CN117924699A

CN117924699A - Polyimide precursor and polyimide resin composition

Info

Publication number: CN117924699A
Application number: CN202311788895.5A
Authority: CN
Inventors: 柏田健; 篠原直志; 奥田敏章; 金田隆行
Original assignee: Asahi Kasei Corp
Current assignee: Asahi Kasei Corp
Priority date: 2019-05-24
Filing date: 2020-05-22
Publication date: 2024-04-26
Also published as: CN113874419A; JPWO2020241523A1; KR20210138663A; KR102618096B1; CN113874419B; JP7300504B2; WO2020241523A1; TW202104369A

Abstract

The present invention relates to a polyimide precursor and a polyimide resin composition. A resin composition comprising: a polyimide precursor or polyimide containing a structural unit represented by a specific general formula; and a compound represented by the following general formula (3), wherein the total amount of the compound having n of 4 in the following general formula (3) is more than 0ppm and not more than 70ppm based on the mass of the resin composition, or the total amount of the compound having n of 5 in the following general formula (3) is more than 0ppm and not more than 30ppm based on the mass of the resin composition.

Description

Polyimide precursor and polyimide resin composition

The present application is a divisional application of application number 202080038151.X, entitled "polyimide precursor and polyimide resin composition" on application day 2020, 5 and 22.

Technical Field

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

Background

Polyimide resin is insoluble and infusible super heat-resistant resin, and has excellent heat oxidation resistance, heat resistance, radiation linearity resistance, low temperature resistance, chemical reagent resistance and the like. Polyimide resins are therefore used in a wide range of fields including electronic materials. Examples of suitable polyimide resins in the field of electronic materials include insulating coating materials, insulating films, semiconductors, and electrode protection films for thin film transistor liquid crystal displays (TFT-LCDs). Recently, use of polyimide films as flexible substrates by virtue of their light weight and flexibility has been studied as an alternative to glass substrates conventionally used in the field of display materials.

For example, patent document 1 describes a resin precursor (weight average molecular weight of 3 to 9 ten thousand) having a siloxane unit, which is polymerized from bis (diaminodiphenyl) sulfone (hereinafter also referred to as DAS). Patent document 1 describes that, in polyimide obtained by curing the precursor, residual stress generated between the polyimide and a support such as glass is low, and chemical resistance is excellent, and that the oxygen concentration in the curing step causes little influence on yellowness (YI value) and total light transmittance. Patent document 2 describes a resin precursor having a siloxane unit, which is polymerized from 2,2' -bis (trifluoromethyl) benzidine (hereinafter also referred to as TFMB). Patent document 2 describes that a polyimide film obtained by curing the precursor has a specific glass transition temperature, low residual stress generated between the polyimide film and an inorganic film, and excellent mechanical properties and thermal stability.

Prior art literature

Patent literature

Patent document 1: international publication No. 2014/148441

Patent document 2: international publication No. 2014/098235

Patent document 3: japanese patent laid-open publication 2016-029126

Patent document 4: japanese patent laid-open No. 2006-028533

Patent document 5: japanese patent laid-open No. 2002-012666

Patent document 6: japanese patent laid-open No. 2007-512568

Patent document 7: japanese patent application laid-open No. 2012-511173

Patent document 8: japanese patent application laid-open No. 2010-067957

Patent document 9: japanese patent laid-open No. 2013-179306

Patent document 10: international publication No. 2005/068535

Non-patent literature

Non-patent document 1: homepage of Xinyue chemical industry Co., ltd., "Q & A", "about silicone grease-oil complex (コ, about line コ, about line)", [ online ], [ search of 4/24/2020 ], internet < URL: https:// www.silicone.jp/contact/qa 103.Shtml >

Disclosure of Invention

Problems to be solved by the invention

In patent documents 1 and 2, a siloxane-containing compound containing a low-molecular-weight cyclic siloxane (hereinafter also referred to as a low-molecular-weight cyclic siloxane) is used as a monomer of a polyimide precursor. It is known that the low-molecular cyclic siloxane is volatile, and thus, outgas is generated, and thus, contact point defects of a manufacturing apparatus of the process may be generated. For example, refer to non-patent document 1.

Patent documents 3 to 5 are cited as prior art documents on polyimide precursors in which the low-molecular cyclic siloxane is reduced by purification. Patent document 3 describes that a low-molecular cyclic siloxane is removed by adding a siloxane-containing compound to acetone, followed by centrifugation and decantation, and the obtained polyimide has transparency and little outgassing. Patent documents 4 and 5 describe that the adhesion of the obtained polyimide is improved by purifying a siloxane-containing compound by stripping the siloxane-containing compound under specific conditions or by dissolving the siloxane-containing compound in 2-butanone and then reprecipitating the compound with methanol.

The present inventors synthesized a polyimide precursor and a polyimide using a siloxane-containing compound purified by the same purification method as described in the above patent documents 3 to 5, and produced a polyimide film using these. As a result, it was found that the degree of improvement in the degree of yellow (YI value) was insufficient when a large amount of polyimide precursor or polyimide resin film was processed in the polyimide film production process, and when the unpurified product was changed to the purified product. Accordingly, an object of the present invention is to provide a polyimide precursor resin composition and a polyimide resin composition which can reduce defects on the surface of a polyimide resin film produced in a polyimide film production process by further improving the YI value as compared with the case of using an unpurified silicone compound.

Solution for solving the problem

As a result of intensive studies, the present inventors have found that some of the compounds represented by the general formula (3) are not sufficiently reduced by the purification methods described in the above prior art documents. It was also found that the above problems can be solved by further purifying the silicon-containing compound and reducing a part of the compound of the general formula (3) to a specific amount. Examples of the embodiments of the present invention are listed in the following [1] to [35 ].

[1] A resin composition comprising:

a polyimide precursor or polyimide containing a structural unit represented by the following general formula (1-1) and/or (1-2) and containing a structural unit represented by the following general formula (2); and

A compound represented by the following general formula (3),

The total amount of the compounds having n of 4 in the following general formula (3) is more than 0ppm and not more than 70ppm based on the mass of the resin composition, or

The total amount of the compounds having n of 5 in the following general formula (3) is more than 0ppm and 30ppm or less based on the mass of the resin composition.

In the formula, { P ₁ represents a 2-valent organic group, P ₂ represents a 4-valent organic group, and P represents a positive integer. }

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

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

[2] The resin composition according to item 1, wherein the total amount of the compounds having n of 4 in the general formula (3) is more than 0ppm and 30ppm or less based on the mass of the resin composition, or

The total amount of the compounds having n of 5 in the general formula (3) is more than 0ppm and 15ppm or less based on the mass of the resin composition.

[3] A resin composition comprising:

A compound represented by the following general formula (3),

The total amount of the compounds having n of 4 in the following general formula (3) is more than 0ppm and 500ppm or less based on the mass of the non-solvent component of the resin composition, or

The total amount of the compounds having n of 5 in the general formula (3) is more than 0ppm and not more than 200ppm based on the mass of the non-solvent component of the resin composition.

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

[4] The resin composition according to item 3, wherein the total amount of the compounds having n of 4 in the general formula (3) is more than 0ppm and 300ppm or less based on the mass of the non-solvent component of the resin composition, or

The total amount of the compounds having n of 5 in the general formula (3) is more than 0ppm and 100ppm or less based on the mass of the non-solvent component of the resin composition.

[5] The resin composition according to item 3, wherein the total amount of the compounds having n of 4 in the general formula (3) is more than 0ppm and 10ppm or less based on the mass of the non-solvent component of the resin composition, or

The total amount of the compounds having n of 5 in the general formula (3) is more than 0ppm and not more than 5ppm based on the mass of the non-solvent component of the resin composition.

[6] A resin composition comprising:

A compound represented by the following general formula (3),

The above resin composition is produced by a method comprising:

A raw material composition containing a silicon-containing compound represented by the following general formula (4) and a compound represented by the following general formula (3) is subjected to polycondensation reaction with tetracarboxylic dianhydride and diamine to provide a polyimide precursor; or imidizing the polyimide precursor to provide polyimide,

The total amount of the compounds having n of 4 in the following general formula (3) contained in the raw material composition is more than 0ppm and not more than 1300ppm, or

The total amount of the compounds having n of 5 in the following general formula (3) contained in the raw material composition is more than 0ppm and 500ppm or less based on the total mass of the silicon-containing compounds represented by the general formulas (3) and (4).

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

{ Formula, R ₁ is a single bond or a divalent organic group having 1to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1to 10 carbon atoms, at least one monovalent aliphatic hydrocarbon group having 1to 5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group having 1to 10 carbon atoms, at least one monovalent aromatic group having 6 to 10 carbon atoms, R ₆ and R ₇ are each independently a monovalent organic group having 1to 10 carbon atoms, 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 acyl halide group, a hydroxyl group, an epoxy group or a mercapto group, i is an integer of 1to 200, j and k are each independently an integer of 0to 200, and j/(i+j+k) is 0.50.}

[7] The resin composition according to item 6, wherein the total amount of the compounds having n of 4 in the general formula (3) contained in the raw material composition is more than 0ppm and not more than 800ppm, or based on the total mass of the silicon-containing compounds represented by the general formulae (3) and (4)

The total amount of the compounds having n of 5 in the general formula (3) contained in the raw material composition is more than 0ppm and 300ppm or less based on the total mass of the silicon-containing compounds represented by the general formulas (3) and (4).

[8] The resin composition according to item 6, wherein the total amount of the compounds having n of 4 in the general formula (3) contained in the raw material composition is more than 0ppm and not more than 30ppm, or based on the total mass of the silicon-containing compounds represented by the general formulae (3) and (4)

The total amount of the compounds having n of 5 in the general formula (3) contained in the raw material composition is more than 0ppm and 15ppm or less based on the total mass of the silicon-containing compounds represented by the general formulas (3) and (4).

[9] A resin composition comprising:

A compound represented by the following general formula (3),

Based on the mass of the resin composition, the total amount of the compounds having n of 3 to 8 in the following general formula (3) is more than 0ppm and 150 ppm.

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

[10] A resin composition comprising:

A compound represented by the following general formula (3),

Based on the mass of the non-solvent component of the resin composition, the total amount of the compounds having n of 3 to 8 in the following general formula (3) is more than 0ppm and 900 ppm.

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

[11] A resin composition comprising:

A compound represented by the following general formula (3),

The above resin composition is produced by a method comprising:

The total amount of compounds of the general formula (3) in which n is 3 to 8 is more than 0ppm and 4500ppm inclusive, based on the total mass of silicon-containing compounds of the general formulas (3) and (4), contained in the raw material composition.

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

[12] The resin composition according to any one of items 6, 7, 8 and 11, wherein L ₁ and L ₂ of the silicon-containing compound represented by the above general formula (4) are each independently selected from the group consisting of an amino group, an acid anhydride group, an epoxy group, a hydroxyl group and a mercapto group.

[13] The resin composition according to any one of items 6, 7, 8 and 11, wherein L ₁ and L ₂ of the silicon-containing compound represented by the above general formula (4) are amino groups.

[14] The resin composition according to any one of items 6, 7, 8 and 11, wherein the functional group equivalent of the silicon-containing compound represented by the above general formula (4) is 800 or more.

[15] The resin composition according to any one of items 6 to 8 and 11 to 14, wherein the tetracarboxylic dianhydride is at least one selected from the group consisting of pyromellitic dianhydride (PMDA), 3', 4' -biphenyl tetracarboxylic dianhydride (BPDA), 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride (BPAF), 4' -oxydiphthalic anhydride (ODPA), 1,2,4, 5-cyclohexane tetracarboxylic dianhydride (HPMDA) and 1,2,3, 4-cyclobutane tetracarboxylic dianhydride (CBDA).

[16] The resin composition according to any one of items 6 to 8 and 11 to 14, wherein the diamine is at least one selected from the group consisting of 4,4' -diaminodiphenyl sulfone (4, 4' -DAS), 3' -diaminodiphenyl sulfone (3, 3' -DAS), 9-bis (4-aminophenyl) fluorene (BAFL), 2' -dimethylbenzidine (mTB), p-Phenylenediamine (PDA), diaminobis (trifluoromethyl) biphenyl (TFMB), 2' -bis [4- (4-aminophenoxy) phenyl ] propane (BAPP), 4' -diaminodiphenyl ether (ODA) and 1, 4-Cyclohexanediamine (CHDA).

[17] The resin composition according to any one of items 1 to 16, wherein a polyimide resin film obtained by curing the resin composition is used for a flexible substrate.

[18] The resin composition according to any one of items 1 to 16, wherein a polyimide resin film obtained by curing the resin composition is used for a flexible display.

[19] The resin composition according to any one of items 1 to 18, wherein, based on the mass of the non-solvent component of the resin composition, d3+d4+d5+d6+d7 is less than 2000ppm and d3+d4 is 10ppm or less, where d3 (ppm) is the total amount of compounds of the general formula (3) in which n is 3, d4 (ppm) is the total amount of compounds of the general formula (3) in which n is 4, d5 (ppm) is the total amount of compounds of the general formula (5) in which n is 5, d6 (ppm) is the total amount of compounds of the general formula (6) and d7 (ppm) is the total amount of compounds of the general formula (7).

[20] A method for producing a resin composition, comprising: a raw material composition containing a silicon-containing compound represented by the following general formula (4) and a compound represented by the following general formula (3) is subjected to polycondensation reaction with tetracarboxylic dianhydride and diamine to provide a polyimide precursor; or imidizing the polyimide precursor to provide polyimide,

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

[21] The method for producing a resin composition according to item 20, wherein,

The total amount of the compounds having n of 4 in the general formula (3) contained in the raw material composition is more than 0ppm and not more than 800ppm, or

The total amount of the compounds having n of 6 in the general formula (3) contained in the raw material composition is more than 0ppm and 300ppm or less based on the total mass of the silicon-containing compounds represented by the general formulas (3) and (4).

[22] A method for producing a resin composition, comprising: a raw material composition containing a silicon-containing compound represented by the following general formula (4) and a compound represented by the following general formula (3) is subjected to polycondensation reaction with tetracarboxylic dianhydride and diamine to provide a polyimide precursor; or imidizing the polyimide precursor to provide polyimide,

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

[23] The method for producing a resin composition according to any one of items 20 to 22, wherein the functional group equivalent of the silicon-containing compound represented by the general formula (4) is 800 or more.

