KR102112483B1 - Polyimide precursor resin composition - Google Patents

Abstract

The polyimide precursor comprising the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) described in this specification, and m in the general formula (3-1) or (3-2) A resin composition comprising at least one compound that is an integer of 3 or more; and optionally, a compound represented by general formula (4). The total amount of the compound in which m is an integer of 3 or more in the general formula (3-1) or (3-2) is more than 0 ppm and 1,100 ppm or less based on the mass of the resin composition, or the general formula (3-1) ) Or the total amount of the compound in which m is an integer of 3 or more in (3-2) and the compound in which n is an integer of 3 or more in general formula (4) is more than 0 ppm and 1,300 ppm or less based on the mass of the resin composition.

Description

Polyimide precursor resin composition

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

The polyimide resin is an insoluble and infusible super-heat-resistant resin, and has excellent properties such as heat 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 the application of the polyimide resin in the field of electronic materials include, for example, insulating coating materials, insulating films, semiconductors, electrode protective films of thin film transistor liquid crystal displays (TFT-LCDs), and the like. In recent years, employing a polyimide film as a flexible substrate has been studied instead of a glass substrate that has been conventionally used in the field of display materials by using lightness and flexibility.

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

International Publication No. 2014/148441 International Publication No. 2014/098235 Japanese Patent Publication No. 2016-029126 Japanese Patent Application Publication No. 2006-028533 Japanese Patent Application Publication No. 2002-012666 Japanese Patent Publication No. 2007-512568 Japanese Patent Publication No. 2012-511173 Japanese Patent Application Publication No. 2010-067957 Japanese Patent Application Publication No. 2013-179306 International Publication No. 2005/068535

 Shin-Etsu Chemical Industry Co., Ltd. homepage, “Q & A”, “About silicone grease and oil compounds”, [online], [Search on March 13, 2017], Internet 〈URL: https: //www.silicone.jp /contact/qa/qa103.shtml>

Patent Documents 1 and 2 use a siloxane-containing compound as a monomer of the polyimide precursor, but such a siloxane-containing compound contains a low molecular weight cyclic siloxane (hereinafter also referred to as a low molecular cyclic siloxane). It is known that this low-molecular cyclic siloxane is volatile, and there is a concern that a contact failure of the process manufacturing apparatus may occur. For example, please refer to Non-Patent Document 1.

Patent documents 3-5 are mentioned as prior art documents about the polyimide precursor which reduced this low molecular cyclic siloxane by purification. In the prior art 3, after adding the siloxane-containing compound to acetone, centrifugation and decantation remove the low-molecular cyclic siloxane, and it is described that the resulting polyimide has less transparency and less outgassing. In Patent Documents 4 and 5, the siloxane-containing compound is purified by stripping the siloxane-containing compound under specific conditions, or by dissolving the siloxane-containing compound in 2-butanone and reprecipitating with methanol, thereby obtaining the adhesiveness of the resulting polyimide. Improvements are described.

The present inventors synthesized a polyimide precursor using a siloxane-containing compound purified by the same purification method as described in Patent Documents 3 to 5, and produced polyimide using the same. As a result, when a large amount of the polyimide precursor is treated in the polyimide manufacturing process, the evaluation of the count count of foreign matters attached to the polyimide film is poor, and the yellowness when using a regular product compared to a crude product (YI value) It was found that the degree of improvement was insufficient. Accordingly, the present invention provides a polyimide precursor resin composition capable of further improving the yellowness (YI value) and reducing foreign matter generated in the polyimide production process, as compared to the case of using the crude siloxane compound. The purpose.

As a result of intensive examination, the present inventors found that the low molecular cyclic siloxane reduced in Patent Documents 3 to 5 is a methyl-side chain (general formula (4) to be described later), and a phenyl-side chain (general formula (3 to be described later). Note that -1) or (3-2)) is not. Then, it has been found that the above problem can be solved by purifying the siloxane compound and using the siloxane compound in which the phenyl side chain of the low-molecular cyclic siloxane is reduced to a specific amount as a polyimide precursor. Hereinafter, examples of the embodiments of the present invention are given in [1] to [34].

[One]

A polyimide precursor comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2);

At least one compound in which m is an integer of 3 or more in the following general formula (3-1) or (3-2);

Optionally, a compound represented by the following general formula (4)

A resin composition comprising:

In the following general formula (3-1) or (3-2), the total amount of the compound in which m is an integer of 3 or more is more than 0 ppm and 1,100 ppm or less, based on the mass of the resin composition, or

In the following general formula (3-1) or (3-2), the total amount of the compound in which m is an integer of 3 or more and the compound in which n is an integer of 3 or more in general formula (4) is based on the mass of the resin composition, More than 0 ppm and 1,300 ppm or less,

Resin composition.

[Formula 1]

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

[Formula 2]

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

[Formula 3]

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

[Formula 4]

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

[2]

The resin composition according to item 1, wherein the total amount of the compound in which m is an integer of 3 or more in the general formula (3-1) or (3-2) is more than 0 ppm and 300 ppm or less based on the mass of the resin composition.

[3]

A polyimide precursor comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2);

At least either compound in which m is 3 or 4 in the following general formula (3-1) or (3-2);

Optionally, a compound represented by the following general formula (4)

A resin composition comprising:

In the following general formula (3-1) or (3-2), the total amount of the compound having m being 3 is more than 0 ppm and less than or equal to 650 ppm, based on the mass of the resin composition, or

In the following general formula (3-1) or (3-2), the total amount of the compound whose m is 4 is more than 0 ppm and less than 350 ppm, based on the mass of the resin composition,

Resin composition.

[Formula 5]

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

[Formula 6]

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

[Formula 7]

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

[Formula 8]

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

[4]

A polyimide precursor comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2),

At least one compound in which m is an integer of 3 or more in the following general formula (3-1) or (3-2);

Optionally, a compound represented by the following general formula (4)

A resin composition comprising:

In the following general formula (3-1) or (3-2), the total amount of the compound in which m is an integer of 3 or more is more than 0 ppm and 7,500 ppm or less, based on the mass of the solid content in the resin composition, or

In the following general formula (3-1) or (3-2), the total amount of the compound in which m is an integer of 3 or more and the compound in which n is an integer of 3 or more in the general formula (4) is based on the mass of the solid content in the resin composition. Thus, the resin composition is more than 0 ppm and 8,600 ppm or less.

[Formula 9]

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

[Formula 10]

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

[Formula 11]

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

[Formula 12]

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

[5]

A polyimide precursor comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2);

At least either compound in which m is 3 or 4 in the following general formula (3-1) or (3-2);

Optionally, a compound represented by the following general formula (4)

A resin composition comprising:

In the following general formula (3-1) or (3-2), the total amount of the compound whose m is 3 is more than 0 ppm and 4,500 ppm or less, based on the mass of the solid content in the resin composition, or

In the following general formula (3-1) or (3-2), the total amount of the compound whose m is 4 is more than 0 ppm and 2,500 ppm or less, based on the mass of the solid content in the resin composition,

Resin composition.

[Formula 13]

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

[Formula 14]

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

[Formula 15]

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

[Formula 16]

[6]

In the compound represented by the general formula (3-1) or (3-2), m is an integer of 3 to 5, the resin composition according to any one of items 1, 2 and 4.

[7]

In the compound represented by the general formula (4), n is an integer of 3 to 8, the resin composition according to any one of items 1, 2 and 4.

[8]

The resin composition according to any one of items 1 to 7, wherein the polyimide resin film obtained by curing the polyimide precursor is used for a flexible substrate.

[9]

The resin composition according to any one of items 1 to 7, wherein the polyimide resin film obtained by curing the polyimide precursor is used for a flexible display.

[10]

A polyimide precursor comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2);

At least one compound in which m is an integer of 3 or more in the following general formula (3-1) or (3-2);

Optionally, a compound represented by the following general formula (4)

A resin composition comprising:

The resin composition is as follows:

A silicon-containing compound represented by the following general formula (5),

At least one compound in which m is an integer of 3 or more in the following general formula (3-1) or (3-2),

Optionally, a raw material composition containing a compound represented by the following general formula (4) is produced by a method comprising polycondensation reaction with tetracarboxylic dianhydride and diamine to provide a polyimide precursor,

The total amount of compounds in which m is an integer of 3 or more in the following general formulas (3-1) or (3-2) contained in the raw material composition is the following general formulas (3-1), (3-2), (4) And, based on the total mass of the silicon-containing compound represented by (5), more than 0 ppm and 46,000 ppm or less, or

The total amount of the compound in which m is an integer of 3 or more in the following general formula (3-1) or (3-2) and the compound in which n is an integer of 3 or more in the general formula (4) included in the raw material composition is the general formula Based on the total mass of the silicon-containing compounds of (3-1), (3-2), (4) and (5), more than 0 ppm and 47,000 ppm or less,

Resin composition.

[Formula 17]

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

[Formula 18]

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

[Formula 19]

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

[Formula 20]

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

[Formula 21]

{In the formula, R ₁ is, 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 Is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group having 1 to 10 carbon atoms, at least one is a monovalent aromatic group having 6 to 10 carbon atoms, R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, at least one is an organic group having an unsaturated aliphatic hydrocarbon group, 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 halide group, a hydroxyl group, an epoxy group, or a mercapto group, i and j are each independently an integer from 1 to 200, and k is an integer from 0 to 200 , 0.05 ≤ j / (i + j + k) ≤ 0.50.}

[11]

In the compound represented by the general formula (3-1) or (3-2), m is an integer of 3 to 5, the resin composition according to item 10.

[12]

In the compound represented by the above general formula (4), n is an integer of 3 to 8, the resin composition according to item 10.

[13]

A polyimide precursor comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2);

At least either compound in which m is 3 or 4 in the following general formula (3-1) or (3-2);

Optionally, a compound represented by the following general formula (4)

A resin composition comprising:

The resin composition is as follows:

A silicon-containing compound represented by the following general formula (5),

At least either compound in which m is 3 or 4 in the following general formula (3-1) or (3-2),

Optionally, a raw material composition containing a compound represented by the following general formula (4) is produced by a method comprising polycondensation reaction with tetracarboxylic dianhydride and diamine to provide a polyimide precursor,

The total amount of compounds in which m is 3 in the following general formulas (3-1) or (3-2) contained in the raw material composition is represented by the following general formulas (3-1), (3-2), (4) and Based on the total mass of the silicon-containing compound of (5), it is more than 0 ppm and 25,000 ppm or less, or

The total amount of compounds in which m is 4 in the following general formulas (3-1) or (3-2) contained in the raw material composition is represented by the following general formulas (3-1), (3-2), (4) and Based on the total mass of the silicon-containing compound (5), more than 0 ppm and 15,000 ppm or less,

Resin composition.

[Formula 22]

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

[Formula 23]

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

[Formula 24]

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

[Formula 25]

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

[Formula 26]

{In the formula, R ₁ is, 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 Is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group having 1 to 10 carbon atoms, at least one is a monovalent aromatic group having 6 to 10 carbon atoms, R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, at least one is an organic group having an unsaturated aliphatic hydrocarbon group, 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 halide group, a hydroxyl group, an epoxy group, or a mercapto group, i and j are each independently an integer from 1 to 200, and k is an integer from 0 to 200 , 0.05 ≤ j / (i + j + k) ≤ 0.50.}

[14]

The resin composition according to any one of items 10 to 13, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (5) are each independently selected from the group consisting of an amino group, an acid anhydride group, and an epoxy group. .

[15]

The resin composition according to any one of items 10 to 14, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (5) are amino groups.

[16]

The resin composition according to any one of items 10 to 15, wherein the compound represented by the general formula (3-1) or (3-2) is a compound represented by the general formula (3-1).

[17]

The tetracarboxylic dianhydride is pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, cyclohexanetetracarboxylic acid The resin composition according to any one of items 10 to 16, which is at least one selected from the group consisting of a dihydride and a cyclobutanetetracarboxylic dianhydride.

[18]

The diamine is 4,4'-diaminodiphenylsulfone, m-tolidine, p-phenylenediamine, 2,2'-bis (trifluoromethyl) benzidine, and 2,2'-bis [4- The resin composition according to any one of items 10 to 17, which is at least one selected from the group consisting of (4-aminophenoxy) phenyl] propane.

