compound of the acid anhydride group) / {acid anhydride monomer in the imidization step (general formula (general formula (1) 10) L ₁ and L ₂ are the total number of moles of the silicon-containing compound of the acid anhydride group) + the acid dianhydride monomer in the amidation step (L ₁ and L ₂ of the general formula (10) are the acid anhydride groups Total number of moles of (including silicon-containing compounds)} * 100

The imidization rate can be determined by the following method using a varnish.
An appropriate amount of water is added to the varnish, and the mixture is heat-treated at 80 ° C. for 3 days to depolymerize the depolymerization component into the acid component and the amine component to obtain an acid monomer and an amine monomer. Then, the solvent is distilled off to obtain a powder in which an acid monomer and an amine monomer are mixed, an acetonitrile solution is prepared, and high performance liquid chromatography mass spectrometry (LC / MS) measurement is performed. Then, the peak area of each monomer can be obtained and calculated from the peak area ratio.

The imidization rate can also be measured using an IR (infrared spectrophotometer). The varnish was reprecipitated with an aqueous solvent, the powder was separated and dried, and KBr was added to make pellets, which were used as a sample. Then, by measuring the infrared absorption spectrum of the resin layer at one time reflection ATR method, with respect to the benzene ring carbon hydrogen bonds 1009Cm ^-1, can be calculated from the absorbance from the imide groups of 1778cm ^-1. Here, the imidization ratio of the polyimide film after heat-treating the varnish at 400 ° C. for 1 hour was set to 100%.

<Ratio of silicon-containing compounds in diamine Difference between imide unit and amide unit>
The difference between the imide unit and the amide unit in the ratio of the silicon-containing compound in the diamine of the resin of the example / comparative example can be obtained from the following formula.
A: Silicon-containing compound ratio (% by mass) in diamine of imide unit = silicon-containing compound used in imidization step / total mass of diamine monomer (including silicon-containing compound) used in imidization step * 100
B: Silicon-containing compound ratio (% by mass) in diamine of the amide unit = total mass of silicon-containing compound used in the imidization step / diamine monomer (including silicon-containing compound) used in the amidation step * 100
A is "among the general formula in (7) of the diamine constituting the _{P 5,} the ratio (mass%) of the general formula (10)" and can turn also.
Further, B can be rephrased as "the ratio (mass%) of the general formula (10) to the diamines constituting _{P 3} in the general formula (6)".
Then, the ratio of the silicon-containing compound in the diamine The difference between the imide unit and the amide unit is expressed as "BA".

Table 5 shows the values of BA of Examples I-14, I-16, I-17 and Comparative Examples I-4 to I-6, their varnishes, and the characteristics of the polyimide film.

<< Example I-1 >>
As shown in Tables 1 and 2, NMP (189 g), toluene (19 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 (73.0 mmol, 11.1 g) and silicon-containing compound (2) (6.699 mmol, 10.72 g) were added with stirring, and then CpODA (38.4 g) as an acid dianhydride was added at room temperature. rice field. 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 for 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, DABA (18.3 mmol, 2.8 g) was added as a diamine with stirring. The molar ratio of acid dianhydride and 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: imide group) ( Hereinafter, it is also referred to as varnish).

<< Example I-2 >>
As shown in Tables 1 and 2, NMP (191 g), toluene (19 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 (13.6 g) and the silicon-containing compound (1) (10.82 g) were added with stirring, and then CpODA (38.4 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 for 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, DABA (0.7 g) was added as a diamine with stirring. The molar ratio of acid dianhydride and diamine was 100: 98. Then, the mixture is stirred at room temperature for 48 hours to prepare 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: imide group). Obtained.

<< Example I-3 >>
As shown in Tables 1 and 2, NMP (191 g), toluene (19 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 (7.3 g) and the silicon-containing compound (3) (10.85 g) were added with stirring, and then CpODA (38.4 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 for 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, DABA (7.3 g) was added as a diamine with stirring. The molar ratio of acid dianhydride and diamine was 100: 98. Then, the mixture is stirred at room temperature for 48 hours to prepare 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: imide group). Obtained.

<< Example I-4 >>
As shown in Tables 1 and 2, NMP (191 g), toluene (19 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 (8.7 g) and the silicon-containing compound (4) (10.85 g) were added with stirring, and then CpODA (38.4 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 for 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, DABA (5.8 g) was added as a diamine with stirring. The molar ratio of acid dianhydride and diamine was 100: 98. Then, the mixture is stirred at room temperature for 48 hours to prepare 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: imide group). Obtained.

<< Example I-5 >>
As shown in Tables 1 and 2, NMP (186 g), toluene (19 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 (14.9 g) was added with stirring, and then CpODA (32.8 g) and a silicon-containing compound (5) (10.51 g) were added as acid dianhydride 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 for 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, CpODA (3.6 g) was added as an acid dianhydride with stirring. The molar ratio of acid dianhydride and diamine was 100: 98. Then, the mixture is stirred at room temperature for 48 hours to prepare 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: imide group). Obtained.