[24] A method for producing a resin composition, comprising: a raw material composition containing a silicon-containing compound represented by the following general formula (4) and a compound represented by the following general formula (3) is subjected to polycondensation reaction with tetracarboxylic dianhydride and diamine to provide a polyimide precursor; or imidizing the polyimide precursor to provide polyimide,

Comprising a step of reducing the total amount of compounds having n of 5 or the total amount of compounds having n of 6 or the total amount of compounds having n of 7 in the following general formula (3) based on the total mass of silicon-containing compounds represented by the following general formulas (4) and (3),

The step of reducing includes treating the composition at 150 to 300 ℃ and 300Pa or less for 2 to 12 hours.

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

[25] The method according to any one of items 20 to 24, wherein L ₁ and L ₂ of the silicon-containing compound represented by the above general formula (4) are each independently selected from the group consisting of an amino group, an acid anhydride group, an epoxy group, a hydroxyl group and a mercapto group.

[26] The method according to any one of items 20 to 24, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (4) are amino groups.

[27] The method according to any one of items 20 to 26, wherein the tetracarboxylic dianhydride is at least one selected from the group consisting of pyromellitic dianhydride (PMDA), 3', 4' -biphenyl tetracarboxylic dianhydride (BPDA), 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride (BPAF), 4' -oxydiphthalic anhydride (ODPA), 1,2,4, 5-cyclohexane tetracarboxylic dianhydride (HPMDA) and 1,2,3, 4-cyclobutane tetracarboxylic dianhydride (CBDA).

[28] The method according to any one of items 20 to 26, wherein the diamine is at least one selected from the group consisting of 4,4' -diaminodiphenyl sulfone (4, 4' -DAS), 3' -diaminodiphenyl sulfone (3, 3' -DAS), 9-bis (4-aminophenyl) fluorene (BAFL), 2' -dimethylbenzidine (mTB), p-Phenylenediamine (PDA), diaminobis (trifluoromethyl) biphenyl (TFMB), 2' -bis [4- (4-aminophenoxy) phenyl ] propane (BAPP), 4' -diaminodiphenyl ether (ODA) and 1, 4-Cyclohexanediamine (CHDA).

[29] A method for producing a polyimide film, comprising:

A coating step of coating the resin composition according to any one of items 1 to 19 on a surface of a support;

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

And a peeling step of peeling the polyimide resin film from the support.

[30] The method of producing a polyimide film according to item 29, further comprising an irradiation step of irradiating the resin composition with laser light from the support side before the peeling step.

[31] A method of manufacturing a display, comprising:

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

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

And a peeling step of peeling the polyimide resin film formed with the element from the support.

[32] A method for producing a laminate, comprising:

And an element forming step of forming an element on the polyimide resin film.

[33] The method of manufacturing a laminate according to item 32, further comprising a step of peeling the polyimide resin film on which the element is formed from the support.

[34] A method of manufacturing a flexible device, comprising manufacturing a laminate using the method of item 32 or 33.

[35] A polyimide film which is a cured product of the resin composition according to any one of items 1 to 19.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a polyimide precursor resin composition can be provided which has reduced defects on the surface of the obtained polyimide resin film and can further improve yellowness (YI value) as compared with the case of using an unpurified silicone compound. The above description should not be construed as disclosing all the embodiments of the present invention and all the advantages of the present invention. Further embodiments of the present invention and advantages thereof will be apparent by reference to the following description.

Drawings

Fig. 1 is a schematic view showing a structure of a top emission type flexible organic EL display, which is an example of the display of the present embodiment, which is located above a polyimide substrate.

Detailed Description

An exemplary embodiment of the present application (hereinafter simply referred to as "the present embodiment") will be described in detail below. The present application is not limited to the present embodiment, and can be implemented by various modifications within the scope of the gist thereof. In the present specification, the upper limit value and the lower limit value of each numerical range may be arbitrarily combined.

Resin composition

Polyimide precursor and polyimide

Structural units of the general formula (1-1) and (1-2)

The resin composition of the present embodiment may contain a polyimide precursor containing a structural unit represented by the following general formula (1-1) or a polyimide containing a structural unit represented by the following general formula (1-2), or may be a polyimide precursor or a polyimide resin composition containing both a structural unit represented by the following general formula (1-1) and a structural unit represented by the general formula (1-2).

The polyimide precursor having the structure represented by the general formula (1-1) and the polyimide having the general formula (1-2) are preferably copolymers of an acid dianhydride having a P ₂ group and a diamine having a P ₁ group.

Acid dianhydride

Examples of the acid dianhydride containing a P ₂ group include pyromellitic dianhydride (PMDA), 3', 4' -biphenyl tetracarboxylic dianhydride (BPDA), 2',3,3' -Biphenyltetracarboxylic acid dianhydride, 4' - (hexafluoroisopropylidene) diphthalic anhydride, 5- (2, 5-dioxotetrahydro-3-furanyl) -3-methyl-cyclohexene-1, 2-dicarboxylic acid anhydride, 1,2,3, 4-benzenetetracarboxylic acid dianhydride, 3',4,4' -benzophenone tetracarboxylic dianhydride, 2', 3' -benzophenone tetracarboxylic dianhydride, 3',4,4' -diphenylsulfone tetracarboxylic dianhydride, methylene-4, 4' -diphthalic dianhydride, 1-ethylidene-4, 4' -diphthalic dianhydride, 2-propylidene-4, 4' -diphthalic dianhydride, 1, 2-ethylene-4, 4' -diphthalic dianhydride, 1, 3-trimethylene-4, 4' -diphthalic dianhydride, 1, 4-tetramethylene-4, 4' -diphthalic dianhydride, 1, 5-pentamethylene-4, 4' -diphthalic dianhydride, 4' -oxydiphthalic dianhydride, P-phenylene bis (trimellitic anhydride), thio-4, 4' -diphthalic dianhydride, sulfonyl-4, 4' -diphthalic dianhydride, 1, 3-bis (3, 4-dicarboxyphenyl) benzene dianhydride, 1, 3-bis (3, 4-dicarboxyphenoxy) benzene dianhydride, 1, 4-bis (3, 4-dicarboxyphenoxy) benzene dianhydride, 1, 3-bis [2- (3, 4-dicarboxyphenyl) -2-propyl ] benzene dianhydride, 1, 4-bis [2- (3, 4-dicarboxyphenyl) -2-propyl ] benzene dianhydride, bis [3- (3, 4-dicarboxyphenoxy) phenyl ] methane dianhydride, bis [4- (3, 4-dicarboxyphenoxy) phenyl ] methane dianhydride, 2-bis [3- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride bis (3, 4-dicarboxyphenoxy) dimethylsilane dianhydride, 1, 3-bis (3, 4-dicarboxyphenyl) -1, 3-tetramethyldisiloxane dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 1,2,5, 6-naphthalene tetracarboxylic dianhydride, 3,4,9, 10-perylene tetracarboxylic dianhydride, 2,3,6, 7-anthracene tetracarboxylic dianhydride, 1,2,7, 8-phenanthrene tetracarboxylic dianhydride, 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride (BPAF), dicyclohexyl-3, 3',4,4' -tetracarboxylic dianhydride (CpODA), 4' -oxydiphthalic anhydride (ODPA), 1,2,4, 5-cyclohexane tetracarboxylic dianhydride (HPMDA), 1,2,3, 4-cyclobutane tetracarboxylic dianhydride (CBDA), and the like.

The acid dianhydride is preferably at least one selected from the group consisting of pyromellitic dianhydride (PMDA), 3', 4' -biphenyl tetracarboxylic dianhydride (BPDA), 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride (BPAF), 4' -oxydiphthalic anhydride (ODPA), 1,2,4, 5-cyclohexane tetracarboxylic dianhydride (HPMDA) and 1,2,3, 4-cyclobutane tetracarboxylic dianhydride (CBDA).

The acid dianhydride may be used alone or in combination of two or more. Among them, pyromellitic dianhydride (PMDA) and biphenyl tetracarboxylic dianhydride (BPDA) are preferable from the viewpoints of mechanical properties of polyimide films, optical properties such as low retardation in the thickness direction (Rth) and low YI value, and high glass transition temperature. The polyimide precursor having the structure represented by the general formula (1-1) and the polyimide having the structure represented by the general formula (1-2) are more preferably copolymers of tetracarboxylic dianhydride and diamine, and the tetracarboxylic dianhydride contains pyromellitic dianhydride (PMDA).

The total content of pyromellitic dianhydride (PMDA) and biphenyl tetracarboxylic dianhydride (BPDA) in the total acid dianhydride is preferably 60 mol% or more, more preferably 80 mol% or more, and still more preferably 100 mol% from the viewpoints of low Rth and YI values and high glass transition temperature of the polyimide film.

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

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

The content ratio of pyromellitic dianhydride (PMDA) to biphenyl tetracarboxylic dianhydride (BPDA) in the acid dianhydride is preferably 20:80 to 80:20, more preferably 30:70 to 70:30, from the viewpoint of simultaneously satisfying low Rth and YI values, high glass transition temperature, elongation, and the like of the polyimide film.

From the viewpoint of in-plane uniformity in the thickness direction Rth of the obtained polyimide resin film, the acid dianhydride more preferably contains 9, 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride (BAPF).

Diamines

As the diamine of the general formula (1-1) and (1-2), examples thereof include diaminodiphenyl sulfone (e.g., 4' -diaminodiphenyl sulfone, 3' -diaminodiphenyl sulfone), p-Phenylenediamine (PDA), m-phenylenediamine, 2' -dimethylbenzidine (mTB), 4' -diaminodiphenyl sulfide, 3,4' -diaminodiphenyl sulfide, and 3,3' -diaminodiphenyl sulfide, 4' -diaminodiphenyl, 3' -diaminodiphenyl, 4' -diaminodiphenyl, 3' -diaminodiphenyl, 4' -diaminodiphenyl methane 3,4' -diaminodiphenylmethane, 3' -diaminodiphenylmethane, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl ] sulfone, 4-bis (4-aminophenoxy) biphenyl, 4-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl ] ether, bis [4- (3-aminophenoxy) phenyl ] ether, 1, 4-bis (4-aminophenyl) benzene, 1, 3-bis (4-aminophenyl) benzene, 9, 10-bis (4-aminophenyl) anthracene, 2, 2-bis (4-aminophenyl) propane, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis [4- (4-aminophenoxy) phenyl) propane, 2-bis [4- (4-aminophenoxy) phenyl) hexafluoropropane, 1, 4-bis (3-aminopropyl dimethylsilyl) benzene, 9-bis (4-aminophenyl) fluorene (BAFL), and the like.

The diamine is preferably at least one selected from the group consisting of 4,4' -diaminodiphenyl sulfone (4, 4' -DAS), 3' -diaminodiphenyl sulfone (3, 3' -DAS), 9-bis (4-aminophenyl) fluorene (BAFL), 2' -dimethylbenzidine (mTB), p-Phenylenediamine (PDA), diaminobis (trifluoromethyl) biphenyl (TFMB), 2' -bis [4- (4-aminophenoxy) phenyl ] propane (BAPP), 4' -diaminodiphenyl ether (ODA), and 1, 4-Cyclohexanediamine (CHDA).

The diamine preferably contains diaminodiphenyl sulfone, for example, 4 '-diaminodiphenyl sulfone (4, 4' -DAS) and/or 3,3 '-diaminodiphenyl sulfone (3, 3' -DAS).

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

The diamino diphenyl sulfone content in the whole diamine may be 50 mol% or more, or 70 mol% or more, or 90 mol% or more, or 95 mol% or more. The larger the amount of diaminodiphenyl sulfone, the more preferable the YI value of the polyimide film is lowered and the higher the glass transition temperature is obtained. As the diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfone is particularly preferable from the viewpoint of lowering YI value.

The diamine may be used singly or in combination of two or more. Preferably, diaminodiphenyl sulfone is copolymerized with other diamines. As other diamines copolymerized with diaminodiphenyl sulfone, diamide biphenyls, more preferably diaminobis (trifluoromethyl) biphenyl (TFMB), are preferably listed from the viewpoints of high heat resistance and low YI value of polyimide films. The content of diaminobis (trifluoromethyl) biphenyl (TFMB) in the entire diamine is preferably 20 mol% or more, more preferably 30 mol% or more, from the viewpoint of a low YI value of the polyimide film. The content of TFMB is preferably 80 mol% or less, more preferably 70 mol% or less, based on the total diamine, from the viewpoint of designing that the diamine may contain other advantageous diamines such as diaminodiphenyl sulfone.

Structural unit of the general formula (2)

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

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

The lower limit of the ratio of the structural part represented by the general formula (2) is preferably 5 mass% or more, more preferably 6 mass% or more, and still more preferably 7 mass% or more, based on the mass of the polyimide precursor or polyimide, from the viewpoint of reducing the residual stress of the polyimide film generated between the polyimide precursor and the support. The upper limit of the ratio of the structural part represented by the general formula (2) is preferably 40 mass% or less, more preferably 30 mass% or less, and still more preferably 25 mass% or less, based on the mass of the polyimide precursor or polyimide, from the viewpoints of transparency and heat resistance of the polyimide film. In the above general formula (2), q is an integer of 1 to 200, and is preferably an integer of 3 to 200 from the viewpoint of heat resistance of the obtained polyimide.

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

Dicarboxylic acid

As the acid component used for forming the polyimide precursor and polyimide in the present embodiment, a dicarboxylic acid may be used in addition to an acid dianhydride (for example, the above-exemplified tetracarboxylic dianhydride) within a range that does not impair the performance thereof. That is, the polyimide precursor of the present disclosure may be a polyamideimide precursor, and the polyimide may be a polyamideimide. Polyimide films obtained from such polyimide precursors or polyimides may have various properties such as mechanical elongation, glass transition temperature Tg, YI value, and the like. Examples of the dicarboxylic acid to be used include dicarboxylic acids having an aromatic ring and alicyclic dicarboxylic acids. In particular, at least one compound selected from the group consisting of aromatic dicarboxylic acids having 8 to 36 carbon atoms and alicyclic dicarboxylic acids having 6 to 34 carbon atoms is preferable. The carbon number referred to herein also includes the carbon number included in the carboxyl group. Among them, dicarboxylic acids having an aromatic ring are preferable.

