KR20220158818A - resin composition - Google Patents

Abstract

{식 중, 각종 부호는 명세서에 정의되는 바와 같다.}A resin composition comprising a polyimide precursor and/or a resin of polyimide and satisfying the following (A) or (B) is provided: (A) a divalent organic group P ₅ and a tetravalent organic group in a polyimide constituent unit; P ₆ is included, P ₅ or P ₆ includes a structural unit derived from a silicon-containing compound of the following formula (10), and the resin composition contains 25% by mass or less of the silicon-containing compound based on the total mass of the resin. ; (B) The constituent unit of the resin includes a divalent organic group P ₁ and a tetravalent organic group P ₂ , P ₁ contains a constitutional unit derived from a compound represented by the following formula (3), and P ₁ or P ₂ is It contains structural units derived from the silicon-containing compound of the following formula (5);

{In the formula, various codes are 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 also relates to a method for producing a polyimide precursor/resin composition containing polyimide, and a method for producing polyimide films, displays, laminates and flexible devices.

Polyimide resin is an insoluble and insoluble super heat-resistant resin, and has excellent properties such as heat oxidation resistance, heat resistance, radiation resistance, low temperature resistance, and chemical resistance. For this reason, 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, and electrode protective films for thin film transistor liquid crystal displays (TFT-LCD). In recent years, taking advantage of the lightness, flexibility, and the like of polyimide films, in the field of display materials, adoption is being considered also as flexible substrates instead of glass substrates conventionally used.

In Patent Document 1, as a monomer, 3,5-diaminobenzamide (hereinafter also referred to as DABA) and the following structural formula:

[Formula 1]

Described is a polyimide film obtained by synthesizing polyimide using a compound of (hereinafter also referred to as CpODA) and other compounds, adding a crosslinking agent to the obtained polyimide varnish, applying it, and drying it. Further, Patent Literature 1 also describes that this film has excellent gas separation performance. Patent Document 2 describes a transparent polyimide film obtained by applying and drying a polyimide varnish using DABA, TFMB (2,2'-bis(trifluoromethyl)benzidine), etc. as diamine and CpODA as acid dianhydride. has been

Japanese Patent Publication No. 6551640 International Publication No. 2019/211972

The polyimide film described in Patent Literature 1 is used as a gas separation membrane and has not been studied as an optical material.

In addition, the present inventors synthesized a polyimide varnish using DABA, TFMB, CpODA, a silicon-containing compound, and the like as monomers and synthesizing a polyimide varnish in the same manner as described in Patent Document 2, and found that the filterability of the varnish required in the varnish manufacturing process was insufficient. Then, it was found that the polyimide film obtained by applying and heating the polyimide varnish had insufficient properties (tensile elongation, etc.) required for display applications. On the other hand, the present inventors, DABA, 3,3'-diaminodiphenylsulfone (33DAS), 4,4'-diaminodiphenylsulfone (44DAS), 9,9-bis (4-aminophenyl) fluorene ( BAFL) and the like, and acid dianhydrides such as CpODA, 4,4'-oxydiphthalic anhydride (ODPA), and 9,9-bis (3,4-dicarboxyphenyl) fluorene diacid anhydride (BPAF), It has been found that polyimides obtained by using other silicon-containing compounds or the like as monomers have excellent properties required for display applications.

Therefore, the present invention was made in view of the above circumstances, and a polyimide film excellent in both the properties required for the production process of a polyimide precursor and/or a polyimide-containing resin composition and other properties required for display applications, And it aims at providing the resin composition for forming it.

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

[First aspect]

<1>

The general formulas (6) and (7) below:

[Formula 2]

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

[Formula 3]

{In the formula, P ₅ represents a divalent organic group, P ₆ represents a tetravalent organic group, and q represents a positive integer.}

As a resin composition containing a resin of the structural unit represented by,

The P ₅ or P ₆ is, the following general formula (10):

[Formula 4]

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid A halide group, a hydroxyl group, an epoxy group, or a mercapto 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}

It includes a structural unit derived from a silicon-containing compound represented by

Comprising 25% by mass or less of the silicon-containing compound based on the total mass of the resin,

resin composition.

<2>

The general formulas (6) and (7) below:

[Formula 5]

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

[Formula 6]

{In the formula, P ₅ represents a divalent organic group, P ₆ represents a tetravalent organic group, and q represents a positive integer.}

As a resin composition containing a resin of the structural unit represented by,

The P ₅ or P ₆ is, the following general formula (10):

[Formula 7]

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid A halide group, a hydroxyl group, an epoxy group, or a mercapto 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}

It includes a structural unit derived from a silicon-containing compound represented by

The imidization rate of the resin is 50% or more,

resin composition.

<3>

The resin composition according to item 1, wherein the resin has an imidation rate of 50% or more.

<4>

The general formulas (6) and (7) below:

[Formula 8]

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

[Formula 9]

{In the formula, P ₅ represents a divalent organic group, P ₆ represents a tetravalent organic group, and q represents a positive integer.}

As a resin composition containing a resin of the structural unit represented by,

The P ₅ or P ₆ is, the following general formula (10):

[Formula 10]

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid A halide group, a hydroxyl group, an epoxy group, or a mercapto 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}

It includes a structural unit derived from a silicon-containing compound represented by

To (a) or (b):

(A) The P ₃ and/or P ₅ is the following general formula (8):

[Formula 11]

It includes structural units derived from the compound represented by ; or

(B) The P ₄ and/or P ₆ is the following general formula (9):

[Formula 12]

It includes structural units derived from the compound represented by ;

A resin composition that satisfies any of the above.

<5>

The general formulas (6) and (7) below:

[Formula 13]

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

[Formula 14]

{In the formula, P ₅ represents a divalent organic group, P ₆ represents a tetravalent organic group, and q represents a positive integer.}

As a resin composition containing a resin of the structural unit represented by,

The P ₅ or P ₆ is, the following general formula (10):

[Formula 15]

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid A halide group, a hydroxyl group, an epoxy group, or a mercapto 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}

It includes a structural unit derived from a silicon-containing compound represented by

The P ₃ and/or P ₅ are each independently;

3,3'-diaminodiphenylsulfone (33DAS);

4,4'-diaminodiphenylsulfone (44DAS), or

9,9-bis(4-aminophenyl)fluorene (BAFL)

The resin composition containing at least 1 structural unit derived from each compound of.

<6>

The general formulas (6) and (7) below:

[Formula 16]

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

[Formula 17]

{In the formula, P ₅ represents a divalent organic group, P ₆ represents a tetravalent organic group, and q represents a positive integer.}

As a resin composition containing a resin of the structural unit represented by,

The P ₅ or P ₆ is, the following general formula (10):

[Formula 18]

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid A halide group, a hydroxyl group, an epoxy group, or a mercapto 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}

It includes a structural unit derived from a silicon-containing compound represented by

The P ₃ and/or P ₅ are each independently;

2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether (6FODA)

The resin composition containing at least 1 structural unit derived from.

<7>

The general formulas (6) and (7) below:

[Formula 19]

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

[Formula 20]

{In the formula, P ₅ represents a divalent organic group, P ₆ represents a tetravalent organic group, and q represents a positive integer.}

As a resin composition containing a resin of the structural unit represented by,

The P ₅ or P ₆ is, the following general formula (10):

[Formula 21]

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, L ₁ and L ₂ are each independently an amino group, i is an integer of 1 to 200, j and k are each independently an integer from 0 to 200, and 0 ≤ j/(i + j + k) ≤ 0.50.}

It includes a structural unit derived from a silicon-containing compound represented by

A (mass %): Ratio of general formula (10) among diamines constituting P ₅ in general formula (7)

B (mass %): Ratio of general formula (10) among diamines constituting P ₃ in general formula (6)

, when B - A is greater than 0 and less than 60,

resin composition.

<8>

the diamine,

The following general formula (8):

[Formula 22]

The compound represented by

3,3'-diaminodiphenylsulfone (33DAS);

4,4'-diaminodiphenylsulfone (44DAS), and

9,9-bis(4-aminophenyl)fluorene (BAFL)

The resin composition according to item 7, which is at least one compound selected from

<9>

In the general 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 The resin composition according to any one of items 1 to 8, comprising at least one structural unit derived from each compound of (3,4-dicarboxyphenyl)fluorene diacid anhydride (BPAF).

<10>

The resin composition according to any one of items 1 to 9, wherein the functional group equivalent of the silicon-containing compound represented by the general formula (10) is 800 or more.

<11>

P ₅ contains a structural unit derived from a compound represented by the general formula (10);

In the general formula (10), L ₁ and L ₂ are each independently an amino group;

The resin composition according to any one of items 1 to 10.

<12>

Any one of items 4 and 9 to 11 in which the compound represented by the general formula (8) is greater than 50 mol% when all diamines (excluding the compound represented by the general formula (10)) are 100 mol%. The resin composition according to the claim.

<13>

The above P ₃ or P ₅ is, each independently, the following formula:

[Formula 23]

The resin composition according to any one of items 1 to 12, comprising a structural unit derived from the compound (BisAM) represented by .

<14>

P ₄ or P ₆ is, each independently, 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride, the following formula:

[Formula 24]

A compound represented by (BzDA), or the formula:

[Formula 25]

The resin composition according to any one of items 1 to 13, comprising a structural unit derived from the compound (BNBDA) represented by .

<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 a polyimide resin film obtained by curing the resin is used for a flexible display.

<17>

A diamine or acid dianhydride of the general formula (10):

[Formula 26]

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid A halide group, a hydroxyl group, an epoxy group, or a mercapto 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}

Polyimide is obtained by polycondensation of the silicon-containing compound represented by

Polycondensation reaction of other compounds to provide a resin composition comprising a polyimide precursor and a resin comprising the polyimide;

Comprising 25% by mass or less of the silicon-containing compound based on the total mass of the resin,

A method for producing a resin composition.

<18>

A diamine or acid dianhydride of the general formula (10):

[Formula 27]

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid A halide group, a hydroxyl group, an epoxy group, or a mercapto 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}

Polyimide is obtained by polycondensation of the silicon-containing compound represented by

Polycondensation reaction of other compounds to provide a resin composition comprising a polyimide precursor and a resin comprising the polyimide;

The imidization rate of the resin is 50% or more,

A method for producing a resin composition.

<19>

The following general formula (8):

[Formula 28]

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

[Formula 29]

A compound represented by and the following general formula (10):

[Formula 30]

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid A halide group, a hydroxyl group, an epoxy group, or a mercapto 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}

After polycondensation of the silicon-containing compound represented by and other compounds to obtain polyimide,

A method for producing a resin composition comprising subjecting other compounds to a polycondensation reaction to provide a resin composition comprising a polyimide precursor and a polyimide.

<20>

3,3'-diaminodiphenylsulfone (33DAS);

4,4'-diaminodiphenylsulfone (44DAS), and

9,9-bis(4-aminophenyl)fluorene (BAFL)

At least one compound selected from

The following general formula (10):

[Formula 31]

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid A halide group, a hydroxyl group, an epoxy group, or a mercapto 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}

After polycondensation of the silicon-containing compound represented by and other compounds to obtain polyimide,

A method for producing a resin composition comprising subjecting other compounds to a polycondensation reaction to provide a resin composition comprising a polyimide precursor and a polyimide.

<21>

At least one compound selected from 4,4'-oxydiphthalic anhydride (ODPA) and 9,9-bis(3,4-dicarboxyphenyl)fluorene diacid anhydride (BPAF), and the following general formula (10) :

[Formula 32]

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid A halide group, a hydroxyl group, an epoxy group, or a mercapto 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}

After polycondensation of the silicon-containing compound represented by and other compounds to obtain polyimide,

A method for producing a resin composition comprising subjecting other compounds to a polycondensation reaction to provide a resin composition comprising a polyimide precursor and a polyimide.

<22>

An application 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 on the surface of the support;

A film forming step of heating the resin composition to form a polyimide resin film;

A method for producing a polyimide resin film including a peeling step of peeling the polyimide resin film from the support.

<23>

The method for producing a polyimide resin film according to item 22, comprising an irradiation step of irradiating a laser to the resin composition from the support side prior to the peeling step.

<24>

An application 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 on the surface of the support;

A film forming step of heating the resin composition to form a polyimide resin film;

an element formation step of forming an element on the polyimide resin film;

A manufacturing method of a display including a peeling step of peeling the polyimide resin film on which the element is formed from the support.

<25>

An application 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 on the surface of the support;

A film forming step of heating the resin composition to form a polyimide resin film;

A method for manufacturing a laminate comprising an element formation step of forming an element on the polyimide resin film.

<26>

The method for manufacturing 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, comprising manufacturing a laminate by the method according to item 25 or 26.

[Second aspect]

<28>

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

[Formula 33]

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

[Formula 34]

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

As a resin composition containing a resin of the structural unit represented by,

P ₁ is the following general formula (3):

[Formula 35]

It includes a structural unit derived from a compound represented by

The P ₁ or P ₂ is the following general formula (5):

[Formula 36]

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, L ₁ and L ₂ are each independently an amino group, i is an integer of 1 to 200, j and k are each independently an integer of 0 to 200, 0 ≤ j/(i + j + k) ≤ 0.50, and a functional group equivalent of 800 or more.}

Containing a structural unit derived from a silicon-containing compound represented by

resin composition.

<29>

The above P ₂ is, the following general formula (4):

[Formula 37]

The resin composition according to item 28, comprising a structural unit derived from a compound represented by

<30>

The general formulas (6) and (7) below:

[Formula 38]

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

[Formula 39]

{In the formula, P ₅ represents a divalent organic group, P ₆ represents a tetravalent organic group, and q represents a positive integer, and P ₅ represents 2,2'-bis(trifluoromethyl) -4,4'-diaminodiphenyl ether (6FODA) is not included.}

As a resin composition containing a resin of the structural unit represented by,

The above P ₃ or P ₄ is the following general formula (10):

[Formula 40]

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, L ₁ and L ₂ are each independently an amino group, i is an integer of 1 to 200, j and k are each independently an integer from 0 to 200, and 0 ≤ j/(i + j + k) ≤ 0.50.}

Containing a structural unit derived from a silicon-containing compound represented by

resin composition.

<31>

The general formulas (6) and (7) below:

[Formula 41]

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

[Formula 42]

{In the formula, P ₅ represents a divalent organic group, P ₆ represents a tetravalent organic group, and q represents a positive integer, and P ₅ represents 2,2'-bis(trifluoromethyl) -4,4'-diaminodiphenyl ether (6FODA) is not included.}

As a resin composition containing a resin of the structural unit represented by,

The above P ₃ or P ₄ is the following general formula (10):

[Formula 43]

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, L ₁ and L ₂ are each independently an amino group, i is an integer of 1 to 200, j and k are each independently an integer from 0 to 200, and 0 ≤ j/(i + j + k) ≤ 0.50.}

It includes a structural unit derived from a silicon-containing compound represented by

To (a) or (b):

(A) The P ₃ and/or P ₅ is the following general formula (8):

[Formula 44]

It includes a structural unit derived from a compound represented by ; or

(B) The P ₄ and/or P ₆ is the following general formula (9):

[Formula 45]

It includes structural units derived from the compound represented by ;

A resin composition that satisfies any of the above.

<32>

The general formulas (6) and (7) below:

[Formula 46]

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

[Formula 47]

{In the formula, P ₅ represents a divalent organic group, P ₆ represents a tetravalent organic group, and q represents a positive integer, and P ₅ represents 2,2'-bis(trifluoromethyl) -4,4'-diaminodiphenyl ether (6FODA) is not included.}

As a resin composition containing a resin of the structural unit represented by,

The above P ₃ or P ₄ is the following general formula (10):

[Formula 48]

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, L ₁ and L ₂ are each independently an amino group, i is an integer of 1 to 200, j and k are each independently an integer from 0 to 200, and 0 ≤ j/(i + j + k) ≤ 0.50.}

It includes a structural unit derived from a silicon-containing compound represented by

The P ₃ and/or P ₅ are,

3,3'-diaminodiphenylsulfone (33DAS), or

4,4'-diaminodiphenylsulfone (44DAS)

The resin composition containing at least 1 structural unit derived from each compound of.

<33>

The general formulas (6) and (7) below:

[Formula 49]

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

[Formula 50]

{In the formula, P ₅ represents a divalent organic group, P ₆ represents a tetravalent organic group, and q represents a positive integer, and P ₅ represents 2,2'-bis(trifluoromethyl) -4,4'-diaminodiphenyl ether (6FODA) is not included.}

As a resin composition containing a resin of the structural unit represented by,

The above P ₃ or P ₄ is the following general formula (10):

[Formula 51]

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, L ₁ and L ₂ are each independently an amino group, i is an integer of 1 to 200, j and k are each independently an integer from 0 to 200, and 0 ≤ j/(i + j + k) ≤ 0.50.}

It includes a structural unit derived from a silicon-containing compound represented by

The P ₃ and/or P ₅ are,

9,9-bis(4-aminophenyl)fluorene (BAFL), or

The following general formula:

[Formula 52]

Compound of (BisAM)

The resin composition containing at least 1 structural unit derived from each compound of.

<34>

The general formulas (6) and (7) below:

[Formula 53]

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

[Formula 54]

{In the formula, P ₅ represents a divalent organic group, P ₆ represents a tetravalent organic group, and q represents a positive integer, and P ₅ represents 2,2'-bis(trifluoromethyl) -4,4'-diaminodiphenyl ether (6FODA) is not included.}

As a resin composition containing a resin of the structural unit represented by,

The above P ₃ or P ₄ is the following general formula (10):

[Formula 55]

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, L ₁ and L ₂ are each independently an amino group, i is an integer of 1 to 200, j and k are each independently an integer from 0 to 200, and 0 ≤ j/(i + j + k) ≤ 0.50.}

It includes a structural unit derived from a silicon-containing compound represented by

The P ₄ and/or P ₆ is,

4,4'-oxydiphthalic anhydride (ODPA);

4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA);

9,9-bis(3,4-dicarboxyphenyl)fluorenedioic acid anhydride (BPAF);

The following general formula:

[Formula 56]

A compound of (BzDA); or

The following general formula:

[Formula 57]

A compound of (BNBDA);

The resin composition containing at least 1 structural unit derived from each compound of.

<35>

Said P ₃ contains a structural unit derived from the compound represented by said General formula (10),

The resin composition according to any one of items 30 to 34, wherein the functional group equivalent of the silicon-containing compound represented by the general formula (10) is 800 or more.

<36>

Said P ₃ contains a structural unit derived from the compound represented by said General formula (10), and

In the general formula (10), L ₁ and L ₂ are each independently an amino group;

The resin composition according to any one of items 30 to 35.