<< Example I-6 >>
As shown in Tables 1 and 2, NMP (184 g), toluene (18 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 (12.9 g) and the silicon-containing compound (1) (10.44 g) were added with stirring, and then CpODA (28.8 g) and ODPA (7.8 g) were added as acid dianhydrides 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 for 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, DABA (1.4 g) was added as a diamine with stirring. The molar ratio of acid dianhydride and diamine was 100: 98. Then, the mixture is stirred at room temperature for 48 hours to prepare 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: imide group). Obtained.

<< Example I-7 >>
As shown in Tables 1 and 2, NMP (194 g), toluene (19 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 (11.1 g) and the silicon-containing compound (2) (11.02 g) were added with stirring, and then CpODA (28.8 g) and 6FDA (11.1 g) were added as acid dianhydrides 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 for 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, DABA (2.8 g) was added as a diamine with stirring. The molar ratio of acid dianhydride and diamine was 100: 98. Then, the mixture is stirred at room temperature for 48 hours to prepare 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: imide group). Obtained.

<< Example I-8 >>
As shown in Tables 1 and 2, NMP (197 g), toluene (20 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 (8.6 g) and the silicon-containing compound (1) (11.19 g) were added with stirring, and then CpODA (28.8 g) and BPAF (11.5 g) were added as acid dianhydrides 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 for 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, DABA (5.7 g) was added as a diamine with stirring. The molar ratio of acid dianhydride and diamine was 100: 98. Then, the mixture is stirred at room temperature for 48 hours to prepare 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: imide group). Obtained.

<< Example I-9 >>
As shown in Tables 1 and 2, NMP (193 g), toluene (19 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 (7.2 g) and the silicon-containing compound (1) (10.92 g) were added with stirring, and then CpODA (28.8 g) and BzDA (10.1 g) were added as acid dianhydrides 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 for 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, DABA (7.2 g) was added as a diamine with stirring. The molar ratio of acid dianhydride and diamine was 100: 98. Then, the mixture is stirred at room temperature for 48 hours to prepare 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: imide group). Obtained.

<< Example I-10 >>
As shown in Tables 1 and 2, NMP (170 g), toluene (17 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 (13.3 g) and the silicon-containing compound (2) (9.62 g) were added with stirring, and then CpODA (28.8 g) and BNBDF (4.1 g) were added as acid dianhydrides 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 for 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, DABA (0.7 g) was added as a diamine with stirring. The molar ratio of acid dianhydride and diamine was 100: 98. Then, the mixture is stirred at room temperature for 48 hours to prepare 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: imide group). Obtained.

<< Example I-11 >>
As shown in Tables 1 and 2, NMP (204 g), toluene (20 g), and diamine 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 (10.3 g), BAFL (5.9 g) and silicon-containing compound (1) (11.57 g) were added with stirring, and then CpODA (38.4 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 for 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, DABA (1.1 g) and BAFL (0.7 g) were added as diamines with stirring. The molar ratio of acid dianhydride and diamine was 100: 98. Then, the mixture is stirred at room temperature for 48 hours to prepare 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: imide group). Obtained.

<< Example I-12 >>
As shown in Tables 1 and 2, NMP (202 g), toluene (20 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 (5.5 g), BisAM (3.1 g) and silicon-containing compound (2) (11.42 g) were added with stirring, and then CpODA (38.4 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 for 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, DABA (5.5 g) and BisAM (3.1 g) were added as diamines with stirring. The molar ratio of acid dianhydride and diamine was 100: 98. Then, the mixture is stirred at room temperature for 48 hours to prepare 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: imide group). Obtained.

<< Example I-13 >>
As shown in Tables 1 and 2, NMP (218 g), toluene (22 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 (5.9 g), BAFL (9.4 g) and silicon-containing compound (1) (12.35 g) were added with stirring, and then CpODA (38.4 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 for 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, DABA (2.5 g) and BAFL (4.0 g) were added as diamines with stirring. The molar ratio of acid dianhydride and diamine was 100: 98. Then, the mixture is stirred at room temperature for 48 hours to prepare 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: imide group). Obtained.

<< Comparative Example I-1 >>
As shown in Tables 1 and 2, NMP (208 g), toluene (21 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 (10.22 g) and TFMB (16.0 g) were added with stirring, followed by CpODA (27.7 g), BPDA (5.3 g) and silicon-containing compound (6) (9.) as acid dianhydride. 95 g) was added at room temperature. The molar ratio of acid dianhydride and diamine was 100: 100. 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 for 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.

<< Comparative Examples I-2 and I-3 >>
In Comparative Example I-1, the same procedure was used for Comparative Example I-1 except that the types and amounts of the solvent, acid dianhydride, and diamine were changed to those shown in Tables 1 and 2.

<< Example I-14 >>
As shown in Tables 3 and 4, NMP (177 g), toluene (18 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. As a silicon-containing compound (2) (4.12 g), 33 DAS (8.5 g), 44 DAS (12.8 g) was added with stirring, and then ODPA (31.0 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 for 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, 33 DAS (0.9 g) and 44 DAS (1.4 g) were added as diamines with stirring. The molar ratio of acid dianhydride and diamine was 100: 98. Then, the mixture is stirred at room temperature for 48 hours to prepare 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: imide group). Obtained.