As the dicarboxylic acid having an aromatic ring, specifically, examples thereof include isophthalic acid, terephthalic acid, 4 '-biphenyldicarboxylic acid, 3' -biphenyldicarboxylic acid, 1, 4-naphthalenedicarboxylic acid, 2, 3-naphthalenedicarboxylic acid, 1, 5-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 4 '-sulfonyldibenzoic acid, and 3,4' -sulfonyldibenzoic acid, 3 '-sulfonyldibenzoic acid, 4' -oxybisbenzoic acid, 3 '-oxybisbenzoic acid, 2-bis (4-carboxyphenyl) propane, 2-bis (3-carboxyphenyl) propane, 2' -dimethyl-4, 4 '-biphenyldicarboxylic acid, 3,4' -sulfonyldibenzoic acid, 3 '-sulfonyldibenzoic acid, 4' -oxybisbenzoic acid, 3,4 '-oxybisbenzoic acid, and 3,3' -oxybisbenzoic acid, 2-bis (4-carboxyphenyl) propane, 2-bis (3-carboxyphenyl) propane, 2 '-dimethyl-4, 4' -biphenyldicarboxylic acid, 4,4 '-bis (4-carboxyphenoxy) -m-terphenyl, 3,4' -bis (4-carboxyphenoxy) -p-terphenyl, 3 '-bis (4-carboxyphenoxy) -p-terphenyl, 3,4' -bis (4-carboxyphenoxy) -m-terphenyl, 3 '-bis (4-carboxyphenoxy) -m-terphenyl, 4' -bis (3-carboxyphenoxy) -p-terphenyl, 4 '-bis (3-carboxyphenoxy) -m-terphenyl 3,4' -bis (3-carboxyphenoxy) -p-terphenyl, 3 '-bis (3-carboxyphenoxy) -p-terphenyl, 3,4' -bis (3-carboxyphenoxy) -m-terphenyl, 3 '-bis (3-carboxyphenoxy) -m-terphenyl, 1-cyclobutanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, 1, 2-cyclohexanedicarboxylic acid, 4' -benzophenone dicarboxylic acid, 1, 3-phenylene diacetic acid, 1, 4-phenylene diacetic acid, and the like; and 5-aminoisophthalic acid derivatives described in International publication No. 2005/068535. When these dicarboxylic acids are actually copolymerized with a polymer, they may be used in the form of an acid chloride derived from thionyl chloride or the like, an active ester or the like.

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

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

The equivalent weight of the functional group of the silicon-containing compound represented by the above general formula (4) is preferably 800 or more, more preferably 1500 or more from the viewpoints of heat resistance (glass transition temperature) and residual stress of the obtained polyimide film. Functional group equivalent here refers to the molecular weight (unit: g/mole) of the silicon-containing compound per 1 mole of functional group. Examples of the functional group include 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, and a mercapto group. The functional group equivalent can be determined by the method described in the examples. When the functional group equivalent of the silicon-containing compound is 800 or more, the residual stress of the polyimide film is thought to be reduced because the siloxane domain is increased and the stress is relaxed.

In the general formula (4), R ₁ is 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 straight-chain or branched alkylene groups such as methylene, ethylene, n-propylene, isopropylene, n-butylene, sec-butylene, tert-butylene, n-pentylene, neopentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene and n-decylene; cycloalkylene such as cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene and cyclooctylene. 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 isopropylene.

In the general formula (4), R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms or 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. Examples of the monovalent organic group having 1 to 10 carbon atoms include straight-chain or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, aromatic groups such as phenyl, tolyl, xylyl, alpha-naphthyl and beta-naphthyl. The monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms may be any of linear, cyclic, and branched, and may be saturated or unsaturated. Examples of the monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms include straight-chain or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl and neopentyl; cycloalkyl groups such as cyclopropyl, cyclobutyl and cyclopentyl. The monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferably at least one selected from the group consisting of methyl, ethyl and n-propyl, and more preferably methyl.

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

In the general formula (4), R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and a part of them may be organic groups having an unsaturated aliphatic hydrocarbon group. The monovalent organic group having 1 to 10 carbon atoms may be any of a linear, cyclic, and branched chain, and examples thereof include a linear or branched alkyl group such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a neopentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a n-nonyl group, and a n-decyl group; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, aromatic groups such as phenyl, tolyl, xylyl, alpha-naphthyl and beta-naphthyl. 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, and may be any of a linear, cyclic, and branched one. Examples of the unsaturated aliphatic hydrocarbon group having 3 to 10 carbon atoms include vinyl, allyl, propenyl, 3-butenyl, 2-butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, octenyl, nonenyl, decenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl and the like. The unsaturated aliphatic hydrocarbon group having 3 to 10 carbon atoms is preferably at least one selected from the group consisting of vinyl groups, allyl groups and 3-butenyl groups.

In the general formula (4), part or all of the hydrogen atoms of R ₁～R₇ may be substituted with a substituent such as a halogen atom such as F, cl or Br, or may be unsubstituted.

I is an integer of 1 to 200, preferably an integer of 2 to 100, more preferably an integer of 4 to 80, and even more preferably an integer of 8 to 40. j and k are each independently an integer of 0 to 200, preferably an integer of 0 to 50, more preferably an integer of 0 to 20, and even more preferably an integer of 0 to 50.

The silicon-containing compound of the general formula (4) is preferably a silicon-containing diamine from the viewpoint of the kind of monomer, cost and molecular weight of the polyimide precursor and polyimide obtained. The silicon-containing diamine is preferably, for example, diamino (poly) siloxane represented by the following formula (6).

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

Preferable structures of P ₃ and P ₄ in the general formula (2) include methyl, ethyl, propyl, butyl, phenyl, and the like. Among them, methyl is preferred. In the above general formula (6), l is an integer of 1 to 200, and is preferably an integer of 3 to 200 from the viewpoint of heat resistance of the obtained polyimide.

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

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

The silicon-containing compound as a monomer for use in the polyimide precursor and polyimide may be synthesized as described above using common technical knowledge at the time of application, or may be commercially available. The commercial products include: two-terminal amine-modified methylphenyl silicone oil (believed chemical Co., ltd.: X22-1660B-3 (functional equivalent 2200), X22-9409 (functional equivalent 670)), two-terminal anhydride-modified methylphenyl silicone oil (believed chemical Co., ltd.: X22-168-P5-B (functional equivalent 2100)), two-terminal epoxy-modified methylphenyl silicone oil (believed chemical Co., ltd.: X22-2000 (functional equivalent 620)), two-terminal amino-modified dimethylsiloxane (believed chemical Co., ltd.: PAM E (functional equivalent 130), X22-161A (functional equivalent 800), X22-161B (functional equivalent 1500), KF8012 (functional equivalent 2200), dow Corning Toray Co.: BY16-853U (functional equivalent 450), JNC company: 533311 (number average molecular weight 1000), two-terminal epoxy-modified dimethylsiloxane (believed to be more than X22-163A), two-terminal epoxy-modified dimethylsiloxane (believed to be more functional equivalent 1700) (believed to be more than two-terminal amine-modified silicone (believed to be more functional equivalent 1700), two-terminal amine-modified dimethylsiloxane (believed to be more functional equivalent 167), two-terminal amine-modified silicone oil (believed to be (functional equivalent 167) and two-terminal amine-modified silicone oil (believed to be represented BY Ltd: B16-853, believed 2, 3) Two terminal anhydride-modified dimethylsiloxane (Xinyue chemical Co., ltd.: X-22-168A (functional group equivalent 1000)), and the like. Among them, the both terminal amine-modified simethicone is preferable from the viewpoints of price, improvement of chemical resistance and improvement of Tg.

The tetracarboxylic dianhydride may be one exemplified for the above general formulae (1-1) and (1-2). The tetracarboxylic dianhydride is preferably at least one selected from the group consisting of pyromellitic dianhydride (PMDA), 3', 4' -biphenyl tetracarboxylic dianhydride (BPDA), 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride (BPAF), 4' -oxydiphthalic anhydride (ODPA), 1,2,4, 5-cyclohexane tetracarboxylic dianhydride (HPMDA), and 1,2,3, 4-cyclobutane tetracarboxylic dianhydride (CBDA).

The diamine may be a diamine exemplified for the above general formulae (1-1) and (1-2). The diamine is preferably at least one selected from the group consisting of 4,4' -diaminodiphenyl sulfone (4, 4' -DAS), 3' -diaminodiphenyl sulfone (3, 3' -DAS), 2' -dimethylbenzidine (mTB), p-Phenylenediamine (PDA), diaminobis (trifluoromethyl) biphenyl (TFMB), 2' -bis [4- (4-aminophenoxy) phenyl ] propane (BAPP), 4' -diaminodiphenyl ether (ODA) and 1, 4-Cyclohexanediamine (CHDA).

Weight average molecular weight

In this embodiment, the weight average molecular weight of the polyimide precursor and the polyimide is preferably 50000 or more, more preferably 60000 or more, from the viewpoint of lowering the YI value of the polyimide film. The weight average molecular weight of the polyimide precursor and polyimide is preferably 150000 or less, more preferably 120000 or less, from the viewpoint of reducing the haze of the polyimide film. The preferred weight average molecular weight of the polyimide precursor and polyimide may vary depending on the intended use, the type of polyimide precursor and polyimide, the non-solvent content of the resin composition, the type of solvent that the resin composition can contain, and the like.

Preferred embodiments of polyimide precursor and polyimide

The polyimide precursor particularly preferred in the present embodiment includes polycondensates of the acid dianhydride component (1) to (4) below and a silicon-containing diamine.

(1) The acid dianhydride component is pyromellitic dianhydride (PMDA) and biphenyl tetracarboxylic dianhydride (BPDA), and the diamine component is polycondensate of diaminodiphenyl sulfone (DAS), diaminobis (trifluoromethyl) biphenyl (TFMB) and silicon-containing diamine. The polycondensate preferably has a weight average molecular weight of 60000 to 110000 and a non-solvent component content of 10 to 25 mass%.

(2) The acid dianhydride component is pyromellitic dianhydride (PMDA) and biphenyl tetracarboxylic dianhydride (BPDA), and the diamine component is polycondensate of diamino diphenyl sulfone (DAS) and silicon-containing diamine. The polycondensate preferably has a weight average molecular weight of 50000 to 110000 and a non-solvent component content of 10 to 25 mass%.

(3) The acid dianhydride component is pyromellitic dianhydride (PMDA) and 9, 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride (BPAF), and the diamine component is polycondensate of diaminodiphenyl sulfone (DAS), diaminobis (trifluoromethyl) biphenyl (TFMB) and siliceous diamine. The polycondensate preferably has a weight average molecular weight of 70000 to 110000 and a content of the non-solvent component of 10 to 25 mass%.

(4) The acid dianhydride component is pyromellitic dianhydride (PMDA), and the diamine component is polycondensate of 9, 9-bis (4-aminophenyl) fluorene (BAFL) and diamine containing silicon. The polycondensate preferably has a weight average molecular weight of 60000 to 110000 and a non-solvent component content of 10 to 25 mass%.

Among the material components of the polycondensates of the above (1) to (4), the diamine containing silicon is preferably a diamino (poly) siloxane represented by the above general formula (6). In this case, the number average molecular weight of the diamino (poly) siloxane is preferably 500 to 12000, and more preferably the diamino (poly) siloxane is a two-terminal amine-modified dimethylsilicone oil.

Cyclic siloxanes

The resin composition of the present embodiment may contain a cyclic siloxane represented by the following general formula (5), and the silicon-containing compound (monomer used in the polycondensation reaction of the polyimide precursor) used in the resin composition of the present embodiment may contain a silicon-containing compound represented by the general formula (3) and a silicon-containing compound represented by the general formula (4).

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

The resin composition of the present embodiment contains a compound represented by a cyclic siloxane represented by the following general formula (3) in a specific ratio among the compounds of the general formula (5).

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

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

When the mass of the non-solvent component in the resin composition is taken as a reference, the total amount of the compound having n of 4 in the general formula (3) is preferably more than 0ppm and 500ppm or less, more preferably more than 0ppm and 400ppm or less, still more preferably more than 0ppm and 300ppm or less, still more preferably more than 0ppm and 10ppm or less. When the mass of the non-solvent component in the resin composition is taken as a reference, the total amount of the compounds having n of 5 in the general formula (3) is preferably more than 0ppm and 200ppm or less, more preferably more than 0ppm and 100ppm or less, still more preferably more than 0ppm and 50ppm or less, still more preferably more than 0ppm and 5ppm or less. When the mass of the non-solvent component in the resin composition is taken as a reference, the total amount of the compound having n of 6 in the general formula (3) is preferably more than 0ppm and 450ppm or less, more preferably more than 0ppm and 300ppm or less, still more preferably more than 0ppm and 250ppm or less, still more preferably more than 0ppm and 230ppm or less. When the mass of the non-solvent component in the resin composition is taken as a reference, the total amount of the compounds having n of 7 in the general formula (3) is preferably more than 0ppm and 500ppm or less, more preferably more than 0ppm and 400ppm or less, still more preferably more than 0ppm and 300ppm or less, still more preferably more than 0ppm and 250ppm or less. If the total amount of the compounds represented by the general formula (3) falls within the above range, defects of a polyimide resin film obtained from the resin composition are reduced, and the YI value is further reduced, which is preferable.

In the present specification, "non-solvent component" refers to all components in the resin composition except for the solvent, and the liquid monomer component is also contained in the mass of the non-solvent component. When the resin composition contains only a solvent and a polyimide precursor, the polyimide precursor corresponds to a non-solvent component. When the resin composition contains only the solvent and the polyimide precursor, the mass of the non-solvent component corresponds to the total mass of all the monomers contained in the polyimide precursor. The mass of the non-solvent component may be obtained by subjecting the resin composition to gas chromatography (hereinafter also referred to as GC) analysis to obtain the mass of the solvent, and subtracting the mass of the solvent from the mass of the resin composition. The mass of the non-solvent component may be obtained by heating the resin composition to volatilize and remove the solvent, and subtracting the mass of the solvent from the mass of the resin composition.

When the total mass of the silicon-containing compounds represented by the general formulae (3) and (4) is taken as a reference, the total amount of the compounds having n of 4 in the general formula (3) is preferably more than 0ppm and 1300ppm or less, more preferably more than 0ppm and 800ppm or less, still more preferably more than 0ppm and 500ppm or less, still more preferably more than 0ppm and 30ppm or less. When the total mass of the silicon-containing compounds represented by the general formulae (3) and (4) is taken as a reference, the total amount of the compounds having n of 5 in the general formula (3) is preferably more than 0ppm and 500ppm or less, more preferably more than 0ppm and 300ppm or less, still more preferably more than 0ppm and 100ppm or less, still more preferably more than 0ppm and 15ppm or less. When the total mass of the silicon-containing compounds represented by the general formulae (3) and (4) is taken as a reference, the total amount of the compounds having n of 6 in the general formula (3) is preferably more than 0ppm and 2000ppm or less, more preferably more than 0ppm and 1000ppm or less, still more preferably more than 0ppm and 500ppm or less, still more preferably more than 0ppm and 20ppm or less. When the total mass of the silicon-containing compounds represented by the general formulae (3) and (4) is taken as a reference, the total amount of the compounds having n of 7 in the general formula (3) is preferably more than 0ppm and 2200ppm or less, more preferably more than 0ppm and 1100ppm or less, still more preferably more than 0ppm and 600ppm or less, still more preferably more than 0ppm and 10ppm or less. If the total amount of the compounds represented by the general formula (3) falls within the above range, defects of a polyimide resin film obtained from the resin composition are reduced, and the YI value is further reduced, which is preferable.