<37>

The compound represented by the above general formula (3) or (8) is more than 50 mol% when all diamines (excluding compounds represented by the above general formula (5) or (10) are 100 mol%) The resin composition according to any one of 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 a polyimide resin film obtained by curing the resin is used for a flexible display.

<40> The following general formula (3):

[Formula 58]

The compound represented by

3,3'-diaminodiphenylsulfone (33DAS), and

4,4'-diaminodiphenylsulfone (44DAS)

At least one diamine selected from

an acid dianhydride;

The following general formula (5):

[Formula 59]

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, L ₁ and L ₂ are each independently an amino group, i is an integer of 1 to 200, j and k are each independently an integer from 0 to 200, and 0 ≤ j/(i + j + k) ≤ 0.50.}

A method for producing a resin composition comprising subjecting a silicon-containing compound represented by to a polycondensation reaction with another compound to provide a polyimide precursor and/or a polyimide.

<41>

After obtaining polyimide by polycondensation reaction of diamine (but not including 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether (6FODA)) and acid dianhydride,

The following general formula (5):

[Formula 60]

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, L ₁ and L ₂ are each independently an amino group, i is an integer of 1 to 200, j and k are each independently an integer from 0 to 200, and 0 ≤ j/(i + j + k) ≤ 0.50.}

A method for producing a resin composition comprising subjecting a silicon-containing compound represented by 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):

[Formula 61]

The compound represented by

3,3'-diaminodiphenylsulfone (33AS), and

4,4'-diaminodiphenylsulfone (44DAS)

At least one diamine selected from

an acid dianhydride;

After polycondensation of other compounds to obtain polyimide,

The following general formula (5):

[Formula 62]

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, L ₁ and L ₂ are each independently an amino group, i is an integer of 1 to 200, j and k are each independently an integer from 0 to 200, and 0 ≤ j/(i + j + k) ≤ 0.50.}

A method for producing a resin composition comprising subjecting a silicon-containing compound represented by to a polycondensation reaction with another compound to provide a resin composition containing a polyimide precursor and a polyimide.

<43>

An application 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 method for producing a polyimide resin film including a peeling step of peeling the polyimide resin film from the support.

<44>

The method for producing a polyimide resin film according to item 43, comprising an irradiation step of irradiating a laser to the resin composition from the support side prior to the peeling step.

<45>

An application 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 formation step of forming an element on the polyimide resin film;

A manufacturing method of a display including a peeling step of peeling the polyimide resin film on which the element is formed from the support.

<46>

An application 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 method for manufacturing a laminate comprising an element formation step of forming an element on the polyimide resin film.

<47>

The method for manufacturing 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, comprising manufacturing a laminate by the method according to item 46 or 47.

According to the present invention, first, a polyimide precursor or polyimide resin composition having excellent properties required for display applications can be provided by using DABA, CpODA, and other silicon-containing compounds as monomers.

According to the present invention, secondly, DABA, a silicon-containing compound and other compounds are used as monomers, or 3,3'-diaminodiphenylsulfone (33DAS) and/or 4,4'-diaminodiphenyl A polyimide precursor or polyimide resin composition having excellent properties required for display applications can be provided by using sulfone (44DAS), a silicon-containing compound, and other compounds as monomers.

In addition, the description mentioned above should not be regarded as disclosing all the embodiments of this invention and all the advantages concerning this invention. Additional embodiments of the present invention and advantages thereof will become clear by referring to the following description.

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 a display of the present embodiment.

Hereinafter, exemplary embodiments of the present invention (hereinafter, abbreviated as “this embodiment”) will be described in detail. The present invention is not limited to the present embodiment, and can be implemented with various modifications within the scope of the gist. In the present specification, the upper and lower limits 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):

[Formula 63]

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

[Formula 64]

{In the formula, P ₅ represents a divalent organic group, P ₆ represents a tetravalent organic group, and q represents a positive integer.}

The resin of the structural unit represented by may be included, and a polyimide precursor partially imidized may be included, and P ₅ or P ₆ is the following general formula (10):

[Formula 65]

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid A halide group, a hydroxyl group, an epoxy group, or a mercapto 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}

It includes a constituent unit derived from a silicon-containing compound represented by In the case of such a partially imidized polyimide precursor, compared to the entire polyimide precursor, the viscosity stability of the composition is excellent, and compared to the entire polyimide, from the viewpoint of ease of synthesis of the polyimide (polyimide precursor) great.

The proportion 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 the viscosity storage stability and filterability of the varnish. In this way, although the mechanism by which the viscosity storage stability and filterability of the varnish are better as the ratio of the silicon-containing compound in the resin is smaller is not clear, it is thought that the aggregation of the dissociated silicon-group-containing compound is correlated.

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 is determined by taking into account the residual stress of the polyimide film, the viscosity storage stability of the varnish, and the filterability. There is a need.

The imidation ratio of the resin is 50% or more. The imidation rate of the resin is preferably 60% or more, more preferably 70% or more, still more preferably 80% or more, and particularly preferably 90% or more from the viewpoint of the viscosity storage stability of the varnish. In this way, although the mechanism of the higher imidation ratio is the better viscosity storage stability of the varnish, it is not clear, but it is thought to be related to the occurrence of partial depolymerization of the amide during varnish storage.

On the other hand, the imidation rate of the resin is preferably 90% or less, more preferably 80% or less, still more preferably 70% or less, from the viewpoint of white turbidity after moisture absorption of the varnish. In this way, although the mechanism by which the moisture absorption cloudiness of the varnish is less likely to occur as the imidation ratio is smaller is not clear, it is thought to be correlated with the solvent solubility of polyimide/polyamide.

The appropriate imidation rate of the resin varies depending on the type and ratio of the diamine monomer and acid dianhydride monomer used, and needs to be determined in consideration of the viscosity storage stability of the varnish, the cloudiness of the varnish after moisture absorption, 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 greater than 0 and is 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 this resin is obtained from the following formula.

A: ratio of silicon-containing compound in diamine of imide unit (% by mass) = total amount of mass of silicon-containing compound used in imidation step/diamine monomer (including silicon-containing compound) used in imidation step * 100

B: Proportion of silicon-containing compound in diamine of amide unit (% by mass) = Total amount of mass of silicon-containing compound used in imidation step/diamine monomer (including silicon-containing compound) used in amidation step * 100

Here, A can also be said interchangeably with "the ratio (mass %) of general formula (10) among the diamine which comprises _P5 in general formula (7)." In addition, B can also be said interchangeably with "the ratio (mass %) of general formula (10) among the diamine which comprises _P3 in general formula (6)."

And the difference between the imide unit and the amide unit of the ratio of the silicon-containing compound in the diamine becomes B - A using the above A and B.

The difference between the imide unit and the amide unit in the ratio of the silicon-containing compound in the diamine monomer is a polyimide precursor (polyamideimide) resin having a structure derived from a silicon-containing compound and partially imidized. It shows the difference of the silicon-containing compound ratio, and it can be said that the imide unit has a structure derived from the silicon-containing compound, so that the value is large. The larger this value is, the better the residual stress of the polyimide film is, and the smaller this value is, the better the blistering property, filterability, and haze (turbidity) of the polyimide film are. And when this value is in the said range, it is preferable because each characteristic, such as blistering property of a varnish, filterability, residual stress of a polyimide film, and haze (turbidity), etc. can be compatible.

Moreover, among these, the diamine used for the said resin,

The following general formula (8):

[Formula 66]

a compound of ;

3,3'-diaminodiphenylsulfone (33DAS);

4,4'-diaminodiphenylsulfone (44DAS); and

9,9-bis(4-aminophenyl)fluorene (BAFL)

In the case of at least one compound selected from the above, since the characteristics of the varnish/polyimide are further improved, it is preferable.

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

[Formula 67]

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

[Formula 68]

{In the formula, P ₅ represents a divalent organic group, P ₆ represents a tetravalent organic group, and q represents a positive integer.}

A polyimide precursor containing a structural unit represented by and partially imidized may be included,

P ₅ or P ₆ is, the following general formula (10):

[Formula 69]

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid A halide group, a hydroxyl group, an epoxy group, or a mercapto 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}

may include a structural unit derived from a silicon-containing compound represented by

Either of the following (a) or (b) may be satisfied:

(A) The P ₃ and/or P ₅ is the following general formula (8):

[Formula 70]

It includes structural units derived from the compound represented by ; or

(B) The P ₄ and/or P ₆ is the following general formula (9):

[Formula 71]

It includes a structural unit derived from a compound represented by

Diamine

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

[Formula 72]

a compound of ;

3,3'-diaminodiphenylsulfone (33DAS);

4,4'-diaminodiphenylsulfone (44DAS);

9,9-bis(4-aminophenyl)fluorene (BAFL) ; or

2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether (6FODA)

It contains at least 1 structural unit chosen from each diamine compound of. Among the diamine compounds represented by General Formula (8), 3,5-diaminobenzoic acid (DABA) is preferable from the viewpoint of transparency of the polyimide film and YI. As a diamine compound, by using at least one selected from DABA, 33DAS, 44DAS, BAFL, and 6FODA, mechanical properties of the polyimide film can be improved (especially tensile elongation) and heat resistance can be improved, so it is preferable.

The content of DABA in all diamines (including compounds in which L ₁ and L ₂ are amino groups in the general formula (10) above) is more than 50 mol%, more than 55 mol%, or 70 mol% or more, or 90 mol% % or more, or 95 mol% or more may be sufficient. Since the tensile elongation of a polyimide film becomes large, so that the quantity of DABA is large, it is preferable.

As diamines other than general formula (8), p-phenylenediamine (PDA), m-phenylenediamine, 2,2'-dimethylbenzidine (mTB), 4,4'-diaminodiphenyl sulfide, 3 ,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diamino Biphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-dia Minodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis( 3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy) Biphenyl, bis[4-(4-aminophenoxy)phenyl] ether, bis[4-(3-aminophenoxy)phenyl] ether, 1,4-bis(4-aminophenyl)benzene, 1,3- Bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane , 2,2-bis[4-(4-aminophenoxy)phenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl)hexafluoropropane, and 1,4-bis(3 -aminopropyldimethylsilyl)benzene, 1,3-bis[1-(4-aminophenyl)-1-methylethyl]benzene] (BiSAM), and the like.

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

acid dianhydride

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

[Formula 73]

A compound represented by (also referred to as CpODA),

4,4'-oxydiphthalic anhydride (ODPA), or

9,9-bis(3,4-dicarboxyphenyl)fluorenedioic anhydride (BPAF)

It contains at least 1 structural unit chosen from each acid dianhydride compound of. Having these structural units is preferable because the mechanical properties of transparency, YI, and heat resistance of the obtained polyimide film can be improved.

The content of CpODA, ODPA, and BPAF in all acid dianhydrides (including compounds in which L ₁ and L ₂ are acid anhydride groups in the above general formula (10)) is 50 mol% or more, 60 mol% or more, or 70 mol% It may be mol% or more, or 90 mol% or more, or 95 mol% or more. The larger the amount of CpODA, ODPA, and BPAF is, the better the transparency of the polyimide film is, so it is preferable.

Examples of acid dianhydrides other than general formula (9) include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 2,2',3 ,3'-biphenyltetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 5-(2,5-dioxotetrahydro-3-furanyl) -3-methyl-cyclohexene-1,2 dicarboxylic acid anhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid 2 Anhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfotetracarboxylic dianhydride, methylene-4,4'-diphthalic acid dianhydride, 1,1-ethylidene-4,4'-diphthalic dianhydride, 2,2-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic acid dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-di Phthalic dianhydride, 4,4'-oxydiphthalic dianhydride, p-phenylenebis(trimellitate acid anhydride), thio-4,4'-diphthalic 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-dicarboxy Phenyl)-2-propyl]benzene dianhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride , 2,2-bis [3- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, bis (3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6 ,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride Silic acid dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracentetracarboxylic dianhydride, and 1,2,7,8-phenanthrenetetracar Boxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA), and 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), structures:

[Formula 74]

A compound of (BzDA); Structure below:

[Formula 75]

A compound of (BNBDA), etc. are mentioned.

The acid dianhydride other than the general formula (9) is preferably at least one selected from the group consisting of BzDA, BNBDA, and 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA). Acid dianhydride may be used individually by 1 type, and may be used in combination of 2 or more type.

<Silicon-containing compound>

The polyimide precursor in the present embodiment may have a structure represented by the above formula (7) together with a structure represented by the above formula (6). It is preferable that the content rate of the structure derived from a silicon-containing compound in a polyimide precursor is 5 mass % or more and 40 mass % or less on the basis of the mass of a polyimide precursor. When the polyimide precursor contains a structure derived from a silicon-containing compound within this numerical range, the resultant polyimide film is preferably compatible with low residual stress and high transparency and heat resistance. The content of the structure derived from the silicon-containing compound may be 6% by mass or more, or 7% by mass or more, and may be 30% by mass or less or 25% by mass or less based on the mass of the polyimide precursor.

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

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

[Formula 76]

{during expression,

R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms;

R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one of R ₂ and R ₃ is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms;

R ₄ and R ₅ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one of R ₄ and R ₅ is a monovalent aromatic group having 6 to 10 carbon atoms;

R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one of R ₆ and R ₇ is an organic group containing an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms;

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 hydroxyl group, an epoxy group, or a mercapto group;

i and j are each independently an integer of 1 to 200;

k is an integer from 0 to 200, and

It satisfies the relationship of 0.05 ≤ j/(i + j + k) ≤ 0.50.}.

R ₁ in Formula (10) is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms. The divalent organic group having 1 to 10 carbon atoms may be linear, cyclic, or branched, and may be saturated or unsaturated. As a C1-C10 divalent aliphatic hydrocarbon group, a methylene group, ethylene group, n-propylene group, i-propylene group, n-butylene group, s-butylene group, t-butylene group, n-pentyl group, for example linear or branched chain alkylene groups such as a rene group, neopentylene group, n-hexylene group, n-heptylene group, n-octylene group, n-nonylene group, and n-decylene group; Cycloalkylene groups, such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, and a cyclooctylene group, are mentioned. It is preferable that it is at least 1 sort(s) selected from the group which consists of an ethylene group, n-propylene group, and i-propylene group as a C1-C10 divalent aliphatic hydrocarbon group.

R ₂ and R ₃ in Formula (10) are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms.

The monovalent organic group having 1 to 10 carbon atoms may be linear, cyclic, or branched, and may be saturated or unsaturated. For example, as a monovalent organic group of 1 to 10 carbon atoms, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, neo linear or branched chain alkyl groups such as pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, and n-decyl group; Cycloalkyl groups, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; Aromatic groups, such as a phenyl group, a tolyl group, a xylyl group, (alpha)-naphthyl group, and (beta)-naphthyl group, etc. are mentioned.

The monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms may be linear, cyclic, or branched, and may be saturated or unsaturated. Examples of monovalent aliphatic hydrocarbon groups of 1 to 5 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, linear or branched chain alkyl groups such as a neopentyl group; Cycloalkyl groups, such as a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group, etc. are mentioned. It is preferable that it is at least 1 sort(s) selected from the group which consists of a methyl group, an ethyl group, and n-propyl group as a C1-C5 monovalent aliphatic hydrocarbon group.

R ₄ and R ₅ in Formula (10) are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one is a monovalent aromatic group having 6 to 10 carbon atoms. The monovalent organic group having 1 to 10 carbon atoms may be linear, cyclic, or branched, and may be saturated or unsaturated. For example, as a monovalent organic group of 1 to 10 carbon atoms, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, neo linear or branched chain alkyl groups such as pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, and n-decyl group; Cycloalkyl groups, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; Aromatic groups, such as a phenyl group, tolyl group, xylyl group, (alpha)-naphthyl group, and (beta)-naphthyl group, etc. are mentioned. The monovalent aromatic group having 6 to 10 carbon atoms includes, for example, a phenyl group, a tolyl group, a xylyl group, an α-naphthyl group, and a β-naphthyl group, and a phenyl group, a tolyl group, or a xylyl group is preferred. .

R ₆ and R ₇ in Formula (10) are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one is an organic group having an unsaturated aliphatic hydrocarbon group. The monovalent organic group having 1 to 10 carbon atoms may be linear, cyclic, or branched. Examples of the monovalent organic group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, neo linear or branched chain alkyl groups such as pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, and n-decyl group; Cycloalkyl groups, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; Aromatic groups, such as a phenyl group, tolyl group, xylyl group, (alpha)-naphthyl group, and (beta)-naphthyl group, etc. are mentioned. It is preferable that it is at least 1 sort(s) chosen from the group which consists of a methyl group, an ethyl group, and a phenyl group as a C1-C10 monovalent organic group.

The organic group having an unsaturated aliphatic hydrocarbon group may be an unsaturated aliphatic hydrocarbon group having 3 to 10 carbon atoms, and may be linear, cyclic, or branched. Examples of the unsaturated aliphatic hydrocarbon group having 3 to 10 carbon atoms include 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 cyclohexenyl group. group, heptenyl group, octenyl group, nonenyl group, decenyl group, ethynyl group, propynyl group, butynyl group, pentynyl group, hexynyl group and the like. It is preferable that it is at least 1 sort(s) selected from the group which consists of a vinyl group, an allyl group, and a 3-butenyl group as a C3-C10 unsaturated aliphatic hydrocarbon group.

Some or all of the hydrogen atoms of R ₁ to R ₇ in formula (10) may be substituted with a substituent such as a halogen atom such as F, Cl, or Br, or may be unsubstituted.

L ₁ and L ₂ in Formula (10) are each independently a monovalent organic group containing an acid anhydride structure (also referred to as an acid anhydride group), an amino group, an isocyanate group, a carboxyl group, an alkoxycarbonyl group, a halogenated carbonyl group, or a hydroxy group. , an epoxy group, or a mercapto group.

As a monovalent organic group containing an acid anhydride structure, for example, the following formula:

[Formula 77]

The 2,5-dioxotetrahydrofuran-3-yl group shown by {In the said formula, "*" represents a bond.} is mentioned. Among these, an amino group and an acid anhydride group are preferable, and an amino group is more preferable from the viewpoint of the viscosity stability of the resin composition.

The alkoxyl group in the alkoxycarbonyl group may be an alkoxyl group having 1 to 6 carbon atoms, and examples thereof include a methoxyl group, an ethoxyl group, an n-propoxyl group, an i-propoxyl group, an n-butoxyl group and an i-butoxyl group. , t-butoxyl group, etc. may be sufficient.