<< Example I-15 >>
As shown in Tables 3 and 4, NMP (170 g), toluene (17 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. The silicon-containing compound (2) (1.70 g), 33DAS (8.7 g) and 44DAS (13.0 g) were added with stirring, and then ODPA (31.0 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 for 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, 33 DAS (1.0 g) and 44 DAS (1.4 g) were added as diamines with stirring. The molar ratio of acid dianhydride and diamine was 100: 98. Then, the mixture is stirred at room temperature for 48 hours to prepare 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: imide group). Obtained.

<< Example I-16 >>
As shown in Tables 3 and 4, NMP (204 g), toluene (20 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. The silicon-containing compound (2) (16.36 g) and DABA (12.0 g) were added with stirring, and then CpODA (38.4 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 for 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, DABA (1.3 g) was added as a diamine with stirring. The molar ratio of acid dianhydride and diamine was 100: 98. Then, the mixture is stirred at room temperature for 48 hours to prepare 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: imide group). Obtained.

<< Example I-17 >>
As shown in Tables 3 and 4, NMP (259 g), toluene (26 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. The silicon-containing compound (1) (15.54 g) and BAFL (29.1 g) were added with stirring, and then CpODA (38.4 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 for 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, BAFL (3.2 g) as a diamine was added with stirring. The molar ratio of acid dianhydride and diamine was 100: 98. Then, the mixture is stirred at room temperature for 48 hours to prepare 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: imide group). Obtained.

<< Example I-18 >>
As shown in Tables 3 and 4, NMP (232 g), toluene (23 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. As a silicon-containing compound (1) (7.73 g), 33 DAS (8.5 g), 44 DAS (12.8 g) was added with stirring, and then BPAF (45.8 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 for 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, 33 DAS (0.9 g) and 44 DAS (1.4 g) were added as diamines with stirring. The molar ratio of acid dianhydride and diamine was 100: 98. Then, the mixture is stirred at room temperature for 48 hours to prepare 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: imide group). Obtained.

<< Example I-19 >>
As shown in Tables 3 and 4, NMP (235 g), toluene (24 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. The silicon-containing compound (1) (7.84 g) and 6FODA (28.9 g) were added with stirring, and then CpODA (38.4 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 for 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, 6FODA (3.2 g) as a diamine was added with stirring. The molar ratio of acid dianhydride and diamine was 100: 98. Then, the mixture is stirred at room temperature for 48 hours to prepare 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: imide group). Obtained.

<< Comparative Example I-4 >>
As shown in Tables 3 and 4, 200 g (0.384 mol) of BPADA was dispersed in 1101 g of 1,2-bis (2-methoxyethoxy) ethane (trigram) and kept at 80 ° C. 172 g (0.115 mol) of a silicon-containing compound X-22-9409 (manufactured by Shin-Etsu Chemical Co., Ltd., both ends: amino group, functional group equal amount: 670) was added thereto, and the mixture was uniformly stirred for 30 minutes. Then, the mixture was heated to 140 ° C. and stirred for 1 hour to complete the reaction, and then the temperature was raised to 180 ° C. and reflux was performed for 3 hours. After completion of the reaction, the mixture was cooled to room temperature and 27.7 g (1.54 mol) of water was added. After stirring uniformly for 30 minutes, the mixture was heated to 80 ° C. and heated under reflux for 3 hours. A solution in which the tetracarboxylic acid (terminal tetracarboxylic acid siloxaneimide oligomer) imidized in this manner was dissolved was obtained.
Then, the solution was cooled to room temperature, 99.7 g (0.230 mol) of mBAPS was added, and the mixture was uniformly stirred at room temperature for 1 hour to obtain a resin composition solution.

<< Comparative Example I-5 >>
As shown in Tables 3 and 4, a cooling tube with a ball equipped with a nitrogen introduction tube, a thermometer, and a water separation trap was attached to the three-necked separable flask. At room temperature of 25 ° C., 15 g of triethylene glycol dimethyl ether (trigram), 35 g of γ-butyrolactone (GBL), 20.0 g of toluene and 10.86 g of ODPA (35.00 mmol) were added and stirred until uniform. Then, the temperature was raised to 80 ° C., 11.30 g (13.78 mmol) of the silicon-containing compound KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd., both ends: amino group, functional group equal amount 430) was added, and the mixture was further stirred for 0.5 hour. After that, the temperature was raised to 170 ° C. and heated for 4 hours. During the reaction, the by-produced water was azeotropically boiled with toluene and dehydrated under reflux using a condenser with a ball equipped with a water separation trap. After draining the by-product water, reflux was stopped and all toluene was drained. After cooling the system to 100 ° C., 0.14 g of maleic anhydride was added and the mixture was stirred for 0.5 hours.
After allowing to stand at room temperature of 25 ° C. for 12 hours and cooling, 6.00 g (20.52 mmol) of APB was added to obtain a resin composition.

<< Comparative Example I-6 >>
A 500 mL five-necked round-bottom flask with a stainless half-moon agitator, a nitrogen inlet tube, a Dean Stark with a condenser, a thermometer, and a glass end cap, as described in Tables 3 and 4. 27.0 g (0.0802 mol) of 6FODA and 56.000 g of NMP were added, and the mixture was stirred at a system temperature of 70 ° C. and a nitrogen atmosphere at a rotation speed of 200 rpm to obtain a solution.