When the mass of the resin composition is taken as a reference, the total amount of the compounds having n of 3 to 8 in the general formula (3) is preferably more than 0ppm and 150ppm or less, more preferably more than 0ppm and 130ppm or less, still more preferably more than 0ppm and 100ppm or less. When the mass of the non-solvent component in the resin composition is taken as a reference, the total amount of the compounds having n of 3 to 8 in the general formula (3) is preferably more than 0ppm and 900ppm or less, more preferably more than 0ppm and 800ppm or less, still more preferably more than 0ppm and 700ppm or less. When the total mass of the silicon-containing compounds represented by the general formulae (3) and (4) is taken as a reference, the total amount of the compounds having n of 3 to 8 in the general formula (3) is preferably more than 0ppm and 4500ppm or less, more preferably more than 0ppm and 4000ppm or less, still more preferably more than 0ppm and 3000ppm or less. If the total amount of the compounds represented by the general formula (3) falls within the above range, defects of a polyimide resin film obtained from the resin composition are reduced, and the YI value is further reduced, which is preferable.

Conventionally, the amount of a compound having n of 4 or less in a cyclic siloxane of the general formula (3) (patent documents 3 to 5, etc.) has been reduced for the purpose of reducing outgas from the obtained polyimide resin film. However, in the case of the method for reducing a cyclic siloxane of the prior art, it has been found that the reduction in the amount of a compound having n of 7 or less in the cyclic siloxane of the general formula (3) is insufficient. Further, it was found that when n is 5 or more and 7 or less in the compound of the general formula (3) is a specific amount, the surface defect of the obtained polyimide resin film is reduced, and the yellowness (YI value) can be further improved. The detailed mechanism of these is not clear, but the inventors presume as follows. The method for producing a polyimide resin film typically includes: a step of applying a composition containing a polyimide precursor composition and a polyimide resin to a support such as a glass substrate, and heating the support in an oven at 100 ℃ for 30 minutes, for example, under reduced pressure, to thereby remove the solvent (a solvent removal step); and a step of forming a polyimide resin film by imidizing (or removing a solvent) by heating at a higher temperature, for example, 400 ℃ for 1 hour. In the case where n is 3 or more and 8 or less, the compound of the general formula (3) (methyl side chain cyclic siloxane) is volatilized and removed in the imidization step (for example, heating at 400 ℃ C. For 1 hour) at a boiling point of 400 ℃ or less under normal pressure. On the other hand, it is considered that the solvent removal step is carried out at a temperature lower than that of the imidization step, and when n is 3 or more and 8 or less, the compound of the general formula (3) is volatilized and removed in the solvent removal step. However, it is estimated that, in particular, when the amount of the compound of the general formula (3) is large, n is 3 or more and 8 or less, a trace of volatilization remains, which forms a defect on the polyimide resin film. Further, it is considered that in the case of distillation at 250 ℃ or higher, which is a conventional purification method, the silicon-containing compound decomposed during cooling is cyclized again due to the high temperature, and the amount of the compounds having n of 4 and 5 in the compound of the general formula (3) increases. As a result, defects on the polyimide resin film were estimated to increase. The inventors of the present invention found that defects in polyimide resin films can be reduced by subjecting compounds of the general formulae (3) and (4) to purification treatment (reduced pressure distillation) under specific conditions, particularly by adjusting the amounts of the compounds of the general formulae (3) in which n is 4 and 5 to specific amounts or adjusting the total amount of the compounds of the general formula (3) in which n is 3 or more and 8 or less to specific amounts.

The YI value is affected by, for example, the amine value (ratio of compounds having amine ends) of the silicon-containing compound used, and if the amine value is high, the YI value tends to be increased, and if the amine value is small, the YI value also tends to be decreased. However, the polyimide precursor obtained by using the purified silicon-containing compound, that is, the polyimide precursor obtained by using the silicon-containing compound having the amount of the compound represented by the general formula (3) in which n is 4 or 5 is within the above range, or the compound having n is 3 or more and 8 or less is liable to have a lower YI value than the polyimide precursor obtained by using the silicon-containing compound having the amount of the compound represented by the general formula (3) reduced in the conventional method. The mechanism is not clear, but the inventors presume as follows. That is, in the case of using the conventional purification method, a diamine having a low molecular weight other than cyclic, which is used for producing a polyimide precursor, remains, and is decomposed to generate radicals when the polyimide is cured, which may cause an increase (deterioration) in YI value. It is considered that by reducing the amount of the cyclic siloxane represented by the compounds having n of 4 or 5 in the general formula (3) or by reducing the amount of the compound having n of 3 or more and 8 or less, not only the cyclic siloxane but also a low-molecular-weight diamine which is not cyclic but is more easily volatilized from the diamine component having an increased amine value is removed during purification. Therefore, it is estimated that according to the present embodiment, the polyimide precursor in which the amount of the compounds represented by the general formula (3) n is reduced by 4 or 5 or the amount of the compound n is reduced by 3 or more and 8 or less further improves the YI value of the polyimide resin film. Since it is considered that it is difficult to reduce a low molecular weight diamine which is not cyclic when a conventional purification method (decantation, reprecipitation, etc.) is used, the degree of improvement in YI value of a polyimide resin film is smaller than in the present embodiment even if purification is performed.

In addition, it is also preferable to reduce the amount of the compound in which n is 3 or more and 8 or less in the compound in the general formula (3) and the amount of the compound in which n is 3 or more and 7 or less and the compound in which n is 3 and 4. That is, when the total amount of the compounds having n of 3 in the general formula (3) is d3 (ppm), the total amount of the compounds having n of 4 is d4 (ppm), the total amount of the compounds having n of 5 is d5 (ppm), the total amount of the compounds having n of 6 is d6 (ppm), and the total amount of the compounds having n of 7 is d7 (ppm), d3+d4+d5+d6+d7 is preferably more than 0ppm and less than 2000ppm based on the mass of the non-solvent component of the resin composition. Further, d3+d4 is preferably more than 0ppm and 10ppm or less. If the amount of the compound having n of 3 or more and 7 or less in the general formula (3) is more than 0ppm and less than 2000ppm, it is preferable from the viewpoint of defect evaluation of the obtained polyimide film. In addition, when the amount of the compounds of the general formula (3) in which n is 3 and 4 is more than 0ppm and 10ppm or less, the difference between the YI values of the polyimide precursor using the purified silicon-containing compound and the polyimide precursor using the non-purified silicon-containing compound and the polyimide film obtained respectively is preferable.

Solvent

The resin composition typically contains a solvent. The solvent is preferably a solvent which has good solubility of the polyimide precursor and polyimide and can appropriately control the solution viscosity of the resin composition, and a reaction solvent of the polyimide precursor can be used as the solvent of the composition. Among them, N-methyl-2-pyrrolidone (NMP), gamma-butyrolactone (GBL), a compound represented by the above general formula (4), and the like are preferable. Specific examples of the solvent composition include N-methyl-2-pyrrolidone (NMP) alone, and a mixed solvent of N-methyl-2-pyrrolidone (NMP) and γ -butyrolactone (GBL). The mass ratio of NMP to GBL may be NMP to GBL (mass ratio) =10:90 to 90:10, for example.

Additive composition

The resin composition of the present embodiment may contain additional components in addition to the polyimide precursor, polyimide, cyclic siloxane and solvent. Examples of the additional component include a surfactant and an alkoxysilane compound.

Surface active agent

The resin composition of the present embodiment can be improved in coatability by adding a surfactant thereto. Specifically, the occurrence of streaks in the coating film can be prevented.

Examples of such surfactants include silicone surfactants, fluorine surfactants, and nonionic surfactants other than these surfactants. Examples of the silicone surfactant include organosiloxane polymers KF-640, 642, 643, KP341, X-70-092, and X-70-093 (trade name, manufactured by Xinyue chemical Co., ltd.); SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (trade name, dow Corning Toray Silicone Co., ltd.); SILWETL-77, L-7001, FZ-2105, FZ-2120, FZ-2154, FZ-2164, FZ-2166, L-7604 (trade name, trade name of );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( by Nippon Unicar Company Limited, manufactured by BYK-Chemie Japan); glanol (trade name, manufactured by co-mings chemical Co., ltd.). Examples of the fluorine-based surfactant include MEGAFACE F, F173, R-08 (trade name, manufactured by DAINIPPON INK AND CHEMICALS, INCORPORATED), fluorine-based FC4430, FC4432 (Sumitomo 3M Limited, trade name), and the like. Examples of the nonionic surfactant other than these surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like.

Among these surfactants, silicone surfactants and fluorine surfactants are preferable from the viewpoint of coatability (suppression of coating streaks) of the resin composition, and silicone surfactants are preferable from the viewpoint of reducing the influence on the YI value and the total light transmittance due to the oxygen concentration at the time of the curing step. When the surfactant is used, the compounding amount thereof 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 compound

When the polyimide film obtained from the resin composition of the present embodiment is used for a flexible substrate or the like, the resin composition may contain 0.01 to 20 parts by mass of an alkoxysilane compound per 100 parts by mass of the polyimide precursor from the viewpoint of obtaining good adhesion between the support and the polyimide film in the production process. When the content of the alkoxysilane compound is 0.01 part by mass or more relative to 100 parts by mass of the polyimide precursor, good adhesion between the support and the polyimide film can be obtained. The content of the alkoxysilane compound is preferably 20 parts by mass or less from the viewpoint of storage stability of the resin composition. The content of the alkoxysilane compound is preferably 0.02 to 15 parts by mass, more preferably 0.05 to 10 parts by mass, and still 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-described adhesion, the coatability of the resin composition (suppression of streak unevenness) can be improved and the influence on the YI value of the polyimide film due to the oxygen concentration at the time of curing can be reduced.

As the alkoxysilane compound, there is used, examples thereof include 3-ureidopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminoethyltrimethoxysilane, gamma-aminoethyltrimutoxysilane, gamma-aminobutyltriethoxysilane gamma-aminobutyltrimethoxysilane, gamma-aminobutyltritutoxysilane, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy (p-tolyl) silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, alkoxysilane compounds represented by the following structures, and the like. The alkoxysilane compound may be used singly or in combination of two or more.

Method for producing resin composition

The method for producing the resin composition according to the present embodiment is not particularly limited, and for example, the following method can be used.

Purification of silicon-containing compounds

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

As a method for purifying the silicon-containing compound, for example, stripping is performed while blowing an inert gas such as nitrogen gas into the silicon-containing compound in an arbitrary container. The stripping temperature is preferably 150 ℃ to 300 ℃, more preferably 200 ℃ to 300 ℃, still more preferably 230 ℃ to 300 ℃. The lower the vapor pressure of the stripping, the more preferable is 1000Pa or less, more preferable 300Pa or less, still more preferable 200Pa or less, still more preferable 133.32Pa (1 mmHg) or less. The time for the stripping is preferably 4 hours to 12 hours, more preferably 6 hours to 10 hours. By adjusting the conditions described above, the compound of the general formula (3) can be effectively removed, and the total amount of the general formulae (3) and (4) can be controlled within a preferable range.

Polyimide precursor and synthesis of polyimide

The polyimide precursor of the present embodiment can be synthesized by subjecting a polycondensation component containing an acid dianhydride, a diamine, and a silicon-containing compound to a polycondensation reaction. The polyimide of the present embodiment can be synthesized by imidizing the polyimide precursor. The silicon-containing compound is preferably the purified silicon-containing compound described above. In a preferred embodiment, the polycondensation component comprises an acid dianhydride, a diamine, and a silicon containing compound. The polycondensation reaction is preferably carried out in a suitable solvent. Specifically, for example, a method in which a predetermined amount of a diamine component and a silicon-containing compound are dissolved in a solvent, and then a predetermined amount of an acid dianhydride is added to the resulting diamine solution and stirred is mentioned.

The molar ratio of the acid dianhydride to the diamine in the synthesis of the polyimide precursor is preferably in the range of acid dianhydride: diamine=100:90 to 100:110 (1 part by mol of diamine to acid dianhydride, 0.90 to 1.10 parts by mol of diamine), more preferably in the range of 100:95 to 100:105 (0.95 to 1.05 parts by mol of diamine to 1 part by mol of acid dianhydride) from the viewpoints of the high molecular weight of the polyimide precursor and the polyimide resin obtained and the slit coating property of the resin composition.

The molecular weight of the polyimide precursor and the polyimide can be controlled by adjusting the types of the acid dianhydride, the diamine, and the silicon-containing compound, the molar ratio of the acid dianhydride to the diamine, the addition of the capping agent, the adjustment of the reaction conditions, and the like. The polyimide precursor and polyimide can be increased in molecular weight as the molar ratio of the acid dianhydride component to the diamine component is closer to 1:1, and the amount of the capping agent used is smaller.

As the acid dianhydride component and the diamine component, high purity products are recommended. The purity is preferably 98% by mass or more, more preferably 99% by mass or more, and still more preferably 99.5% by mass or more, respectively. By reducing the moisture content in the acid dianhydride component and the diamine component, high purity can be achieved. When a plurality of acid dianhydride components and/or a plurality of diamine components are used, the above-mentioned purity is preferably provided as the whole of the acid dianhydride component and as the whole of the diamine component, and more preferably all kinds of the acid dianhydride components and the diamine components used each have the above-mentioned purity.