The halogen atom in the halogenated carbonyl group is preferably a halogen atom other than a fluorine atom, more preferably a chlorine atom or an iodine atom.

From the viewpoint of filterability of the resin composition, the functional group equivalent of the silicon-containing compound represented by Formula (10) is preferably 800 or more, more preferably 1000 or more, and even more preferably 1500 or more. On the other hand, when the functional group equivalent is 500 or less, 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). A functional group equivalent can be measured by a well-known method. Moreover, when the functional group equivalent of a silicon-containing compound is 800 or more, since the residual stress of a polyimide film in nitrogen atmosphere is small, it is preferable. The reason for this is considered to be because, when the functional group equivalent is more than a specific value, the silicon domain increases and the stress is relaxed.

In addition, the functional group equivalent can be measured according to an existing standard or the like.

i in Formula (10) is an integer of 1 to 200, preferably an integer of 2 to 100, more preferably an integer of 4 to 80, still more preferably an integer of 8 to 40. j and k are each independently an integer of 0 to 200, preferably an integer of 0 to 50, more preferably an integer of 0 to 20, still more preferably an integer of 0 to 50.

When the polyimide in the resin composition has a structure derived from formula (10), the residual stress of the polyimide film measured in a nitrogen atmosphere is good (small), so it is preferable. The reason for measuring under a nitrogen atmosphere is that in the display process, when forming an inorganic film such as SiO or SiN on a polyimide film, it may be exposed to a nitrogen atmosphere, and residual stress under a nitrogen atmosphere is required to be small. to be.

[Second aspect]

<<resin composition>>

<Resin/Polyimide Precursor/Polyimide>

The resin composition of the present embodiment,

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

[Formula 78]

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

[Formula 79]

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

The resin of the structural unit represented by may be included, and may contain a polyimide precursor (hereinafter also referred to as all polyimide precursors) or polyimide (hereinafter also referred to as all polyimides), and P ₁ is the following general formula ( 3):

[Formula 80]

It includes a structural unit derived from a compound represented by, and as desired, P ₂ is the following general formula (4):

[Formula 81]

It may include a structural unit derived from a compound represented by .

Moreover, P ₁ or P ₂ is the following general formula (5):

[Formula 82]

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, L ₁ and L ₂ are each independently an amino group, i is an integer of 1 to 200, j and k are each independently an integer of 0 to 200, 0 ≤ j/(i + j + k) ≤ 0.50, and a functional group equivalent of 8000 or more}

It includes a structural unit derived from a silicon-containing compound represented by

Polyimide is obtained by thermal imidation of a polyimide precursor, and can also be chemically imidated. From the viewpoint of the transparency of the polyimide film obtained, thermal imidation is preferable.

Moreover, a polyimide resin composition is preferable compared with a polyimide precursor resin composition from a viewpoint of viscosity stability of a composition.

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

[Formula 83]

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

[Formula 84]

{In the formula, P ₅ represents a divalent organic group, P ₆ represents a tetravalent organic group, and q represents a positive integer, and P ₅ represents 2,2'-bis(trifluoromethyl) It does not contain -4,4'-diaminodiphenyl ether (6FODA) or structural units derived therefrom.}

A polyimide precursor containing a structural unit represented by and partially imidized may be included, and P ₃ and/or P ₅ are represented by the following general formula (8):

[Formula 85]

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

Moreover, P ₃ and/or P ₅ is

3,3'-diaminodiphenylsulfone (33DAS); or

4,4'-diaminodiphenylsulfone (44DAS)

At least one structural unit derived from each compound of can be included.

Moreover, P ₃ and/or P ₅ is

9,9-bis(4-aminophenyl)fluorene (BAFL) ; or

The following general formula:

[Formula 86]

Compound of (BisAM)

At least one structural unit derived from each compound of can be included.

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

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

[Formula 87]

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

In addition, P ₄ and/or P ₆ are

4,4'-oxydiphthalic anhydride (ODPA);

4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA);

9,9-bis(3,4-dicarboxyphenyl)fluorene diacid anhydride (BPAF); The following general formula:

[Formula 88]

A compound of (BzDA); and

The following general formula:

[Formula 89]

A compound of (BNBDA);

It may contain at least one structural unit derived from the compound of

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

Moreover, in one embodiment, P ₃ or P ₄ is the following general formula (10):

[Formula 90]

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid A halide group, a hydroxyl group, an epoxy group, or a mercapto 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, and the functional group equivalent is 8000 or more}

It includes a constituent 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 compared to the above-mentioned all polyimide precursors, and compared to the above-mentioned all polyimide, the synthesis of polyimide (polyimide precursor) Excellent in terms of ease of use.

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

Diamine

The resin composition has the following general formula (3):

[Formula 91]

A structural unit derived from a diamine compound represented by is included. Among the diamine compounds represented by 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 (especially tensile elongation) and heat resistance can be improved. Although the reason why such a characteristic is improved is not clear, it is thought that it is because intermolecular interaction acts by the action of a carboxyl group.

The content of DABA in all diamines (including compounds in which L ₁ and L ₂ are amino groups in formulas (5) and (10) above) is more than 50 mol%, more than 55 mol%, or 70 mol% or more , or 90 mol% or more, or 95 mol% or more may be sufficient. Since the tensile elongation of a polyimide film becomes large, so that the quantity of DABA is large, it is preferable.

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

The total content of 33DAS and/or 44DAS in all diamines (including compounds in which L ₁ and L ₂ are amino groups in formulas (5) and (10) above) is more than 50 mol%, more than 55 mol%, Alternatively, it may be 70 mol% or more, or 90 mol% or more, or 95 mol% or more. Since mechanical strength of a polyimide film improves so that the quantity of 33DAS and/or 44DAS is large, it is preferable.

As diamines other than general formula (3), p-phenylenediamine (PDA), m-phenylenediamine, 2,2'-dimethylbenzidine (mTB), 4,4'-diaminodiphenyl sulfide, 3 ,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diamino Biphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-dia Minodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis( 3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy) Biphenyl, bis[4-(4-aminophenoxy)phenyl] ether, bis[4-(3-aminophenoxy)phenyl] ether, 1,4-bis(4-aminophenyl)benzene, 1,3- Bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane , 2,2-bis[4-(4-aminophenoxy)phenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl)hexafluoropropane, and 1,4-bis(3 -aminopropyldimethylsilyl)benzene, 9,9-bis(4-aminophenyl)fluorene (BAFL), 1,3-bis[1-(4-aminophenyl)-1-methylethyl]benzene] (BiSAM) etc. can be mentioned.

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

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

acid dianhydride

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

[Formula 92]

A structural unit derived from a compound represented by (also referred to as CpODA) is included. Having this structural unit is preferable because the mechanical properties of transparency, YI, and heat resistance of the obtained polyimide film can be improved.

The content of CpODA in all acid dianhydrides (including compounds in which L ₁ and L ₂ are acid anhydride groups in formulas (5) and (10) above) is 50 mol% or more, 60 mol% or more, or 70 mol% or more. It may be mol% or more, or 90 mol% or more, or 95 mol% or more. Since transparency of a polyimide film improves so that the amount of CpODA is large, it is preferable.

Moreover, a resin composition contains the structural unit derived from ODPA. Having this structural unit is preferable because the viscosity stability of the varnish, the viewpoint of filterability, and the transparency of the obtained polyimide film can be improved.

The content of ODPA in all acid dianhydrides (including compounds in which L ₁ and L ₂ are acid anhydride groups in the general formulas (5) and (10) above) is 50 mol% or more, 60 mol% or more, or 70 It may be mol% or more, or 90 mol% or more, or 95 mol% or more. Since the transparency of a polyimide film improves, so that there are many amounts of ODPA, it is preferable.

Examples of acid dianhydrides other than general formula (4) include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 2,2',3 ,3'-biphenyltetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 5-(2,5-dioxotetrahydro-3-furanyl) -3-methyl-cyclohexene-1,2 dicarboxylic acid anhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid 2 Anhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfotetracarboxylic dianhydride, methylene-4,4'-diphthalic acid dianhydride, 1,1-ethylidene-4,4'-diphthalic dianhydride, 2,2-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic acid dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-di Phthalic dianhydride, 4,4'-oxydiphthalic dianhydride, p-phenylenebis(trimellitate acid anhydride), thio-4,4'-diphthalic 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-dicarboxy Phenyl)-2-propyl]benzene dianhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride , 2,2-bis [3- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, bis (3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6 ,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride Silic acid dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracentetracarboxylic dianhydride, and 1,2,7,8-phenanthrenetetracar Boxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorenedioic anhydride (BPAF), 4,4'-oxydiphthalic anhydride (ODPA), 1,2,4,5-cyclohexane Tetracarboxylic dianhydride (HPMDA), and 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), have the following structures:

[Formula 93]

A compound of (BzDA); Structure below:

[Formula 94]

A compound of (BNBDA), etc. are mentioned.

Acid dianhydrides other than the general formula (4) are 6FDA, 9,9-bis (3,4-dicarboxyphenyl) fluorene diacid anhydride (BPAF), BzDA, BNBDA, 1,2,4,5-cyclo It is preferably at least one selected from the group consisting of hexanetetracarboxylic dianhydride (HPMDA). Acid dianhydride may be used individually by 1 type, and may be used in combination of 2 or more type.

<Silicon-containing compound>

The polyimide precursor in this embodiment may have the structure represented by the said formula (2) with the structure represented by said formula (1). It is preferable that the content rate of the structure derived from a silicon-containing compound in a polyimide precursor is 5 mass % or more and 40 mass % or less on the basis of the mass of a polyimide precursor. When the polyimide precursor contains a structure derived from a silicon-containing compound within this numerical range, the resultant polyimide film is preferably compatible with low residual stress and high transparency and heat resistance. The content of the structure derived from the silicon-containing compound may be 6% by mass or more, or 7% by mass or more, and may be 30% by mass or less or 25% by mass or less based on the mass of the polyimide precursor.

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

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

[Formula 95]

{during expression,

R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms;

R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one of R ₂ and R ₃ is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms;

R ₄ and R ₅ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one of R ₄ and R ₅ is a monovalent aromatic group having 6 to 10 carbon atoms;

R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one of R ₆ and R ₇ is an organic group containing an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms;

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 hydroxyl group, an epoxy group, or a mercapto group;

i and j are each independently an integer of 1 to 200;

k is an integer from 0 to 200, and

It satisfies the relationship of 0.05 ≤ j/(i + j + k) ≤ 0.50.}.

R ₁ in Formula (5) is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms. The divalent organic group having 1 to 10 carbon atoms may be linear, cyclic, or branched, and may be saturated or unsaturated. As a C1-C10 divalent aliphatic hydrocarbon group, a methylene group, ethylene group, n-propylene group, i-propylene group, n-butylene group, s-butylene group, t-butylene group, n-pentyl group, for example linear or branched chain alkylene groups such as a rene group, neopentylene group, n-hexylene group, n-heptylene group, n-octylene group, n-nonylene group, and n-decylene group; Cycloalkylene groups, such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, and a cyclooctylene group, are mentioned. It is preferable that it is at least 1 sort(s) selected from the group which consists of an ethylene group, n-propylene group, and i-propylene group as a C1-C10 divalent aliphatic hydrocarbon group.

R ₂ and R ₃ in Formula (5) are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms.

The monovalent organic group having 1 to 10 carbon atoms may be linear, cyclic, or branched, and may be saturated or unsaturated. For example, as a monovalent organic group of 1 to 10 carbon atoms, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, neo linear or branched chain alkyl groups such as pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, and n-decyl group; Cycloalkyl groups, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; Aromatic groups, such as a phenyl group, tolyl group, xylyl group, (alpha)-naphthyl group, and (beta)-naphthyl group, etc. are mentioned.

The monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms may be linear, cyclic, or branched, and may be saturated or unsaturated. Examples of monovalent aliphatic hydrocarbon groups of 1 to 5 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, linear or branched chain alkyl groups such as a neopentyl group; Cycloalkyl groups, such as a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group, etc. are mentioned. It is preferable that it is at least 1 sort(s) selected from the group which consists of a methyl group, an ethyl group, and n-propyl group as a C1-C5 monovalent aliphatic hydrocarbon group.

R ₄ and R ₅ in formula (5) are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one is a monovalent aromatic group having 6 to 10 carbon atoms. The monovalent organic group having 1 to 10 carbon atoms may be linear, cyclic, or branched, and may be saturated or unsaturated. For example, as a monovalent organic group of 1 to 10 carbon atoms, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, neo linear or branched chain alkyl groups such as pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, and n-decyl group; Cycloalkyl groups, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; Aromatic groups, such as a phenyl group, tolyl group, xylyl group, (alpha)-naphthyl group, and (beta)-naphthyl group, etc. are mentioned. The monovalent aromatic group having 6 to 10 carbon atoms includes, for example, a phenyl group, a tolyl group, a xylyl group, an α-naphthyl group, and a β-naphthyl group, and a phenyl group, a tolyl group, or a xylyl group is preferred. .

R ₆ and R ₇ in Formula (5) are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one is an organic group having an unsaturated aliphatic hydrocarbon group. The monovalent organic group having 1 to 10 carbon atoms may be linear, cyclic, or branched. Examples of the monovalent organic group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, neo linear or branched chain alkyl groups such as pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, and n-decyl group; Cycloalkyl groups, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; Aromatic groups, such as a phenyl group, tolyl group, xylyl group, (alpha)-naphthyl group, and (beta)-naphthyl group, etc. are mentioned. It is preferable that it is at least 1 sort(s) chosen from the group which consists of a methyl group, an ethyl group, and a phenyl group as a C1-C10 monovalent organic group.

The organic group having an unsaturated aliphatic hydrocarbon group may be an unsaturated aliphatic hydrocarbon group having 3 to 10 carbon atoms, and may be linear, cyclic, or branched. Examples of the unsaturated aliphatic hydrocarbon group having 3 to 10 carbon atoms include 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 cyclohexenyl group. group, heptenyl group, octenyl group, nonenyl group, decenyl group, ethynyl group, propynyl group, butynyl group, pentynyl group, hexynyl group and the like. It is preferable that it is at least 1 sort(s) selected from the group which consists of a vinyl group, an allyl group, and a 3-butenyl group as a C3-C10 unsaturated aliphatic hydrocarbon group.

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

L ₁ and L ₂ in Formula (5) are each independently a monovalent organic group containing an acid anhydride structure (also referred to as an acid anhydride group), an amino group, an isocyanate group, a carboxyl group, an alkoxycarbonyl group, a halogenated carbonyl group, or 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.

As a monovalent organic group containing an acid anhydride structure, for example, the following formula:

[Formula 96]

The 2,5-dioxotetrahydrofuran-3-yl group shown by {In the said formula, "*" represents a bond.} is mentioned. Among these, an amino group and an acid anhydride group are preferable, and an amino group is more preferable from the viewpoint of the viscosity stability of the resin composition.

The alkoxyl group in the alkoxycarbonyl group may be an alkoxyl group having 1 to 6 carbon atoms, and examples thereof include a methoxyl group, an ethoxyl group, an n-propoxyl group, an i-propoxyl group, an n-butoxyl group and an i-butoxyl group. , t-butoxyl group, etc. may be sufficient.

The halogen atom in the halogenated carbonyl group is preferably a halogen atom other than a fluorine atom, more preferably a chlorine atom or an iodine atom.

From the viewpoint of filterability of the resin composition, the functional group equivalent of the silicon-containing compound represented by Formula (5) is preferably 800 or more, more preferably 1000 or more, and even more preferably 1500 or more. On the other hand, when the functional group equivalent is 500 or less, 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). A functional group equivalent can be measured by a well-known method. Moreover, when the functional group equivalent of a silicon-containing compound is 800 or more, since the residual stress of a polyimide film in nitrogen atmosphere is small, it is preferable. The reason for this is considered to be because, when the functional group equivalent is more than a specific value, the silicon domain increases and the stress is relaxed.

In addition, the functional group equivalent can be measured according to an existing standard or the like.

i in Formula (5) is an integer of 1 to 200, preferably an integer of 2 to 100, more preferably an integer of 4 to 80, still more preferably an integer of 8 to 40. j and k are each independently an integer of 0 to 200, preferably an integer of 0 to 50, more preferably an integer of 0 to 20, still more preferably an integer of 0 to 50.

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

[Components and Preferred Embodiments Common to First and Second Aspects]

Components common to the first and second aspects of the present invention and preferred embodiments of the present invention will be described below. In addition, the components of the first aspect and the second aspect may be interchanged or combined.

<Diamine containing silicon>

It is preferable that the silicon-containing compound of the general formula (5) or (10) described above is a silicon-containing diamine from the viewpoint of the kind of monomer, the cost, and the molecular weight of the obtained polyimide precursor. As silicon-containing diamine, for example, following formula (11):

[Formula 97]

{In the formula, P ₅ each independently represents a divalent hydrocarbon group, may be the same or different, and P ₃ and P ₄ are R ₂ , R ₃ defined in general formula (5) or (10) and It is the same, and l represents an integer from 1 to 200.}

The diamino (poly) siloxane represented by is preferable.

Preferred structures of P ₃ and P ₄ in the general formula (11) include a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group. Among these, a methyl group is preferable.

l in the said general formula (11) is an integer of 1-200, and it is preferable that it is an integer of 3-200 from a viewpoint of the heat resistance of the polyimide obtained using the silicon-containing diamine represented by Formula (11).

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 above-mentioned general formula (10).

The copolymerization ratio of the silicon-containing diamine is preferably from 0.5 to 30% by mass, more preferably from 1.0% by mass to 25% by mass, still more preferably from 1.5% by mass to 20% with respect to the total mass of the polyimide precursor/polyimide. is mass %. When the silicon-containing diamine is 0.5% by mass or more, residual stress generated between the substrate and the support can be effectively reduced. When the silicon-containing diamine is 30% by mass or less, the obtained polyimide film has good transparency (particularly low HAZE), and is preferable from the viewpoint of realization of high total light transmittance and high glass transition temperature.