[19]

A silicon-containing compound represented by the following general formula (5),

At least one compound in which m is an integer of 3 or more in the following general formula (3-1) or (3-2),

Optionally, a method for producing a resin composition comprising providing a polyimide precursor by polycondensing a raw material composition containing a compound represented by the following general formula (4) with tetracarboxylic dianhydride and diamine,

The total amount of compounds in which m is an integer of 3 or more in the following general formulas (3-1) or (3-2) contained in the raw material composition is the following general formulas (3-1), (3-2), (4) And, based on the total mass of the silicon-containing compound represented by (5), more than 0 ppm and 46,000 ppm or less, or

The total amount of the compound in which m is an integer of 3 or more in the following general formula (3-1) or (3-2) and the compound in which n is an integer of 3 or more in the general formula (4) included in the raw material composition is the general formula Based on the total mass of the silicon-containing compounds of (3-1), (3-2), (4) and (5), more than 0 ppm and 47,000 ppm or less,

Method of manufacturing a resin composition.

[Formula 27]

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

[Formula 28]

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

[Formula 29]

{In the formula, R ₁ is, 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 Is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group having 1 to 10 carbon atoms, at least one is a monovalent aromatic group having 6 to 10 carbon atoms, R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, at least one is an organic group having an unsaturated aliphatic hydrocarbon group, 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 halide group, a hydroxyl group, an epoxy group, or a mercapto group, i and j are each independently an integer from 1 to 200, and k is an integer from 0 to 200 , 0.05 ≤ j / (i + j + k) ≤ 0.50.}

[20]

The method according to item 19, wherein in the compound represented by the general formula (3-1) or (3-2), m is an integer from 3 to 5.

[21]

The method according to item 19, wherein in the compound represented by the general formula (4), n is an integer from 3 to 8.

[22]

A silicon-containing compound represented by the following general formula (5),

At least either compound in which m is 3 or 4 in the following general formula (3-1) or (3-2),

Optionally, a method for producing a resin composition comprising providing a polyimide precursor by polycondensing a raw material composition containing a compound represented by the following general formula (4) with tetracarboxylic dianhydride and diamine,

The total amount of compounds in which m is 3 in the following general formulas (3-1) or (3-2) contained in the raw material composition is represented by the following general formulas (3-1), (3-2), (4) and Based on the total mass of the silicon-containing compound of (5), it is more than 0 ppm and 25,000 ppm or less, or

The total amount of compounds in which m is 4 in the following general formulas (3-1) or (3-2) contained in the raw material composition is represented by the following general formulas (3-1), (3-2), (4) and Based on the total mass of the silicon-containing compound (5), more than 0 ppm and 15,000 ppm or less,

Method of manufacturing a resin composition.

[Formula 30]

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

[Formula 31]

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

[Formula 32]

{In the formula, R ₁ is, 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 Is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group having 1 to 10 carbon atoms, at least one is a monovalent aromatic group having 6 to 10 carbon atoms, R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, at least one is an organic group having an unsaturated aliphatic hydrocarbon group, 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 halide group, a hydroxyl group, an epoxy group, or a mercapto group, i and j are each independently an integer from 1 to 200, and k is an integer from 0 to 200 , 0.05 ≤ j / (i + j + k) ≤ 0.50.}

[23]

The method according to any one of items 19 to 22, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (5) are each independently selected from the group consisting of an amino group, an acid anhydride group, and an epoxy group.

[24]

The method according to any one of items 19 to 23, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (5) are amino groups.

[25]

The method according to any one of items 19 to 24, wherein the compound represented by the general formula (3-1) or (3-2) is a compound represented by the general formula (3-1).

[26]

The tetracarboxylic dianhydride is pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, cyclohexanetetracarboxylic acid The method according to any one of items 19 to 25, which is at least one selected from the group consisting of a dihydride and a cyclobutanetetracarboxylic dianhydride.

[27]

The diamine is 4,4'-diaminodiphenylsulfone, m-tolidine, p-phenylenediamine, 2,2'-bis (trifluoromethyl) benzidine, and 2,2'-bis [4- The method according to any one of items 19 to 26, which is at least one selected from the group consisting of (4-aminophenoxy) phenyl] propane.

[28]

A coating step of applying the resin composition according to any one of items 1 to 18 on the surface of the support;

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

Peeling step of peeling the polyimide resin film from the support,

The manufacturing method of a polyimide film containing the.

[29]

The manufacturing method of the polyimide film of item 28 including the irradiation process of irradiating a laser to the said resin composition from the said support side prior to the said peeling process.

[30]

A coating step of applying the resin composition according to any one of items 1 to 18 on the surface of the support;

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

An element forming process for forming an element on the polyimide resin film,

A peeling step of peeling the polyimide resin film on which the device is formed from the support,

A method of manufacturing a display comprising:

[31]

A coating step of applying the resin composition according to any one of items 1 to 18 on the surface of the support;

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

An element forming process of forming an element on the polyimide resin film,

The manufacturing method of a laminated body containing a.

[32]

The manufacturing method of the laminated body of item 31 further comprising the process of peeling the said polyimide resin film in which the said element was formed from the said support body.

[33]

A method for manufacturing a flexible device, comprising producing a laminate by the method described in item 31 or 32.

[34]

A polyimide film which is a cured product of the resin composition according to any one of items 1 to 18.

According to the present invention, compared to the case of using the crude siloxane compound, the yellowness (YI value) is improved, and a polyimide precursor resin composition capable of reducing foreign substances generated in the polyimide production process can be provided. have. In addition, the above-mentioned description should not be regarded as disclosing all the embodiments of the present invention and all the advantages related to the present invention. Additional embodiments of the present invention and its advantages will become apparent by referring to the following description.

1 is a schematic diagram showing a structure of a top emission type flexible organic EL display, which is an upper structure of a polyimide substrate, as an example of the display of the present embodiment.

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

<< resin composition >>

<Polyimide precursor>

Structural unit of formula (1)

First embodiment

The resin composition of this embodiment contains the polyimide precursor which contains the structural unit represented by the following general formula (1) in 1st embodiment.

[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.}

It is preferable that the polyimide precursor having a structure represented by the general formula (1) is a copolymer of an acid anhydride having a P ₂ group and a diamine having a P ₁ group.

Acid anhydride

As the acid 2 anhydride containing the P ₂ group, pyromellitic acid 2 anhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid 2 anhydride, 2,2', 3,3'-biphenyltetracar Acidic anhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, 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 dianhydride, 2,2', 3,3 ' -Benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride, methylene-4,4'-diphthalic acid 2 anhydride, 1,1-ethylidene-4 , 4'-diphthalic anhydride, 2,2-propylidene-4,4'-diphthalic anhydride, 1,2-ethylene-4,4'-diphthalic anhydride 2, 1,3-trimethylene-4 , 4'-diphthalic anhydride, 1,4-tetramethylene-4,4'-diphthalic acid 2 anhydride, 1,5-pentamethylene 4,4'-diphthalic acid 2 anhydride, 4,4'-oxydiphthalic acid 2 Anhydride, p-phenylenebis (trimelli Yt acid anhydride), thio-4,4'-diphthalic acid anhydride, sulfonyl-4,4'-diphthalic anhydride, 1,3-bis (3,4-dicarboxyphenyl) benzene 2 anhydride, 1, 3-bis (3,4-dicarboxyphenoxy) benzene 2 anhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene 2 anhydride, 1,3-bis [2- (3,4-di Carboxyphenyl) -2-propyl] benzene dihydrate, 1,4-bis [2- (3,4-dicarboxyphenyl) -2-propyl] benzene dihydrate, bis [3- (3,4-dicarboxyphenoxy City) phenyl] methane 2 anhydride, bis [4- (3,4-dicarboxyphenoxy) phenyl] methane 2 anhydride, 2,2-bis [3- (3,4-dicarboxyphenoxy) phenyl] propane 2 Anhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane 2 anhydride, bis (3,4-dicarboxyphenoxy) dimethylsilane 2 anhydride, 1,3-bis (3, 4-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane 2 anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxyl Acid 2 anhydride, 1,2,5,6-naphthalenetetracarboxyl 2 anhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, and 1,2,7,8-phenanthrenetetracarboxyl Acid 2 anhydride and the like.

The acid 2 anhydride may be used alone or in combination of two or more. Among these, pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic dianhydride (BPDA) have mechanical properties of a polyimide film, low thickness direction retardation (Rth), and low yellowness (YI value). It is preferable from the viewpoint of optical properties and high glass transition temperature. The polyimide precursor having a structure represented by formula (1) is a copolymer of tetracarboxylic dianhydride and diamine, and the tetracarboxylic dianhydride contains pyromellitic dianhydride (PMDA). desirable.

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

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

The content of biphenyltetracarboxylic dianhydride (BPDA) in all the acid anhydrides is preferably 0 mol% or more, preferably 10 mol% or more, from the viewpoint of low Rth and YI values of the polyimide film, 20 mol% or more is preferable, 100 mol% or less is preferable, and 90 mol% or less is preferable.

The content ratio of pyromellitic dianhydride (PMDA): biphenyltetracarboxylic dianhydride (BPDA) in the acid anhydride is compatible with low Rth and YI values of polyimide films, high glass transition temperature, elongation, etc. From the viewpoint of making it, 20: 80-80: 20 is preferable and 30: 70-70: 30 is more preferable.

Diamine

As the diamine containing the P ₁ group in formula (1), diaminodiphenylsulfone (for example, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone), p- Phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 4,4 ' -Diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3 ' -Diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis (4-aminophenoxy ) Benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, 4,4- Bis (4-aminophenoxy) biphenyl, 4,4-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) Si) phenyl] ether, 1,4-bis (4-aminophen ) 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 And 1,4-bis (3-aminopropyldimethylsilyl) benzene.

As the diamine containing the P ₁ group in formula (1), diaminodiphenylsulfone, for example, 4,4'-diaminodiphenylsulfone, and / or 3,3'-diaminodiphenylsulfone It is preferred to include.

The content of diaminodiphenylsulfone in all diamines may be 50 mol% or more, or 70 mol% or more, or 90 mol% or more, or 95 mol% or more. The higher the amount of diaminodiphenylsulfone, the lower the YI value of the polyimide film, and a higher glass transition temperature is obtained, which is preferable. As diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone is particularly preferable from the viewpoint of reducing the YI value.

Diamine may be used individually by 1 type, or may be used in combination of 2 or more type. It is preferred to copolymerize diaminodiphenylsulfone with other diamines. Other diamines to be copolymerized with diaminodiphenylsulfone are preferably diamide biphenyls, more preferably diaminobis (trifluoromethyl) from the viewpoints of high heat resistance and low YI value of the polyimide film. Biphenyl (TFMB). The content of diaminobis (trifluoromethyl) biphenyl (TFMB) in all diamines is preferably 20 mol% or more, more preferably 30 mol% or more, from the viewpoint of the low YI value of the polyimide film. From the design point of view of allowing the diamine to contain other advantageous diamines such as diaminodiphenylsulfone, the content of TFMB is preferably 80 mol% or less, more preferably 70 mol% or less.

Structural unit of formula (2)

The polyimide precursor in the resin composition of this embodiment further contains the structural unit represented by the following general formula (2).

[Formula 34]

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

Based on the mass of the polyimide precursor, the lower limit of the ratio of the structural site represented by the general formula (2) is preferably 5% by mass or more from the viewpoint of reducing the residual stress of the polyimide film generated between the supports. , More preferably, it is 6% by mass or more, and still more preferably, 7% by mass or more. Based on the mass of the polyimide precursor, the upper limit of the proportion of the structural site represented by the general formula (2) is preferably 40% by mass or less, more preferably 30 from the viewpoint of transparency and heat resistance of the polyimide film. It is mass% or less, More preferably, it is 25 mass% or less.

In said general formula (2), q is an integer of 1-200, and the integer of 3-200 is preferable from the viewpoint of heat resistance of the polyimide obtained.