The solvent for the reaction is not particularly limited as long as it can dissolve the acid dianhydride component and the diamine component, and the polyimide precursor and polyimide produced, and thus a polymer having a high molecular weight can be obtained. Examples of such solvents include aprotic solvents, phenolic solvents, ethers, and glycol solvents. Examples of the aprotic solvent include N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N-methylcaprolactam, 1, 3-dimethylimidazolidinone, tetramethylurea, N-dimethylisobutyl amide, dimethylacetamide, 1, 3-dimethyl-2-imidazolidinone, and amide solvents of the following general formula (7):

{ formula, wherein R ₁₂ = EK-Amide M100 (trade name: manufactured by Kaikovia Kaisha Co., ltd.) shown by methyl group, and R ₁₂ = EK-Amide B100 (trade name: manufactured by Kaikovia Kaisha Co., ltd.) shown by n-butyl group; lactone solvents such as gamma-butyrolactone and gamma-valerolactone; a phosphorus-containing amide solvent such as hexamethylphosphoramide and hexamethylphosphinotricin; sulfur-containing solvents such as dimethyl sulfone, dimethyl sulfoxide, and sulfolane; ketone solvents such as cyclohexanone and methylcyclohexanone; tertiary amine solvents such as picoline and pyridine; and ester solvents such as 2-methoxy-1-methylethyl acetate, 3-methoxy-3-methyl-1-butyl acetate and diethylene glycol monobutyl ether acetate. Examples of the phenol-based solvent include phenol, o-cresol, m-cresol, p-cresol, 2, 3-xylenol, 2, 4-xylenol, 2, 5-xylenol, 2, 6-xylenol, 3, 4-xylenol, 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, bis [2- (2-methoxyethoxy) ethyl ] ether, tetrahydrofuran, 1, 4-dioxane, dipropylene glycol methyl ether acetate, dipropylene glycol dimethyl ether, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. These solvents may be used alone or in combination of 2 or more.

The boiling point of the polyimide precursor and the solvent used for synthesizing the polyimide at normal pressure is preferably 60 to 300 ℃, more preferably 140 to 280 ℃, and even more preferably 170 to 270 ℃. The solvent is formed by a drying process for a short time with a boiling point below 300 ℃. When the boiling point of the solvent is 60 ℃ or higher, cracking of the surface of the resin film, mixing of bubbles into the resin film, and the like are less likely to occur in the drying step, and a more uniform film can be obtained. In particular, it is preferable to use a solvent having a boiling point of 170 to 270℃and/or a vapor pressure of 250Pa or less at 20℃from the viewpoints of solubility and abnormal edge reduction at the time of coating. More specifically, 1 or more selected from the group consisting of N-methyl-2-pyrrolidone (NMP), γ -butyrolactone (GBL), and a compound represented by the general formula (7) is preferable.

For the moisture content in the solvent, for example, 3000 mass ppm or less is preferable in order to perform the polycondensation reaction satisfactorily. The content of the molecules having a molecular weight of less than 1000 in the resin composition of the present embodiment is preferably less than 5 mass%. The presence of molecules having a molecular weight of less than 1000 in the resin composition is considered to be related to the solvent used in the synthesis and the moisture content of the raw materials (acid dianhydride, diamine). That is, it is considered that the acid anhydride gene of a part of the acid dianhydride monomer is hydrolyzed by moisture to form a carboxyl group, and remains in a low molecular state, and does not have a high molecular weight. Therefore, the smaller the moisture content of the solvent used in the polycondensation reaction, the more preferable. The moisture content of the solvent is preferably 3000 mass ppm or less, more preferably 1000 mass ppm or less. Similarly, the amount of water contained in the raw material is preferably 3000 mass ppm or less, more preferably 1000 mass ppm or less.

The moisture content of the solvent is considered to be related to the grade of the solvent used (dehydration grade, general grade, etc.), the solvent container (bottle, 18L tank, small tank, etc.), the state of storage of the solvent (presence or absence of rare gas encapsulation, etc.), the time from unsealing until use (use immediately after unsealing or use after elapsed time after unsealing, etc.), and the like. It is considered that the present invention also relates to the presence or absence of rare gas exchange in the reactor before synthesis and the like in the rare gas circulation during synthesis. Therefore, it is recommended to use a high-purity product as a raw material in the synthesis of a polyimide precursor, use a solvent having a small amount of moisture, and take such measures that moisture is not mixed into the system from the environment before and during the reaction.

When each polycondensation component is dissolved in a solvent, heating may be performed as needed. From the viewpoint of obtaining a polyimide precursor having a high polymerization degree, the reaction temperature at the time of synthesizing the polyimide precursor may be preferably 0 to 120 ℃,40 to 100 ℃, or 60 to 100 ℃, and the polymerization time may be preferably 1 to 100 hours, or 2 to 10 hours. A polyimide precursor having a uniform polymerization degree is formed by a polymerization time of 1 hour or more, and a polyimide precursor having a high polymerization degree is obtained by a polymerization time of 100 hours or less.

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

The polyimide precursor in the present embodiment may be partially imidized (partially imidized). By partially imidizing the polyimide precursor, the viscosity stability at the time of storing the resin composition can be improved. The imidization ratio in this case is preferably 5% or more, more preferably 8% or more, still more preferably 80% or less, still more preferably 70% or less, and still more preferably 50% or less, from the viewpoint of obtaining a balance between the solubility of the polyimide precursor in the resin composition and the storage stability of the solution. The partial imidization is obtained by dehydrating and ring-closing a polyimide precursor by heating. The heating may be performed at a temperature of preferably 120 to 200 ℃, more preferably 150 to 180 ℃, preferably 15 minutes to 20 hours, more preferably 30 minutes to 10 hours.

The polyamide acid obtained by the above reaction may be partially or completely esterified by adding N, N-dimethylformamide dimethyl acetal or N, N-dimethylformamide diethyl acetal and heating, and then used as the polyimide precursor of the present embodiment. By esterification, the viscosity stability upon storage can be improved. These ester-modified polyamic acids can be obtained by a method in which the acid dianhydride component is reacted with a monohydric alcohol having 1 equivalent to the acid anhydride group, and a dehydration condensing agent such as thionyl chloride or dicyclohexylcarbodiimide, followed by a condensation reaction with a diamine component.

Synthesis of polyimide

As a more preferred embodiment, the polyimide varnish can be produced as follows: the polyimide solution (also referred to as a polyimide varnish) containing polyimide and a solvent is produced by dissolving an acid dianhydride component and a diamine component in a solvent, for example, an organic solvent, adding an azeotropic solvent such as toluene, and removing water generated during imidization from the system. The reaction conditions are not particularly limited, and the reaction temperature is, for example, 0 to 180℃and the reaction time is 3 to 72 hours. In order to sufficiently react with the diamine having a sulfo group, the reaction is preferably carried out by heating at 180℃for about 12 hours. In the reaction, an inert atmosphere such as argon or nitrogen is preferable.

Adjustment of resin composition

When the solvent used for synthesizing the polyimide precursor or polyimide is the same as the solvent contained in the resin composition, the polyimide precursor solution or polyimide solution thus synthesized may be used as the resin composition of the present embodiment. If necessary, the resin composition may be adjusted by further adding 1 or more of the solvent and the additional component to the polyimide precursor or polyimide solution at a temperature in the range of room temperature (25 ℃) to 80℃and stirring and mixing the mixture. The stirring and mixing may be performed by using an appropriate device such as a three-in-one motor (manufactured by Xindong chemical Co., ltd.) having stirring blades, a rotation and revolution mixer, or the like. The resin composition may be heated to 40℃to 100℃as required.

On the other hand, when the solvent used for synthesizing the polyimide precursor or polyimide is different from the solvent contained in the resin composition, the polyimide precursor or polyimide may be separated by removing the solvent from the polyimide precursor solution or polyimide solution to be synthesized by an appropriate method such as reprecipitation or solvent distillation. Then, a desired solvent and optional additional components are added to the separated polyimide precursor or polyimide at a temperature in the range of room temperature (25 ℃) to 80℃and stirred and mixed, whereby a resin composition can be produced.

In the case of a resin composition containing a polyimide precursor, after the resin composition is produced as described above, a part of the polyimide precursor may be dehydrated and imidized (partially imidized) by heating the resin composition at 130 to 200 ℃ for 5 minutes to 2 hours, for example, to such an extent that the polymer does not precipitate. The imidization rate can be controlled by controlling the heating temperature and the heating time. By partially imidizing the polyimide precursor, the viscosity stability at the time of storing the resin composition can be improved.

The solution viscosity of the resin composition is preferably 500 to 100000mpa·s, more preferably 1000 to 50000mpa·s, and even more preferably 3000 to 20000mpa·s from the viewpoint of the slit coating property. Specifically, from the viewpoint of being less likely to leak liquid from the slit nozzle, it is preferably 500mpa·s or more, more preferably 1000mpa·s or more, and still more preferably 3000mpa·s or more. From the viewpoint of the difficulty in clogging of the slit nozzle, it is preferably 100000mpa·s or less, more preferably 50000mpa·s or less, and further preferably 20000mpa·s or less.

The solution viscosity of the polyimide precursor or the resin composition at the time of polyimide synthesis is preferably 200000mpa·s or less from the viewpoint of facilitating stirring at the time of synthesis. However, even if the solution has a high viscosity during the synthesis, a resin composition having a viscosity excellent in handling properties can be obtained by adding a solvent and stirring the mixture after the completion of the reaction. The solution viscosity of the resin composition in this embodiment is a value measured at 23℃using an E-type viscometer (for example, VISCONICEHD, manufactured by DONGMENTS INDUSTRIAL Co., ltd.).

The water content of the resin composition of the present embodiment is preferably 3000 mass ppm or less, more preferably 2500 mass ppm or less, still more preferably 2000 mass ppm or less, still more preferably 1500 mass ppm or less, particularly preferably 1000 mass ppm or less, particularly preferably 500 mass ppm or less, particularly preferably 300 mass ppm or less, particularly preferably 100 mass ppm or less, from the viewpoint of viscosity stability at the time of storing the resin composition.

Polyimide film and method for producing the same

The method for producing the polyimide film according to the present embodiment will be described below. The first method includes a coating step of coating (casting) a solution of a polyimide precursor onto a support, and a film formation step of forming a polyimide resin film by heating the coated solution to dry and imidize the same (as method 1). The production method 1 may optionally include a step of peeling the polyimide resin film from the support to obtain a polyimide film. The second method includes a coating step of coating (casting) a polyimide solution (polyimide varnish) onto a support, and a film forming step of forming a polyimide resin film by heating the coated solution and drying the same (as method 2-1). The production method 2-1 may optionally include a step of peeling the polyimide resin film from the support to obtain a polyimide film. In the second method, since the polyimide film is formed from a polyimide solution which has been imidized in advance, the polyimide film can be produced by temporarily drying, then separating the polyimide film from the support, and further drying the polyimide film (as method 2-2).

Coating process

In the coating step, the resin composition of the present embodiment is coated on the surface of the support. The support is not particularly limited as long as it has heat resistance to the heating temperature in the subsequent film forming step (heating step) and good peelability in the peeling step. Examples of the support include a glass substrate, for example, an alkali-free glass substrate; a silicon wafer; resin substrates such as PET (polyethylene terephthalate), OPP (drawn polypropylene), polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, polyamideimide, polyetherimide, polyetheretherketone, polyethersulfone, polyphenylsulfone, and polyphenylene sulfide; stainless steel, aluminum oxide, copper, nickel, etc.

In the case of forming a polyimide molded article in a film shape, for example, a glass substrate, a silicon wafer, or the like is preferable, and in the case of forming a polyimide molded article in a film shape or a sheet shape in a thick film shape, for example, a support formed of PET (polyethylene terephthalate), OPP (stretched polypropylene), or the like is preferable.

Examples of the coating method include coating methods such as a blade coater, an air knife coater, a roll coater, a spin coater, a flow coater, a die coater, and a bar coater, and coating methods such as spin coating, spray coating, and dip coating; printing techniques typified by screen printing, gravure printing, and the like. The resin composition of the present embodiment is preferably coated by slit coating. 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 in the order of 1 μm to 1000 μm. The temperature in the coating step may be room temperature to improve workability for reducing viscosity, or the resin composition may be heated to, for example, 40 to 80 ℃.

Optional drying procedure

After the coating step, the drying step may be performed, or the drying step may be omitted and the subsequent film forming step (heating step) may be performed directly. The drying step is performed to remove the organic solvent in the resin composition. In the case of performing the drying step, for example, a suitable apparatus such as a heating plate, a box dryer, or a conveyor type dryer may be used. The temperature of the drying step is preferably 80 to 200 ℃, more preferably 100 to 150 ℃. The drying step is preferably performed for 1 minute to 10 hours, more preferably 3 minutes to 1 hour. A coating film containing a polyimide precursor is formed on the support as described above.

Film forming process

Next, a film forming step (heating step) is performed. In the case of the polyimide precursor solution, the heating step is a step of removing the organic solvent contained in the coating film and imidizing the polyimide precursor in the coating film to obtain a polyimide resin film. In the case of the polyimide solution, the heating step is a step of removing the organic solvent contained in the coating film and obtaining a polyimide resin film. The heating step may be performed using, for example, an inert gas oven, a hot plate, a box dryer, a conveyor type dryer, or the like. This step may be performed simultaneously with the drying step or sequentially.

The heating step may be performed under an air atmosphere, but is preferably performed under an inert gas atmosphere from the viewpoints of obtaining good transparency, low thickness direction Rth, and low YI value of the obtained polyimide film. Examples of the inert gas include nitrogen and argon. In the case of the polyimide precursor solution, the heating temperature may be appropriately set depending on the kind of polyimide precursor and the kind of solvent in the resin composition, but is preferably 250 to 550 ℃, more preferably 300 to 450 ℃. When the temperature is 250 ℃ or higher, imidization proceeds satisfactorily, and when the temperature is 550 ℃ or lower, the problems such as lowering of transparency and deterioration of heat resistance of the obtained polyimide film can be avoided. In the case of the polyimide solution, the heating temperature may be appropriately set depending on the kind of polyimide and the kind of solvent in the resin composition, but is preferably 50 to 450 ℃. The heating time is preferably about 6 minutes to 10 hours.

In the present embodiment, in the case of the polyimide precursor solution, the oxygen concentration of the surrounding atmosphere in the heating step is preferably 2000 mass ppm or less, more preferably 100 mass ppm or less, and still more preferably 10 mass ppm or less, from the viewpoints of transparency and YI value of the obtained polyimide film. By heating in an atmosphere having an oxygen concentration of 2000 mass ppm or less, the YI value of the obtained polyimide film can be set to 30 or less.

Stripping procedure

In the peeling step, the polyimide resin film on the support may be peeled off after cooling to, for example, room temperature (25 ℃) to 50 ℃. Examples of the stripping step include the following modes (1) to (4).

Method (1): after the structure containing the polyimide resin film and the support is produced by the above method, laser light is irradiated from the support side of the structure, and the interface between the support and the polyimide resin film is subjected to ablation processing, thereby peeling the polyimide resin. Examples of the type of laser include a solid (YAG) laser and a gas (UV excimer) laser. It is preferable to use a spectrum having a wavelength of 308nm or the like (see Japanese patent application laid-open No. 2007-512568, japanese patent application laid-open No. 2012-511173, and the like).