As described above, the silicon-containing compound as a monomer used for the polyimide precursor/polyimide may be synthesized using the technical common sense at the time of application, or a commercial item may be used. Commercially available products include both terminal amine-modified methylphenyl silicone oil (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 (Shin-Etsu Chemical Co., Ltd.: X22-168-P5-B (functional group equivalent: 2100)), both terminal epoxy-modified methylphenyl silicone oil (Shin-Etsu Chemical Co., Ltd.: X22-2000 (functional group equivalent: 620)), both terminal amino-modified dimethyl silicone (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), Toray Dow Corning: BY16-853U (functional group equivalent 450), manufactured by JNC: 4 Elaplane FM3311 (number average molecular weight: 1000)), epoxy-modified dimethylsilicone at both ends (manufactured by Shin-Etsu Chemical Co.: X-22-163A (functional group equivalent: 1750), alicyclic epoxy-modified dimethylsilicone at both ends (manufactured by Shin-Etsu Chemical Co.: X-22-163A) 169B (functional group equivalent: 1700)), both terminal hydroxyl group-modified dimethylsilicone (Shin-Etsu Chemical Co., Ltd.: KF-6000), both terminal mercapto-modified dimethylsilicone (Shin-Etsu Chemical Co., Ltd.: X-22-167B (functional group equivalent: 1700)), Acid anhydride-modified dimethylsilicone at both terminals (manufactured by Shin-Etsu Chemical Co., Ltd.: X-22-168A (functional group equivalent: 1000)), etc. Among these, from the viewpoint of improving price, chemical resistance, and Tg, both terminals amine-modified Dimethylsilicone oil is preferred.

<menstruum>

The resin composition typically includes a solvent. The solvent is preferably one that has good solubility of the polyimide/polyimide precursor and can appropriately control the solution viscosity of the resin composition, and a 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) related to the first aspect, and the above general formula (4 related to the second aspect) ), and the like are preferred. 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). can The mass ratio of NMP and GBL may be, for example, NMP:GBL (mass ratio) = 10:90 to 90:10.

<Additional Ingredients>

The resin composition of the present embodiment may further contain additional components in addition to the polyimide/polyimide precursor, low molecular weight cyclic siloxane, and solvent. As an additional component, surfactant, an alkoxysilane compound, etc. are mentioned, for example.

Surfactants

By adding a surfactant to the resin composition of the present embodiment, the coating properties of the resin composition can be improved. Specifically, generation of streaks in the coated film can be prevented.

Examples of such surfactants include silicone surfactants, fluorochemical surfactants, and nonionic surfactants other than these. Examples of silicone surfactants include organosiloxane polymers KF-640, 642, 643, KP341, X-70-092, and X-70-093 (a brand name, manufactured by Shin-Etsu Chemical Co., Ltd.); SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (trade names, manufactured by Toray Dow Corning Silicon Co., Ltd.); SILWET L-77, L-7001, FZ-2105, FZ-2120, FZ-2154, FZ-2164, FZ-2166, L-7604 (trade name, manufactured by Nippon Unica 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); and Granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.). Examples of the fluorine-based surfactant include Megafac F171, F173, and R-08 (made by Dainippon Ink & Chemicals, Inc., brand name); Fluorad FC4430, FC4432 (Sumitomo 3M Co., Ltd., trade name), etc. are mentioned. As nonionic surfactants other than these, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether etc. are mentioned, for example.

Among these surfactants, from the viewpoint of coatability (stripe suppression) of the resin composition, silicone-based surfactants and fluorine-based surfactants are preferable, and from the viewpoint of reducing the effect on the YI value and total light transmittance due to the oxygen concentration during the curing step , silicone-based surfactants are preferred. When using a surfactant, the compounding amount 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.

Alkoxysilane compounds

When the polyimide film obtained from the resin composition of the present embodiment is used for a flexible substrate or the like, from the viewpoint of obtaining good adhesion between the support and the polyimide film in the manufacturing process, the resin composition is based on 100 parts by mass of the polyimide precursor, 0.01-20 mass parts of alkoxysilane compounds can be contained. When the content of the alkoxysilane compound relative to 100 parts by mass of the polyimide precursor is 0.01 part by mass or more, good adhesion between the support and the polyimide film can be obtained. Moreover, it is preferable from a viewpoint of the storage stability of a resin composition that content of an alkoxysilane compound is 20 mass parts or less. The content of the alkoxysilane compound is preferably from 0.02 to 15 parts by mass, more preferably from 0.05 to 10 parts by mass, still more preferably from 0.1 to 8 parts by mass, based on 100 parts by mass of the polyimide precursor. By using the alkoxysilane compound, in addition to the above-mentioned improvement in adhesion, the coatability of the resin composition is improved (stripe unevenness suppressed), and the influence of the oxygen concentration at the time of curing on the YI value of the polyimide film can be reduced. have.

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-aminoethyltribu Toxysilane, γ-aminobutyltriethoxysilane, γ-aminobutyltrimethoxysilane, γ-aminobutyltripropoxysilane, γ-aminobutyltributoxysilane, phenylsilanetriol, trimethoxyphenylsilane, Trimethoxy(p-tolyl)silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and the following structure:

[Formula 98]

The alkoxysilane compound etc. which are represented by each of are mentioned. An alkoxysilane compound may be used individually by 1 type, and may be used in combination of 2 or more type.

<<Method for Producing Resin Composition>>

The manufacturing method of the resin composition in this embodiment is not specifically limited, For example, it can be based on the following method.

<Purification of silicon-containing compounds>

The resin composition of the present embodiment can be produced by polycondensation reaction of a polycondensation component containing an acid dianhydride, a diamine, and a silicon-containing compound. As a method for reducing the total amount of cyclic silicon-containing compounds contained in the resin composition of the present embodiment, the total amount of cyclic silicon-containing compounds is reduced by, for example, purifying the silicon-containing compounds before the polycondensation reaction. reduction can be heard. Alternatively, after the polycondensation reaction, the resin composition may be purified to reduce the total amount of the cyclic silicon-containing compound.

As a method of purifying the silicon-containing compound, stripping is exemplified while blowing an inert gas, for example, nitrogen gas, to 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, still more preferably 240°C or higher and 300°C or lower. The vapor pressure of stripping is preferably lower, and is preferably 1000 Pa or less, more preferably 300 Pa or less, still more preferably 200 Pa or less, still more preferably 133.32 Pa (1 mmHg) or less. As time of stripping, Preferably they are 4 hours or more and 12 hours or less, More preferably, they are 6 hours or more and 10 hours or less. By adjusting to the above conditions, the cyclic silicon-containing compound can be efficiently removed, and the total amount of the cyclic silicon-containing compound can be controlled within a preferred range.

<Synthesis of polyimide/polyimide precursor>

The polyimide precursor of the present embodiment can be synthesized by polycondensation reaction of polycondensation components containing acid dianhydride, diamine, and silicon-containing compound.

Regarding the synthesis of the polyimide/polyimide precursor according to the first aspect, for example, any of the following steps:

Polyimide is obtained by polycondensation of the compound represented by the above-described general formula (8) or the compound represented by the general formula (9) and the silicon-containing compound represented by the general formula (10), followed by polycondensation of other compounds Step of reacting to provide a resin composition containing a polyimide precursor and polyimide;

Polyimide is obtained by polycondensation of the above-described diamine or acid dianhydride and the silicon-containing compound represented by the general formula (10), followed by polycondensation of other compounds to form a polyimide precursor and a polyimide-containing resin. process of providing the composition

A method for producing a resin composition comprising a is provided.

Regarding the synthesis of the polyimide/polyimide precursor according to the second aspect, for example, any of the following steps:

Polyimide precursor or polyimide by polycondensation reaction of the compound represented by the above-described general formula (3), the compound represented by the general formula (4), the silicon-containing compound represented by the general formula (5), and other compounds Step of providing a resin composition containing;

Polyimide is obtained by subjecting the compound represented by the above-described general formula (3) and other compounds to a polycondensation reaction with the compound represented by the general formula (4) and other compounds, followed by the above-described general formula (5) A step of subjecting an indicated silicon-containing compound to a polycondensation reaction of another compound to provide a polyimide precursor and a resin composition containing polyimide; or

Polyimide is obtained by polycondensation of the above-described diamine and acid dianhydride, followed by polycondensation of a silicon-containing compound represented by the general formula (5) and other compounds to obtain a polyimide precursor and a polyimide-containing resin. process of providing a composition;

A method for producing a resin composition comprising a is provided.

In addition, as the silicon-containing compound, it is preferable to use the purified one described above. In a preferred embodiment, the polycondensation component is composed of acid dianhydride, diamine, and silicon-containing compound. The polycondensation reaction is preferably carried out in a suitable solvent. Specifically, after dissolving a diamine component and a silicon-containing compound in a solvent in a predetermined amount, a method in which a predetermined amount of acid dianhydride is added to the obtained diamine solution and stirred is exemplified.

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

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

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

The reaction solvent is not particularly limited as long as it is a solvent capable of dissolving the acid dianhydride component, the diamine component, and the polyimide/polyimide precursor to be produced and yielding a high molecular weight polymer. Examples of such a solvent include aprotic solvents, phenolic solvents, ether and glycol solvents, and the like.

As the aprotic solvent, for example, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N-methylcapro A lactam, 1,3-dimethylimidazolidinone, tetramethylurea, and an amide-based solvent of the general formula:

[Formula 99]

{In the formula, Ekamide M100 represented by R ₁₂ = methyl group (trade name: manufactured by Idemitsu Kogyo Co., Ltd.), and Ekamide B100 represented by R ₁₂ = n-butyl group (trade name: manufactured by Idemitsu Kogyo Co., Ltd.)}; lactone solvents such as γ-butyrolactone and γ-valerolactone; phosphorus-containing amide solvents such as hexamethylphosphoricamide and hexamethylphosphinetriamide; sulfur-containing solvents such as dimethyl sulfone, dimethyl sulfoxide, and sulfolane; ketone solvents such as cyclohexanone and methylcyclohexanone; tertiary amine solvents such as picoline and pyridine; Ester solvents, such as acetic acid (2-methoxy-1-methylethyl), etc. are mentioned.

Phenolic solvents include, for example, phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2, 6-xylenol, 3,4-xylenol, 3,5-xylenol, etc. are mentioned.

Ether and glycol solvents include, for example, 1,2-dimethoxyethane, bis(2-methoxyethyl) ether, 1,2-bis(2-methoxyethoxy)ethane, bis[2-( 2-methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,4-dioxane, etc. are mentioned.

You may use these solvent individually or in mixture of 2 or more types.

The boiling point of the solvent used for synthesis of the polyimide/polyimide precursor at normal pressure is preferably 60 to 300°C, more preferably 140 to 280°C, still more preferably 170 to 270°C. When 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, generation of roughness on the surface of the resin film and entrainment of air bubbles into the resin film 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 abnormalities during coating. More specifically, N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), and compounds represented by the general formula (6) related to the first and second aspects are selected from the group consisting of At least 1 type is preferable.

The water content in the solvent is preferably, for example, 3,000 mass ppm or less in order to favorably advance the polycondensation reaction. In the resin composition in the present embodiment, the content of molecules having a molecular weight of less than 1,000 is preferably less than 5% by mass. The presence of molecules with a molecular weight of less than 1,000 in the resin composition is considered to be due to the involvement of the solvent used in the synthesis and the moisture content of the raw materials (acid dianhydride, diamine). That is, it is considered that the acid anhydride groups of some of the acid dianhydride monomers are hydrolyzed by moisture to become carboxyl groups, and remain in a low molecular weight state without being converted to a high molecular weight. Therefore, the smaller the moisture content of the solvent used in the polycondensation reaction, the better. The moisture content of the solvent is preferably 3,000 ppm by mass or less, and more preferably 1,000 ppm by mass or less. Similarly, the amount of moisture contained in the raw material is preferably 3,000 ppm by mass or less, and more preferably 1,000 ppm by mass or less.

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

When dissolving each polycondensation component in a solvent, you may heat as needed. From the viewpoint of obtaining a polyimide precursor with 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, Preferably it may be 1 to 100 hours or 2 to 10 hours. By setting the polymerization time to 1 hour or more, a polyimide precursor having a uniform polymerization degree can be obtained, and by setting the polymerization time to 100 hours or less, a polyimide precursor having a high polymerization degree can be obtained.

The resin composition of this embodiment may also contain other additional polyimide precursors other than the polyimide/polyimide precursor in this embodiment. However, the mass ratio of the additional polyimide/polyimide precursor is preferably 30 to the total amount of polyimide/polyimide precursor in the resin composition, from the viewpoint of reducing the oxygen dependence of the YI value and total light transmittance of the polyimide film. It is mass % or less, More preferably, it is 10 mass % or less.

A part of the polyimide precursor in this embodiment may be imidated (partial imidation). Viscosity stability at the time of preserving a resin composition can be improved by partially imidating a polyimide precursor. The imidation rate in this case is preferably 5% or more, more preferably 8% or more, and preferably 80% or less from the viewpoint of balancing the solubility of the polyimide precursor in the resin composition and the storage stability of the solution. , more preferably 70% or less, still more preferably 50% or less. This partial imidation is obtained by heating a polyimide precursor and subjecting it to dehydration ring closure. This heating is performed 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 20 hours. 10 hours can be done.

A part or all of carboxylic acid is esterified by adding N,N-dimethylformamide dimethyl acetal or N,N-dimethylformamide diethyl acetal to the polyimide/polyimide precursor obtained by the reaction described above and heating the mixture. You may use one as the polyimide precursor of this embodiment. Viscosity stability during storage can be improved by esterification. These ester-modified polyamic acids are obtained by sequentially reacting the above-mentioned acid dianhydride component with 1 equivalent of a monohydric alcohol relative to the acid anhydride group, and a dehydration condensation agent such as thionyl chloride or dicyclohexylcarbodiimide, It can also be obtained by a diamine component and a method of condensation reaction.

<Synthesis of polyimide>

In a more preferable aspect, the polyimide varnish is obtained by dissolving the acid dianhydride component and the diamine component in a solvent such as an organic solvent, adding an azeotrope solvent such as toluene, and removing water generated during imidation to the outside of the system. By removing it, it can manufacture as a polyimide solution (it is also called polyimide varnish) containing polyimide and a solvent. Here, the reaction conditions 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 advance the reaction with sulfone group-containing diamines, it is preferable to heat the reaction at 180°C for about 12 hours. Moreover, it is preferable that it is an inert atmosphere, such as argon or nitrogen, at the time of reaction.

<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 the resin composition as it is. As needed, you may prepare a resin composition by adding at least 1 type of additional solvent and additional component to a polyimide precursor in the temperature range of room temperature (25 degreeC) - 80 degreeC, and mixing by stirring. This agitation and mixing can be performed using an appropriate apparatus such as a three-one motor equipped with a stirring blade (manufactured by Shinto Chemical Co., Ltd.) or a self-revolution/revolution mixer. You may heat a resin composition at 40 degreeC - 100 degreeC as needed.

On the other hand, when the solvent used when synthesizing the polyimide/polyimide precursor is different from the solvent to be contained in the resin composition, the solvent in the synthesized polyimide precursor solution is removed by appropriate methods such as reprecipitation and solvent distillation. may be removed to isolate the polyimide/polyimide precursor. Then, in the temperature range of room temperature (25 degreeC) - 80 degreeC, you may prepare a resin composition by adding additional components to the isolated polyimide precursor, and stirring and mixing a desired solvent and as needed.

After preparing the resin composition as described above, by heating the resin composition at, for example, 130 to 200°C for, for example, 5 minutes to 2 hours, a part of the polyimide precursor is dehydrated to such an extent that the polymer does not precipitate. It may be deoxidized (partial imidization). The imidization rate can be controlled by controlling the heating temperature and heating time. Viscosity stability at the time of preserving a resin composition can be improved by partially imidating a polyimide precursor.

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. Specifically, it is preferably 500 mPa·s or more, more preferably 1,000 mPa·s or more, and still more preferably 3,000 mPa·s or more, in view of the difficulty of liquid leakage from the slit nozzle. From the viewpoint of preventing clogging of the slit nozzle, it is preferably 100,000 mPa·s or less, more preferably 50,000 mPa·s or less, still more preferably 20,000 mPa·s or less.

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

The water content of the resin composition of the present embodiment is preferably 3,000 ppm by mass or less, more preferably 2,500 ppm by mass or less, still more preferably 2,000 ppm by mass or less, from the viewpoint of viscosity stability during storage of the resin composition. More preferably, it is 1,500 ppm by mass or less, particularly preferably 1,000 ppm by mass or less, particularly preferably 500 ppm by mass or less, particularly preferably 300 ppm by mass or less, and particularly preferably 100 ppm by mass or less.

<<Polyimide film and manufacturing method thereof>>

A polyimide film (hereinafter also referred to as a polyimide resin film) can be provided using the resin composition of the present embodiment. The manufacturing method of the polyimide film of this embodiment is the application|coating process of apply|coating the resin composition of this embodiment on the surface of a support body; a film forming step of heating the resin composition to form a polyimide resin film; and a peeling step of peeling the polyimide resin film from the support.

<Coating process>

In the application step, the resin composition of the present embodiment is applied onto 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 formation step (heating step) and has good releasability in the peeling step. As a support body, it is a glass substrate, for example, an alkali-free glass substrate, for example; silicon wafer; PET (polyethylene terephthalate), OPP (stretched polypropylene), polyethylene glycol terephthalate, polyethylene glycol naphthalate, polycarbonate, polyimide, polyamideimide, polyetherimide, polyetheretherketone, polyethersulfone, polyphenylene resin substrates such as sulfone and polyphenylene sulfide; Metal substrates, such as stainless steel, alumina, copper, and nickel, etc. are mentioned.

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

As a coating method, generally, coating methods, such as a doctor blade knife coater, an air knife coater, a roll coater, a rotary coater, a flow coater, a die coater, a bar coater, and a coating method such as spin coating, spray coating, and dip coating; Printing techniques represented by screen printing, gravure printing, etc., etc. are mentioned. The resin composition of the present embodiment is preferably applied by slit coating. Although 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, it 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 lower the viscosity and improve workability.

<Optional drying process>

A drying step may be performed subsequent to the application step, or the drying step may be omitted and the film formation step (heating step) may proceed directly to the next one. The drying process is performed for the purpose of removing the organic solvent in the resin composition. In the case of carrying out the drying process, suitable devices such as a hot plate, box type dryer, conveyor type dryer, etc. can be used, for example. 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. In the above manner, a coating film containing the polyimide precursor is formed on the support.

<film formation process>

Then, a film formation process (heating process) is performed. The heating step is a step of obtaining a polyimide resin film by advancing the imidation reaction of the polyimide precursor in the coating film while removing the organic solvent contained in the coating film. This heating process can be performed using apparatuses, such as an inert gas oven, a hot plate, a box type dryer, and a conveyor type dryer, for example. This step may be performed simultaneously with the drying step, or both steps may be performed sequentially.