After adding 19.2 g (0.050 mol) of CpODA and 14.000 g of NMP to this solution in a batch, 0.253 g of TEA was added as an imidization catalyst, and the mixture was heated by a mantle heater over about 20 minutes. The temperature inside the reaction system was raised to 190 ° C. The components to be distilled off were collected, and the temperature inside the reaction system was maintained at 190 ° C. and refluxed for 1 hour while adjusting the rotation speed according to the increase in viscosity. Then, 85.806 g of NMP was added to cool the temperature inside the reaction system to 50 ° C. to obtain a solution containing an oligomer having an imide repeating structural unit.

9.7 g (0.033 mol) of BPDA and 7.527 g of NMP were collectively added to the obtained solution, and the mixture was stirred at 50 ° C. for 5 hours. Then, after adding 100.000 g of NMP to homogenize, 13.2 g (0.003 mol) of X-22-1660B-3 (modified silicone oil, functional group equal amount 2200, Shin-Etsu Chemical Co., Ltd.) was added to 16.667 g of NMP. The dissolved mixed solution is added, and the mixture is further stirred for about 1 hour to partially imidize a polyimide precursor (functional group other than silicon-containing compound: amide group or imide group, functional group of silicon-containing compound: amide group). ) NMP solution (hereinafter, also referred to as varnish) was obtained.

Using the resin compositions of Examples and Comparative Examples, each evaluation of viscosity stability and filterability was performed, and each evaluation of tensile elongation and residual stress was performed using the obtained polyimide resin film. The evaluation results are shown in Tables 1 to 4.

The abbreviations in the examples and comparative examples are as follows;
<Acid dianhydride>
CpODA: A compound of the following general formula

ODPA: 4,4'-oxydiphthalic anhydride 6FDA: 4,4'-(hexafluoroisopropylidene) diphthalic acid anhydride BPAF: 9,9-bis (3,4-dicarboxyphenyl) fluorene diic acid anhydride BzDA : Compound of the following general formula

BNBDA: Compound of the following general formula

BPADA: 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride

<Diamine>
DABA: 3,5-diaminobenzoic acid 3,3'-diaminodiphenyl sulfone (33DAS)
4,4'-Diaminodiphenyl sulfone (44DAS)
BAFL: 9,9-bis (4-aminophenyl) fluorene BisAM: a compound of the following general formula

TFMB: Diaminobis (trifluoromethyl) biphenyl BAPP: Compound of the following general formula

mBAPS: Bis [4- (3-aminophenoxy) phenyl] Sulfone APB: 1,3-Bis (3-aminophenoxy) benzene

<Silicon-containing compound>
Silicon-containing compound (1): (In the general formula (10), L ₁ and L ₂ are amino groups (-NH ₂ ), R ₁ is a trimethylene group (-CH ₂ CH ₂ CH _2- ), and R ₂ ,. A compound in which R ₃ is a methyl group, j and k are 0, and a functional group equivalent is 1500).
Silicon-containing compound (2): (In the general formula (10), L ₁ and L ₂ are amino groups (-NH ₂ ), R ₁ is a trimethylene group (-CH ₂ CH ₂ CH _2- ), and R ₂ ,. A compound in which R ₃ is a methyl group, j and k are 0, and a functional group equivalent is 800).
Silicon-containing compound (3): (In the general formula (10), L ₁ and L ₂ are amino groups (-NH ₂ ), R ₁ is a trimethylene group (-CH ₂ CH ₂ CH _2- ), and R ₂ ,. A compound in which R ₃ is a methyl group, j and k are 0, and a functional group equivalent is 2200).
Silicon-containing compound (4): In the general formula (10), L ₁ and L ₂ are amino groups, R ₁ is −CH ₂ CH ₂ CH ₂ −, and R ₂ , R ₃ , R ₆ and R ₇ are methyl. Group, R ₄ , R ₅ are phenyl group, j / (i + j + k) = 0.15, functional group equivalent 2200 compound Silicon-containing compound (5): (In the general formula (10), L ₁ and L ₂ are The acid anhydride group (-CH (C = O) ₂ O), R ₁ is a trimethylene group (-CH ₂ CH ₂ CH _2- ), R ₂ and R ₃ are methyl groups, and j and k are 0. , A compound having a functional group equivalent of 1000)
Silicon-containing compound (6): (In the general formula (10), L ₁ and L ₂ are acid anhydride groups (-CH (C = O) ₂ O), 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 500).