Method (2): before the support is coated with the resin composition, a release layer is formed on the support, and then a structure containing a polyimide resin film/release layer/support is obtained, and the polyimide resin film is peeled off. Examples of the release layer include Parylene (registered trademark, manufactured by Parylene Japan LLC), and tungsten oxide; mold release agents such as vegetable oils, silicones, fluorides, and alkyds (see JP-A2010-067957, JP-A2013-179306, etc.) may also be used.

The laser irradiation of the method (2) and the method (1) may be used in combination.

Method (3): an etchable metal substrate is used as a support, and after a structure containing a polyimide resin film/support is obtained, the metal is etched with an etchant, thereby obtaining a polyimide resin film. As the metal, copper (specific example, electrolytic copper foil "DFF" manufactured by mitsubishi metal mining corporation), aluminum, and the like can be used. As the etchant, ferric chloride or the like can be used for copper, and dilute hydrochloric acid or the like can be used for aluminum.

Method (4): after the structure containing the polyimide resin film and the support is obtained by the above-described method, an adhesive film is stuck to the surface of the polyimide resin film, the adhesive film and the polyimide resin film are separated from the support, and then the polyimide resin film is separated from the adhesive film.

Among these peeling methods, the method (1) or (2) is preferable from the viewpoints of refractive index difference, YI value and elongation of the front and rear surfaces of the obtained polyimide resin film. From the viewpoint of the refractive index difference between the front and rear surfaces of the obtained polyimide resin film, it is more preferable to perform the irradiation step of irradiating the laser light from the support side before the method (1), i.e., the peeling step. In the method (3), when copper is used as the support, the YI value of the obtained polyimide resin film tends to increase and the elongation tends to decrease. This is thought to be due to the effect of copper ions.

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

Yellow (YI value)

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

The YI value is affected by, for example, the amine value of the silicon-containing compound used, and if the amine value is high, the YI value tends to be increased, and if the amine value is small, the YI value also tends to be decreased. However, the polyimide precursor in which the total amount of the compounds represented by the general formula (3) is in the above range, which is a purified silicon-containing compound, tends to have a lower YI value than a polyimide precursor in which a non-purified silicon-containing compound having the same amine value is used. The mechanism is not clear, but the inventors presume as follows. That is, in the case of using the conventional purification method, a diamine having a low molecular weight other than cyclic, which is used for producing a polyimide precursor, remains, and is decomposed to generate radicals when the polyimide is cured, which may cause an increase (deterioration) in YI value. By reducing the amount of the cyclic siloxane represented by the general formula (3), it is considered that not only the cyclic siloxane represented by the general formula (3) but also a low-molecular-weight diamine which is relatively easily volatilized from the diamine component having an increased amine value is removed during purification. Therefore, it is estimated that the polyimide precursor in which the total amount of the compound represented by the general formula (3) is reduced further improves the YI value of the polyimide resin film according to the present embodiment. Since it is considered that it is difficult to reduce a low molecular weight diamine which is not cyclic when using the conventional purification method, the degree of improvement in YI value of the polyimide resin film is smaller than that of the present embodiment even if purification is performed.

In this embodiment, the difference between the YI value of the polyimide precursor using the purified silicon-containing compound and the YI value of the polyimide precursor using the non-purified silicon-containing compound is obtained from the following formula.

(Difference in YI values) = (YI value of polyimide resin film obtained by curing polyimide precursor obtained using silicon compound that has not been purified) - (YI value of polyimide resin film obtained by curing polyimide precursor obtained using silicon compound that has been purified)

A larger difference in YI values means a further improvement in YI, and is therefore preferable. In this embodiment, the difference in YI value is preferably 1.5 or more, more preferably 2 or more, and further preferably 2.5 or more. The YI value measurement method is described in the column of examples.

Use of polyimide film

The polyimide film obtained by curing the resin composition of the present embodiment can be suitably used as, for example, a semiconductor insulating film, a thin film transistor liquid crystal display (TFT-LCD) insulating film, an electrode protecting film, and a transparent substrate for a display device such as a liquid crystal display, an organic electroluminescent display, a field emission display, or electronic paper. In particular, the polyimide film obtained by curing the resin composition of the present embodiment can be suitably used for the production of flexible devices, such as flexible substrates, flexible displays, thin Film Transistor (TFT) substrates, color filter substrates, touch panel substrates, and substrates of transparent conductive films (ITO, indium Thin Oxide). Examples of the flexible device to which the polyimide film according to the present embodiment can be applied include a TFT device for a flexible display, a flexible solar cell, a flexible touch panel, flexible lighting, a flexible battery, a flexible printed circuit board, a flexible color filter, a surface-covering lens for a smart phone, and the like.

The step 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 ℃. Specifically, in the case of manufacturing a TFT device using amorphous silicon, a process temperature of 250 to 350 ℃ is generally required, and the polyimide film of the present embodiment needs to be resistant to such a temperature, and therefore, specifically, a polymer structure having a glass transition temperature and a thermal decomposition start temperature of not less than the process temperature needs to be appropriately selected.

In the case of manufacturing a TFT device using a metal oxide semiconductor (IGZO or the like), a process temperature of 320 to 400 ℃ is generally required, and since the polyimide film of the present embodiment is required to be resistant to such a temperature, a polymer structure having a glass transition temperature and a thermal decomposition start temperature equal to or higher than the highest temperature of the TFT manufacturing process is required to be appropriately selected.

In the case of manufacturing a TFT device using Low Temperature Polysilicon (LTPS), a process temperature of 380 to 520 ℃ is generally required, and since the polyimide film of the present embodiment is required to be resistant to such a temperature, it is necessary to appropriately select a glass transition temperature and a thermal decomposition start temperature equal to or higher than the highest temperature of the TFT manufacturing process.

On the other hand, the optical properties (in particular, the light transmittance, rth and YI values) of the polyimide film tend to be lower as the polyimide film is exposed to a high-temperature process due to these thermal histories. However, the polyimide obtained from the polyimide precursor of the present embodiment has good optical properties even after thermal history.

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

Display manufacturing method

The method for manufacturing the display of the present embodiment includes: a coating step of coating 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; an element forming step of forming an element on the polyimide resin film; and a peeling step of peeling the polyimide resin film formed with the element from the support. The display may be a flexible display.

Manufacturing example of Flexible organic EL display

Fig. 1 is a schematic view showing a structure of a top emission type flexible organic EL display, which is an example of the display of the present embodiment, which is located above a polyimide substrate. The organic EL structure 25 of fig. 1 will be described. For example, the organic EL elements 250a emitting red light, the organic EL elements 250b emitting green light, and the organic EL elements 250c emitting blue light are arranged in a matrix as 1 unit, and the light emitting regions of the organic EL elements are defined by partition walls (banks) 251. Each organic EL element is composed of a lower electrode (anode) 252, a hole transport layer 253, a light emitting layer 254, and an upper electrode (cathode) 255. A plurality of TFTs 256 (selected from Low Temperature Polysilicon (LTPS), metal oxide semiconductor (IGZO, etc.), an interlayer insulating film 258 having contact holes 257, and a lower electrode 259 for driving an organic EL element are provided on a lower substrate 2a representing a CVD multilayer film (multilayer barrier layer) formed of silicon nitride (SiN) or silicon oxide (SiO). The organic EL elements are sealed by the sealing substrate 2b, and a hollow 261 is formed between each organic EL element and the sealing substrate 2 b.

The manufacturing process of the flexible organic EL display includes: a step of producing a polyimide film on a glass substrate support and producing the organic EL substrate shown in fig. 1 on the polyimide film; a step of manufacturing a sealing substrate; an assembling step of bonding the two substrates; and a peeling step of peeling the organic EL display formed on the polyimide film from the glass substrate support. The organic EL substrate manufacturing process, the sealing substrate manufacturing process, and the assembling process can be applied to known manufacturing processes. Examples of this are given below, but the present invention is not limited thereto. The peeling step is the same as the polyimide film peeling step.

For example, referring to fig. 1, a polyimide film is first formed on a glass substrate support by the above-described method, a multilayer barrier layer (lower substrate 2a in fig. 1) formed of a multilayer structure of silicon nitride (SiN) and silicon oxide (SiO) is formed on the upper portion by a CVD method or a sputtering method, and a metal wiring layer for driving a TFT is formed on the upper portion by using a photoresist or the like. An Active buffer layer such as SiO is formed on the upper portion thereof by 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 formed on the upper portion thereof. After manufacturing the TFT substrate for a flexible display, an interlayer insulating film 258 having a contact hole 257 is formed using a photosensitive acrylic resin or the like. An ITO film is formed by sputtering or the like, and a lower electrode 259 is formed so as to face the TFT.

Next, after forming a partition wall (bank) 251 using 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. In addition, an upper electrode (cathode) 255 is formed so as to cover the light emitting layer 254 and the partition wall (bank) 251. Then, using a fine metal mask or the like as a mask, an organic EL material emitting red light (corresponding to the organic EL element 250a emitting red light in fig. 1), an organic EL material emitting green light (corresponding to the organic EL element 250b emitting green light in fig. 1), and an organic EL material emitting blue light (corresponding to the organic EL element 250c emitting blue light in fig. 1) are deposited by a known method, thereby producing an organic EL substrate. The organic EL substrate is sealed with a sealing film or the like (sealing substrate 2b in fig. 1), and the device above the polyimide substrate is peeled off from the glass substrate support by a known peeling method such as laser peeling, thereby producing a top emission type flexible organic EL display. When the polyimide according to the present embodiment is used, a see-through (see-through) flexible organic EL display can be manufactured. The bottom emission type flexible organic EL display may be manufactured by a known method.

Manufacturing example of flexible liquid crystal display

The polyimide film of the present embodiment can be used to manufacture a flexible liquid crystal display. Specifically, a polyimide film is formed on a glass substrate support by the above method, and a TFT substrate made of, for example, amorphous silicon, a metal oxide semiconductor (IGZO, etc.), or low-temperature polysilicon is formed by the above method. In addition, according to the coating step and the film forming step of the present embodiment, a polyimide film is formed on the glass substrate support, and a color filter glass substrate (CF substrate) including the polyimide film is formed by using a color resist or the like according to a known method. A sealing material made of thermosetting epoxy resin or the like is applied to one of the TFT substrate and the CF substrate in a frame-like pattern of a portion lacking a liquid crystal injection port by screen printing, and spherical spacers made of plastic or silica having a diameter corresponding to the thickness of the liquid crystal layer are dispersed on the other substrate.

Then, the TFT substrate and the CF substrate are bonded to each other, and the sealing material is cured. Next, a liquid crystal material was injected into a space surrounded by the TFT substrate, the CF substrate, and the sealing material by a decompression method, a thermosetting resin was applied to the liquid crystal injection port, and the liquid crystal material was sealed by heating, thereby forming a liquid crystal layer. Finally, the glass substrate on the CF side and the glass substrate on the TFT side are peeled off at the interface between the polyimide film and the glass substrate by a laser peeling method or the like, whereby a flexible liquid crystal display can be produced.

Method for producing laminate

The method for manufacturing a laminate according to the present embodiment includes: a coating step of coating 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 an element forming step of forming an element on the polyimide resin film.

Examples of the element in the laminate include elements exemplified in the production of the flexible device. As the support, for example, a glass substrate can be used. The preferable specific steps of the coating step and the film forming step are the same as those described in the above-mentioned method for producing a polyimide film. In the element forming step, the element is formed on a polyimide resin film as a flexible substrate formed on a support. The polyimide resin film and the element can then be peeled off from the support in any peeling step, thereby obtaining a flexible substrate.

Examples

Embodiments of the present invention will be specifically described below by way of examples and comparative examples, but the present invention is not limited to these examples and comparative examples.

Method for measurement and evaluation

Non-solvent component

The total mass of the monomers used in the polyimide precursor may be used as the mass of the non-solvent component contained in the resin composition. Alternatively, the mass of the non-solvent component can be determined as follows: the mass of the solvent is determined by subjecting the resin composition to gas chromatography (hereinafter also referred to as GC) analysis, and the mass of the non-solvent component is determined by subtracting the mass of the solvent from the mass of the resin composition.

The conditions for GC include the following conditions.

The device comprises: gas chromatograph (Agilent Technologies system, gas chromatograph 6890N type)

Injection port temperature: 280 DEG C

Injection amount: 1 mu L

Oven temperature: after maintaining at 50℃for 1 minute, the temperature was raised to 350℃at a heating rate of 20℃per minute, and the mixture was maintained at 350℃for 5 minutes.

Carrier gas: he. 1.0 ml/min

Chromatographic column: BPX5 (0.25 mm. Phi. Times.30 m, film thickness 0.25 μm) manufactured by SGE Co., ltd

Split ratio: 50:1

A detector: hydrogen flame ionization type detector

Detector temperature: 355 DEG C

Weight average molecular weight

The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by Gel Permeation Chromatography (GPC) using the following conditions. As the solvent, NMP (manufactured by Wako pure chemical industries, ltd., for high performance liquid chromatography, for example) was used, and 24.8 mmol/L of lithium bromide monohydrate (manufactured by Wako pure chemical industries, ltd., purity: 99.5%) and 63.2 mmol/L of phosphoric acid (manufactured by Wako pure chemical industries, ltd., for high performance liquid chromatography) were added and dissolved. The standard curve for calculating the weight average molecular weight was prepared using standard polystyrene (TOSOH CORPORATION).

Chromatographic column: shodex KD-806M (manufactured by Zhaoyao electric Co., ltd.)

Flow rate: 1.0 mL/min

Column temperature: 40 DEG C

And (3) a pump: PU-2080Plus (manufactured by JASCO Co., ltd.)

A detector: RI-2031Plus (RI: differential refractometer, manufactured by JASCO Co., ltd.) and UV-2075Plus (UV-VIS: ultraviolet visible photometer, manufactured by JASCO Co., ltd.)

Functional group equivalent

The functional group equivalent is measured according to the existing standards and the like as described below.

The functional group equivalent of the amino group was measured according to JIS K7237.

The functional group equivalent of the epoxy group was measured according to JIS K7236.

The functional group equivalent of the hydroxyl group was measured according to JIS K0070.

The molecular weight of the silicon-containing compound per 1 mol of the functional group was determined by titration of the other functional groups.

Analysis of Cyclic siloxane concentration

The analysis of the concentration of the cyclic siloxane of the general formula (3) contained in the resin composition containing the polyimide precursor and the silicon-containing compound (general formula (3)) was quantitatively performed by GC (gas chromatography analysis) as shown below (hereinafter referred to as analysis of the concentration of the cyclic siloxane (silicon-containing compound basis)).