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

[Formula 35]

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

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

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

 As the compound represented by the general formula (6), specifically, sock-end amine-modified methylphenylsilicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400), X22-9409 (number average molecular weight 1340)), Soxic acid anhydride-modified methylphenylsilicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-168-P5-B (number average molecular weight 4200)), Sock-end epoxy-modified methylphenylsilicone oil (manufactured by Shin-Etsu Chemical Company: X22-2000 (number average molecular weight 1240)) , Amino-modified dimethylsilicone at the end of socks (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-161A (number average molecular weight 1600), X22-161B (number average molecular weight 3000), KF8021 (number average molecular weight 4400), manufactured by Torre Dow Corning: BY16-835U (male) Average molecular weight 900) Chisso Corporation make: Sailine plane FM3311 (number average molecular weight 1000)) etc. are mentioned. Among these, from the viewpoint of improving chemical resistance and improving Tg, sock-ended amine-modified methylphenylsilicone oil is preferred.

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

Dicarboxylic acid

As an acid component for forming the polyimide precursor in the present embodiment, in addition to the acid dihydride (e.g., the tetracarboxylic dianhydride exemplified above), dica in a range that does not impair its performance. You may use carboxylic acid. That is, the polyimide precursor of the present disclosure may be a polyamideimide precursor. The film obtained from such a polyimide precursor may have good performances such as mechanical elongation, glass transition temperature Tg, and YI value. Examples of the dicarboxylic acid to be used include dicarboxylic acids having an aromatic ring and alicyclic dicarboxylic acids. It is particularly preferable that it is at least one compound selected from the group consisting of an aromatic dicarboxylic acid having 8 to 36 carbon atoms and an alicyclic dicarboxylic acid having 6 to 34 carbon atoms. The number of carbons referred to herein includes the number of carbons contained in the carboxyl group. Of these, dicarboxylic acids having aromatic rings are preferred.

As a dicarboxylic acid having an aromatic ring, specifically, for example, isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid, 3,4'-biphenyldicarboxylic acid, 3,3 '-Biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4 , 4'-sulfonylbisbenzoic acid, 3,4'-sulfonylbisbenzoic acid, 3,3'-sulfonylbisbenzoic acid, 4,4'-oxybisbenzoic acid, 3,4'-oxybisbenzoic acid, 3,3 '-Oxybisbenzoic acid, 2,2-bis (4-carboxyphenyl) propane, 2,2-bis (3-carboxyphenyl) propane, 2,2'-dimethyl-4,4'-biphenyldicarboxylic acid , 3,3'-dimethyl-4,4'-biphenyldicarboxylic acid, 2,2'-dimethyl-3,3'-biphenyldicarboxylic acid, 9,9-bis (4- (4- Carboxyphenoxy) phenyl) fluorene, 9,9-bis (4- (3-carboxyphenoxy) phenyl) fluorene, 4,4'-bis (4-carboxyphenoxy) biphenyl, 4,4'- Bis (3-carboxyphenoxy) biphenyl, 3,4'-bis (4-carboxyphenoxy) biphenyl, 3,4'-bis (3-carboxyphenoxy) biphenyl, 3,3'-bis (4-carboxyphenoxy) biphenyl, 3,3'-bis (3 -Carboxyphenoxy) biphenyl, 4,4'-bis (4-carboxyphenoxy) -p-terphenyl, 4,4'-bis (4-carboxyphenoxy) -m-terphenyl, 3,4 ' -Bis (4-carboxyphenoxy) -p-terphenyl, 3,3'-bis (4-carboxyphenoxy) -p-terphenyl, 3,4'-bis (4-carboxyphenoxy) -m- Terphenyl, 3,3'-bis (4-carboxyphenoxy) -m-terphenyl, 4,4'-bis (3-carboxyphenoxy) -p-terphenyl, 4,4'-bis (3- Carboxyphenoxy) -m-terphenyl, 3,4'-bis (3-carboxyphenoxy) -p-terphenyl, 3,3'-bis (3-carboxyphenoxy) -p-terphenyl, 3, 4'-bis (3-carboxyphenoxy) -m-terphenyl, 3,3'-bis (3-carboxyphenoxy) -m-terphenyl, 1,1-cyclobutanedicarboxylic acid, 1,4 -Cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4,4'-benzophenone dicarboxylic acid, 1,3-phenylene diacetic acid, 1,4-phenylene diacetic acid, etc .; And bureau And the like can be mentioned 5-amino isophthalic acid derivative described in Publication No. 2005/068535 call. When these dicarboxylic acids are actually copolymerized with the polymer, they may be used in the form of acid chlorides derived from thionyl chloride or the like, and active esters.

2nd embodiment

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

[Formula 36]

{In the formula, R ₁ is, 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 Is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group having 1 to 10 carbon atoms, at least one is a monovalent aromatic group having 6 to 10 carbon atoms, R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, at least one is an organic group having an unsaturated aliphatic hydrocarbon group, 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 halide group, a hydroxyl group, an epoxy group, or a mercapto group, i and j are each independently an integer from 1 to 200, and k is an integer from 0 to 200 , 0.05 ≤ j / (i + j + k) ≤ 0.50.}

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

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

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

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

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

In General Formula (5), some or all of the hydrogen atoms of R ₁ to R ₇ may be substituted with substituents such as halogen atoms such as F, Cl, and Br, or unsubstituted.

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

The tetracarboxylic dianhydride in 2nd Embodiment may be the tetracarboxylic dianhydride illustrated with respect to said general formula (1). The tetracarboxylic dianhydride in the second embodiment is pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, It is preferable that it is at least one member selected from the group consisting of cyclohexanetetracarboxylic dianhydride and cyclobutanetetracarboxylic dianhydride.

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

Weight average molecular weight

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

Preferred embodiments of the polyimide precursor

The following (1)-(9) are mentioned as a polyimide precursor especially preferable in this embodiment.

(1) A polycondensate in which the acid anhydride component is pyromellitic acid anhydride (PMDA) and biphenyltetracarboxylic acid anhydride (BPDA), and the diamine component is diaminodiphenylsulfone (DAS) and silicon-containing diamine. More preferably, the weight average molecular weight is 80,000 to 100,000, and the solid content is 10 to 25 mass%.

(2) The acid anhydride component is pyromellitic acid anhydride (PMDA) and biphenyltetracarboxylic acid anhydride (BPDA), and the diamine component contains diaminobis (trifluoromethyl) biphenyl (TFMB) and silicon Polyamine, a polycondensate. More preferably, the weight average molecular weight is 65,000 to 90,000, and the solid content is 10 to 25 mass%.

(3) The acid anhydride component is pyromellitic acid anhydride (PMDA) and biphenyltetracarboxylic acid anhydride (BPDA), and the diamine component is diaminodiphenylsulfone (DAS), diaminobis (trifluoromethyl) ) Biphenyl (TFMB) and silicon-containing diamine polycondensate. More preferably, the weight average molecular weight is 95,000 to 120,000, and the solid content is 10 to 25 mass%.

4) A polycondensate wherein the acid anhydride component is pyromellitic acid anhydride (PMDA), and the diamine component is diaminodiphenylsulfone (DAS) and silicon-containing diamine. More preferably, the weight average molecular weight is 100,000 to 110,000, and the solid content is 10 to 25 mass%.

(5) A polycondensate wherein the acid 2 anhydride component is pyromellitic acid 2 anhydride (PMDA), and the diamine component is diaminobis (trifluoromethyl) biphenyl (TFMB) and silicon-containing diamine. More preferably, the weight average molecular weight is 100,000 to 110,000, and the solid content is 10 to 25 mass%.

(6) Polycondensation wherein the acid anhydride component is pyromellitic acid anhydride (PMDA), and the diamine component is diaminodiphenylsulfone (DAS), diaminobis (trifluoromethyl) biphenyl (TFMB) and silicon-containing diamine. Merging. More preferably, the weight average molecular weight is 110,000 to 120,000, and the solid content is 10 to 25 mass%.

(7) A polycondensate wherein the acid anhydride component is biphenyltetracarboxylic acid anhydride (BPDA), and the diamine component is diaminodiphenylsulfone (DAS) and silicon-containing diamine. More preferably, the weight average molecular weight is 70,000 to 80,000, and the solid content is 10 to 25 mass%.

(8) The acid anhydride component is biphenyltetracarboxylic dianhydride (BPDA), and the diamine component contains diaminodiphenylsulfone (DAS), diaminobis (trifluoromethyl) biphenyl (TFMB) and silicon. Polyamine, a polycondensate. More preferably, the weight average molecular weight is 90,000 to 100,000, and the solid content is 10 to 25 mass%.

(9) A polycondensation product in which the acid anhydride component is biphenyltetracarboxylic dianhydride (BPDA), and the diamine component is diaminobis (trifluoromethyl) biphenyl (TFMB) and silicon-containing diamine. More preferably, the weight average molecular weight is 70,000 to 80,000, and the solid content is 10 to 25 mass%.

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

<Low molecular cyclic siloxane>

 Compound of general formula (3)

The resin composition of the present embodiment includes at least one low molecular cyclic siloxane in which m is an integer of 3 or more among the low molecular cyclic siloxanes represented by the following general formula (3-1) or (3-2) (simply `` ( 3) ”means“ (3-1) or (3-2) ”). The composition of this embodiment may contain the compound whose m is 1 or 2 in general formula (3-1) or (3-2), or may not contain it. The resin composition of the present embodiment may contain only one of the general formulas (3-1) or (3-2), or may contain both of them. The compound represented by the general formula (3-1) or (3-2) is preferably a compound represented by the general formula (3-1). That is, the resin composition of the present embodiment preferably contains at least a compound represented by the general formula (3-1).

[Formula 37]

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

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

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

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

When based on the mass of the solid content in the resin composition, the total amount of the compound in which m is an integer of 3 or more in the general formula (3) is preferably more than 0 ppm and less than 7,500 ppm, more preferably more than 0 ppm and 2,000 ppm Hereinafter, more preferably, it is more than 0 ppm and 1,100 ppm or less. When based on the mass of the solid content in the resin composition, the total amount of the compound of m 3 in general formula (3) is preferably more than 0 ppm and 4,500 ppm or less, more preferably more than 0 ppm and 1,000 ppm or less, More preferably, it is more than 0 ppm and 500 ppm or less. When based on the mass of the solid content in the resin composition, the total amount of the compound in which m is 4 in general formula (3) is preferably more than 0 ppm and 2,500 ppm or less, more preferably more than 0 ppm and 700 ppm or less, More preferably, it is more than 0 ppm and 400 ppm or less. When the total amount of the compound represented by the general formula (3) is within the above range, it is preferable because the YI value of the polyimide resin film obtained from the resin composition is further lowered.

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

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

Compound of general formula (4)

The resin composition of this embodiment may further contain the compound represented by the following general formula (4) in addition to the compound represented by the above general formula (3).

[Formula 38]

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

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

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

The total amount of the compound in which m is an integer of 3 or more in general formula (3) and the compound in which n is an integer of 3 or more in general formula (4) is preferably greater than 0 ppm and less than 1,300 ppm, based on the mass of the resin composition, More preferably, it is more than 0 ppm and 400 ppm or less, and more preferably, it is more than 0 ppm and may be 230 ppm or less. The total amount of the compound in which m is an integer of 3 or more in general formula (3) and the compound in which n is an integer of 3 or more in general formula (4) is within the above range, and the total amount of the compound in which m is an integer of 3 or more in general formula (3) , Based on the mass of the resin composition, preferably more than 0 ppm and 1,100 ppm or less, more preferably more than 0 ppm and 800 ppm or less, more preferably more than 0 ppm and 600 ppm or less, particularly preferably 0 It is preferably more than ppm and 300 ppm or less, particularly preferably more than 0 ppm and 180 ppm or less.

 The total amount of the compound in which m is an integer of 3 or more in general formula (3), and the compound in which n is an integer of 3 or more in general formula (4) is within the above range, and m of 3 to 5 in general formula (3) Based on the mass of the resin composition, the total amount is preferably more than 0 ppm and 1,100 ppm or less, more preferably more than 0 ppm and 800 ppm or less, more preferably more than 0 ppm and 600 ppm or less, particularly preferably Is more than 0 ppm and 300 ppm or less, particularly preferably more than 0 ppm and preferably 180 ppm or less. When the total amount of the compound represented by the general formula (3) and the compound represented by the general formula (4) is within the above range, it is preferable in that the total number of foreign substances adhering in the production process of the polyimide resin film is reduced.