The heating step may be performed in an air atmosphere, but from the viewpoints of obtaining safety, good transparency of the obtained polyimide film, low thickness direction retardation (Rth) and low YI value, it is preferable to carry out the heating step in an inert gas atmosphere. As an inert gas, nitrogen, argon, etc. are mentioned, for example. The heating temperature may be appropriately set according to the type of polyimide precursor and the type of solvent in the resin composition, but is preferably 250°C to 550°C, more preferably 300 to 450°C. If the temperature is 250°C or higher, imidation proceeds satisfactorily, and if the temperature is 550°C or lower, problems such as decrease in transparency and deterioration in 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 ppm by mass or less, more preferably 100 ppm by mass or less, and furthermore, from the viewpoint of the transparency and YI value of the polyimide film obtained. Preferably it is 10 mass ppm or less. By heating in an atmosphere with an oxygen concentration of 2,000 ppm by mass or less, the YI value of the obtained polyimide film can be made 30 or less.

<Peel 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. As this peeling process, the aspect of the following (1)-(4) is mentioned, for example.

(1) After manufacturing a structure comprising a polyimide resin film/support by the above method, a laser is irradiated from the support side of the structure, and the interface between the support and the polyimide resin film is subjected to ablation processing to obtain a polyimide resin. How to exfoliate. Types of lasers include solid-state (YAG) lasers, gas (UV excimer) lasers, and the like. It is preferable to use a spectrum with 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 of forming a release layer on a support before coating the resin composition on the support, and then obtaining a structure comprising a polyimide resin film/release layer/support, and then peeling off the polyimide resin film. Examples of the peeling layer include parylene (registered trademark, manufactured by Nippon Parylene Corporation) and tungsten oxide; You may use release agents, such as a vegetable oil type, silicone type, fluorine type, and an alkyd type (refer Unexamined-Japanese-Patent No. 2010-067957, Unexamined-Japanese-Patent No. 2013-179306 etc.).

You may use this method (2) and the laser irradiation of method (1) together.

(3) A method of obtaining a polyimide resin film by etching the metal with an etchant after obtaining a structure comprising a polyimide resin film/support using an etchable metal substrate as a support. As a metal, copper (as a specific example, electrolytic copper foil "DFF" by Mitsui Metal Mining Co., Ltd.), aluminum, etc. can be used. As an 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 comprising the 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 A method for separating a polyimide resin film.

Among these peeling methods, 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 surfaces of the obtained polyimide resin film, it is more preferable to perform the irradiation step of irradiating a laser from the support body side prior to the method (1), that is, the peeling step. In addition, in the method (3), when copper is used as the support, the YI value of the resulting polyimide resin film tends to increase and elongation decreases. This is considered to be an effect of copper ions.

Although the thickness of the obtained polyimide film is not limited, Preferably it is 1-200 micrometers, More preferably, it is 5-100 micrometers.

<<Use of Polyimide Film>>

The polyimide film obtained from the resin composition of the present embodiment can be used, for example, as a semiconductor insulating film, a thin film transistor liquid crystal display (TFT-LCD) insulating film, or an electrode protective film, and also as a liquid crystal display, organic electroluminescence display, field emission It can be applied as a transparent substrate of a display device such as a display or electronic paper. In particular, the polyimide film obtained from the resin composition of the present embodiment is used as a thin film transistor (TFT) substrate, a color filter substrate, a touch panel substrate, and a transparent conductive film (ITO, Indium Thin Oxide) substrate in the manufacture of a flexible device. can be preferably used. As a flexible device to which the polyimide film in this embodiment can be applied, for example, a TFT device for a flexible display, a flexible solar cell, a flexible touch panel, a flexible lighting, a flexible battery, a flexible printed circuit board, a flexible color filter, and a smart surface cover lenses for phones; and the like.

The process of forming a TFT on a flexible substrate using a polyimide film is typically performed 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 the temperature. As such, it is necessary to appropriately select a polymer structure having a glass transition temperature and a thermal decomposition start temperature equal to or higher than the process temperature.

In the case of 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 needs to be able to withstand the temperature. It is necessary to appropriately select a polymer structure having a glass transition temperature and thermal decomposition onset temperature equal to or higher than the highest temperature in the TFT manufacturing process.

When manufacturing a TFT device using low-temperature polysilicon (LTPS), a process temperature of 380°C to 520°C is generally required, and the polyimide film of the present embodiment needs to be able to withstand the temperature. It is necessary to appropriately select the glass transition temperature and thermal decomposition start temperature equal to or higher than the maximum manufacturing process temperature. On the one hand, because of these thermal histories, the optical properties (particularly light transmittance, retardation properties, and YI value) of the polyimide film tend to deteriorate as it is exposed to a high-temperature process. However, the polyimide obtained from the polyimide precursor of the present embodiment has good optical properties even through thermal history.

Below, as a use example of the polyimide film of this embodiment, the manufacturing method of a display and a laminated body is demonstrated.

<Manufacturing method of display>

The manufacturing method of the display of this embodiment is the application|coating process of apply|coating the resin composition of this embodiment on the surface of a support body; a film forming step of heating the resin composition to form a polyimide resin film; an element formation 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

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 a display of the present embodiment. The organic EL structure part 25 of FIG. 1 is demonstrated. For example, an organic EL element 250a emitting red light, an organic EL element 250b emitting green light, and an organic EL element 250c emitting blue light are arranged in a matrix form as a unit, The light emitting area of each organic EL element is defined by partition walls (banks) 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 representing the CVD multi-layer film (multi-barrier layer) made of silicon nitride (SiN) or silicon oxide (SiO), TFTs 256 (low-temperature polysilicon (LTPS) or metal oxide semiconductors) for driving organic EL elements are (It is selected from IGZO etc.), the interlayer insulating film 258 provided with the contact hole 257, and the lower electrode 259 are formed in multiple numbers. The organic EL element is sealed with a sealing substrate 2b, and a hollow part 261 is formed between each organic EL element and the sealing substrate 2b.

The manufacturing process of a flexible organic EL display includes a process of manufacturing a polyimide film on a glass substrate support, manufacturing an organic EL substrate shown in FIG. 1 thereon, a process of manufacturing a sealing substrate, and bonding both substrates together. It includes an assembling process and a peeling process of peeling the organic EL display manufactured on the polyimide film from the glass substrate support. Known manufacturing processes can be applied to the organic EL substrate manufacturing process, the sealing substrate manufacturing process, and the assembling process. Although an example is given below, it is not limited to this. The peeling process is the same as the above-mentioned peeling process of the polyimide film.

For example, referring to FIG. 1 , first, a polyimide film is prepared on a glass substrate support by the above method, and silicon nitride (SiN) and silicon oxide (SiO) are coated thereon by a CVD method or a sputtering method. A multi-barrier layer having a multi-layer structure (lower substrate 2a in Fig. 1) is manufactured, and a metal wiring layer for driving a TFT is manufactured thereon using a photoresist or the like. An active buffer layer of SiO or the like is fabricated thereon using the CVD method, and a TFT device (TFT 256 in FIG. 1) of metal oxide semiconductor (IGZO) or low-temperature polysilicon (LTPS) or the like is fabricated thereon. After manufacturing the TFT substrate for a flexible display, an interlayer insulating film 258 having contact holes 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 to form a pair with a TFT.

Next, after forming barrier ribs (banks) 251 of photosensitive polyimide or the like, a hole transport layer 253 and a light emitting layer 254 are formed in each space partitioned by the barrier ribs. An upper electrode (cathode) 255 is formed so as to cover the light emitting layer 254 and the barrier rib (bank) 251 . Then, using a fine metal mask or the like as a mask, an organic EL material emitting red light (corresponding to the organic EL element 250a emitting red light in FIG. 1) and an organic EL material emitting green light (in FIG. 1, An organic EL substrate emitting green light) and an organic EL material emitting blue light (corresponding to organic EL element 250c emitting blue light in FIG. 1) by a known method. to manufacture The organic EL substrate is sealed with a sealing film or the like (sealing substrate 2b in Fig. 1), and the device above the polyimide substrate is separated from the glass substrate support by a known peeling method such as laser peeling. An EL display can be manufactured. In the case of using the polyimide of the present embodiment, a see-through type flexible organic EL display can be manufactured. You may manufacture a bottom emission type flexible organic electroluminescent display by a well-known method.

Manufacture example of flexible liquid crystal display

A flexible liquid crystal display can be manufactured using the polyimide film of this embodiment. As a specific manufacturing method, a polyimide film is manufactured on a glass substrate support by the above method, and is composed of, for example, amorphous silicon, a metal oxide semiconductor (IGZO, etc.), and low-temperature polysilicon using the above method. Fabricate a TFT substrate. Separately, according to the application process and the film formation process of the present embodiment, a polyimide film is prepared on a glass substrate support, and a color filter glass substrate with a polyimide film is prepared using a color resist or the like according to a known method ( CF substrate) is prepared. A sealing material made of a thermosetting epoxy resin or the like is applied to one of the TFT substrate and the CF substrate by screen printing in a frame-shaped pattern minus the liquid crystal inlet portion, and to the other substrate, having a diameter corresponding to the thickness of the liquid crystal layer, , spherical spacers made of plastic or silica are spread.

Next, the TFT substrate and the CF substrate are bonded together, and the sealing material is cured. Then, a liquid crystal layer is formed by injecting a liquid crystal material into a space surrounded by a TFT substrate, a CF substrate, and a sealing material by a pressure reducing method, applying a thermosetting resin to the liquid crystal inlet, and sealing the liquid crystal material by heating. 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 manufacturing method of the laminated body of this embodiment is the application|coating process of apply|coating the resin composition of this embodiment on the surface of a support body; a film forming step of heating the resin composition to form a polyimide resin film; and an element forming step of forming an element on the polyimide resin film.

As an element in a laminated body, what was illustrated in manufacture of said flexible device is mentioned. As a support body, a glass substrate can be used, for example. Preferred specific procedures of the application step and the film formation step are the same as those described for the method for producing the above polyimide film. In the element forming step, the above element is formed on a polyimide resin film as a flexible substrate formed on a support. Thereafter, the polyimide resin film and the element may be optionally separated from the support in a peeling step.

Example

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 number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) under the following conditions.

As a solvent, NMP (manufactured by Wako Pure Chemical Industries, Ltd., for high-performance liquid chromatography, immediately before measurement, 24.8 mmol/L lithium bromide monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.5%) and 63.2 mmol/L phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd.) , for high-performance liquid chromatography) was added and dissolved) was used. A calibration curve for calculating the weight average molecular weight was prepared using standard polystyrene (manufactured by Tosoh Corporation).

Column: Shodex KD-806M (manufactured by Showa Denko)

Flow rate: 1.0 mL/min

Column temperature: 40 ℃

Pump: PU-2080Plus (manufactured by JASCO)

Detector: RI-2031Plus (RI: differential refractometer, manufactured by JASCO) and UV-2075Plus (UV-VIS: UV-visible absorbance meter, manufactured by JASCO)

<Evaluation of viscosity stability of composition (varnish)>

The resin compositions prepared in Examples and Comparative Examples were left to stand for 24 hours in an atmosphere of 23° C. and 50% RH, and the viscosity at the initial stage (day 0) of the resin composition was measured using a viscometer with a temperature controller (VISCOMATER TVE manufactured by Toki Sangyo Co., Ltd.) -35H) was used. Then, the resin composition was left to stand for 10 days in an atmosphere of 23°C and 50% RH, 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 greater than 4%/day and less than 7%/day “Good”

C: Viscosity stability greater than 6%/day and less than 10%/day 「Good」

D: Viscosity stability greater than 8%/day “Good”

<Evaluation of filterability of composition (varnish)>

The resin compositions prepared in Examples and Comparative Examples were subjected to pressure filtration at a pressure of 0.25 MPa using a polyethylene membrane filter having a size of 900 mmφ and a weight per unit area of 0.2 μm in an atmosphere of 23° C. and 50% RH. did The mass of the filtered resin composition at this time was measured, and the filtration rate was calculated. Filterability was evaluated according to the following criteria.

A: Filtration rate 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 "good"

D: Filtration rate less than 500 g/hr "Not good"

<Evaluation of tensile elongation of polyimide resin film>

As a support, a 6-inch silicon wafer substrate having an aluminum deposition layer formed on the surface was used, and the resin composition prepared in Examples and Comparative Examples was applied to the surface of the aluminum deposition layer, and the film thickness of the polyimide resin film was 10 μm. It was spin-coated so as to form a coating film. After prebaking this coating film at 100 ° C. for 6 minutes, a vertical curer (manufactured by Koyo Thermo System Co., Ltd., model name “VF-2000B”) in which the oxygen concentration in the chamber is adjusted to 10 mass ppm or less was used and heated at 400°C for 1 hour to form a polyimide film on the wafer. Then, using a dicing saw (manufactured by Disco Co., Ltd., product name "DAD 3350"), a 3 mm wide cut was made on the obtained polyimide film, and then the wafer with the polyimide film was immersed in a dilute hydrochloric acid solution overnight. After dipping, 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. 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 using TENSILON (manufactured by Orientec Co., Ltd., model name "UTM-II-20"). Tensile elongation was evaluated according to the following criteria.

A: Tensile elongation over 40% "excellent"

B: Tensile elongation greater than 30% and less than 40% "good"

C: Tensile elongation greater than 20% and less than 30% "Good"

D: Tensile elongation of 20% or less "Poor"

<Evaluation of residual stress of polyimide resin film>

On a 6-inch silicon wafer having a thickness of 625 μm ± 25 μm, the “warpage amount” of which was measured in advance, the resin composition prepared in Examples and Comparative Examples was applied by a spin coater, and prebaked at 100 ° C. for 7 minutes. . Then, using a vertical curing furnace (manufactured by Koyo Lindbergh Co., Ltd., model name VF-2000B), the oxygen concentration in the chamber was adjusted to be 10 mass ppm or less, and a heat curing treatment (curing treatment) at 400 ° C. for 1 hour was carried out to prepare a silicon wafer with a polyimide resin film having a film thickness of 10 µm after curing.

The amount of warpage of this wafer was measured using a residual stress measuring device (model: FLX-2320 manufactured by Tencor Co., Ltd.), and the residual stress generated between the silicon wafer and the resin film "in a nitrogen atmosphere" was evaluated.

A: Residual stress less than 35 MPa "good"

B: Residual stress of 35 MPa or more and less than 45 MPa "Good"

C: Residual stress of 45 MPa or more “Not good”

<Ratio of silicon-containing compounds in all resins>

The ratio (mass %) of the silicon group-containing compound in the total mass of all the resins of the resin compositions of Examples/Comparative Examples was calculated as follows.

Ratio of silicon group-containing compound (% by mass) = mass of silicon group-containing compound (g)/total amount of mass of each monomer (acid dianhydride monomer, diamine monomer, silicon group-containing compound) (g) * 100

In addition, the ratio of a silicon group-containing compound can be calculated|required by the following method using a varnish.

An appropriate amount of water is added to the varnish, heat treatment is performed at 80°C for 3 days, and the depolymerization component is depolymerized with the acid component and the amine component to obtain an acid monomer and an amine monomer. Thereafter, a powder in which the acid monomer and the amine monomer are mixed is obtained by solvent distillation, an acetonitrile solution is prepared, and high performance liquid chromatography mass spectrometry (LC/MS) measurement is performed. Then, the peak area of each monomer is obtained, and it can be calculated from the peak area ratio.

<Imidization rate>

The imidation rate (%) of the resin of Example/Comparative Example was calculated as follows.

(When L ₁ and L ₂ in Formula (10) are amino groups)

Imidization rate (%) =

Total number of moles of diamine monomers in the imidation step (including silicon-containing compounds in which L ₁ and L ₂ of the general formula (10) are amino groups) / {diamine monomers in the imidation step (L ₁ and L ₂ in the general formula (10) are total number of moles of diamine monomers in the amidation step (including silicon-containing compounds in which L ₁ and L ₂ are amino groups in the general formula (10)) * 100

For example, in the case of Example I-1,

Total number of moles of diamine monomers in the imidation step (including silicon-containing compounds in which L ₁ and L ₂ of formula (10) are amino groups): 93.6 mmol

Total number of moles of diamine monomers in the amidation step (including silicon-containing compounds in which L ₁ and L ₂ of formula (10) are amino groups): 111.9 mmol

and the imidation rate is 83.7%.

(When L ₁ and L ₂ in Formula (10) are an acid anhydride group)

Imidization rate (%) =

Total number of moles of acid dianhydride monomers in the imidation step (including silicon-containing compounds in which L ₁ and L ₂ of the general formula (10) are acid anhydride groups)/{acid anhydride monomers in the imidation step (L ₁ in the general formula (10) and silicon-containing compounds in which L ₂ is an acid anhydride group) + total number of moles of acid dianhydride monomers in the amidation step (including silicon-containing compounds in which L ₁ and L ₂ are acid anhydride groups in the general formula (10))}* 100

In addition, an imidation rate can be calculated|required by the following method using a varnish.

An appropriate amount of water is added to the varnish, heat treatment is performed at 80°C for 3 days, and the depolymerization component is depolymerized with the acid component and the amine component to obtain an acid monomer and an amine monomer. Thereafter, a powder in which the acid monomer and the amine monomer are mixed is obtained by solvent distillation, an acetonitrile solution is prepared, and high performance liquid chromatography mass spectrometry (LC/MS) measurement is performed. Then, the peak area of each monomer is obtained, and it can be calculated from the peak area ratio.

Moreover, an imidation rate can also be measured using IR (infrared spectrophotometer). After re-precipitation of the varnish with an aqueous solvent, the powder was separated and dried, and then KBr was added to form pellets, which were used as samples. Then, by measuring the infrared absorption spectrum of the resin layer by the single reflection ATR method, it can be calculated from the absorbance derived from the imide group at 1778 cm ^-1 based on the benzene ring carbon hydrogen bond at 1009 cm ^-1 . Here, the imidation rate of the polyimide film after heat-processing the varnish at 400 degreeC for 1 hour was 100%.

<Difference between silicon-containing compound ratio imide unit and amide unit in diamine>

The difference between the imide unit and the amide unit in the ratio of the silicon-containing compound in the diamine of the resins of Examples/Comparative Examples is obtained from the following formula.

A: ratio of silicon-containing compound in diamine of imide unit (% by mass) = total amount of mass of silicon-containing compound used in imidation step/diamine monomer (including silicon-containing compound) used in imidation step * 100

B: Proportion of silicon-containing compound in diamine of amide unit (% by mass) = Total amount of mass of silicon-containing compound used in imidation step/diamine monomer (including silicon-containing compound) used in amidation step * 100

A can also be said interchangeably with "the ratio (mass %) of general formula (10) among the diamine which comprises _P5 in general formula (7)."