Analysis of Cyclic siloxane concentration (composition base-non-solvent base) >

(1) Summary of the inventionsummary

A standard curve for quantifying the amount of cyclic siloxane was prepared. The standard curve was prepared by using a standard (manufactured by tokyo chemical industry) of cyclic siloxane (hereinafter also referred to as D4 body) having n=4 of the general formula (3) according to the method described below. The amount of cyclic siloxane contained in the resin composition was measured by heating the resin composition at 150℃for 30 minutes in a pyrolyzer and analyzing the volatile components produced by GC/MS. The peak area of each compound obtained was converted to the D4 body concentration using a standard curve prepared in advance.

GC/MS measurements were performed using the following apparatus.

A pyrolyzer: py-3030iD (Frontier Laboratories Ltd.)

GC system：7890B(Agilent Technologies)

MSD：5977A(Agilent Technologies)

Chromatographic column: UA-1 (inner diameter 0.25mm, length 15m, liquid phase thickness 0.25 μm) (Frontier Laboratories Ltd.)

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

Chromatographic column temperature: hold at 40 ℃ for 5 minutes, warm up at 20 ℃/minute, hold at 320 ℃ for 11 minutes, total 30 minutes

Injection port temperature: 320 DEG C

Injection method: split flow method (split ratio 1/20)

Interface temperature: 320 DEG C

Ion source temperature: 230 DEG C

Ionization method: electron ionization method (EI)

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

(2) Preparation of a Standard Curve

A standard (manufactured by tokyo chemical industry) of a compound of general formula (3) n=4 (hereinafter also referred to as D4 body) was measured in a 10mL volumetric flask, and a sample having a D4 body concentration of 0.1mg/mL and a sample having a D4 body concentration of 0.01mg/mL were prepared by using chloroform as a solvent. A sample collector for a liquid sample was mounted on a pyrolyzer set at 400℃and 1. Mu.L of the sample with the concentration adjusted was measured by a microinjector and injected into the pyrolyzer. During heating of the pyrolyzer to 400 ℃, the column was immersed in liquid nitrogen, trapping the volatile components into the column. After 1 minute from the end of heating, the column was removed from the liquid nitrogen and subjected to GC/MS measurement. The slope of the D4 body standard curve was obtained from the D4 body concentration and the obtained peak area. The retention times of cyclic siloxanes in GC/MS measurements using the apparatus used and the measurement conditions are shown in table 1 below. The same applies to the subsequent GC/MS measurement.

TABLE 1

Name of the Compound	Retention time (minutes)
		D3	3:08
D4	7:35
		D5	9:12
D6	10:30
		D7	11:37
D8	12:30

Dn (n=3 to 8) in table 1 is a cyclic siloxane corresponding to n=3 to 8 of the general formula (3).

(3) Analysis of the concentration of Cyclic siloxane of the general formula (3) in the resin composition

The concentration of the compound of the general formula (3) contained in the resin composition was measured by heating the resin composition to 150℃and performing GC/MS measurement of the volatile components produced. 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 do not overlap with other compounds, the peak area determined from the Total Ion Chromatogram (TIC) is used. When the compound overlaps with other compounds, a peak area obtained from a mass chromatogram (MS) of m/z=281 is used.

A sample cup containing about 1mg of the resin composition was charged in a heating furnace (He atmosphere) of a pyrolyzer set at 150℃and heated at 150℃for 30 minutes. The volatile components produced were determined by analysis by GC/MS. The peak area of each compound obtained was converted to the D4 body concentration using a standard curve prepared in advance.

Dn (μg/g) = { Dn (GC-Area) }/{ slope of D4 body standard curve }/{ mass of resin composition weighed (mg) } ×1000

Wherein n corresponds to the carbon number n of the general formula (3), and n is an integer of 3 or more.

< Analysis of Cyclic siloxane concentration contained in raw Material composition (silicon-containing Compound basis) >)

(Summary)

The analysis of the concentration of the cyclic siloxane was determined by analyzing a solution of a silicon-containing compound (silicon-containing compound of the general formula (3)) dissolved in acetone (n-tetradecane is contained as an internal standard substance) by GC. From the peak areas of the obtained compounds, the concentrations of the compounds were determined based on the peak areas of n-tetradecane according to the method described below.

GC measurements were performed using the following apparatus.

GC system：7890A(Agilent Technologies)

Chromatographic column: j & W SCIENTIFIC Durabond DB-5MS (MEGABORE inner diameter 0.53mm, length 30m, liquid phase thickness 1.0 μm)

The GC measurements were all performed under the following measurement conditions.

Chromatographic column temperature: heating at 50deg.C at 10deg.C/min, maintaining at 280 deg.C for 17 min, and total 40min

Injection port temperature: 270 DEG C

Carrier gas: he (He)

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

A detector: FID (300 ℃ C.)

(Calculation of cyclic siloxane amount)

The amount of cyclic siloxane of the general formula (3) is calculated according to the following formula.

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

The GC-Area Factor in the formula is calculated according to the following formula.

GC-Area Factor = molecular weight/carbon number

The retention time (minutes) of the cyclic siloxane in the GC measurement using the apparatus used and the above measurement conditions is shown in table 2 below. The same applies to the subsequent GC measurement.

TABLE 2

Name of the Compound	Retention time (minutes)
		D3	3.8
D4	6.1
		D5	8.4
D6	10.7
		D7	12.8
D8	14.6
		N-tetradecane	12.2

Dn (n=3 to 8) in table 2 is a cyclic siloxane corresponding to n of the general formula (3).

(Analysis of Cyclic siloxane concentration)

The analysis of the concentration of the cyclic siloxane of the general formula (3) contained in the silicon-containing compound was performed by the following procedure. Silicon-containing compound (0.1 g) was dissolved in acetone (10 mL) (20. Mu.g/mL of n-tetradecane as an internal standard substance) and left for 16 hours. The solution thus placed was measured by a microinjection apparatus at 1. Mu.L and introduced into a GC for measurement. In the obtained chromatogram, peak areas of each cyclic siloxane and n-tetradecane were calculated by software attached to GC, and cyclic siloxane concentrations were obtained by the calculation formula shown above.

< Evaluation of defects of polyimide resin film >

In this evaluation, it is assumed that mass production is performed, and defects on the surface of the polyimide precursor or polyimide resin composition coating film when solvent removal and heat curing of the polyimide precursor or polyimide resin composition are continuously performed are evaluated. The polyimide precursor compositions of examples and comparative examples were applied to an alkali-free glass substrate (hereinafter also referred to as "glass substrate" or simply as "substrate") having a thickness of 0.5mm and a thickness of 300mm in the longitudinal direction and 350mm in the transverse direction so that the film thickness after curing was 10. Mu.m, in a region from the end of the glass substrate to the inside of 5 mm. The coating was performed using a slot coater (LC-R300G, SCREEN FINETECH Solutions Co., ltd.). The solvent was removed from the obtained coated glass substrate by using a vacuum dryer (Tokyo industrial Co., ltd.) at 80℃under 100Pa for 30 minutes to obtain a coated glass substrate having a polyimide precursor composition coating film of 290mm in the longitudinal direction, 340mm in the transverse direction and 10. Mu.m. At this time, 10 sheets of the composition formed on the glass substrate of the same composition were continuously processed. In the case of treating the other composition, the composition was used after being dried at 600℃for 5 hours or more with a vacuum dryer. The obtained glass substrate having the polyimide precursor or polyimide resin composition coating film was heated in an oven (INH-9N1 Koyo Thermo Systems Co, manufactured by ltd.) under a nitrogen atmosphere (oxygen concentration 300ppm or less) at 400 ℃ for 1 hour to form a polyimide resin film on the glass substrate.

The surface of the 10 th polyimide resin film was subjected to the continuous processing of 10 sheets, and the defects were evaluated by using a defect inspection apparatus (LCF-5505 XU, manufactured by TAKANO co., ltd.). The number of defects of 10 μm or more is detected.

The number of defects is 0 or more and less than 25: a (good)

The number of defects is 25 or more and less than 50: b (pass)

The number of defects is more than 50: c (failing)

Evaluation of YI value difference of polyimide resin film

In this evaluation, a polyimide resin film was obtained by heating a polyimide precursor or polyimide obtained using a purified silicon compound and a polyimide precursor or polyimide obtained using a silicon compound that was not purified, respectively, and the difference in YI value of the obtained polyimide resin film was evaluated. The YI value was measured using the polyimide resin film produced in the above-mentioned "defect evaluation" using a spectrometer (SE 600) manufactured by Nippon Denshoku Co., ltd. The light source uses a D65 light source. The difference between YI values is obtained by the following formula.

(Difference in YI values) = (YI value of polyimide resin film obtained by curing polyimide precursor or polyimide obtained by using silicon compound which has not been purified) - (YI value of polyimide resin film obtained by curing polyimide precursor or polyimide obtained by using silicon compound which has been purified)

When the YI value difference is obtained, the curing of the polyimide precursor or polyimide obtained using the silicon compound that has not been purified and the curing of the polyimide precursor or polyimide obtained using the silicon compound that has been purified are performed in the same oven batch, and the equipment errors are eliminated.

In-plane uniformity of retardation (Rth) of polyimide resin film

The polyimide resin film produced in the above "defect evaluation" was used to evaluate the in-plane uniformity of Rth. The thickness direction Rth (converted to 10 μm) was measured by using a retardation birefringence measuring device (KOBRA-WR, manufactured by prince measuring instruments) at measurement points of 16 total parts (4×4) in the longitudinal direction (290 mm width), with 4 parts spaced apart by 80mm from the inside 25mm from the end of the polyimide resin film, and in the transverse direction (340 mm width), with 4 parts spaced apart by 80mm from the inside 50mm from the end of the polyimide resin film. From the result, the range of.+ -. 3 sigma was calculated, and the in-plane uniformity of Rth of the PI precursor coating film was evaluated according to the following criteria.

A: in-plane uniformity (+ -3 sigma) of less than 10

B: in-plane uniformity (+ -3 sigma) of 10 or more and less than 20

C: in-plane uniformity (+ -3 sigma) of 20 or more

Evaluation of residual stress of polyimide resin film

Each resin composition was applied by a spin coater to a 6-inch silicon wafer having a thickness of 625 μm.+ -.25 μm, in which the "warpage" was measured in advance, and prebaked at 100℃for 7 minutes. Then, a silicon wafer having a polyimide resin film with a thickness of 10 μm after curing was produced by performing a heat curing treatment (curing treatment) at 430℃for 1 hour by adjusting the oxygen concentration in the furnace to 10 mass ppm or less using a vertical curing furnace (model name VF-2000B, manufactured by KOYO LINDBERG). The warp amount of the wafer was measured by a residual stress measuring device (model name FLX-2320 manufactured by Tencor corporation) to evaluate the residual stress generated between the silicon wafer and the resin film.

Purification method of silicon-containing Compound

The silicon-containing compound described in examples and comparative examples described below was treated by the following purification method to reduce the cyclic siloxane contained therein. The concentration of the purified cyclic siloxane was analyzed by the method described above.

Purification A

10Kg of a silicon-containing compound was charged into the flask, and the mixture was stripped at 160℃under 270Pa for 8 hours while blowing nitrogen.

Purification of B

10Kg of a silicon-containing compound was charged into the flask, and the mixture was stripped at 200℃under 200Pa for 8 hours while blowing nitrogen.

Synthesis example of two terminal amino group-modified silicone oil (purified product) according to Japanese patent application laid-open No. 2016-029126

To 100g of the silicon-containing compound, 1000g of acetone was added, and the mixture was stirred at room temperature for 30 minutes. The acetone and silicone oil were separated by centrifugation at 2500rpm for 15 minutes using a centrifuge, and then the acetone was removed by decantation. After repeating this operation 3 times, acetone was distilled off by an evaporator to obtain a purified silicon-containing compound.

Purification of D > according to purification example 1 described in Japanese patent application laid-open No. 2006-028533

500G of a silicon-containing compound was charged into the flask, and stripping was performed at a temperature of 250℃and a pressure of 1330Pa for 2 hours while blowing nitrogen gas.

Purification of E according to purification example 2 described in Japanese patent laid-open No. 2006-028533

100G of silicon-containing compound was added to 300g of 2-butanone and dissolved uniformly. The solution was slowly poured into methanol with stirring, and reprecipitation was performed. The reprecipitation was repeated a total of 3 times, and then dried to obtain a purified silicon-containing compound.

Purification F

10Kg of a silicon-containing compound was charged into the flask, and after stripping at a temperature of 230℃and a pressure of 200Pa for 8 hours while blowing nitrogen gas, the stripping was performed at a temperature of 200℃and a pressure of 200Pa for 8 hours.

Example 1

As shown in Table 3, the silicon-containing compound (a) (a compound in which L ₁ and L ₂ are amino groups (-NH ₂)、R₁ is trimethylene group (-CH ₂CH₂CH₂-),R₂、R₃ is methyl group, j and k are 0, and the functional group equivalent weight is 1500) was purified by the method of purification B. To a 3L separable flask with a stirring rod, nitrogen gas was introduced, and while stirring, NMP (330 g) as a solvent, 4' -DAS (13.9 g) as a diamine, TFMB (12.0 g), and purified silicon-containing compound (a) (10.50 g) were added, then PMDA (21.8 g) as an acid dianhydride and a diamine were added in a molar ratio of 100:97. The mixture was stirred at room temperature for 48 hours to obtain a clear NMP solution of polyamic acid (hereinafter also referred to as a varnish). The obtained varnish was stored at a freezer (set at-20 ℃ C. And the same) and thawed for use at the time of evaluation.

Examples 2 to 39 and 41 to 53

The procedure of example 1 was repeated except that the types and amounts of the solvent, the acid dianhydride, the diamine, and the silicon-containing compound in example 1 were changed to those shown in tables 3 and 4.

The types of the silicon-containing compounds in the table are as follows.