When based on the mass of the solid content in the resin composition, the total amount of the compound in which n is an integer of 3 or more in the general formula (4) is preferably more than 0 ppm and 1,100 ppm or less, more preferably more than 0 ppm and 700 ppm or less , More preferably more than 0 ppm and less than 400 ppm. When based on the mass of the solid content in the resin composition, the total amount of the compound in which m is an integer of 3 or more in general formula (3) and the compound in which n is an integer of 3 or more in general formula (4) is preferably more than 0 ppm and 8,600 ppm or less, more preferably more than 0 ppm and 2,700 ppm or less, still more preferably more than 0 ppm and 1,500 ppm or less. When the total amount of the compound represented by the general formula (3) and the compound represented by the general formula (4) is within the above range, it is preferable in that the total number of foreign substances adhering in the production process of the polyimide resin film is reduced.

When based on the mass of the silicon-containing compound of the general formulas (3), (4) and (5), the total amount of the compound in which n is an integer of 3 or more in the general formula (4) is preferably more than 0 ppm and 200 ppm Hereinafter, it is more preferably more than 0 ppm and 100 ppm or less, and more preferably more than 0 ppm and 50 ppm or less. When based on the total mass of the silicon-containing compounds of the general formulas (3), (4) and (5), m in the general formula (3) is an integer of 3 or more, and n in the general formula (4) is 3 or more The total amount of the compound which is an integer is preferably more than 0 ppm and 4,700 ppm or less, more preferably more than 0 ppm and 1,100 ppm or less, still more preferably more than 0 ppm and 6,300 ppm or less. When the total amount of the compound represented by the general formula (3) and the compound represented by the general formula (4) is within the above range, it is preferable in that the total number of foreign substances adhering in the production process of the polyimide resin film is reduced.

Foreign substance count

Based on the mass of each of the resin composition, the solid content, and the silicon-containing compound, m in general formula (3) is cyclic siloxane having an integer of 3 or more (preferably m is 3 to 5) and n in general formula (4) The smaller the total amount of the cyclic siloxane, which is an integer of 3 or more (preferably n is 3 to 8), is preferable because a small amount of foreign substances adhered in the production process of the polyimide resin film. Although this mechanism is unclear, the inventors estimate as follows. That is, in the production of a polyimide resin film, typically, a resin composition comprising a polyimide precursor composition is applied to a support such as a glass substrate and heated in a single oven, for example, at 100 ° C. for 30 minutes, for a solvent. Is removed and imidized by heating in a same oven continuously at a higher temperature, for example, 350 ° C. for 1 hour to form a polyimide resin film. Here, the cyclic siloxane of the general formula (4) tends to volatilize more than the cyclic siloxane of the general formula (3). Therefore, when removing a solvent, it is thought that the cyclic siloxane of general formula (4) volatilizes, and the cyclic siloxane of general formula (3) volatilizes at the time of imidation, and adheres in an oven. In particular, when the number of samples to be input into the oven is large, it is considered that the cyclic siloxanes of the general formulas (3) and (4) are more deposited in the oven, and when they fall, they become foreign matters attached to the polyimide resin film. Therefore, it is considered that the smaller the total amount of the cyclic siloxane of the general formula (3) and the cyclic siloxane of the general formula (4), the smaller the amount of foreign matter adhering in the production process of the polyimide resin film.

<menstruum>

The resin composition typically includes a solvent. As the solvent, it is preferable that the solubility of the polyimide precursor is good, and that the solution viscosity of the resin composition can be appropriately controlled, and the reaction solvent of the polyimide precursor can be used as the solvent of the composition. Especially, N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), the compound represented by the said general formula (4), etc. are preferable. Specific examples of the solvent composition include N-methyl-2-pyrrolidone (NMP) alone or a mixed solvent of N-methyl-2-pyrrolidone (NMP) and γ-butyrolactone (GBL). Can be. 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 an additional component in addition to the polyimide precursor, the low-molecular cyclic siloxane, and the solvent. As an additional component, surfactant, an alkoxysilane compound, etc. are mentioned, for example.

Surfactants

By adding surfactant to the resin composition of this embodiment, the coating property of a resin composition can be improved. Specifically, the occurrence of streaks in the coated film can be prevented.

Examples of such surfactants include silicone-based surfactants, fluorine-based surfactants, and nonionic surfactants other than these. As a silicone surfactant, For example, organosiloxane polymers KF-640, 642, 643, KP341, X-70-092, X-70-093 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.); SH-28PA, SH- 190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (trade name, manufactured by Toray Dow Corning, Inc.); SILWET L-77, L-7001, FZ-2105, FZ- 2120, FZ-2154, FZ-2164, FZ-2166, L-7604 (trade name, manufactured by Nippon Unicar); DBE-814, DBE-224, DBE-621, CMS-626, CMS-222, KF-352A, KF-354L, KF-355A, KF-6020, DBE-821, DBE-712 (Gelest), BYK-307, BYK-310, BYK-378, BYK-333 (trade name, manufactured by BIC Chemie Japan); (Trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and the like. Examples of the fluorine-based surfactant include Megapak F171, F173, R-08 (manufactured by Dainippon Ink Chemical Industry Co., Ltd., trade name); Fluorad FC4430, FC4432 (Sumitomo 3M Co., Ltd. trade name) and the like. Nonionic surfactants other than these include, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like.

Among these surfactants, from the viewpoint of coatability (stripes suppression) of the resin composition, silicone-based surfactants and fluorine-based surfactants are preferred, and from the viewpoint of reducing the effect on the YI value and total light transmittance by oxygen concentration during the curing process. , Silicone-based surfactants are preferred. When a surfactant is used, the blending amount is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, relative to 100 parts by mass of the polyimide precursor in the resin composition.

Alkoxysilane 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, The alkoxysilane compound may contain 0.01 to 20 parts by mass. When the content of the alkoxysilane compound to 100 parts by mass of the polyimide precursor is 0.01 parts by mass or more, good adhesion between the support and the polyimide film can be obtained. Moreover, it is preferable from a viewpoint of 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 0.02 to 15 parts by mass, more preferably 0.05 to 10 parts by mass, and even more preferably 0.1 to 8 parts by mass relative to 100 parts by mass of the polyimide precursor. By using the alkoxysilane compound, in addition to the above-mentioned improvement in adhesion, the coating property of the resin composition is improved (stripping non-uniformity), and the influence of the polyimide film on the YI value of the polyimide film by curing can be reduced. have.

Examples of the alkoxysilane compound include 3-ureidpropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ -Aminopropyltrimethoxysilane, γ-aminopropyltripropoxysilane, γ-aminopropyltributoxysilane, γ-aminoethyltriethoxysilane, γ-aminoethyltripropoxysilane, γ-aminoethyltribu Methoxysilane, γ-aminobutyltriethoxysilane, γ-aminobutyltrimethoxysilane, γ-aminobutyltripropoxysilane, γ-aminobutyltributoxysilane, phenylsilanetriol, trimethoxyphenylsilane, Trimethoxy (p-tolyl) silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and alkoxysilane represented by each of the following structures And compounds. The alkoxysilane compound may be used alone or in combination of two or more.

[Formula 39]

<< method of manufacturing resin composition >>

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

<Refining of silicon-containing compounds>

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

As a method of purifying a silicon-containing compound, for example, stripping is performed while blowing an inert gas, for example, nitrogen gas, into the silicon-containing compound in an arbitrary container. The temperature of stripping is preferably 200 ° C or more and 300 ° C or less, more preferably 220 ° C or more and 300 ° C or less, and even more preferably 240 ° C or more and 300 ° C or less. The vapor pressure of stripping is preferably lower, and is preferably 1000 MPa or less, more preferably 300 MPa or less, more preferably 200 MPa or less, and even more preferably 133.32 MPa (1 mmHg) or less. The time of stripping is preferably 4 hours or more and 12 hours or less, more preferably 6 hours or more and 10 hours or less. By adjusting under the conditions described above, the compound of the general formula (3) can be efficiently removed, and the total amount of the general formulas (3) and (4) can be controlled in a preferred range.

<Synthesis of polyimide precursor>

The polyimide precursor of the present embodiment can be synthesized by polycondensation reaction of a polycondensation component comprising an acid anhydride, a diamine, and a silicon-containing compound. As for the silicon-containing compound, it is preferable to use the above purified one. In a preferable aspect, a polycondensation component consists of an acid anhydride, a diamine, and a silicon-containing compound. It is preferable to perform a polycondensation reaction in a suitable solvent. Specifically, for example, after dissolving a predetermined amount of a diamine component and a silicon-containing compound in a solvent, a predetermined amount of an acid anhydride is added to the obtained diamine solution, followed by stirring.

The molar ratio of the acid 2 anhydride to the diamine when synthesizing the polyimide precursor is from the viewpoint of high molecular weight of the polyimide precursor resin and slit coating properties of the resin composition, the acid 2 anhydride: diamine = 100: 90-100: 110 ( The range of diamine 0.90 to 1.10 mol parts with respect to 1 mol part of the acid anhydride is preferred, and the range of 100: 95 to 100: 105 (0.95 to 1.05 mol parts of the diamine with respect to 1 mol part of the acid anhydride) is more preferable.

The molecular weight of the polyimide precursor can be controlled by adjusting the type of the acid-anhydride, diamine and silicon-containing compound, adjusting the molar ratio of the acid-anhydride and diamine, adding a terminal encapsulant, and adjusting the reaction conditions. Do. The more the molar ratio of the acid anhydride component and the diamine component is closer to 1: 1, and the less the amount of the terminal sealant is used, the higher the polyimide precursor can be.

It is recommended to use a high-purity product as the acid anhydride component and the diamine component. The purity is, respectively, preferably 98 mass% or more, more preferably 99 mass% or more, still more preferably 99.5 mass% or more. High purity can also be achieved by reducing the water content in the acid anhydride component and the diamine component. When a plurality of types of acid anhydride components and / or a plurality of types of diamine components are used, it is preferable to have the above-mentioned purity as a whole of the acid 2 anhydride component, and as a whole of the diamine component. And it is more preferable that a diamine component has the said purity, respectively.

The solvent of the reaction is not particularly limited as long as it is a solvent in which an acid anhydride component, a diamine component, and a generated polyimide precursor can be dissolved, and a high molecular weight polymer is obtained. Examples of such solvents include aprotic solvents, phenolic solvents, ether and glycol solvents, and the like. As aprotic solvents, for example, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N-methylcapro Lactam, 1,3-dimethylimidazolidinone, tetramethylurea, and amide solvents of the following general formula (6):

[Formula 40]

{In the formula, R ₁₂ = Ecamide M100 represented by a methyl group (trade name: manufactured by Idemitsu Heungsan), and Ecamide B100 represented by R ₁₂ = n-butyl group (brand name: manufactured by Idemitsu Heungsan)}; γ-butyrolactone , lactone-based solvents such as γ-valerolactone; phosphorus-based amide solvents such as hexamethylphosphoricamide and hexamethylphosphine triamide; sulfur-based solvents such as dimethyl sulfone, dimethyl sulfoxide and sulfolane; cyclohexanone , Ketone solvents such as methylcyclohexanone; tertiary amine solvents such as picoline and pyridine; ester solvents such as acetic acid (2-methoxy-1-methylethyl) and the like.

As a phenolic solvent, for example, phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2, And 6-xyllenol, 3,4-xyllenol, and 3,5-xylenol.

Examples of the ether and glycol solvents include 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane and bis [2- ( 2-methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,4-dioxane, and the like.