[Second aspect]
<< 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 (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph, 24.8 mmol / L lithium bromide monohydrate (manufactured by 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 performance 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 rate: 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 absorptiometer, 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 at a pressure of 0.25 MPa at 23 ° C. and 50% RH using a polyethylene membrane filter having a size of 900 mmφ and a basis weight of 0.2 μm. Was done. 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>
A 6-inch silicon wafer substrate having an aluminum-deposited layer on its surface was used as a support, and the resin compositions prepared in Examples and Comparative Examples were placed on the surface of the aluminum-deposited layer, and the thickness of the polyimide resin film was 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, a dicing saw (manufactured by Disco Co., Ltd., product name "DAD 3350") was used to make a 3 mm wide cut in the obtained polyimide film, and then the wafer with the polyimide film was immersed in a dilute hydrochloric acid aqueous 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"

<< Example II-1 >>
As shown in Tables 6 and 7, NMP (191 g) as a solvent, DABA (14.4 g) as a diamine, and a silicon-containing compound (1) (1) while introducing nitrogen gas into a 3 L separable flask with a stirring rod. 10.82 g) was added with stirring, followed by CpODA (38.4 g) as acid dianhydride. The molar ratio of acid dianhydride and 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.

<< Example II-2 >>
As shown in Tables 6 and 7, NMP (191 g), toluene (19 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 (14.4 g) and the silicon-containing compound (1) (10.82 g) were added with stirring, and then CpODA (38.4 g) as an acid dianhydride was added at room temperature. The molar ratio of acid dianhydride and 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 for 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.

<< Example II-3 >>
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, as shown in any of Tables 6 to 9, NMP (189 g) and toluene (19 g) were used as solvents. ), DABA (13.9 g) as a diamine was added with stirring, and then CpODA (38.4 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 for 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 (2) (10.72 g) was added with stirring. The molar ratio of acid dianhydride and 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).

<< Example II-16 >>
As shown in Tables 8 and 9, NMP (177 g), toluene (18 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. 33 DAS (8.5 g) and 44 DAS (12.8 g) were added with stirring, and then ODPA (31.0 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 for 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, 33 DAS (0.9 g) and 44 DAS (1.4 g) as diamines and the silicon-containing compound (2) (4.12 g) were added with stirring. The molar ratio of acid dianhydride and 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).

<< Example II-17 >>
As shown in Tables 8 and 9, NMP (173 g), toluene (17 g), as solvents, while introducing nitrogen gas into a separable flask with a stirring rod equipped with a Dane Stark tube and a reflux tube at the top. DABA (13.0 g) was added as a diamine with stirring, followed by CpODA (38.4 g) as an acid dianhydride 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 for 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, DABA (1.4 g) and the silicon-containing compound (2) (4.80 g) were added as diamines with stirring. The molar ratio of acid dianhydride and 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).

<< Comparative Example II-4 >>
A 500 mL five-necked round-bottom flask with a stainless half-moon agitator, a nitrogen inlet tube, a Dean Stark with a condenser, a thermometer, and a glass end cap, as described in Tables 8 and 9. 27.0 g (0.0802 mol) of 6FODA and 56.000 g of NMP were added, and the mixture was stirred at a system temperature of 70 ° C. and a nitrogen atmosphere at a rotation speed of 200 rpm to obtain a solution.

<< Examples II-4, II-5, II-7, II-9, II-10, II-12, II-14, II-15 >>
In Example II-3, the same procedure was used for Example II-3, except that the types and amounts of the solvent, acid dianhydride, diamine, and silicon-containing compound were changed to those shown in Tables 6 and 7. ..

<< Reference Example II-6, Examples II-8, II-11, II-13, Comparative Examples II-1 to II-3 >>
In Example II-2, the same procedure was used for Example II-2, except that the types and amounts of the solvent, acid dianhydride, diamine, and silicon-containing compound were changed to those shown in Tables 6 and 7. ..

Using the resin compositions of Examples and Comparative Examples, each evaluation of viscosity stability and filterability was performed, and each evaluation of tensile elongation and residual stress was performed using the obtained polyimide resin film. The evaluation results are shown in Tables 6 to 9.

BNBDA: Compound of the following general formula

<Diamine>
DABA: 3,5-diaminobenzoic acid BAFL: 9,9-bis (4-aminophenyl) fluorene BisAM: a compound of the following general formula

33DAS: 3,3'-diaminodiphenyl sulfone 44DAS: 3,3'-diaminodiphenyl sulfone 6FODA: 2,2'-bis (trifluoromethyl) -4,4'-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 800).
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, R ₁ is -CH ₂ CH ₂ CH _2- , and R ₂ , R ₃ , R ₆ , R ₇ is a methyl group, R ₄ , R ₅ is a phenyl group, j / (i + j + k) = 0.15, and a functional group equivalent of 2200 is a compound Silicon-containing compound (5): (general formula (5), (10). ), L ₁ and L ₂ are acid anhydride groups (-CH (C = O) ₂ O), R ₁ is a trimethylene group (-CH ₂ CH ₂ CH _2- ), and R ₂ and R ₃ are methyl. A compound having 0 groups, j and k, and a functional group equivalent of 1000)
Silicon-containing compound (6): (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 500).