In addition, B can also be said interchangeably with "the ratio (mass %) of general formula (10) among the diamine which comprises _P3 in general formula (6)."

And the ratio of the silicon-containing compound in the diamine The difference between the imide unit and the amide unit is represented by "B - A".

Table 5 shows the values of B-A in Examples I-14, I-16, and I-17 and Comparative Examples I-4 to I-6, and the properties of their varnishes and polyimide films.

《Example I-1》

NMP (189 g) and toluene (19 g) as solvents, as shown in Tables 1 and 2, while nitrogen gas was introduced into a separable flask equipped with a stir bar equipped with a Dean Stark tube and a reflux tube at the top, , DABA (73.0 mmol, 11.1 g) as a diamine and silicon-containing compound (2) (6.699 mmol, 10.72 g) were added with stirring, followed by addition of CpODA (38.4 g) as an acid dianhydride at room temperature. After that, the internal temperature was raised to 160°C, heated to reflux at 160°C for 1 hour, and imidation was performed. After completion of imidation, the temperature was raised to 180°C, and the reaction was continued while extracting toluene. After 12 hours of reaction, the oil bath was removed and returned to room temperature. Next, DABA (18.3 mmol, 2.8 g) as a diamine 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 to obtain 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) in an NMP solution (hereinafter also referred to as varnish). do) was obtained.

《Example I-2》

NMP (191 g) and toluene (19 g) as solvents, as shown in Tables 1 and 2, while nitrogen gas was introduced into a separable flask equipped with a stirring bar equipped with a Dean Stark tube and a reflux tube at the top, , DABA (13.6 g) as a diamine and silicon-containing compound (1) (10.82 g) were added with stirring, followed by addition of CpODA (38.4 g) as an acid dianhydride at room temperature. After that, the internal temperature was raised to 160°C, heated to reflux at 160°C for 1 hour, and imidation was performed. After completion of imidation, the temperature was raised to 180°C, and the reaction was continued while extracting toluene. After 12 hours of reaction, the oil bath was removed and returned to room temperature. Next, DABA (0.7 g) as a diamine 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 to obtain an NMP solution of a partially imidized polyimide precursor (functional groups other than silicon-containing compounds: amide group or imide group, functional groups of silicon-containing compounds: imide group).

《Example I-3》

NMP (191 g) and toluene (19 g) as solvents, as shown in Tables 1 and 2, while nitrogen gas was introduced into a separable flask equipped with a stirring bar equipped with a Dean Stark tube and a reflux tube at the top, , DABA (7.3 g) as a diamine and silicon-containing compound (3) (10.85 g) were added with stirring, followed by addition of CpODA (38.4 g) as an acid dianhydride at room temperature. After that, the internal temperature was raised to 160°C, heated to reflux at 160°C for 1 hour, and imidation was performed. After completion of imidation, the temperature was raised to 180°C, and the reaction was continued while extracting toluene. After 12 hours of reaction, the oil bath was removed and returned to room temperature. Next, DABA (7.3 g) as a diamine 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 to obtain an NMP solution of a partially imidized polyimide precursor (functional groups other than silicon-containing compounds: amide group or imide group, functional groups of silicon-containing compounds: imide group).

《Example I-4》

NMP (191 g) and toluene (19 g) as solvents, as shown in Tables 1 and 2, while nitrogen gas was introduced into a separable flask equipped with a stirring bar equipped with a Dean Stark tube and a reflux tube at the top, , DABA (8.7 g) as a diamine and silicon-containing compound (4) (10.85 g) were added with stirring, followed by addition of CpODA (38.4 g) as an acid dianhydride at room temperature. After that, the internal temperature was raised to 160°C, heated to reflux at 160°C for 1 hour, and imidation was performed. After completion of imidation, the temperature was raised to 180°C, and the reaction was continued while extracting toluene. After 12 hours of reaction, the oil bath was removed and returned to room temperature. Next, DABA (5.8 g) as a diamine 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 to obtain an NMP solution of a partially imidized polyimide precursor (functional groups other than silicon-containing compounds: amide group or imide group, functional groups of silicon-containing compounds: imide group).

《Example I-5》

NMP (186 g) and toluene (19 g) as solvents, as shown in Tables 1 and 2, while nitrogen gas was introduced into a separable flask equipped with a stirring rod equipped with a Dean Stark tube and a reflux tube at the top, , DABA (14.9 g) as a diamine was added while stirring, and then CpODA (32.8 g) and a silicon-containing compound (5) (10.51 g) as an acid dianhydride were added at room temperature. After that, the internal temperature was raised to 160°C, heated to reflux at 160°C for 1 hour, and imidation was performed. After completion of imidation, the temperature was raised to 180°C, and the reaction was continued while extracting toluene. After 12 hours of reaction, the oil bath was removed and returned to room temperature. Next, CpODA (3.6 g) as acid dianhydride 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 to obtain an NMP solution of a partially imidized polyimide precursor (functional groups other than silicon-containing compounds: amide group or imide group, functional groups of silicon-containing compounds: imide group).

《Example I-6》

NMP (184 g) and toluene (18 g) as solvents, as shown in Tables 1 and 2, while nitrogen gas was introduced into a separable flask equipped with a stirring bar equipped with a Dean Stark tube and a reflux tube at the top, , DABA (12.9 g) as a diamine and silicon-containing compound (1) (10.44 g) were added while stirring, followed by addition of CpODA (28.8 g) and ODPA (7.8 g) as an acid dianhydride at room temperature. After that, the internal temperature was raised to 160°C, heated to reflux at 160°C for 1 hour, and imidation was performed. After completion of imidation, 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 returned to room temperature. Next, DABA (1.4 g) as a diamine 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 to obtain an NMP solution of a partially imidized polyimide precursor (functional groups other than silicon-containing compounds: amide group or imide group, functional groups of silicon-containing compounds: imide group).

《Example I-7》

NMP (194 g) and toluene (19 g) as solvents, as shown in Tables 1 and 2, while nitrogen gas was introduced into a separable flask equipped with a stirring bar equipped with a Dean Stark tube and a reflux tube at the top, , DABA (11.1 g) as a diamine and silicon-containing compound (2) (11.02 g) were added while stirring, followed by addition of CpODA (28.8 g) and 6FDA (11.1 g) as an acid dianhydride at room temperature. After that, the internal temperature was raised to 160°C, heated to reflux at 160°C for 1 hour, and imidation was performed. After completion of imidation, the temperature was raised to 180°C, and the reaction was continued while extracting toluene. After 12 hours of reaction, the oil bath was removed and returned to room temperature. Next, DABA (2.8 g) as a diamine 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 to obtain an NMP solution of a partially imidized polyimide precursor (functional groups other than silicon-containing compounds: amide group or imide group, functional groups of silicon-containing compounds: imide group).

《Example I-8》

NMP (197 g) and toluene (20 g) as solvents, as shown in Tables 1 and 2, while introducing nitrogen gas into a separable flask equipped with a stirring bar equipped with a Dean Stark tube and a reflux tube at the top, , DABA (8.6 g) as a diamine and silicon-containing compound (1) (11.19 g) were added with stirring, followed by addition of CpODA (28.8 g) and BPAF (11.5 g) as an acid dianhydride at room temperature. After that, the internal temperature was raised to 160°C, heated to reflux at 160°C for 1 hour, and imidation was performed. After completion of imidation, the temperature was raised to 180°C, and the reaction was continued while extracting toluene. After 12 hours of reaction, the oil bath was removed and returned to room temperature. Next, DABA (5.7 g) as a diamine 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 to obtain an NMP solution of a partially imidized polyimide precursor (functional groups other than silicon-containing compounds: amide group or imide group, functional groups of silicon-containing compounds: imide group).

《Example I-9》

NMP (193 g) and toluene (19 g) as solvents, as shown in Tables 1 and 2, while introducing nitrogen gas into a separable flask equipped with a stirring bar equipped with a Dean Stark tube and a reflux tube at the top, , DABA (7.2 g) as a diamine and silicon-containing compound (1) (10.92 g) were added while stirring, followed by addition of CpODA (28.8 g) and BzDA (10.1 g) as an acid dianhydride at room temperature. After that, the internal temperature was raised to 160°C, heated to reflux at 160°C for 1 hour, and imidation was performed. After completion of imidation, the temperature was raised to 180°C, and the reaction was continued while extracting toluene. After 12 hours of reaction, the oil bath was removed and returned to room temperature. Next, DABA (7.2 g) as a diamine 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 to obtain an NMP solution of a partially imidized polyimide precursor (functional groups other than silicon-containing compounds: amide group or imide group, functional groups of silicon-containing compounds: imide group).

《Example I-10》

As described in Tables 1 and 2, NMP (170 g) and toluene (17 g) were used as solvents while nitrogen gas was introduced into a separable flask equipped with a stirrer rod equipped with a Dean Stark tube and a reflux tube at the top. , DABA (13.3 g) as a diamine and silicon-containing compound (2) (9.62 g) were added while stirring, followed by addition of CpODA (28.8 g) and BNBDF (4.1 g) as an acid dianhydride at room temperature. After that, the internal temperature was raised to 160°C, heated to reflux at 160°C for 1 hour, and imidation was performed. After completion of imidation, the temperature was raised to 180°C, and the reaction was continued while extracting toluene. After 12 hours of reaction, the oil bath was removed and returned to room temperature. Next, DABA (0.7 g) as a diamine 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 to obtain an NMP solution of a partially imidized polyimide precursor (functional groups other than silicon-containing compounds: amide group or imide group, functional groups of silicon-containing compounds: imide group).

《Example I-11》

NMP (204 g) and toluene (20 g) as solvents, as shown in Tables 1 and 2, while introducing nitrogen gas into a separable flask equipped with a stirring bar 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) as diamines were added with stirring, followed by addition of CpODA (38.4 g) as acid dianhydride at room temperature. After that, the internal temperature was raised to 160°C, heated to reflux at 160°C for 1 hour, and imidation was performed. After completion of imidation, the temperature was raised to 180°C, and the reaction was continued while extracting toluene. After 12 hours of reaction, the oil bath was removed and returned to room temperature. Next, DABA (1.1 g) and BAFL (0.7 g) were added as diamines while stirring. The molar ratio of acid dianhydride and diamine was 100:98. Then, the mixture was stirred at room temperature for 48 hours to obtain an NMP solution of a partially imidized polyimide precursor (functional groups other than silicon-containing compounds: amide group or imide group, functional groups of silicon-containing compounds: imide group).

《Example I-12》

NMP (202 g) and toluene (20 g) as solvents, as shown in Tables 1 and 2, while nitrogen gas was introduced into a separable flask equipped 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) as diamines were added with stirring, followed by addition of CpODA (38.4 g) as acid dianhydride at room temperature. After that, the internal temperature was raised to 160°C, heated to reflux at 160°C for 1 hour, and imidation was performed. After completion of imidation, the temperature was raised to 180°C, and the reaction was continued while extracting toluene. After 12 hours of reaction, the oil bath was removed and returned to room temperature. Next, DABA (5.5 g) and BisAM (3.1 g) were added as diamines while stirring. The molar ratio of acid dianhydride and diamine was 100:98. Then, the mixture was stirred at room temperature for 48 hours to obtain an NMP solution of a partially imidized polyimide precursor (functional groups other than silicon-containing compounds: amide group or imide group, functional groups of silicon-containing compounds: imide group).

《Example I-13》

NMP (218 g) and toluene (22 g) as solvents, as shown in Tables 1 and 2, while introducing nitrogen gas into a separable flask equipped with a stirring bar 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) as diamines were added with stirring, followed by addition of CpODA (38.4 g) as acid dianhydride at room temperature. After that, the internal temperature was raised to 160°C, heated to reflux at 160°C for 1 hour, and imidation was performed. After completion of imidation, the temperature was raised to 180°C, and the reaction was continued while extracting toluene. After 12 hours of reaction, the oil bath was removed and returned to room temperature. Next, DABA (2.5 g) and BAFL (4.0 g) were added as diamines while stirring. The molar ratio of acid dianhydride and diamine was 100:98. Then, the mixture was stirred at room temperature for 48 hours to obtain an NMP solution of a partially imidized polyimide precursor (functional groups other than silicon-containing compounds: amide group or imide group, functional groups of silicon-containing compounds: imide group).

《Comparative Example I-1》

NMP (208 g) and toluene (21 g) as solvents, as shown in Tables 1 and 2, while introducing nitrogen gas into a separable flask equipped with a stirring bar equipped with a Dean Stark tube and a reflux tube at the top, , DABA (10.22 g) and TFMB (16.0 g) as diamines were added while stirring, and then CpODA (27.7 g), BPDA (5.3 g) and silicon-containing compound (6) (9.95 g) as acid dianhydrides were added at room temperature. added in. The molar ratio of acid dianhydride and diamine was 100:100. After that, the internal temperature was raised to 160°C, heated to reflux at 160°C for 1 hour, and imidation was performed. After completion of imidation, 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 returned to room temperature to obtain an NMP solution of polyimide resin (functional groups other than silicon-containing compounds: imide group, functional groups of silicon-containing compounds: imide group). The obtained varnish was stored in a freezer (setting -20°C, the same below), and was thawed and used for evaluation.

《Comparative Examples I-2, I-3》

In Comparative Example I-1, the same procedure as in Comparative Example I-1 was carried out except that the types and amounts of the solvent, acid dianhydride and diamine were changed to those described in Tables 1 and 2.

《Example I-14》

NMP (177 g) and toluene (18 g) as solvents, as shown in Tables 3 and 4, while nitrogen gas was introduced into a separable flask equipped with a stirring bar equipped with a Dean Stark tube and a reflux tube at the top, , Silicon-containing compound (2) (4.12 g), 33DAS (8.5 g), and 44DAS (12.8 g) as diamines were added while stirring, and then ODPA (31.0 g) was added as an acid dianhydride at room temperature. After that, the internal temperature was raised to 160°C, heated to reflux at 160°C for 1 hour, and imidation was performed. After completion of imidation, the temperature was raised to 180°C, and the reaction was continued while extracting toluene. After 12 hours of reaction, the oil bath was removed and returned to room temperature. Next, 33DAS (0.9 g) and 44DAS (1.4 g) were added as diamines while stirring. The molar ratio of acid dianhydride and diamine was 100:98. Then, the mixture was stirred at room temperature for 48 hours to obtain an NMP solution of a partially imidized polyimide precursor (functional groups other than silicon-containing compounds: amide group or imide group, functional groups of silicon-containing compounds: imide group).

《Example I-15》

NMP (170 g) and toluene (17 g) as solvents, as shown in Tables 3 and 4, while nitrogen gas was introduced into a separable flask equipped with a stirring bar equipped with a Dean Stark tube and a reflux tube at the top, , Silicon-containing compound (2) (1.70 g), 33DAS (8.7 g), and 44DAS (13.0 g) as diamines were added while stirring, and then ODPA (31.0 g) was added as acid dianhydride at room temperature. After that, the internal temperature was raised to 160°C, heated to reflux at 160°C for 1 hour, and imidation was performed. After completion of imidation, the temperature was raised to 180°C, and the reaction was continued while extracting toluene. After 12 hours of reaction, the oil bath was removed and returned to room temperature. Next, 33DAS (1.0 g) and 44DAS (1.4 g) were added as diamines while stirring. The molar ratio of acid dianhydride and diamine was 100:98. Then, the mixture was stirred at room temperature for 48 hours to obtain an NMP solution of a partially imidized polyimide precursor (functional groups other than silicon-containing compounds: amide group or imide group, functional groups of silicon-containing compounds: imide group).

《Example I-16》

NMP (204 g) and toluene (20 g) as solvents, as shown in Tables 3 and 4, while introducing nitrogen gas into a separable flask equipped with a stirring bar equipped with a Dean Stark tube and a reflux tube at the top, , Silicon-containing compound (2) (16.36 g) and DABA (12.0 g) as diamines were added with stirring, followed by addition of CpODA (38.4 g) as an acid dianhydride at room temperature. After that, the internal temperature was raised to 160°C, heated to reflux at 160°C for 1 hour, and imidation was performed. After completion of imidation, the temperature was raised to 180°C, and the reaction was continued while extracting toluene. After 12 hours of reaction, the oil bath was removed and returned to room temperature. Next, DABA (1.3 g) as a diamine 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 to obtain an NMP solution of a partially imidized polyimide precursor (functional groups other than silicon-containing compounds: amide group or imide group, functional groups of silicon-containing compounds: imide group).

《Example I-17》

NMP (259 g) and toluene (26 g) as solvents, as shown in Tables 3 and 4, while nitrogen gas was introduced into a separable flask equipped with a stirring bar equipped with a Dean Stark tube and a reflux tube at the top, , Silicon-containing compound (1) (15.54 g) and BAFL (29.1 g) as diamines were added with stirring, followed by addition of CpODA (38.4 g) as an acid dianhydride at room temperature. After that, the internal temperature was raised to 160°C, heated to reflux at 160°C for 1 hour, and imidation was performed. After completion of imidation, the temperature was raised to 180°C, and the reaction was continued while extracting toluene. After 12 hours of reaction, the oil bath was removed and 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 was stirred at room temperature for 48 hours to obtain an NMP solution of a partially imidized polyimide precursor (functional groups other than silicon-containing compounds: amide group or imide group, functional groups of silicon-containing compounds: imide group).

《Example I-18》

NMP (232 g) and toluene (23 g) as solvents, as shown in Tables 3 and 4, while introducing nitrogen gas into a separable flask equipped with a stirring bar equipped with a Dean Stark tube and a reflux tube at the top, , Silicon-containing compound (1) (7.73 g), 33DAS (8.5 g), and 44DAS (12.8 g) as diamines were added with stirring, followed by addition of BPAF (45.8 g) as acid dianhydride at room temperature. After that, the internal temperature was raised to 160°C, heated to reflux at 160°C for 1 hour, and imidation was performed. After completion of imidation, the temperature was raised to 180°C, and the reaction was continued while extracting toluene. After 12 hours of reaction, the oil bath was removed and returned to room temperature. Next, 33DAS (0.9 g) and 44DAS (1.4 g) were added as diamines while stirring. The molar ratio of acid dianhydride and diamine was 100:98. Then, the mixture was stirred at room temperature for 48 hours to obtain an NMP solution of a partially imidized polyimide precursor (functional groups other than silicon-containing compounds: amide group or imide group, functional groups of silicon-containing compounds: imide group).