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

The boiling point at normal pressure of the solvent used for the synthesis of the polyimide precursor is preferably 60 to 300 ° C, more preferably 140 to 280 ° C, and even more preferably 170 to 270 ° C. When the boiling point of the solvent is lower than 300 ° C, the drying process becomes short. When the boiling point of the solvent is 60 ° C or higher, during the drying step, roughness on the surface of the resin film, incorporation of bubbles into the resin film, and the like are less likely to occur, and a more uniform film can be obtained. In particular, it is preferable from the standpoint of solubility and reduction of edges or more during coating to use a solvent having a boiling point of 170 to 270 ° C, and / or a vapor pressure of 250 MPa or less at 20 ° C. More specifically, one or more selected from the group consisting of N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), and compounds represented by the general formula (6) is preferable.

The moisture content in the solvent is preferably, for example, 3,000 ppm by mass or less in order to favorably advance the polycondensation reaction. It is preferable that the content of the molecule | numerator of molecular weight less than 1,000 in resin composition in this embodiment is less than 5 mass%. It is thought that the presence of a molecule having a molecular weight of less than 1,000 in the resin composition is due to the fact that the amount of water in the solvent or raw material (acid anhydride, diamine) used in synthesis is involved. That is, it is considered that the acid anhydride group of a part of the acid anhydride monomer is hydrolyzed by moisture to become a carboxyl group and remains in a low molecular state without high molecular weight. Therefore, the smaller the water content of the solvent used in the polycondensation reaction, the more preferable. The water content of the solvent is preferably 3,000 ppm by mass or less, and more preferably 1,000 ppm by mass or less. Similarly, the amount of water contained in the raw material is also preferably 3,000 ppm by mass or less, and more preferably 1,000 ppm by mass or less.

The water content of the solvent is the grade of the solvent used (dehydration grade, general purpose grade, etc.), solvent container (bottle, 18 liter can, canister can, etc.), storage condition of the solvent (with or without rare gas encapsulation), from opening to use. It is considered that time (whether used immediately after opening, whether it is used after a lapse of time after opening, etc.), etc. It is considered that the replacement of the rare gas in the reactor before synthesis and the presence or absence of a rare gas distribution during synthesis are also involved. Therefore, when synthesizing the polyimide precursor, it is recommended to use a high-purity product as a raw material, use a solvent with a small amount of moisture, 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 having a high degree of polymerization, the reaction temperature for synthesizing the polyimide precursor is preferably 0 ° C to 120 ° C, 40 ° C to 100 ° C, or 60 to 100 ° C, and the polymerization time is 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 is obtained, and by setting it to 100 hours or less, a polyimide precursor having a high polymerization degree can be obtained.

The resin composition of this embodiment may contain other further polyimide precursors other than the polyimide precursor in this embodiment. However, the mass ratio of the additional polyimide precursor is preferably 30% by mass or less relative to the total amount of the 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 preferably 10% by mass or less.

A part of the polyimide precursor in the present embodiment may be imidized (partial imidization). By partially imidizing the polyimide precursor, viscosity stability at the time of preserving the resin composition can be improved. The imidation ratio 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 storage stability of the solution. , More preferably 70% or less, still more preferably 50% or less. This partial imidization is obtained by heating the polyimide precursor and dehydrating the ring. The heating is preferably carried out at a temperature of 120 to 200 ° C, more preferably 150 to 180 ° C, preferably 15 minutes to 20 hours, more preferably 30 minutes to 10 hours.

What esterified a part or all of carboxylic acid by heating by adding N, N-dimethylformamide dimethylacetal or N, N-dimethylformamide diethyl acetal to the polyamic acid obtained by the above-mentioned reaction, You may use it as a polyimide precursor of this embodiment. By esterification, the viscosity stability during storage can be improved. After these ester-modified polyamic acids are sequentially reacted with the acid anhydride component described above with an equivalent of a monohydric alcohol equivalent to an acid anhydride group and a dehydrating condensing agent such as thionyl chloride or dicyclohexylcarbodiimide, It can also be obtained by a condensation reaction with a diamine component.

<Adjustment of resin composition>

When the solvent used when the polyimide precursor is synthesized and the solvent contained in the resin composition are the same, the synthesized polyimide precursor solution can be used as it is as the resin composition. If necessary, the resin composition may be adjusted by adding one or more additional solvents and additional components to the polyimide precursor in a temperature range of room temperature (25 ° C) to 80 ° C and stirring and mixing. This stirring and mixing can be carried out using an appropriate device such as a three-one motor (manufactured by Shinto Chemical Co., Ltd.) equipped with a stirring blade, a rotating revolution mixer, or the like. You may heat a resin composition to 40 degreeC-100 degreeC as needed.

On the other hand, when the solvent used when the polyimide precursor is synthesized and the solvent contained in the resin composition are different, the solvent in the synthesized polyimide precursor solution is removed by an appropriate method such as reprecipitation and solvent distillation removal. The polyimide precursor may be isolated. Subsequently, in the temperature range of room temperature (25 ° C) to 80 ° C, a resin composition may be prepared by adding the desired solvent and, if necessary, additional components to the isolated polyimide precursor and stirring and mixing.

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

From the viewpoint of slit coat performance, the solution viscosity of the resin composition is preferably 500 to 100,000 mPa · s, more preferably 1,000 to 50,000 mPa · s, and even more preferably 3,000 to 20,000 mPa · s. Specifically, it is preferably 500 mPa · s or more, more preferably 1,000 mPa · s or more, and still more preferably 3,000 mPa · s or more, because the liquid does not leak easily from the slit nozzle. From the point that the slit nozzle is not clogged, it is preferably 100,000 mPa · s or less, more preferably 50,000 mPa · s or less, and even more preferably 20,000 mPa · s or less.

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

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

<< polyimide film and its manufacturing method >>

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 a coating process of apply | coating the resin composition of this embodiment on the surface of a support body; The film formation process of heating the said resin composition to form a polyimide resin film; And a peeling step of peeling the mid resin film from the support.

<Application process>

In the application step, the resin composition of the present embodiment is applied on the surface of the support. The support is not particularly limited as long as it has heat resistance to the heating temperature in the subsequent film forming step (heating step) and has good peelability in the peeling step. As the support, for example, a glass substrate, for example, an alkali-free glass substrate; a silicon wafer; PET (polyethylene terephthalate), OPP (stretched polypropylene), polyethylene glycol terephthalate, polyethylene glycol naphthalate, polycarbonate, poly Resin substrates such as mid, polyamideimide, polyetherimide, polyether ether ketone, polyether sulfone, polyphenylene sulfone, and polyphenylene sulfide; and metal substrates such as stainless, alumina, copper, and nickel.

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

As a coating method, generally, a coating method, 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, a spin coat, a spray coat, a dip coat, etc .; And printing techniques typified by screen printing and gravure printing. The resin composition of the present embodiment is preferably coated with a slit coat. The coating thickness should be appropriately adjusted depending on the desired thickness of the resin film and the content of the polyimide precursor in the resin composition, but is preferably about 1 to 1,000 μm. The temperature in the coating step may be room temperature, or the resin composition may be heated to, for example, 40 to 80 ° C in order to lower the viscosity and improve workability.

<Arbitrary drying process>

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

<Film formation process>

Subsequently, a film forming process (heating process) is performed. The heating step is a step of performing an imidation reaction of the polyimide precursor in the coating film while removing the organic solvent contained in the coating film to obtain a polyimide resin film. This heating process can be performed, for example, using an apparatus such as an inert gas oven, a hot plate, a box-type dryer, or a conveyor-type dryer. 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 it is preferably performed in an inert gas atmosphere from the viewpoint of safety, good transparency of the resulting polyimide film, low thickness direction retardation (Rth), and low YI value. As an inert gas, nitrogen, argon, etc. are mentioned, for example. The heating temperature may be appropriately set depending on the type of the polyimide precursor and the type of the solvent in the resin composition, but is preferably 250 ° C to 550 ° C, more preferably 300 to 450 ° C. If it is 250 ° C or higher, imidization proceeds satisfactorily, and if it is 550 ° C or lower, problems such as deterioration of transparency and deterioration of heat resistance of the resulting polyimide film can be avoided. The heating time is preferably about 0.1 to 10 hours.

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

<Peeling process>

In the peeling step, the polyimide resin film on the support is peeled off after cooling to room temperature (25 ° C) to about 50 ° C, for example. As this peeling process, the following aspect (1)-(4) is mentioned, for example.

(1) A polyimide resin film / support was prepared by the method described above, and then a laser was irradiated from the support side of the structure to ablate the interface between the support and the polyimide resin film, thereby producing polyimide resin. How to peel. As a kind of laser, a solid (YAG) laser, a gas (UV excimer) laser, etc. are mentioned. It is preferable to use a spectrum having a wavelength of 308 nm or the like (see Japanese Patent Publication No. 2007-512568, Japanese Patent Publication No. 2012-511173, etc.).

(2) A method of forming a release layer on the support before coating the resin composition on the support, and then obtaining a construct comprising a polyimide resin film / peeling layer / support to peel the polyimide resin film. Examples of the release layer include parylene (registered trademark, manufactured by Nippon Parylene Co., Ltd.) and tungsten oxide; a release agent such as a plant oil-based, silicone-based, fluorine-based or alkyd-based material may be used (Japanese Patent Application Publication No. 2010-067957 No., Japanese Patent Publication No. 2013-179306, etc.).

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

(3) A method of obtaining a polyimide resin film by etching a metal with an etchant after obtaining a construct comprising a polyimide resin film / support using a etchable metal substrate as a support. As a metal, copper (for example, Mitsui Metal Mining Co., Ltd. electrolytic copper foil "DFF"), aluminum, etc. can be used, for example. As the etchant, ferric chloride or the like can be used for copper, and dilute hydrochloric acid or the like can be used for aluminum.

(4) After obtaining a construct comprising a polyimide resin film / support by the above method, an adhesive film is attached to the surface of the polyimide resin film to separate the adhesive film / polyimide resin film from the support, and thereafter A method of separating a polyimide resin film from an adhesive film.

Among these peeling methods, the method (1) or (2) is preferable from the viewpoints of the difference in refractive index, YI value and elongation of the front and back of the resulting polyimide resin film. From the viewpoint of the difference in refractive index between the front and back of the resulting polyimide resin film, it is more preferable to perform the irradiation step of irradiating the laser from the support side before 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 becomes large and elongation tends to be small. This is considered to be the influence of copper ions.

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

<Yellowness (YI value)>

The YI value at a film thickness of 10 μm of the polyimide film obtained from the resin composition of the present embodiment is preferably 20 or less, more preferably 18 or less, and even more preferably 16 from the viewpoint of obtaining good optical properties. Below, particularly preferably 14 or less, particularly preferably 13 or less, particularly preferably 10 or less, particularly preferably 7 or less. Although the YI value differs depending on the monomer skeleton of the polyimide precursor, if the same monomer skeleton, the larger the weight average molecular weight of the polyimide precursor, the smaller the YI value tends to be.

The YI value is influenced by, for example, the amine value of the silicon-containing compound to be used, and if the amine value is high, the YI value is large, and if the amine value is small, the YI value tends to be small. However, the polyimide precursor using the purified silicon-containing compound, that is, the total amount of the compound represented by the general formula (3) is within the above range, compared to the polyimide precursor using the unpurified silicon-containing compound having the same amine value. The polyimide resin film tends to have a low YI value. Although this mechanism is still not clear, the inventors estimate as follows. That is, in the conventional purification method, a non-cyclic low molecular weight diamine used for the production of the polyimide precursor remains, decomposes upon curing of the polyimide, generates radicals, and increases (degrades) the YI value. Can be By reducing the amount of the cyclic siloxane represented by the general formula (3), not only the cyclic siloxane represented by the general formula (3) is removed during purification, but among the diamine components that increase the amine value, a relatively low volatility molecular weight It is thought that the diamine of is also removed. Therefore, it is estimated that the YI value of the polyimide resin film is further improved in the polyimide precursor in which the total amount of the compound represented by the general formula (3) is reduced according to the present embodiment. In the conventional purification method, it is difficult to reduce a diamine having a low molecular weight other than a cyclic form, so it is considered that the degree of improvement of the YI value of the polyimide resin film is smaller than that of the present embodiment, even if purification is performed.