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

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 containing a resin of a structural unit represented by.
Wherein P 5 or P 6 is represented by 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 the silicon-containing compound represented by, and contains 25% by mass or less of the silicon-containing compound based on the total mass of the resin.
Resin composition.
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 containing a resin of a structural unit represented by.
Wherein P 5 or P 6 is represented by 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 imidization ratio of the resin is 50% or more.
Resin composition.
The resin composition according to claim 1, wherein the imidization ratio of the resin is 50% or more.
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 containing a resin of a structural unit represented by.
Wherein P 5 or P 6 is represented by 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 (a) or (b) below.
(A) The P 3 and / or P 5 is the following general formula (8):

In comprising a structural unit derived from a compound represented; or (b) the P 4 and / or P 6 is represented by the following general formula (9):

Includes structural units derived from the compounds represented by;
A resin composition that satisfies any of the above.
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 containing a resin of a structural unit represented by.
Wherein P 5 or P 6 is represented by 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 a structural unit derived from the silicon-containing compound represented by, and the P 3 and / or P 5 are independent of each other.
3,3'-Diaminodiphenyl sulfone (33DAS),
4,4'-Diaminodiphenyl sulfone (44DAS), or 9,9-bis (4-aminophenyl) fluorene (BAFL)
A resin composition containing at least one structural unit derived from each of the above compounds.
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 containing a resin of a structural unit represented by.
Wherein P 5 or P 6 is represented by 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 a structural unit derived from the silicon-containing compound represented by, and the P 3 and / or P 5 are independent of each other.
2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ether (6FODA)
A resin composition containing at least one structural unit derived from.
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 containing a resin of a structural unit represented by.
Wherein P 5 or P 6 is represented by 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. , Each independently is an amino group, i is an integer of 1 to 200, and j and k are independently integers of 0 to 200, with 0 ≦ j / (i + j + k) ≦ 0.50. be. }
Containing a structural unit derived from in the silicon-containing compound represented, and A (wt%): Of the diamine that constitutes the P 5 in the general formula (7), the proportion of the general formula (10) B (wt%): of the diamine that constitutes the P 3 in the general formula (6), when the ratio of the general formula (10), B-a is greater than 0 and less than 60,
Resin composition.
The diamine
The following general formula (8):

Compound represented by,
3,3'-Diaminodiphenyl sulfone (33DAS),
4,4'-Diaminodiphenyl sulfone (44DAS), and 9,9-bis (4-aminophenyl) fluorene (BAFL)
The resin composition according to claim 7, which is at least one compound selected from the above.
In Formula (6) and / or the general formula (7), P 4 and / or P 6 are each independently, 4,4'-oxydiphthalic anhydride (ODPA), or 9,9-bis ( 3,4-Dicarboxyphenyl) The resin composition according to any one of claims 1 to 8, which comprises at least one structural unit derived from each compound of fluorene diacid anhydride (BPAF).
The resin composition according to any one of claims 1 to 9, wherein the silicon-containing compound represented by the general formula (10) has a functional group equivalent of 800 or more.
The P 5 contains a structural unit derived from the compound represented by the general formula (10), and the L 1 and L 2 in the general formula (10) are independently amino groups.
The resin composition according to any one of claims 1 to 10.
The compound represented by the general formula (8) is more than 50 mol% when the total diamine (excluding the compound represented by the general formula (10)) is 100 mol%, according to claims 4 and 9 to 11. The resin composition according to any one of the above.
Wherein P 3 or P 5 are each independently, the following formula:

The resin composition according to any one of claims 1 to 12, which comprises a structural unit derived from the compound (BisAM) represented by.
Wherein P 4 or P 6 are each independently, 4,4 '- (hexafluoro isopropylidene) diphthalic anhydride, the following formula:

Compound represented by (BzDA), or the following formula:

The resin composition according to any one of claims 1 to 13, which comprises a structural unit derived from the compound represented by (BNBDA).
The resin composition according to any one of claims 1 to 14, wherein the polyimide resin film obtained by heating the resin is used for a flexible substrate.
The resin composition according to any one of claims 1 to 15, wherein the polyimide resin film obtained by curing the resin is used for a flexible display.
Diamine or acid dianhydride and 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. }
After polycondensation reaction of the silicon-containing compound represented by
It comprises polycondensing reaction with other compounds to provide a resin composition containing a polyimide precursor and a resin containing polyimide.
The silicon-containing compound is contained in an amount of 25% by mass or less based on the total mass of the resin.
A method for producing a resin composition.
Diamine or acid dianhydride and 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. }
After polycondensation reaction of the silicon-containing compound represented by
It comprises polycondensing reaction with other compounds to provide a resin composition containing a polyimide precursor and a resin containing polyimide.
The imidization rate of the resin is 50% or more.
A method for producing a resin composition.
The following general formula (8):

The compound represented by, or the following general formula (9):