《Example I-19》

NMP (235 g) and toluene (24 g) as solvents, as shown in Tables 3 and 4, while introducing nitrogen gas into a separable flask equipped with a stirring bar equipped with a Dean Stark tube and a reflux tube at the top, , Silicon-containing compound (1) (7.84 g) and 6FODA (28.9 g) as a diamine were added while stirring, followed by addition of CpODA (38.4 g) as an acid dianhydride at room temperature. After that, the internal temperature was raised to 160°C, heated to reflux at 160°C for 1 hour, and imidation was performed. After completion of imidation, the temperature was raised to 180°C, and the reaction was continued while extracting toluene. After 12 hours of reaction, the oil bath was removed and 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 was stirred at room temperature for 48 hours to obtain an NMP solution of a partially imidized polyimide precursor (functional groups other than silicon-containing compounds: amide group or imide group, functional groups of silicon-containing compounds: imide group).

《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 (triglam) and maintained at 80°C. To this, 172 g (0.115 mol) of silicon-containing compound X-22-9409 (manufactured by Shin-Etsu Chemical Co., Ltd., both ends: amino group, functional group equivalent: 670) was introduced, and uniform stirring was performed for 30 minutes. Next, after heating to 140 degreeC, stirring for 1 hour, and completion|finish of reaction, it heated up to 180 degreeC and performed heating and refluxing for 3 hours. After completion of the reaction, it was cooled to room temperature and 27.7 g (1.54 mol) of water was added thereto. After stirring uniformly for 30 minutes, it heated to 80 degreeC and heated and refluxed for 3 hours. Thus, a solution in which the imidized tetracarboxylic acid (terminal tetracarboxylic acid siloxanimide oligomer) was dissolved was obtained.

Then, the solution was cooled to room temperature, 99.7 g (0.230 mol) of mBAPS was added, and uniform stirring was performed at room temperature for 1 hour to obtain a resin composition solution.

《Comparative Example I-5》

As shown in Tables 3 and 4, a nitrogen inlet pipe, a thermometer, and a ball-attached cooling pipe equipped with a water separation trap were attached to a three-necked separable flask. At room temperature of 25°C, 15 g of triethylene glycol dimethyl ether (Triglam), 35 g of γ-butyrolactone (GBL), 20.0 g of toluene, and 10.86 g (35.00 mmol) of ODPA were added and stirred until uniform. Thereafter, after raising the temperature to 80°C and adding 11.30 g (13.78 mmol) of silicon-containing compound KF-8010 (manufactured by Shin-Etsu Chemical Industry, both ends: amino group, functional group equivalent 430), and further stirring for 0.5 hour, the temperature was raised to 170°C. The temperature was raised and heated for 4 hours. During the reaction, the by-produced water was azeotroped with toluene, and dehydration was performed under reflux using a cooling tube equipped with a ball equipped with a water separation trap. After draining the by-product water, reflux was stopped and all of the toluene was removed. After cooling the system to 100 degreeC, 0.14 g of maleic anhydride was added and it stirred for 0.5 hour.

After leaving still and cooling at room temperature 25 degreeC for 12 hours, APB 6.00g (20.52 mmol) was added and the resin composition was obtained.

《Comparative Example I-6》

As shown in Tables 3 and 4, 27.0 g of 6FODA was added to a 500 mL five-necked round bottom flask equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen inlet pipe, a Dean Stark equipped with a cooling pipe, a thermometer, and a glass end cap. (0.0802 mol) and 56.000 g of NMP were charged, and the mixture was stirred at a rotational speed of 200 rpm under a nitrogen atmosphere at a system internal temperature of 70°C to obtain a solution.

To this solution, 19.2 g (0.050 mol) of CpODA and 14.000 g of NMP were added at once, then 0.253 g of TEA was added as an imidation catalyst, heated with a mantle heater, and the temperature in the reaction system was raised to 190 °C over about 20 minutes. raised to °C. Components to be distilled off were collected and refluxed for 1 hour while maintaining the internal temperature of the reaction system at 190°C while adjusting the number of rotations according to the increase in viscosity. After that, 85.806 g of NMP was added, the temperature in the reaction system was cooled to 50°C, and a solution containing an oligomer having an imide repeating structural unit was obtained.

BPDA 9.7g (0.033 mol) and NMP 7.527g were added all at once to the obtained solution, and it stirred at 50 degreeC for 5 hours. Thereafter, 100.000 g of NMP was added and homogenized, and then a mixed solution in which 13.2 g (0.003 mol) of X-22-1660B-3 (modified silicone oil, functional group equivalent 2200, Shin-Etsu Chemical) was dissolved in 16.667 g of NMP was added, Further, an NMP solution (hereinafter also referred to as varnish) 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) was prepared by stirring for about 1 hour. got it

Each evaluation of tensile elongation and residual stress was performed using the obtained polyimide resin film for each evaluation of viscosity stability and filterability using the resin compositions of Examples and Comparative Examples. An evaluation result is shown to Tables 1-4.

The abbreviations in Examples and Comparative Examples are as follows;

<Acid dianhydride>

CpODA: a compound of the following general formula

[Formula 100]

ODPA: 4,4'-oxydiphthalic anhydride

6FDA: 4,4'-(hexafluoroisopropylidene)diphthalic anhydride

BPAF: 9,9-bis(3,4-dicarboxyphenyl)fluorene diacid anhydride

BzDA: a compound of the general formula

[Formula 101]

BNBDA: a compound of the general formula

[Formula 102]

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

<diamine>

DABA: 3,5-diaminobenzoic acid

3,3'-diaminodiphenylsulfone (33DAS)

4,4'-diaminodiphenylsulfone (44DAS)

BAFL: 9,9-bis(4-aminophenyl)fluorene

BisAM: a compound of the general formula

[Formula 103]

TFMB: Diaminobis(trifluoromethyl)biphenyl

BAPP: a compound of the following general formula

[Formula 104]

mBAPS: bis[4-(3-aminophenoxy)phenyl]sulfone

APB: 1,3-bis(3-aminophenoxy)benzene

<Silicon-containing compound>

Silicon-containing compound (1): (In formula (10), L ₁ and L ₂ are amino groups (-NH ₂ ), R ₁ is trimethylene group (-CH ₂ CH ₂ CH ₂ -), R ₂ , A compound in which R ₃ is a methyl group, j and k are 0, and a functional group equivalent of 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 -), R ₂ , A compound in which R ₃ is a methyl group, j and k are 0, and a functional group equivalent of 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 -), R ₂ , A compound in which R ₃ is a methyl group, j and k are 0, and a functional group equivalent of 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 -, R ₂ , R ₃ , R ₆ , and R ₇ are methyl groups; A compound in which R ₄ and R ₅ are a phenyl group, j/(i + j + k) = 0.15, and a functional group equivalent of 2200

Silicon-containing compound (5): (In formula (10), L ₁ and L ₂ are an acid anhydride group (-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 a compound having a functional group equivalent of 1000)

Silicon-containing compound (6): (In formula (10), L ₁ and L ₂ are an acid anhydride group (-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 a compound having a functional group equivalent of 500)

[Second aspect]

《Measurement and Evaluation Method》

<weight average molecular weight>

The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) under the following conditions.

As a solvent, NMP (manufactured by Wako Pure Chemical Industries, Ltd., for high-performance liquid chromatography, immediately before measurement, 24.8 mmol/L lithium bromide monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.5%) and 63.2 mmol/L phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd.) , for high-performance liquid chromatography) was added and dissolved) was used. A calibration curve for calculating the weight average molecular weight was prepared using standard polystyrene (manufactured by Tosoh Corporation).

Column: Shodex KD-806M (manufactured by Showa Denko)

Flow rate: 1.0 mL/min

Column temperature: 40 ℃

Pump: PU-2080Plus (manufactured by JASCO)

Detector: RI-2031Plus (RI: differential refractometer, manufactured by JASCO) and UV-2075Plus (UV-VIS: UV-visible absorbance meter, manufactured by JASCO)

<Evaluation of viscosity stability of composition (varnish)>

The resin compositions prepared in Examples and Comparative Examples were left to stand for 24 hours in an atmosphere of 23° C. and 50% RH, and the viscosity at the initial stage (day 0) of the resin composition was measured using a viscometer with a temperature controller (VISCOMATER TVE manufactured by Toki Sangyo Co., Ltd.) -35H) was used. Then, the resin composition was left to stand for 7 days in an atmosphere of 23°C and 50% RH, 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 greater than 1%/day and less than 3%/day “Good”

C: Viscosity stability greater than 3%/day and less than 5%/day 「Good」

D: Viscosity stability greater than 5%/day “Good”

<Evaluation of filterability of composition (varnish)>

The resin compositions prepared in Examples and Comparative Examples were subjected to pressure filtration at a pressure of 0.25 MPa using a polyethylene membrane filter having a size of 900 mmφ and a weight per unit area of 0.2 μm in an atmosphere of 23° C. and 50% RH. did The mass of the filtered resin composition at this time was measured, and the filtration rate was calculated. Filterability was evaluated according to the following criteria.

A: Filtration rate of 2000 g/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 "Good"

D: Filtration rate less than 1000 g/hr "Not good"

<Evaluation of tensile elongation of polyimide resin film>

As a support, a 6-inch silicon wafer substrate having an aluminum deposition layer formed on the surface was used, and the resin composition prepared in Examples and Comparative Examples was applied to the surface of the aluminum deposition layer, and the film thickness of the polyimide resin film was 10 μm. It was spin-coated so as to form a coating film. After prebaking this coating film at 100 ° C. for 6 minutes, using a vertical curer (manufactured by Koyo Thermo System Co., Ltd., model name “VF-2000B”) in which the oxygen concentration in the chamber is adjusted to 10 mass ppm or less, It heated at 400 degreeC for 1 hour, and formed the polyimide film on the wafer. Then, using a dicing saw (manufactured by Disco Co., Ltd., product name "DAD 3350"), a 3 mm wide cut was made on the obtained polyimide film, and then the wafer with the polyimide film was immersed in a dilute hydrochloric acid solution overnight. After dipping, 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. 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 using TENSILON (manufactured by Orientec Co., Ltd., model name "UTM-II-20"). Tensile elongation was evaluated according to the following criteria.

A: Tensile elongation over 50% "excellent"

B: Tensile elongation more than 40% and less than 50% "good"

C: Tensile elongation greater than 30% and less than 40% "Good"

D: Tensile elongation of 30% or less "Poor"

<Evaluation of residual stress of polyimide resin film>

On a 6-inch silicon wafer having a thickness of 625 μm ± 25 μm, the “warpage amount” of which was measured in advance, the resin composition prepared in Examples and Comparative Examples was applied by a spin coater, and prebaked at 100 ° C. for 7 minutes. . Then, using a vertical curing furnace (manufactured by Koyo Lindbergh Co., Ltd., model name VF-2000B), the oxygen concentration in the chamber was adjusted to be 10 mass ppm or less, and a heat curing treatment (curing treatment) at 400 ° C. for 1 hour was carried out to prepare a silicon wafer with a polyimide resin film having a film thickness of 10 µm after curing.

The amount of warpage of this wafer was measured using a residual stress measuring device (model: FLX-2320 manufactured by Tencor Co., Ltd.), and the residual stress generated between the silicon wafer and the resin film "in a nitrogen atmosphere" was evaluated.

A: Residual stress less than 30 MPa "good"

B: Residual stress of 30 MPa or more and less than 40 MPa "Good"

C: Residual stress of 40 MPa or more "not good"

《Example II-1》

Into a 3 L separable flask equipped with a stirring bar, NMP (191 g) as a solvent, DABA (14.4 g) as a diamine, and a silicon-containing compound (1) as shown in Tables 6 and 7 while introducing nitrogen gas (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 groups other than silicon-containing compounds: amide groups, functional groups of silicon-containing compounds: amide groups). The obtained varnish was stored in a freezer (setting -20°C, the same below), and was thawed and used for evaluation.

《Example II-2》

NMP (191 g) and toluene (19 g) as solvents, as shown in Tables 6 and 7, while nitrogen gas was introduced into a separable flask equipped with a stirring bar equipped with a Dean Stark tube and a reflux tube at the top, , DABA (14.4 g) as a diamine, and silicon-containing compound (1) (10.82 g) were added with stirring, followed by addition of CpODA (38.4 g) as an acid dianhydride at room temperature. The molar ratio of acid dianhydride and diamine was 100:98. After that, the internal temperature was raised to 160°C, heated to reflux at 160°C for 1 hour, and imidation was performed. After completion of imidation, 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 returned to room temperature to obtain an NMP solution of polyimide resin (functional groups other than silicon-containing compounds: imide group, functional groups of silicon-containing compounds: imide group). The obtained varnish was stored in a freezer (setting -20°C, the same below), and was thawed and used for evaluation.

《Example II-3》

As described in any one of Tables 6 to 9, while introducing nitrogen gas into a separable flask equipped with a stirring bar equipped with a Dean Stark tube and a reflux tube at the top, NMP (189 g) and toluene (19 g), DABA (13.9 g) as diamine was added with stirring, followed by addition of CpODA (38.4 g) as acid dianhydride at room temperature. After that, the internal temperature was raised to 160°C, heated to reflux at 160°C for 1 hour, and imidation was performed. After completion of imidation, the temperature was raised to 180°C, and the reaction was continued while extracting toluene. After 12 hours of reaction, the oil bath was removed and 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 to obtain 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) NMP solution (hereinafter also referred to as varnish) do) was obtained.

《Example II-16》

NMP (177 g) and toluene (18 g) as solvents, as shown in Tables 8 and 9, while nitrogen gas was introduced into a separable flask equipped with a stirring bar equipped with a Dean Stark tube and a reflux tube at the top, , 33DAS (8.5 g) and 44DAS (12.8 g) as diamines were added with stirring, followed by addition of ODPA (31.0 g) as acid dianhydride at room temperature. After that, the internal temperature was raised to 160°C, heated to reflux at 160°C for 1 hour, and imidation was performed. After completion of imidation, the temperature was raised to 180°C, and the reaction was continued while extracting toluene. After 12 hours of reaction, the oil bath was removed and returned to room temperature. Next, 33DAS (0.9 g) and 44DAS (1.4 g) as diamines and silicon-containing compound (2) (4.12 g) were added while stirring. The molar ratio of acid dianhydride and diamine was 100:98. Then, the mixture was stirred at room temperature for 48 hours to obtain 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) NMP solution (hereinafter also referred to as varnish) do) was obtained.

《Example II-17》

NMP (173 g) and toluene (17 g) as solvents, as shown in Tables 8 and 9, while introducing nitrogen gas into a separable flask equipped with a stirring bar equipped with a Dean Stark tube and a reflux tube at the top, , DABA (13.0 g) as a diamine was added with stirring, followed by addition of CpODA (38.4 g) as an acid dianhydride at room temperature. After that, the internal temperature was raised to 160°C, heated to reflux at 160°C for 1 hour, and imidation was performed. After completion of imidation, the temperature was raised to 180°C, and the reaction was continued while extracting toluene. After 12 hours of reaction, the oil bath was removed and returned to room temperature. Next, DABA (1.4 g) as a diamine and silicon-containing compound (2) (4.80 g) were added while stirring. The molar ratio of acid dianhydride and diamine was 100:98. Then, the mixture was stirred at room temperature for 48 hours to obtain 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) NMP solution (hereinafter also referred to as varnish) do) was obtained.

《Comparative Example II-4》

As shown in Tables 8 and 9, 27.0 g of 6FODA was added to a 500 mL 5-necked round bottom flask equipped with a stainless steel half-moon shaped stirring blade, a nitrogen inlet pipe, a Dean Stark equipped with a cooling pipe, a thermometer, and a glass end cap. (0.0802 mol) and 56.000 g of NMP were charged, and the mixture was stirred at a rotational speed of 200 rpm under a nitrogen atmosphere at a system internal temperature of 70°C to obtain a solution.

To this solution, 19.2 g (0.050 mol) of CpODA and 14.000 g of NMP were added at once, then 0.253 g of TEA was added as an imidation catalyst, heated with a mantle heater, and the temperature in the reaction system was raised to 190 °C over about 20 minutes. raised to °C. Components to be distilled off were collected and refluxed for 1 hour while maintaining the internal temperature of the reaction system at 190°C while adjusting the number of rotations according to the increase in viscosity. After that, 85.806 g of NMP was added, the temperature in the reaction system was cooled to 50°C, and a solution containing an oligomer having an imide repeating structural unit was obtained.

BPDA 9.7g (0.033 mol) and NMP 7.527g were added all at once to the obtained solution, and it stirred at 50 degreeC for 5 hours. Thereafter, 100.000 g of NMP was added and homogenized, and then a mixed solution in which 13.2 g (0.003 mol) of X-22-1660B-3 (modified silicone oil, functional group equivalent 2200, Shin-Etsu Chemical) was dissolved in 16.667 g of NMP was added, Further, an NMP solution (hereinafter also referred to as varnish) 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) was prepared by stirring for about 1 hour. got it

《Example II-4, II-5, II-7, II-9, II-10, II-12, II-14, II-15》

Example II-3 was carried out in the same manner as Example II-3, except that the types and amounts of the solvent, acid dianhydride, diamine, and silicon-containing compound were changed to those described in Tables 6 and 7.

<<Reference Example II-6, Examples II-8, II-11, II-13, Comparative Examples II-1 to II-3>

Example II-2 was carried out in the same manner as Example II-2, except that the types and amounts of the solvent, acid dianhydride, diamine, and silicon-containing compound were changed to those described in Tables 6 and 7.

Each evaluation of tensile elongation and residual stress was performed using the obtained polyimide resin film for each evaluation of viscosity stability and filterability using the resin compositions of Examples and Comparative Examples. An evaluation result is shown in Table 6 - Table 9.