In the present embodiment, the difference between the YI values of the polyimide precursor using the purified silicon-containing compound and the polyimide precursor using the unpurified silicon-containing compound is obtained from the following formula.

(Difference of YI value) = (YI value of the polyimide resin film obtained by curing the polyimide precursor obtained using the unpurified silicon compound)-(Polyimide obtained by curing the polyimide precursor obtained using the purified silicon compound) Mid resin film YI value)

The larger the difference in YI value is, the more preferable it is because YI is improved. In the present embodiment, the difference in YI value is preferably 1.5 or more, more preferably 2 or more, and even more preferably 2.5 or more. For the method of measuring the YI value, please refer to the Example column.

《Use of polyimide film》

The polyimide film obtained from the resin composition of the present embodiment is, for example, a semiconductor insulating film, a thin film transistor liquid crystal display (TFT-LCD) insulating film, an electrode protective film, and also a liquid crystal display, an organic electroluminescence display, and 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 a thin film transistor (TFT) substrate, a color filter substrate, a touch panel substrate, a transparent conductive film (ITO, Indium Thin Oxide) substrate in the production of a flexible device. It can be used suitably. As a flexible device to which the polyimide film in the present embodiment can be applied, for example, TFT devices for flexible displays, flexible solar cells, flexible touch panels, flexible lighting, flexible batteries, flexible printed boards, flexible color filters, smart And surface cover lenses for phones.

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, in the case of manufacturing a TFT device using amorphous silicon, a process temperature of 250 ° C to 350 ° C is generally required, and the polyimide film of this embodiment needs to be able to withstand the temperature. It is necessary to appropriately select a polymer structure having a glass transition temperature equal to or higher than the process temperature and a thermal decomposition initiation temperature.

In the case of manufacturing a TFT device using a metal oxide semiconductor (such as IGZO), a process temperature of 320 ° C to 400 ° C is generally required, and the polyimide film of this embodiment needs to be able to withstand that temperature. It is necessary to appropriately select a polymer structure having a glass transition temperature or a thermal decomposition initiation temperature equal to or higher than the TFT manufacturing process maximum temperature.

In the case of 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, so TFT It is necessary to appropriately select and have a glass transition temperature or a thermal decomposition initiation temperature equal to or higher than the manufacturing process maximum temperature.

On the other hand, by these thermal histories, the optical properties (especially light transmittance, retardation properties, and YI value) of the polyimide film tend to deteriorate to the extent that they are exposed to high temperature processes. However, the polyimide obtained from the polyimide precursor of the present embodiment has good optical properties even through a 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.

<Method of manufacturing a display>

The manufacturing method of the display of this embodiment comprises: a coating step of applying the resin composition of the present embodiment on the surface of a support; a film forming step of heating the resin composition to form a polyimide resin film; and the polyimide resin. And an element forming step of forming an element on the 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 diagram showing a structure above the polyimide substrate of a top emission type flexible organic EL display as an example of the display of the present embodiment. The organic EL structure 25 in Fig. 1 will be described. For example, the organic EL element 250a that emits red light, the organic EL element 250b that emits green light, and the organic EL element 250c that emits blue light are arranged in a matrix as one unit. And the light-emitting region of each organic EL element is defined by the partition (bank) 251. Each organic EL element is composed of a lower electrode (anode) 252, a hole transport layer 253, a light emitting layer 254, and an upper electrode (cathode) 255. On the lower layer 2a showing a CVD multilayer film (multi-barrier layer) made of silicon nitride (SiN) or silicon oxide (SiO), a TFT 256 for driving an organic EL element (low temperature polysilicon (LTPS) or metal oxide semiconductor) (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 portion 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 the organic EL substrate shown in FIG. 1 above, a process of manufacturing a sealing substrate, and both substrates. It includes an assembly process to be combined, and a peeling process to peel the organic EL display produced on the polyimide film from the glass substrate support. A well-known manufacturing process can be applied to the organic EL substrate manufacturing process, the sealing substrate manufacturing process, and the assembly process. Below, although an example is given, it is not limited to this. The peeling step is the same as the peeling step of the polyimide film described above.

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

Next, after forming a partition wall (bank) 251 with a photosensitive polyimide or the like, a hole transport layer 253 and a light emitting layer 254 are formed in each space partitioned by the partition wall. An upper electrode (cathode) 255 is formed to cover the light emitting layer 254 and the partition wall (bank) 251. Thereafter, 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), an organic EL material emitting green light (Fig. In one, the organic EL element 250b emitting green light and the organic EL material emitting blue light (corresponding to the organic EL element 250c emitting blue light in Fig. 1) are known. By vapor deposition, an organic EL substrate is produced. Top-emission flexible organic by sealing the organic EL substrate with a sealing film or the like (sealing substrate 2b in Fig. 1) and peeling the device above the polyimide substrate from a glass substrate support by a known peeling method such as laser peeling. An EL display can be produced. When the polyimide of this embodiment is used, a see-through flexible organic EL display can be produced. A bottom emission type flexible organic EL display may be produced by a known method.

Manufacturing example of flexible liquid crystal display

A flexible liquid crystal display can be produced using the polyimide film of this embodiment. As a specific manufacturing method, a polyimide film is prepared on a glass substrate support by the above method, and it is made of, for example, amorphous silicon, a metal oxide semiconductor (IGZO, etc.), and low temperature polysilicon using the above method. TFT substrates are manufactured. Separately, according to the coating process and film forming process of the present embodiment, a polyimide film is prepared on a glass substrate support, and a color filter glass substrate provided with a polyimide film is prepared using a color resist or the like according to a known method ( CF substrate). On one of the TFT substrate and the CF substrate, by screen printing, a seal material made of a thermosetting epoxy resin or the like is applied in a frame-like pattern lacking a portion of the liquid crystal injection port, and a diameter corresponding to the thickness of the liquid crystal layer on the other substrate. And a spherical spacer made of plastic or silica.

Subsequently, the TFT substrate and the CF substrate are bonded, and the seal 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 seal material by a pressure-sensitive method, applying a thermosetting resin to the liquid crystal injection port, and sealing the liquid crystal material by heating. Finally, a flexible liquid crystal display can be produced 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.

<Method for manufacturing a laminate>

The manufacturing method of the layered product of this embodiment comprises: a coating step of applying the resin composition of the present embodiment on the surface of a support; a film forming step of heating the resin composition to form a polyimide resin film; and the polyimide And an element forming process of forming elements on the resin film.

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

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.

《Measurement and evaluation method》

<Solid content>

The total mass of the monomer used in the polyimide precursor can be used as the mass of the solids contained in the resin composition. Alternatively, the mass of the solid content can be obtained by obtaining the mass of the solvent by performing gas chromatography (hereinafter also referred to as GC) analysis of the resin composition, and subtracting the mass of the solvent from the mass of the resin composition.

The following conditions are mentioned as GC conditions.

Apparatus: Gas chromatograph (manufactured by Agilent, gas chromatograph 6890N type)

Inlet temperature ： 280 ℃

Injection volume: 1 μl

Oven temperature: After holding at 50 ° C for 1 minute, the temperature is raised to 350 ° C at a heating rate of 20 ° C / min, and held at 350 ° C for 5 minutes.

Carrier gas: He, 1.0 ml / min

Column: manufactured by SGE, BPX5 (0.25 mmφ × 30 m, film thickness 0.25 μm)

Split ratio: 50: 1

Detector: Hydrogen salt ionization type detector

Detector temperature: 355 ℃

<Weight average molecular weight>

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

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

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

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: Ultraviolet visible absorbometer, manufactured by JASCO)

<Analysis of low molecular cyclic siloxane concentration>

The analysis of the low molecular cyclic siloxane concentrations of the general formulas (3) and (4) contained in the resin composition containing the polyimide precursor and the silicon-containing compounds (general formulas (3) and (4)) is as follows. As shown, quantification was performed by GC (gas chromatography analysis) (see below, analysis of low molecular cyclic siloxane concentrations (based on silicon-containing compounds)).

<Analysis of low-molecular cyclic siloxane concentration (based on composition and solid content)>

(1) Overview

A calibration curve was prepared to quantify the amount of cyclic siloxane. The calibration curve was prepared in accordance with the method described below, using a standard product (produced by Tokyo Chemical Industry Co., Ltd.) of n = 4 cyclic siloxane (hereinafter also referred to as D4 sieve) of the general formula (4).

The amount of the low-molecular cyclic siloxane contained in the resin composition was measured by heating the resin composition at 150 ° C and 200 ° C for 30 minutes in a pyrrolyzer, and analyzing the generated volatile components by GC / MS. Using the previously prepared calibration curve, the peak area of each obtained compound was converted into a D4 sieve concentration.

GC / MS measurement was performed using the following apparatus.

Pyrolizer: Py-3030iD (Frontier Labo)

GC system ： 7890B (Agilent Technology)

MSD: 5977A (Agilent Technology)

Column: UA-1 (inner diameter 0.25 mm, length 15 m, liquid thickness 0.25 µm) (Frontier Labo)

All GC / MS measurements were performed under the following measurement conditions.

Column temperature: maintained at 40 ° C for 5 minutes, heated to 20 ° C / min, held at 320 ° C for 11 minutes, total 30 minutes

Inlet temperature: 320 ℃

Injection method: Split method (1/2 split ratio)

Interface temperature: 320 ℃

Ion source temperature: 230 ℃

Ionization method: Electron ionization method (EI)

Measurement method: SCAN method (m / z 10-800)

(2) Preparation of calibration curve

A sample of a compound of formula (4) of n = 4 (hereinafter also referred to as D4 sieve) (manufactured by Tokyo Chemical Industries, Ltd.) was weighed into a 10 ml volumetric flask, chloroform was used as a solvent, and the concentration of the D4 sieve was 0.1. Samples of mg / ml phosphorus and samples of 0.01 mg / ml phosphorus were prepared.

A sampler for liquid samples was mounted on a pyrrolizer set at 400 ° C., and the sample with the adjusted concentration was weighed 1 μl with a micro syringe and injected into the pyrrolizer. The column was immersed in liquid nitrogen while the pyrrolizer was heated to 400 ° C., and the volatile components were trapped in the column. One minute after the completion of heating, the column was taken out from liquid nitrogen, and GC / MS measurement was performed. The slope of the D4 sieve calibration curve was determined from the concentration of the D4 sieve and the obtained peak area.

The retention time of the cyclic siloxane in GC / MS measurement using the apparatus and measurement conditions used is shown in Table 1 below. It is the same in subsequent GC / MS measurements.

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

(3) Analysis of low molecular cyclic siloxane concentrations of general formulas (3) and (4) in the resin composition

The concentration of the phenyl side chains of the general formula (3) contained in the resin composition was measured by heating the resin composition to 200 ° C and performing GC / MS measurement of the volatile components generated. The concentration of the methyl-side chain in the general formula (4) was measured by heating the resin composition to 150 ° C and performing GC / MS measurement of the volatile components generated. The concentration of each compound was calculated from the peak area of the measurement result of the volatile component of the resin composition. If the peaks of each compound did not overlap with other compounds, the peak area obtained from the total ion chromatogram (TIC) was used. In the case of overlapping with other compounds, the peak area obtained from the macrogram (MS) of m / z = 281 was used.

A. Analysis of low molecular cyclic siloxane concentration of general formula (3) (phenyl side chain) in the resin composition

A sample cup containing a resin composition weighed at about 1 mg was placed in a heating furnace (He atmosphere) of a pyrrolizer set at 200 ° C, and heated at 200 ° C for 30 minutes. The generated volatile components were measured by GC / MS analysis. Using the previously prepared calibration curve, the peak area of each obtained compound was converted into a D4 sieve concentration. The amount of the low-molecular cyclic siloxane in the general formula (3) was calculated according to the following formula.

Dmφ (µg / g) = {Dmφ (GC-Area)} / {Slope of D4 sieve calibration curve} / {mass of weighed resin composition (mg)} × 1000

M in the formula corresponds to the carbon number m in the general formula (3), and m is an integer of 3 or more.