The compound represented by the following and 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. }
After polycondensation reaction of the silicon-containing compound represented by (1) and other compounds to obtain polyimide,
A method for producing a resin composition, which comprises subjecting a resin composition containing a polyimide precursor and a polyimide by polycondensation reaction with other compounds.
3,3'-Diaminodiphenyl sulfone (33DAS),
4,4'-Diaminodiphenyl sulfone (44DAS), and 9,9-bis (4-aminophenyl) fluorene (BAFL)
With at least one compound selected from
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. }
After polycondensation reaction of the silicon-containing compound represented by (1) and other compounds to obtain polyimide,
A method for producing a resin composition, which comprises subjecting a resin composition containing a polyimide precursor and a polyimide by polycondensation reaction with other compounds.
At least one compound selected from 4,4'-oxydiphthalic anhydride (ODPA) and 9,9-bis (3,4-dicarboxyphenyl) fluorene diic acid anhydride (BPAF), and 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. }
After polycondensation reaction of the silicon-containing compound represented by (1) and other compounds to obtain polyimide,
A method for producing a resin composition, which comprises subjecting a resin composition containing a polyimide precursor and a polyimide by polycondensation reaction with other compounds.
Coating on the surface of the support by applying the resin composition according to any one of claims 1 to 16 or the resin composition obtained by the method according to any one of claims 17 to 21. Process and
A film forming step of heating the resin composition to form a polyimide resin film,
A peeling step of peeling the polyimide resin film from the support,
A method for producing a polyimide resin film, including.
The method for producing a polyimide resin film according to claim 22, further comprising an irradiation step of irradiating the resin composition with a laser from the support side prior to the peeling step.
Coating on the surface of the support by applying the resin composition according to any one of claims 1 to 16 or the resin composition obtained by the method according to any one of claims 17 to 21. Process and
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.
Coating on the surface of the support by applying the resin composition according to any one of claims 1 to 16 or the resin composition obtained by the method according to any one of claims 17 to 21. Process and
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 manufacturing a laminate according to claim 25, 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 25 or 26.
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 resin composition containing a resin of a structural unit represented by.
The P 1 is the following general formula (3):

Containing a structural unit derived from in the compound represented by, and the P 1 The P 2 is 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. , Each independently is an amino group, i is an integer of 1 to 200, j and k are each independently an integer of 0 to 200, and 0 ≦ j / (i + j + k) ≦ 0.50. Yes, and the functional group equivalent is 800 or more. }
Containing structural units derived from silicon-containing compounds represented by
Resin composition.
The above P 2 is the following general formula (4):

28. The resin composition according to claim 28, which comprises a structural unit derived from the compound represented by.
The following general formulas (6) and (7):

{In the formula, P 3 represents a divalent organic group, P 4 represents a tetravalent organic group, p represents a positive integer, and P 3 represents a 2,2'-bis (tri). Fluoromethyl) -4,4'-diaminodiphenyl ether (6FODA) is not included. }

{In the formula, P 5 indicates a divalent organic group, P 6 indicates a tetravalent organic group, q indicates a positive integer, and P 5 indicates a 2,2'-bis (tri). Fluoromethyl) -4,4'-diaminodiphenyl ether (6FODA) is not included. }
A resin composition containing a resin of 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. , Each independently is an amino group, i is an integer of 1 to 200, and j and k are independently integers of 0 to 200, with 0 ≦ j / (i + j + k) ≦ 0.50. be. }
Containing structural units derived from silicon-containing compounds represented by
Resin composition.
The following general formulas (6) and (7):

{In the formula, P 3 represents a divalent organic group, P 4 represents a tetravalent organic group, p represents a positive integer, and P 3 represents a 2,2'-bis (tri). Fluoromethyl) -4,4'-diaminodiphenyl ether (6FODA) is not included. }

{In the formula, P 5 indicates a divalent organic group, P 6 indicates a tetravalent organic group, q indicates a positive integer, and P 5 indicates a 2,2'-bis (tri). Fluoromethyl) -4,4'-diaminodiphenyl ether (6FODA) is not included. }
A resin composition containing a resin of 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. , Each independently is an amino group, i is an integer of 1 to 200, and j and k are independently integers of 0 to 200, with 0 ≦ j / (i + j + k) ≦ 0.50. be. }
It contains a structural unit derived from a silicon-containing compound represented by (a) or (b) below.
(A) The P 3 and / or P 5 is the following general formula (8):

In comprising a structural unit derived from a compound represented; or (b) the P 4 and / or P 6 is represented by the following general formula (9):

Includes structural units derived from the compounds represented by;
A resin composition that satisfies any of the above.
The following general formulas (6) and (7):

{In the formula, P 3 represents a divalent organic group, P 4 represents a tetravalent organic group, p represents a positive integer, and P 3 represents a 2,2'-bis (tri). Fluoromethyl) -4,4'-diaminodiphenyl ether (6FODA) is not included. }

{In the formula, P 5 indicates a divalent organic group, P 6 indicates a tetravalent organic group, q indicates a positive integer, and P 5 indicates a 2,2'-bis (tri). Fluoromethyl) -4,4'-diaminodiphenyl ether (6FODA) is not included. }
A resin composition containing a resin of 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. , Each independently is an amino group, i is an integer of 1 to 200, and j and k are independently integers of 0 to 200, with 0 ≦ j / (i + j + k) ≦ 0.50. be. }
Containing a structural unit derived from in the silicon-containing compound represented, and the P 3 and / or P 5 is
3,3'-diaminodiphenyl sulfone (33DAS), or 4,4'-diaminodiphenyl sulfone (44DAS)
A resin composition containing at least one structural unit derived from each of the above compounds.
The following general formulas (6) and (7):

{In the formula, P 3 represents a divalent organic group, P 4 represents a tetravalent organic group, p represents a positive integer, and P 3 represents a 2,2'-bis (tri). Fluoromethyl) -4,4'-diaminodiphenyl ether (6FODA) is not included. }