The abbreviations in Examples and Comparative Examples are as follows;

<Acid dianhydride>

CpODA: a compound of the following general formula

[Formula 105]

ODPA: 4,4'-oxydiphthalic anhydride

6FDA: 4,4'-(hexafluoroisopropylidene)diphthalic anhydride

BPAF: 9,9-bis(3,4-dicarboxyphenyl)fluorene diacid anhydride

BzDA: a compound of the general formula

[Formula 106]

BNBDA: a compound of the general formula

[Formula 107]

<diamine>

DABA: 3,5-diaminobenzoic acid

BAFL: 9,9-bis(4-aminophenyl)fluorene

BisAM: a compound of the general formula

[Formula 108]

TFMB: Diaminobis(trifluoromethyl)biphenyl

BAPP: a compound of the following general formula

[Formula 109]

33DAS: 3,3'-diaminodiphenylsulfone

44DAS: 3,3'-diaminodiphenylsulfone

6FODA: 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether

<Silicone-containing compound>

Silicon-containing compound (1): (In formulas (5) and (10), L ₁ and L ₂ are an amino group (-NH ₂ ) and R ₁ is a trimethylene group (-CH ₂ CH ₂ CH ₂ -) , R ₂ , R ₃ are methyl groups, j and k are 0, and a compound having a functional group equivalent of 1500)

Silicon-containing compound (2): (In formulas (5) and (10), L ₁ and L ₂ are an amino group (-NH ₂ ) and R ₁ is a trimethylene group (-CH ₂ CH ₂ CH ₂ -) , R ₂ , R ₃ are methyl groups, j and k are 0, and a compound having a functional group equivalent of 800)

Silicon-containing compound (3): (In general formulas (5) and (10), L ₁ and L ₂ are an amino group (-NH ₂ ), R ₁ is a trimethylene group (-CH ₂ CH ₂ CH ₂ -), , R ₂ , R ₃ are methyl groups, j and k are 0, and a compound having a functional group equivalent of 2200)

Silicon-containing compound (4): in general formulas (5) and (10), L ₁ and L ₂ are amino groups, R ₁ is -CH ₂ CH ₂ CH ₂ -, R ₂ , R ₃ , R ₆ , R ₇ is a methyl group, R ₄ and R ₅ are a phenyl group, j/(i + j + k) = 0.15, and a compound having a functional group equivalent of 2200

Silicon-containing compound (5): (In formulas (5) and (10), L ₁ and L ₂ are an acid anhydride group (-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 a functional group equivalent of 1000 compounds)

Silicon-containing compound (6): (In formulas (5) and (10), L ₁ and L ₂ are an acid anhydride group (-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 a functional group equivalent of 500 compounds)

2a: lower substrate
2b: encapsulation substrate
25: organic EL structure
250a: organic EL element emitting red light
250b: organic EL element emitting green light
250c: organic EL element emitting blue light
251: bulkhead (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 (48)

The general formulas (6) and (7) below:

{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.}
As a resin composition containing a resin of the structural unit represented by,
The P ₅ or P ₆ is, the following general formula (10):

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid A halide group, a hydroxyl group, an epoxy group, or a mercapto 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}
It includes a structural unit derived from a silicon-containing compound represented by
Comprising 25% by mass or less of the silicon-containing compound based on the total mass of the resin,
resin composition. The general formulas (6) and (7) below:

{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.}
As a resin composition containing a resin of the structural unit represented by,
The P ₅ or P ₆ is, the following general formula (10):

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid A halide group, a hydroxyl group, an epoxy group, or a mercapto 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}
It includes a structural unit derived from a silicon-containing compound represented by
The imidization rate of the resin is 50% or more,
resin composition. According to claim 1,
The resin composition whose imidation rate of the said resin is 50 % or more. The general formulas (6) and (7) below:

{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.}
As a resin composition containing a resin of the structural unit represented by,
The P ₅ or P ₆ is, the following general formula (10):

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid A halide group, a hydroxyl group, an epoxy group, or a mercapto 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}
It includes a structural unit derived from a silicon-containing compound represented by
To (a) or (b):
(A) The P ₃ and/or P ₅ is the following general formula (8):

It includes structural units derived from the compound represented by ; or
(B) The P ₄ and/or P ₆ is the following general formula (9):

It includes structural units derived from the compound represented by ;
A resin composition that satisfies any of the above. The general formulas (6) and (7) below:

{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.}
As a resin composition containing a resin of the structural unit represented by,
The P ₅ or P ₆ is, the following general formula (10):

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid A halide group, a hydroxyl group, an epoxy group, or a mercapto 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}
It includes a structural unit derived from a silicon-containing compound represented by
The P ₃ and/or P ₅ are each independently;
3,3'-diaminodiphenylsulfone (33DAS);
4,4'-diaminodiphenylsulfone (44DAS), or
9,9-bis(4-aminophenyl)fluorene (BAFL)
The resin composition containing at least 1 structural unit derived from each compound of. The general formulas (6) and (7) below:

{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.}
As a resin composition containing a resin of the structural unit represented by,
The P ₅ or P ₆ is, the following general formula (10):

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid A halide group, a hydroxyl group, an epoxy group, or a mercapto 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}
It includes a structural unit derived from a silicon-containing compound represented by
The P ₃ and/or P ₅ are each independently;
2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether (6FODA)
The resin composition containing at least 1 structural unit derived from. The general formulas (6) and (7) below:

{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.}
As a resin composition containing a resin of the structural unit represented by,
The P ₅ or P ₆ is, the following general formula (10):

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, L ₁ and L ₂ are each independently an amino group, i is an integer of 1 to 200, j and k are each independently an integer from 0 to 200, and 0 ≤ j/(i + j + k) ≤ 0.50.}
It includes a structural unit derived from a silicon-containing compound represented by
A (mass %): Ratio of general formula (10) among diamines constituting P ₅ in general formula (7)
B (mass %): Ratio of general formula (10) among diamines constituting P ₃ in general formula (6)
, when B - A is greater than 0 and less than 60,
resin composition. According to claim 7,
the diamine,
The following general formula (8):

The compound represented by
3,3'-diaminodiphenylsulfone (33DAS);
4,4'-diaminodiphenylsulfone (44DAS), and
9,9-bis(4-aminophenyl)fluorene (BAFL)
The resin composition which is at least 1 compound chosen from. According to any one of claims 1 to 8,
In the general 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 A resin composition containing at least one structural unit derived from each compound of (3,4-dicarboxyphenyl)fluorene diacid anhydride (BPAF). According to any one of claims 1 to 9,
The resin composition whose functional group equivalent of the silicon-containing compound represented by the said General formula (10) is 800 or more. According to any one of claims 1 to 10,
P ₅ contains a structural unit derived from a compound represented by the general formula (10);
In the general formula (10), L ₁ and L ₂ are each independently an amino group;
resin composition. The method of any one of claims 4 and 9 to 11,
The resin composition in which the amount of the compound represented by the general formula (8) is more than 50 mol% when all diamines (excluding compounds represented by the general formula (10)) are 100 mol%. According to any one of claims 1 to 12,
The above P ₃ or P ₅ is, each independently, the following formula:

The resin composition containing the structural unit derived from the compound (BisAM) represented by. According to any one of claims 1 to 13,
P ₄ or P ₆ is, each independently, 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride, the following formula:

A compound represented by (BzDA), or the formula:

The resin composition containing the structural unit derived from the compound (BNBDA) represented by. According to any one of claims 1 to 14,
The resin composition in which the polyimide resin film obtained by heating the said resin is used for a flexible board|substrate. According to any one of claims 1 to 15,
The resin composition in which the polyimide resin film obtained by hardening the said resin is used for a flexible display. A diamine or acid dianhydride of the general formula (10):

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid A halide group, a hydroxyl group, an epoxy group, or a mercapto 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}
Polyimide is obtained by polycondensation of the silicon-containing compound represented by
Polycondensation reaction of other compounds to provide a resin composition comprising a polyimide precursor and a resin comprising the polyimide;
Comprising 25% by mass or less of the silicon-containing compound based on the total mass of the resin,
A method for producing a resin composition. A diamine or acid dianhydride of the general formula (10):

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid A halide group, a hydroxyl group, an epoxy group, or a mercapto 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}
Polyimide is obtained by polycondensation of the silicon-containing compound represented by
Polycondensation reaction of other compounds to provide a resin composition comprising a polyimide precursor and a resin comprising the polyimide;
The imidization rate of the resin is 50% or more,
A method for producing a resin composition. The following general formula (8):

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

A compound represented by and the following general formula (10):

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid A halide group, a hydroxyl group, an epoxy group, or a mercapto 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}
After polycondensation of the silicon-containing compound represented by and other compounds to obtain polyimide,
A method for producing a resin composition comprising subjecting other compounds to a polycondensation reaction to provide a resin composition comprising a polyimide precursor and a polyimide. 3,3'-diaminodiphenylsulfone (33DAS);
4,4'-diaminodiphenylsulfone (44DAS), and
9,9-bis(4-aminophenyl)fluorene (BAFL)
At least one compound selected from
The following general formula (10):

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid A halide group, a hydroxyl group, an epoxy group, or a mercapto 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}
After polycondensation of the silicon-containing compound represented by and other compounds to obtain polyimide,
A method for producing a resin composition comprising subjecting other compounds to a polycondensation reaction to provide a resin composition comprising a polyimide precursor and a polyimide. At least one compound selected from 4,4'-oxydiphthalic anhydride (ODPA) and 9,9-bis(3,4-dicarboxyphenyl)fluorene diacid anhydride (BPAF), and the following general formula (10) :

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and L ₁ and L ₂ are each independently an amino group, an acid anhydride group, an isocyanate group, a carboxyl group, an acid ester group, an acid A halide group, a hydroxyl group, an epoxy group, or a mercapto 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}
After polycondensation of the silicon-containing compound represented by and other compounds to obtain polyimide,
A method for producing a resin composition comprising subjecting other compounds to a polycondensation reaction to provide a resin composition comprising a polyimide precursor and a polyimide. An application step of 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 on the surface of the support;
A film forming step of heating the resin composition to form a polyimide resin film;
A method for producing a polyimide resin film including a peeling step of peeling the polyimide resin film from the support. 23. The method of claim 22,
The manufacturing method of the polyimide resin film including the irradiation process of irradiating a laser to the said resin composition from the said support body side prior to the said peeling process. An application step of 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 on the surface of the support;
A film forming step of heating the resin composition to form a polyimide resin film;
an element formation step of forming an element on the polyimide resin film;
A manufacturing method of a display including a peeling step of peeling the polyimide resin film on which the element is formed from the support. An application step of 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 on the surface of the support;
A film forming step of heating the resin composition to form a polyimide resin film;
A method for manufacturing a laminate comprising an element formation step of forming an element on the polyimide resin film. 26. The method of claim 25,
The manufacturing method of the laminated body which further includes the process of peeling the said polyimide resin film on which the said element was formed from the said support body. A method for manufacturing a flexible device comprising 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 further positive integer.}
As a resin composition containing a resin of the structural unit represented by,
The P ₁ is the following general formula (3):

It includes a structural unit derived from a compound represented by
The P ₁ or P ₂ is the following general formula (5):

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, L ₁ and L ₂ are each independently an amino group, i is an integer of 1 to 200, j and k are each independently an integer of 0 to 200, 0 ≤ j/(i + j + k) ≤ 0.50, and a functional group equivalent of 800 or more.}
Containing a structural unit derived from a silicon-containing compound represented by
resin composition. 29. The method of claim 28,
The P ₂ is, the following general formula (4):

The resin composition containing the structural unit derived from the compound represented by. The general formulas (6) and (7) below:

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

{In the formula, P ₅ represents a divalent organic group, P ₆ represents a tetravalent organic group, and q represents a positive integer, and P ₅ represents 2,2'-bis(trifluoromethyl) -4,4'-diaminodiphenyl ether (6FODA) is not included.}
As a resin composition containing a resin of the structural unit represented by,
The above P ₃ or P ₄ is the following general formula (10):

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, L ₁ and L ₂ are each independently an amino group, i is an integer of 1 to 200, j and k are each independently an integer from 0 to 200, and 0 ≤ j/(i + j + k) ≤ 0.50.}
Containing a structural unit derived from a silicon-containing compound represented by
resin composition. The general formulas (6) and (7) below:

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

{In the formula, P ₅ represents a divalent organic group, P ₆ represents a tetravalent organic group, and q represents a positive integer, and P ₅ represents 2,2'-bis(trifluoromethyl) -4,4'-diaminodiphenyl ether (6FODA) is not included.}
As a resin composition containing a resin of the structural unit represented by,
The above P ₃ or P ₄ is the following general formula (10):

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, L ₁ and L ₂ are each independently an amino group, i is an integer of 1 to 200, j and k are each independently an integer from 0 to 200, and 0 ≤ j/(i + j + k) ≤ 0.50.}
It includes a structural unit derived from a silicon-containing compound represented by
To (a) or (b):
(A) The P ₃ and/or P ₅ is the following general formula (8):

It includes structural units derived from the compound represented by ; or
(B) The P ₄ and/or P ₆ is the following general formula (9):

It includes structural units derived from the compound represented by ;
A resin composition that satisfies any of the above. The general formulas (6) and (7) below:

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

{In the formula, P ₅ represents a divalent organic group, P ₆ represents a tetravalent organic group, and q represents a positive integer, and P ₅ represents 2,2'-bis(trifluoromethyl) -4,4'-diaminodiphenyl ether (6FODA) is not included.}
As a resin composition containing a resin of the structural unit represented by,
The above P ₃ or P ₄ is the following general formula (10):

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, L ₁ and L ₂ are each independently an amino group, i is an integer of 1 to 200, j and k are each independently an integer from 0 to 200, and 0 ≤ j/(i + j + k) ≤ 0.50.}
It includes a structural unit derived from a silicon-containing compound represented by
The P ₃ and / or P ₅ is,
3,3'-diaminodiphenylsulfone (33DAS), or
4,4'-diaminodiphenylsulfone (44DAS)
The resin composition containing at least 1 structural unit derived from each compound of. The general formulas (6) and (7) below:

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

{In the formula, P ₅ represents a divalent organic group, P ₆ represents a tetravalent organic group, and q represents a positive integer, and P ₅ represents 2,2'-bis(trifluoromethyl) -4,4'-diaminodiphenyl ether (6FODA) is not included.}
As a resin composition containing a resin of the structural unit represented by,
The above P ₃ or P ₄ is the following general formula (10):

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, L ₁ and L ₂ are each independently an amino group, i is an integer of 1 to 200, j and k are each independently an integer from 0 to 200, and 0 ≤ j/(i + j + k) ≤ 0.50.}
It includes a structural unit derived from a silicon-containing compound represented by
The P ₃ and / or P ₅ is,
9,9-bis(4-aminophenyl)fluorene (BAFL), or
The following general formula:

Compound of (BisAM)
The resin composition containing at least 1 structural unit derived from each compound of. The general formulas (6) and (7) below:

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

{In the formula, P ₅ represents a divalent organic group, P ₆ represents a tetravalent organic group, and q represents a positive integer, and P ₅ represents 2,2'-bis(trifluoromethyl) -4,4'-diaminodiphenyl ether (6FODA) is not included.}
As a resin composition containing a resin of the structural unit represented by,
The above P ₃ or P ₄ is the following general formula (10):

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, L ₁ and L ₂ are each independently an amino group, i is an integer of 1 to 200, j and k are each independently an integer from 0 to 200, and 0 ≤ j/(i + j + k) ≤ 0.50.}
It includes a structural unit derived from a silicon-containing compound represented by
The P ₄ and/or P ₆ are,
4,4'-oxydiphthalic anhydride (ODPA);
4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA);
9,9-bis(3,4-dicarboxyphenyl)fluorenedioic acid anhydride (BPAF);
The following general formula:

A compound of (BzDA); or
The following general formula:

A compound of (BNBDA);
The resin composition containing at least 1 structural unit derived from each compound of. According to any one of claims 30 to 34,
Said P ₃ contains a structural unit derived from the compound represented by said General formula (10),
The resin composition whose functional group equivalent of the silicon-containing compound represented by the said General formula (10) is 800 or more. 36. The method of any one of claims 30 to 35,
Said P ₃ contains a structural unit derived from the compound represented by said General formula (10), and
In the general formula (10), L ₁ and L ₂ are each independently an amino group;
resin composition. The method of any one of claims 28, 29 and 31,
A resin in which the compound represented by the general formula (3) or (8) is more than 50 mol% when all diamines (excluding compounds represented by the general formula (5) or (10) are 100 mol%) composition. The method of any one of claims 28 to 37,
The resin composition in which the polyimide resin film obtained by heating the said resin is used for a flexible board|substrate. According to any one of claims 28 to 38,
The resin composition in which the polyimide resin film obtained by hardening the said resin is used for a flexible display. The following general formula (3):

The compound represented by
3,3'-diaminodiphenylsulfone (33DAS), and
4,4'-diaminodiphenylsulfone (44DAS)
At least one diamine selected from
an acid dianhydride;
The following general formula (5):

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, L ₁ and L ₂ are each independently an amino group, i is an integer of 1 to 200, j and k are each independently an integer from 0 to 200, and 0 ≤ j/(i + j + k) ≤ 0.50.}
A method for producing a resin composition comprising subjecting a silicon-containing compound represented by to a polycondensation reaction with another compound to provide a polyimide precursor and/or a polyimide. After obtaining polyimide by polycondensation reaction of diamine (but not including 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether (6FODA)) and acid dianhydride,
The following general formula (5):

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, L ₁ and L ₂ are each independently an amino group, i is an integer of 1 to 200, j and k are each independently an integer from 0 to 200, and 0 ≤ j/(i + j + k) ≤ 0.50.}
A method for producing a resin composition comprising subjecting a silicon-containing compound represented by to a polycondensation reaction with another compound to provide a resin composition containing a polyimide precursor and a polyimide. The following general formula (3):

The compound represented by
3,3'-diaminodiphenylsulfone (33AS), and
4,4'-diaminodiphenylsulfone (44DAS)
At least one diamine selected from
an acid dianhydride;
After polycondensation of other compounds to obtain polyimide,
The following general formula (5):

{In the formula, R ₁ is each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least 1 is a monovalent aliphatic hydrocarbon group of 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms; , R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, L ₁ and L ₂ are each independently an amino group, i is an integer of 1 to 200, j and k are each independently an integer from 0 to 200, and 0 ≤ j/(i + j + k) ≤ 0.50.}
A method for producing a resin composition comprising subjecting a silicon-containing compound represented by to a polycondensation reaction with another compound to provide a resin composition containing a polyimide precursor and a polyimide. An application step of 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 on the surface of the support;
A film forming step of heating the resin composition to form a polyimide resin film;
A method for producing a polyimide resin film including a peeling step of peeling the polyimide resin film from the support. 44. The method of claim 43,
The manufacturing method of the polyimide resin film including the irradiation process of irradiating a laser to the said resin composition from the said support body side prior to the said peeling process. An application step of 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 on the surface of the support;
A film forming step of heating the resin composition to form a polyimide resin film;
an element formation step of forming an element on the polyimide resin film;
A manufacturing method of a display including a peeling step of peeling the polyimide resin film on which the element is formed from the support. An application step of 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 on the surface of the support;
A film forming step of heating the resin composition to form a polyimide resin film;
A method for manufacturing a laminate comprising an element formation step of forming an element on the polyimide resin film. 47. The method of claim 46,
The manufacturing method of the laminated body which further includes the process of peeling the said polyimide resin film on which the said element was formed from the said support body. A method for manufacturing a flexible device comprising manufacturing a laminate by the method according to claim 46 or 47.

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