B. Analysis of low molecular cyclic siloxane concentration of general formula (4) (methyl-side chain) in the resin composition

A sample cup containing a resin composition of about 1 mg was placed in a heating furnace (He atmosphere) of a pyrrolizer set at 150 ° C, and heated at 150 ° C for 30 minutes. The generated volatile components were measured by GC / MS analysis. Using the previously prepared calibration curve, the peak area of each obtained compound was converted into a D4 sieve concentration.

Dn (µg / g) = {Dn (GC-Area)} / {Slope of the D4 sieve calibration curve} / {mass of the weighed resin composition (mg)} × 1000

N in the formula corresponds to the carbon number n of the general formula (4), n is an integer of 3 or more.

(5) Analysis of low molecular cyclic siloxane concentrations of general formulas (3) and (4) in the solids contained in the resin composition

The analysis of the low molecular cyclic siloxane concentrations of the general formulas (3) and (4) contained in the solid content was calculated from the low molecular cyclic siloxane concentrations of the general formulas (3) and (4) in the aforementioned resin composition. That is, the total mass of the monomers used in the polyimide precursors of each of the Examples and Comparative Examples is the mass of the solids contained in the resin composition, from the concentration of the cyclic siloxanes of the general formulas (3) and (4) in the resin composition and the total mass thereof. , Cyclic siloxane concentrations of formulas (3) and (4) in the solid content were calculated. The mass of the solids contained in the resin composition is obtained by GC analysis of the resin composition, as described above, to obtain the mass of the solvent, subtract the mass of the solvent from the mass of the resin composition, or heat the resin composition and volatilize the solvent. It can also be obtained by removing, obtaining the mass of the solvent, and subtracting the mass of the solvent from the mass of the resin composition.

<Analysis of low molecular cyclic siloxane concentration in raw material composition (based on silicon-containing compound)>

(summary)

Analysis of the low molecular cyclic siloxane concentration contains silicon-containing compounds (silicon-containing compounds of general formulas (3), (4) and (5)) dissolved in acetone (including n-tetradecane as an internal standard) It was measured by analyzing the solution of GC. From the peak area of each obtained compound, the concentration of each compound was determined based on the peak area of n-tetradecane according to the method described later.

GC measurement was performed using the following apparatus.

GC system ： 7890A (Agilent Technology)

Column: J & W Scientific Durabond DB-5MS (MEGABORE inner diameter 0.53 mm, length 30 m, liquid thickness 1.0 µm)

All GC measurements were performed under the following measurement conditions.

Column temperature: heated to 50 ° C and 10 ° C / min, held at 280 ° C for 17 minutes, total 40 minutes

Inlet temperature: 270 ℃

Carrier gas: He

Injection method: Split method (1/10 split ratio)

Detector: FID (300 ℃)

(Calculation of low molecular cyclic siloxane content)

The amount of the low-molecular cyclic siloxane in the general formula (3) was calculated according to the following formula.

Dmφ (μm / g) = {total amount of compound of general formula (3) (μg)} / {total mass of compound of general formulas (3-1), (3-2), (4) and (5) ( g)} = {Dmφ (GC-Area)} / {n-tetradecane (GC-Area) × GC-Area Factor} × 20 × 100

M in the formula corresponds to the carbon number m in the general formula (3), and m is an integer of 3 or more.

GC-Area Factor in the equation was calculated according to the following equation.

GC-Area Factor = molecular weight / carbon number

The amount of the low-molecular cyclic siloxane in the general formula (4) was calculated according to the following formula.

Dn (μg / g) = {total amount of compound of formula (4) (μg)} / {total mass of compounds of formula (3-1), (3-2), (4) and (5) ( g)} = {Dn (GC-Area)} / {n-tetradecane (GC-Area) × GC-Area Factor} × 20 × 100

N in the formula corresponds to the carbon number n of the general formula (4), n is an integer of 3 or more.

GC-Area Factor in the equation was calculated according to the following equation.

GC-Area Factor = molecular weight / carbon number

Table 2 below shows the retention time (minutes) of the cyclic siloxane in the GC measurement using the apparatus used and the measurement conditions. It is the same for subsequent GC measurements.

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

(Analysis of low molecular cyclic siloxane concentration)

The analysis of the low molecular cyclic siloxane concentrations of the general formulas (3) and (4) contained in the silicon-containing compound was performed in the following procedure. 0.1 g of silicon-containing compound was dissolved in 10 ml of acetone (containing 20 µg / ml of n-tetradecane as an internal standard) and left standing for 16 hours. The neglected solution was weighed 1 μl with a micro syringe, introduced into a GC, and measured. In the obtained chromatogram, the peak area of each low-molecular cyclic siloxane and n-tetradecane was calculated by software attached to GC, and the low-molecular cyclic siloxane concentration was determined by the calculation formula shown above.

<Evaluation of foreign material counts in polyimide resin film>

In this evaluation, after the polyimide precursor was dried and cured in a large amount using an oven, a polyimide resin film attached to the surface of the polyimide resin film in the case where a polyimide resin film was produced in the same oven was used. Was evaluated.

The resin compositions of Examples and Comparative Examples were applied to an alkali-free glass substrate having a width of 200 mm (hereinafter also referred to as a glass substrate) so as to have a film thickness of 10 µm after curing to form a coating film. A slit coater (TN25000, manufactured by Tokyo Oka Industries) was used for the application. At this time, for each resin composition, a resin composition formed on 50 glass substrates was prepared. For one of the glass substrates having a coating film of the resin composition, in an oven (KLO-30NH, manufactured by Koyo Thermo Systems) under nitrogen atmosphere (oxygen concentration of 300 ppm or less), dried at 100 ° C. for 30 minutes to remove the solvent. . Subsequently, under a nitrogen atmosphere (oxygen concentration of 300 ppm or less), heating was performed at 350 ° C for 1 hour to form a polyimide resin film on the glass substrate. The size and number of foreign matters were counted using a microscope (VHX-6000, manufactured by Keyence) for the range of the center width and height of 50 mm in the obtained polyimide resin film having a width and width of 200 mm.

The observation conditions are as follows.

Lens: 100 times

Threshold: Auto

Then, the number of foreign matters having a major diameter of 50 μm or more and less than 1000 μm was evaluated based on the following criteria.

The number of foreign substances is 10 or more and less than 50: A (Good)

The number of foreign substances is 50 or more and less than 100: B (possible)

The number of foreign substances is 100 or more: C (not available)

As a result of EDS analysis (elemental analysis) of the observed foreign material using a scanning electron microscope (JSM-IT500HR, manufactured by Nihon Electronics Co., Ltd.), C, Si, and O elements were observed, and N element was not observed. From these results, it is presumed that the foreign matter had low molecular cyclic siloxanes volatilized during vacuum drying, which adhered to the inner wall of the dryer, and dropped or adhered.

In addition, when evaluating resin compositions of different types, the oven was evacuated at 600 ° C for 5 hours or more to evaluate.

<Evaluation of difference in YI value>

In this evaluation, the difference in YI value of the polyimide resin film obtained by curing each of the polyimide precursor obtained using the purified silicon compound and the polyimide precursor obtained using the unpurified silicon compound was evaluated.

The resin compositions of Examples and Comparative Examples were applied to an alkali-free glass substrate having a width of 200 mm (hereinafter also referred to as a glass substrate) so as to have a film thickness of 10 µm after curing to form a coating film. Application was performed using a slit coater (TN25000, Tokyo Oka Industries). One of the glass substrates having a coating film of the obtained resin composition was dried in an oven (KLO-30NH, Koyo Thermo System) under nitrogen atmosphere (oxygen concentration of 300 ppm or less) at 100 ° C for 30 minutes to remove the solvent. Then, under nitrogen atmosphere (oxygen concentration 300 ppm or less), it heated at 400 degreeC for 1 hour, and formed the polyimide resin film on a glass substrate.

Using the obtained polyimide resin film, the YI value was measured using Nippon Electric Color Co., Ltd. (Spectrophotometer: SE600). A D65 light source was used as the light source. The difference in YI value was calculated | required from the following formula.

(Difference of YI value) = (YI value of the polyimide resin film obtained by curing the polyimide precursor obtained using the unpurified silicon compound)-(Polyimide obtained by curing the polyimide precursor obtained using the purified silicon compound) Mid resin film YI value)

In addition, in obtaining the difference in YI value, curing of the polyimide precursor obtained by using the unpurified silicon compound and curing of the polyimide precursor obtained by using the purified silicon compound are performed in the same batch of oven. The device error was eliminated by heat treatment.

<< Method for purifying silicon-containing compound >>

The silicon-containing compounds described in Examples and Comparative Examples described below were treated by the following purification method to reduce the contained low-molecular cyclic siloxanes. The concentration of the low molecular cyclic siloxane after purification was analyzed by the above method.

<Tablet A>

10 kg of the silicon-containing compound was placed in a flask, and stripping was performed for 8 hours at a temperature of 160 ° C and a pressure of 270 MPa while blowing nitrogen gas.

<Tablet B-1>

1 kg of the silicon-containing compound was placed in a flask, and stripping was performed for 8 hours at a temperature of 200 ° C and a pressure of 200 MPa while blowing nitrogen gas.

<Tablet B-2>

10 kg of the silicon-containing compound was placed in a flask, and stripping was performed for 8 hours at a temperature of 200 ° C and a pressure of 200 MPa while blowing nitrogen gas.

<Tablet C> Based on the synthesis example of the amino acid modified silicone oil (regular product) of the socks described in Japanese Patent Laid-Open No. 2016-029126.

In 100 g of silicon-containing compound, 1000 g of acetone was added and stirred at room temperature for 30 minutes. After centrifugation at 2500 rpm for 15 minutes with a centrifuge, and acetone and silicone oil were separated, acetone was removed by decantation. After repeating this operation three times, acetone was distilled off with an evaporator to obtain a purified silicon-containing compound.

<Tablet D> Based on the purification example 1 described in Japanese Unexamined Patent Publication No. 2006-028533

500 g of the silicon-containing compound was placed in a flask, and stripping was performed at a temperature of 250 ° C. and a pressure of 1330 MPa for 8 hours while blowing nitrogen gas.

<Tablet E> Based on Purification Example 2 described in JP2006-028533 A.

100 g of the silicon-containing compound was dissolved in 300 g of 2-butanone to dissolve uniformly. The solution was slowly added while stirring in methanol, and reprecipitation was performed. The above reprecipitation was repeated 3 times in total, followed by drying to obtain a purified silicon-containing compound.

<Example 1 >>

As shown in Table 2, the silicon-containing compound (1) (in general formula (1), 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 were methyl groups, R ₄ and R ₅ were phenyl groups, j / (i + j + k) = 0.15, and a compound having a number average molecular weight of 4400) was purified by the method of purification B. NMP (332 g) as a solvent, 4,4'-DAS (14.2 g), TFMB (37.8 g) as a diamine, and purified silicon-containing compound while introducing nitrogen gas into a 3 L separable flask with a stir bar (1) (10.56 g) was added with stirring, and PMDA (21.8 g) was subsequently added as an acid anhydride. The molar ratio of the acid anhydride and diamine was 100: 97. The mixture was stirred at room temperature for 48 hours to obtain a transparent polyamic acid NMP solution (hereinafter also referred to as varnish). The obtained varnish was stored in a freezer (set at -20 deg. C, same as below), and used for thawing when evaluating.

<< Examples 2-32 and Comparative Examples 17-19 >>

In Example 1, it was carried out in the same manner as in Example 1, except that the type and amount of the solvent, acid 2 anhydride, diamine, and silicon-containing compound were changed to those described in Tables 2 and 3.

The types of the silicon-containing compound in Table 3 are as follows.