{In the formula, P 5 indicates a divalent organic group, P 6 indicates a tetravalent organic group, q indicates a positive integer, and P 5 indicates a 2,2'-bis (tri). Fluoromethyl) -4,4'-diaminodiphenyl ether (6FODA) is not included. }
A resin composition containing a resin of 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. , Each independently is an amino group, i is an integer of 1 to 200, and j and k are independently integers of 0 to 200, with 0 ≦ j / (i + j + k) ≦ 0.50. be. }
Containing a structural unit derived from in the silicon-containing compound represented, and the P 3 and / or P 5 is
9,9-Bis (4-aminophenyl) fluorene (BAFL), or the following general formula:

Compound (BisAM)
A resin composition containing at least one structural unit derived from each of the above compounds.
The following general formulas (6) and (7):

{In the formula, P 3 represents a divalent organic group, P 4 represents a tetravalent organic group, p represents a positive integer, and P 3 represents a 2,2'-bis (tri). Fluoromethyl) -4,4'-diaminodiphenyl ether (6FODA) is not included. }

{In the formula, P 5 indicates a divalent organic group, P 6 indicates a tetravalent organic group, q indicates a positive integer, and P 5 indicates a 2,2'-bis (tri). Fluoromethyl) -4,4'-diaminodiphenyl ether (6FODA) is not included. }
A resin composition containing a resin of 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. , Each independently is an amino group, i is an integer of 1 to 200, and j and k are independently integers of 0 to 200, with 0 ≦ j / (i + j + k) ≦ 0.50. be. }
In comprising a structural unit derived from silicon-containing compound represented, and the P 4 and / or P 6 is
4,4'-Oxydiphthalic anhydride (ODPA),
4,4'-(Hexafluoroisopropylidene) diphthalic acid anhydride (6FDA),
9,9-Bis (3,4-dicarboxyphenyl) fluorene diic acid anhydride (BPAF),
The following general formula:

Compound (BzDA); or the following general formula:

Compound (BNBDA);
A resin composition containing at least one structural unit derived from each of the above compounds.
The P 3 contains a structural unit derived from the compound represented by the general formula (10).
The resin composition according to any one of claims 30 to 34, wherein the silicon-containing compound represented by the general formula (10) has a functional group equivalent of 800 or more.
The P 3 contains a structural unit derived from the compound represented by the general formula (10), and the L 1 and L 2 in the general formula (10) are independently amino groups.
The resin composition according to any one of claims 30 to 35.
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 28, 29 and 31.
The resin composition according to any one of claims 28 to 37, wherein the polyimide resin film obtained by heating the resin is used for a flexible substrate.
The resin composition according to any one of claims 28 to 38, wherein the polyimide resin film obtained by curing the resin is used for a flexible display.
The following general formula (3):

Compound represented by,
3,3'-Diaminodiphenyl sulfone (33DAS), and 4,4'-diaminodiphenyl sulfone (44DAS),
With at least one diamine selected from,
Acid dianhydride and
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. , Each independently is an amino group, i is an integer of 1 to 200, and j and k are independently integers of 0 to 200, with 0 ≦ j / (i + j + k) ≦ 0.50. be. }
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 polyimide precursor and / or a polyimide.
After polycondensation reaction of diamine (however, 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ether (6FODA) is not contained) and acid dianhydride 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. , Each independently is an amino group, i is an integer of 1 to 200, and j and k are independently integers of 0 to 200, with 0 ≦ j / (i + j + k) ≦ 0.50. be. }
A method for producing a resin composition, which comprises subjecting a silicon-containing compound represented by (1) to a polycondensation reaction with another compound to provide a resin composition containing a polyimide precursor and a polyimide.
The following general formula (3):

Compound represented by,
3,3'-Diaminodiphenyl sulfone (33AS), and 4,4'-diaminodiphenyl sulfone (44DAS),
With at least one diamine selected from,
Acid dianhydride and
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 s 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. , Each independently is an amino group, i is an integer of 1 to 200, and j and k are independently integers of 0 to 200, with 0 ≦ j / (i + j + k) ≦ 0.50. be. }
A method for producing a resin composition, which comprises subjecting a silicon-containing compound represented by (1) to a polycondensation reaction with another compound to provide a resin composition containing a polyimide precursor and a polyimide.
Coating on the surface of the support by applying the resin composition according to any one of claims 28 to 39 or the resin composition obtained by the method according to any one of claims 40 to 42. Process and
A film forming step of heating the resin composition to form a polyimide resin film,
A peeling step of peeling the polyimide resin film from the support,
A method for producing a polyimide resin film, including.
The method for producing a polyimide resin film according to claim 43, which comprises an irradiation step of irradiating the resin composition with a laser from the support side prior to the peeling step.
Coating on the surface of the support by applying the resin composition according to any one of claims 28 to 39 or the resin composition obtained by the method according to any one of claims 40 to 42. Process and
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.
Coating on the surface of the support by applying the resin composition according to any one of claims 28 to 39 or the resin composition obtained by the method according to any one of claims 40 to 42. Process and
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 manufacturing a laminate according to claim 46, 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 46 or 47.