Silicon-containing compound (2): In general formula (1), L ₁ and L ₂ are amino groups, R ₁ is -CH ₂ CH ₂ CH _2- , and R ₂ , R ₃ , R ₆ and R ₇ are methyl groups, R ₄ and R ₅ are phenyl groups, j / (i + j + k) = 0.15, and the compound having a number average molecular weight of 1340

Silicon-containing compound (3): In general formula (1), L ₁ and L ₂ are acid anhydride groups, R ₁ is -CH ₂ CH ₂ CH _2- , and R ₂ , R ₃ , R ₆ and R ₇ are A methyl group, R ₄ and R ₅ are phenyl groups, j / (i + j + k) = 0.15, and a compound having a number average molecular weight of 4200

Silicon-containing compound (4): In the general formula (1), L ₁ and L ₂ are epoxy groups, R ₁ is -CH ₂ CH ₂ CH _2- , and R ₂ , R ₃ , R ₆ and R ₇ are methyl groups, R ₄ and R ₅ are phenyl groups, j / (i + j + k) = 0.15, and a compound having a number average molecular weight of 1240

<Comparative Example 1>

As shown in Table 3, while introducing nitrogen gas into a 3 L separable flask with a stir bar, NMP (319 g) as a solvent, 4,4'-DAS (14.3 g) as a diamine, and TFMB (12.3 g) ), Crude silicon-containing compound (in general formula (1), L ₁ and L ₂ are amino groups, R ₁ is -CH ₂ CH ₂ CH _2- , and R ₂ , R ₃ , R ₆ , R ₇ are A methyl group, R ₄ , R ₅ is a phenyl group, j is 15, i + j + k is 10, a number average molecular weight 4400 compound) (5.72 g) is added with stirring, and PMDA (15.3 g) is subsequently added as an acid anhydride. . The molar ratio between the acid anhydride and diamine was 100: 97. Next, the mixture was stirred at room temperature for 48 hours to obtain a transparent polyamic acid NMP solution (hereinafter also referred to as varnish). The obtained varnish was stored in a freezer (set at -20 deg. C, same as below), and used for thawing when evaluating.

<< Comparative Example 2-Comparative Example 16 >>

In Comparative Example 1, it was carried out in the same manner as in Comparative Example 1, except that the type and amount of the solvent, acid 2 anhydride, diamine, and silicon-containing compound were changed to those shown in Table 3.

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

2a: lower substrate
2b: sealing substrate
25: organic EL structure
250a: Organic EL device emitting red light
250b: organic EL device emitting green light
250c: organic EL device 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

Claims (34)

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

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

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

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

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

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

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

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

{In the formula, n is an integer of 2 or more.} A polyimide precursor comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2),
At least one compound in which m is an integer of 3 or more in the following general formula (3-1) or (3-2);
Optionally, a compound represented by the following general formula (4)
A resin composition comprising:
In the following general formula (3-1) or (3-2), the total amount of the compound in which m is an integer of 3 or more is more than 0 ppm and 7,500 ppm or less, based on the mass of the solid content in the resin composition, or
In the following general formula (3-1) or (3-2), the total amount of the compound in which m is an integer of 3 or more and the compound in which n is an integer of 3 or more in the general formula (4) is based on the mass of the solid content in the resin composition. Thus, the resin composition is more than 0 ppm and 8,600 ppm or less.

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

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

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

{In the formula, n is an integer of 2 or more.} A polyimide precursor comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2);
At least either compound in which m is 3 or 4 in the following general formula (3-1) or (3-2);
Optionally, a compound represented by the following general formula (4)
A resin composition comprising:
In the following general formula (3-1) or (3-2), the total amount of the compound whose m is 3 is more than 0 ppm and 4,500 ppm or less, based on the mass of the solid content in the resin composition, or
In the following general formula (3-1) or (3-2), the total amount of the compound whose m is 4 is more than 0 ppm and 2,500 ppm or less, based on the mass of the solid content in the resin composition,
Resin composition.

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

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

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

The method according to any one of claims 1, 2, and 4,
In the compound represented by the general formula (3-1) or (3-2), m is an integer of 3 to 5, the resin composition. The method according to any one of claims 1, 2, and 4,
In the compound represented by the general formula (4), n is an integer of 3 to 8, the resin composition. The method according to any one of claims 1 to 5,
A resin composition in which a polyimide resin film obtained by curing the polyimide precursor is used for a flexible substrate. The method according to any one of claims 1 to 5,
A resin composition in which a polyimide resin film obtained by curing the polyimide precursor is used for a flexible display. A polyimide precursor comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2);
At least one compound in which m is an integer of 3 or more in the following general formula (3-1) or (3-2);
Optionally, a compound represented by the following general formula (4)
A resin composition comprising:
The resin composition is as follows:
A silicon-containing compound represented by the following general formula (5),
At least one compound in which m is an integer of 3 or more in the following general formula (3-1) or (3-2),
Optionally, a raw material composition containing a compound represented by the following general formula (4) is produced by a method comprising polycondensation reaction with tetracarboxylic dianhydride and diamine to provide a polyimide precursor,
The total amount of compounds in which m is an integer of 3 or more in the following general formulas (3-1) or (3-2) included in the raw material composition is the following general formulas (3-1), (3-2), (4) And, based on the total mass of the silicon-containing compound represented by (5), more than 0 ppm and 46,000 ppm or less, or
The total amount of the compound in which m is an integer of 3 or more in the following general formula (3-1) or (3-2) and the compound in which n is an integer of 3 or more in the general formula (4) included in the raw material composition is the general formula Based on the total mass of the silicon-containing compounds of (3-1), (3-2), (4) and (5), more than 0 ppm and 47,000 ppm or less,
Resin composition.

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

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

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

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

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

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

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

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

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

{In the formula, R ₁ is, 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 Is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group having 1 to 10 carbon atoms, at least one is a monovalent aromatic group having 6 to 10 carbon atoms, R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, at least one is an organic group having an unsaturated aliphatic hydrocarbon group, 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 halide group, a hydroxyl group, an epoxy group, or a mercapto group, i and j are each independently an integer from 1 to 200, and k is an integer from 0 to 200 , 0.05 ≤ j / (i + j + k) ≤ 0.50.} The method according to any one of claims 10 to 13,
The resin composition of the silicon-containing compound represented by the general formula (5), L ₁ and L ₂ are each independently selected from the group consisting of an amino group, an acid anhydride group and an epoxy group. The method according to any one of claims 10 to 13,
The resin composition in which L ₁ and L ₂ of the silicon-containing compound represented by the general formula (5) is an amino group. The method according to any one of claims 10 to 13,
The resin composition, wherein the compound represented by the general formula (3-1) or (3-2) is a compound represented by the general formula (3-1). The method according to any one of claims 10 to 13,
The tetracarboxylic dianhydride is pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, cyclohexanetetracarboxylic acid A resin composition, which is at least one selected from the group consisting of dihydride and cyclobutanetetracarboxylic dianhydride. The method according to any one of claims 10 to 13,
The diamine is 4,4'-diaminodiphenylsulfone, m-tolidine, p-phenylenediamine, 2,2'-bis (trifluoromethyl) benzidine, and 2,2'-bis [4- (4-Aminophenoxy) phenyl] at least one member selected from the group consisting of propane, the resin composition. A silicon-containing compound represented by the following general formula (5),
At least one compound in which m is an integer of 3 or more in the following general formula (3-1) or (3-2),
Optionally, a method for producing a resin composition comprising providing a polyimide precursor by polycondensing a raw material composition containing a compound represented by the following general formula (4) with tetracarboxylic dianhydride and diamine,
The total amount of compounds in which m is an integer of 3 or more in the following general formulas (3-1) or (3-2) contained in the raw material composition is the following general formulas (3-1), (3-2), (4) And, based on the total mass of the silicon-containing compound represented by (5), more than 0 ppm and 46,000 ppm or less, or
The total amount of the compound in which m is an integer of 3 or more in the following general formula (3-1) or (3-2) and the compound in which n is an integer of 3 or more in the general formula (4) included in the raw material composition is the general formula Based on the total mass of the silicon-containing compounds of (3-1), (3-2), (4) and (5), more than 0 ppm and 47,000 ppm or less,
Method of manufacturing a resin composition.

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

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

{In the formula, R ₁ is, 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 Is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group having 1 to 10 carbon atoms, at least one is a monovalent aromatic group having 6 to 10 carbon atoms, R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, at least one is an organic group having an unsaturated aliphatic hydrocarbon group, 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 halide group, a hydroxyl group, an epoxy group, or a mercapto group, i and j are each independently an integer from 1 to 200, and k is an integer from 0 to 200 , 0.05 ≤ j / (i + j + k) ≤ 0.50.} The method of claim 19,
In the compound represented by the general formula (3-1) or (3-2), m is an integer of 3 to 5, the method for producing a resin composition. The method of claim 19,
In the compound represented by the general formula (4), n is an integer of 3 to 8, the method for producing a resin composition. A silicon-containing compound represented by the following general formula (5),
At least either compound in which m is 3 or 4 in the following general formula (3-1) or (3-2),
Optionally, a method for producing a resin composition comprising providing a polyimide precursor by polycondensing a raw material composition containing a compound represented by the following general formula (4) with tetracarboxylic dianhydride and diamine,
The total amount of the compound in which m is 3 in the following general formula (3-1) or (3-2) contained in the raw material composition is represented by the following general formulas (3-1), (3-2), (4) and Based on the total mass of the silicon-containing compound of (5), it is more than 0 ppm and 25,000 ppm or less, or
The total amount of compounds in which m is 4 in the following general formulas (3-1) or (3-2) contained in the raw material composition is represented by the following general formulas (3-1), (3-2), (4) and Based on the total mass of the silicon-containing compound (5), more than 0 ppm and 15,000 ppm or less,
Method of manufacturing a resin composition.

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

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

{In the formula, R ₁ is, 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 Is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group having 1 to 10 carbon atoms, at least one is a monovalent aromatic group having 6 to 10 carbon atoms, R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, at least one is an organic group having an unsaturated aliphatic hydrocarbon group, 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 halide group, a hydroxyl group, an epoxy group, or a mercapto group, i and j are each independently an integer from 1 to 200, and k is an integer from 0 to 200 , 0.05 ≤ j / (i + j + k) ≤ 0.50.} The method according to any one of claims 19 to 22,
The method for producing a resin composition in which L ₁ and L ₂ of the silicon-containing compound represented by the general formula (5) are each independently selected from the group consisting of an amino group, an acid anhydride group, and an epoxy group. The method according to any one of claims 19 to 22,
The method for producing a resin composition in which L ₁ and L ₂ of the silicon-containing compound represented by the general formula (5) are amino groups. The method according to any one of claims 19 to 22,
The method for producing a resin composition, wherein the compound represented by the general formula (3-1) or (3-2) is a compound represented by the general formula (3-1). The method according to any one of claims 19 to 22,
The tetracarboxylic dianhydride is pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, cyclohexanetetracarboxylic acid A method for producing a resin composition, which is at least one selected from the group consisting of dihydride and cyclobutanetetracarboxylic dianhydride. The method according to any one of claims 19 to 22,
The diamine is 4,4'-diaminodiphenylsulfone, m-tolidine, p-phenylenediamine, 2,2'-bis (trifluoromethyl) benzidine, and 2,2'-bis [4- (4-Aminophenoxy) phenyl] at least one selected from the group consisting of propane, a method for producing a resin composition. A coating step of applying the resin composition according to any one of claims 1 to 5 and 10 to 13 on the surface of the support,
A film forming step of heating the resin composition to form a polyimide resin film,
Peeling step of peeling the polyimide resin film from the support,
The manufacturing method of a polyimide film containing the. The method of claim 28,
A method for producing a polyimide film comprising an irradiation step of irradiating a laser to the resin composition from the support side prior to the peeling step. A coating step of applying the resin composition according to any one of claims 1 to 5 and 10 to 13 on the surface of the support,
A film forming step of heating the resin composition to form a polyimide resin film,
An element forming process for forming an element on the polyimide resin film,
A peeling step of peeling the polyimide resin film on which the device is formed from the support,
A method of manufacturing a display comprising: A coating step of applying the resin composition according to any one of claims 1 to 5 and 10 to 13 on the surface of the support,
A film forming step of heating the resin composition to form a polyimide resin film,
An element forming process of forming an element on the polyimide resin film,
The manufacturing method of a laminated body containing a. The method of claim 31,
A method of manufacturing a laminate further comprising the step of peeling the polyimide resin film on which the device is formed from the support. A method for manufacturing a flexible device, comprising producing a laminate by the method according to claim 31. A polyimide film that is a cured product of the resin composition according to any one of claims 1 to 5 and 10 to 13.

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