Silicon-containing compound (b): in the general formula (4), L ₁ and L ₂ are amino groups (-NH ₂),R₁ is trimethylene group (-CH ₂CH₂CH₂-),R₂、R₃ is methyl group, j and k are 0, and the functional group equivalent is 2200)

Silicon-containing compound (d): in the general formula (4), L ₁ and L ₂ are epoxy groups (-CH (O) CH ₂),R₁ is trimethylene groups (-CH ₂CH₂CH₂-),R₂、R₃ is methyl groups, j and k are 0, and the equivalent weight of the functional group is 1750)

Silicon-containing compound (e): in the general formula (4), L ₁ and L ₂ are hydroxyl groups (-OH), R ₁ is trimethylene groups (-CH ₂CH₂CH₂-),R₂、R₃ is methyl, j and k are 0, and the functional group equivalent is 900

Silicon-containing compound (f): in the general formula (4), L ₁ and L ₂ are mercapto (-SH), R ₁ is trimethylene (-CH ₂CH₂CH₂-),R₂、R₃ is methyl, j and k are 0, and the functional group equivalent is 1700)

Silicon-containing compound (g): in the general formula (4), L ₁ and L ₂ are amino groups (-NH ₂),R₁ is trimethylene group (-CH ₂CH₂CH₂-),R₂、R₃ is methyl group, j and k are 0, and the functional group equivalent is 800)

Silicon-containing compound (h): in the general formula (4), L ₁ and L ₂ are amino groups (-NH ₂),R₁ is trimethylene group (-CH ₂CH₂CH₂-),R₂、R₃ is methyl group, j and k are 0, and the equivalent of the functional group is 650)

Silicon-containing compound (i): in the general formula (4), L ₁ and L ₂ are amino groups (-NH ₂),R₁ is trimethylene group (-CH ₂CH₂CH₂-),R₂、R₃ is methyl group, j and k are 0, and the equivalent of the functional group is 430)

Example 54

A nitrogen gas was introduced into a detachable flask equipped with a dean-Stark tube and a reflux tube in the upper part, and as described in Table 4, a silicon-containing compound (a) (a compound in the general formula (4) in which L ₁ and L ₂ are amino groups (-NH ₂),R₁ is trimethylene group (-CH ₂CH₂CH₂-),R₂、R₃ is methyl group, j and k are 0, and the equivalent of the functional group is 1500) was purified by a method of purification B), nitrogen gas was introduced into a 3L detachable flask equipped with a stirrer, and after stirring, NMP (330 g), toluene (119.6 g), 4' -DAS (23.2 g) as diamine, and purified silicon-containing compound (a) (10.56 g) were added, and then PMDA (13.1 g), BPDA (11.8 g) as acid dianhydride, and diamine were added at room temperature, and then the temperature was raised to 160℃for 1 hour at which was heated and refluxed for imidization was completed, and after the completion of imidization, the temperature was raised to 180℃and at the same time, the temperature was further raised to room temperature, and the reaction was continued at room temperature was set to be called as a varnish, and a varnish was obtained, and a varnish solution was further cooled and stored at room temperature was set to be called a varnish (a temperature, and cooled).

Examples 55 to 57

A polyimide varnish was produced in the same manner as in example 54, except that the amounts of the acid dianhydride, the silicon compound, the solvent, and the like were changed as shown in table 4.

Comparative example 1

As shown in Table 5, nitrogen gas was introduced into a 3L separable flask equipped with a stirring bar, and while stirring, NMP (345 g), 4' -DAS (13.9 g), TFMB (12.0 g), and a silicon-containing compound (a) (in the general formula (4), L ₁ and L ₂ are amino groups (-a compound in which NH ₂),R₁ is trimethylene group (-CH ₂CH₂CH₂-),R₂、R₃ is methyl group, j and k are 0, and the functional group equivalent is 3000) (10.97 g) were added as solvents, and then PMDA (15.3 g), BPDA (8.8 g), and the molar ratio of acid dianhydride to diamine were 100:97 were added, and then stirred at room temperature for 48 hours to obtain a clear NMP solution of polyamic acid (hereinafter also referred to as varnish). The obtained varnish was stored at a freezer (set at-20 ℃ C. Or below) and was used for evaluation.

Comparative examples 2 to 23 and comparative examples 25 to 27

The procedure of comparative example 1 was repeated except that the types and amounts of the solvent, acid dianhydride, diamine, and silicon compound in comparative example 1 were changed to those shown in Table 5.

Comparative examples 24 and 28 to 30

The procedure of example 1 was repeated except that the types and amounts of the solvent, the acid dianhydride, the diamine, and the silicon-containing compound in example 1 were changed to those shown in Table 5.

Comparative examples 31 to 35

Comparative examples 31 to 35 were conducted in the same manner as examples 9, 45, 48, 51 and 19, respectively, except that the purification of the silicon-containing compound was not conducted as shown in Table 9. The results are shown in Table 10.

For the resin compositions of examples and comparative examples, cyclic siloxane concentrations were determined for the resin composition basis, the non-solvent component basis, and the silicon-containing compound basis; molecular weight of polyimide precursor; evaluating defects of the polyimide resin film; evaluation of the difference in YI value of the polyimide resin film; the in-plane uniformity of the retardation (Rth) of the polyimide resin film was evaluated. The results are shown in tables 6 to 8. In tables 6 to 8, "n=4 compound", "n=5 compound", "n=6 compound", "n=7 compound" corresponds to the compounds of the general formula (3) in which n is 4,5, 6, 7, respectively. In table 10, "the total amount of n3 to n8 compounds" is a value indicating the sum of the concentrations of compounds having n of 3 to 8 in the general formula (3).

Abbreviations in examples and comparative examples are as follows.

Acid dianhydride

PMDA: pyromellitic dianhydride

BPDA:3,3', 4' -biphenyltetracarboxylic dianhydride

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

ODPA:4,4' -Oxyphthalic anhydride

HPMDA:1,2,4, 5-cyclohexane tetracarboxylic dianhydride

CBDA:1,2,3, 4-cyclobutane tetracarboxylic dianhydride

Diamine

4,4' -DAS:4,4' -diaminodiphenyl sulfone

3,3' -DAS:3,3' -diaminodiphenyl sulfone

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

TFMB: diamino bis (trifluoromethyl) biphenyl

MTB:2,2' -dimethylbenzidine

PDA: para-phenylenediamine

BAPP:2, 2-bis [4- (4-aminophenoxy) phenyl ] propane

ODA:4,4' -diaminodiphenyl ether

CHDA:1, 4-cyclohexanediamine

TABLE 3

TABLE 4

TABLE 5

TABLE 6

TABLE 7

TABLE 8

TABLE 9

TABLE 10

Table 10

Description of the reference numerals

2A lower substrate

2B sealing substrate

25. Organic EL structure part

250A red light-emitting organic EL element

250B green light-emitting organic EL element

250C blue light-emitting organic EL element

251. Partition wall (bank)

252. Lower electrode (anode)

253. Hole transport layer

254. Light-emitting layer

255. Upper electrode (cathode)

256 TFT

257. Contact hole

258. Interlayer insulating film

259. Lower electrode

261. Hollow part

Claims

1. A resin composition comprising:

A compound represented by the following general formula (3),

The total amount of the compounds having n of 4 in the following general formula (3) is more than 0ppm and 70ppm or less based on the mass of the resin composition, or

The total amount of the compounds having n of 5 in the following general formula (3) is more than 0ppm and 30ppm or less based on the mass of the resin composition,

In the general formula (1-1), P ₁ represents a 2-valent organic group, P ₂ represents a 4-valent organic group, P represents a positive integer,

In the general formula (1-2), P ₁ represents a 2-valent organic group, P ₂ represents a 4-valent organic group, P represents a positive integer,

In the general formula (2), 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, q is an integer of 1 to 200,

In the general formula (3), n is an integer of 2 or more.

2. The resin composition according to claim 1, wherein the total amount of the compounds having n of 4 in the general formula (3) is more than 0ppm and 30ppm or less based on the mass of the resin composition, or

3. A resin composition comprising:

A compound represented by the following general formula (3),

The total amount of the compounds having n of 5 in the general formula (3) is more than 0ppm and 200ppm or less based on the mass of the non-solvent component of the resin composition,

In the general formula (3), n is an integer of 2 or more.

4. The resin composition according to claim 3, wherein the total amount of the compounds having n of 4 in the general formula (3) is more than 0ppm and 300ppm or less based on the mass of the non-solvent component of the resin composition, or

5. The resin composition according to claim 3, wherein the total amount of the compounds having n of 4 in the general formula (3) is more than 0ppm and 10ppm or less based on the mass of the non-solvent component of the resin composition, or

The total amount of the compounds having n of 5 in the general formula (3) is more than 0ppm and 5ppm or less based on the mass of the non-solvent component of the resin composition.

6. A resin composition comprising:

A compound represented by the following general formula (3),

The resin composition is produced by a method comprising:

a raw material composition containing a silicon-containing compound represented by the following general formula (4) and a compound represented by the following general formula (3) is subjected to polycondensation reaction with tetracarboxylic dianhydride and diamine to provide a polyimide precursor; or imidizing the polyimide precursor to provide a polyimide,

The total amount of the compounds having n of 5 in the following general formula (3) contained in the raw material composition is more than 0ppm and 500ppm or less based on the total mass of the silicon-containing compounds represented by the general formulas (3) and (4),

In the general formula (3), n is an integer of 2 or more,

In the general formula (4), R ₁ is a single bond or a divalent organic group with 1-10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group with 1-10 carbon atoms, at least one monovalent aliphatic hydrocarbon group with 1-5 carbon atoms, R ₄ and R ₅ are each independently a monovalent organic group with 1-10 carbon atoms, at least one monovalent aromatic group with 6-10 carbon atoms, R ₆ and R ₇ are each independently a monovalent organic group with 1-10 carbon atoms, 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 acyl halide group, a hydroxyl group, an epoxy group or a mercapto group, i is an integer of 1-200, j and k are each independently an integer of 0-200, and j/(i+j+k) is not more than 0.50.

7. The resin composition according to claim 6, wherein the total amount of the compounds having n of 4 in the general formula (3) contained in the raw material composition is more than 0ppm and not more than 800ppm, or

8. The resin composition according to claim 6, wherein the total amount of the compounds having n of 4 in the general formula (3) contained in the raw material composition is more than 0ppm and 30ppm or less based on the total mass of the silicon-containing compounds represented by the general formulae (3) and (4), or

9. A resin composition comprising:

A compound represented by the following general formula (3),

Based on the mass of the resin composition, the total amount of compounds having n of 3 to 8 in the following general formula (3) is more than 0ppm and 150ppm,

In the general formula (3), n is an integer of 2 or more.

10. A resin composition comprising:

A compound represented by the following general formula (3),

Based on the mass of the non-solvent component of the resin composition, the total amount of compounds having n of 3 to 8 in the following general formula (3) is more than 0ppm and 900ppm,

In the general formula (3), n is an integer of 2 or more.

11. A resin composition comprising:

A compound represented by the following general formula (3),

The resin composition is produced by a method comprising:

The total amount of compounds having n of 3 to 8 in the general formula (3) contained in the raw material composition is more than 0ppm and 4500ppm or less based on the total mass of silicon-containing compounds represented by the general formulas (3) and (4),

In the general formula (3), n is an integer of 2 or more,

12. The resin composition according to any one of claims 6, 7, 8 and 11, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (4) are each independently selected from the group consisting of an amino group, an acid anhydride group, an epoxy group, a hydroxyl group and a mercapto group.

13. The resin composition according to any one of claims 6, 7, 8 and 11, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (4) are amino groups.

14. The resin composition according to any one of claims 6, 7, 8 and 11, wherein the functional group equivalent of the silicon-containing compound represented by the general formula (4) is 800 or more.

15. The resin composition according to any one of claims 6 to 8 and 11 to 14, wherein the tetracarboxylic dianhydride is at least one selected from the group consisting of pyromellitic dianhydride (PMDA), 3', 4' -biphenyl tetracarboxylic dianhydride (BPDA), 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride (BPAF), 4' -oxydiphthalic anhydride (ODPA), 1,2,4, 5-cyclohexane tetracarboxylic dianhydride (HPMDA) and 1,2,3, 4-cyclobutane tetracarboxylic dianhydride (CBDA).

16. The resin composition according to any one of claims 6 to 8 and 11 to 14, wherein the diamine is at least one selected from the group consisting of 4,4' -diaminodiphenyl sulfone (4, 4' -DAS), 3' -diaminodiphenyl sulfone (3, 3' -DAS), 9-bis (4-aminophenyl) fluorene (BAFL), 2' -dimethylbenzidine (mTB), p-Phenylenediamine (PDA), diaminobis (trifluoromethyl) biphenyl (TFMB), 2' -bis [4- (4-aminophenoxy) phenyl ] propane (BAPP), 4' -diaminodiphenyl ether (ODA) and 1, 4-Cyclohexanediamine (CHDA).

17. The resin composition according to any one of claims 1 to 16, wherein a polyimide resin film obtained by curing the resin composition is used for a flexible substrate.

18. The resin composition according to any one of claims 1 to 16, wherein a polyimide resin film obtained by curing the resin composition is used for a flexible display.

19. The resin composition according to any one of claims 1 to 18, wherein d3+d4+d5+d6+d7 is less than 2000ppm and d3+d4 is 10ppm or less, based on the mass of the non-solvent component of the resin composition, where d3 (ppm) is the total amount of compounds of the general formula (3) n and d4 (ppm), d5 (ppm) is the total amount of compounds of the general formula (3) n and d6 (ppm) is the total amount of compounds of the general formula (5), d6 (ppm) is the total amount of compounds of the general formula (6) n and d7 (ppm) is the total amount of compounds of the general formula (3) n and n 7.

20. A method for producing a resin composition, comprising: a raw material composition containing a silicon-containing compound represented by the following general formula (4) and a compound represented by the following general formula (3) is subjected to polycondensation reaction with tetracarboxylic dianhydride and diamine to provide a polyimide precursor; or imidizing the polyimide precursor to provide a polyimide,

In the general formula (3), n is an integer of 2 or more,

21. The method for producing a resin composition according to claim 20, wherein,

The total amount of the compounds having n of 4 in the general formula (3) contained in the raw material composition is more than 0ppm and 800ppm or less based on the total mass of the silicon-containing compounds represented by the general formulae (3) and (4), or

22. A method for producing a resin composition, comprising: a raw material composition containing a silicon-containing compound represented by the following general formula (4) and a compound represented by the following general formula (3) is subjected to polycondensation reaction with tetracarboxylic dianhydride and diamine to provide a polyimide precursor; or imidizing the polyimide precursor to provide a polyimide,

In the general formula (3), n is an integer of 2 or more,

23. The method for producing a resin composition according to any one of claims 20 to 22, wherein the functional group equivalent of the silicon-containing compound represented by the general formula (4) is 800 or more.

24. A method for producing a resin composition, comprising: a raw material composition containing a silicon-containing compound represented by the following general formula (4) and a compound represented by the following general formula (3) is subjected to polycondensation reaction with tetracarboxylic dianhydride and diamine to provide a polyimide precursor; or imidizing the polyimide precursor to provide a polyimide,

The step of reducing includes treating the composition at 150 to 300 ℃ and 300Pa or less for 2 to 12 hours,

In the general formula (3), n is an integer of 2 or more,

25. The method according to any one of claims 20 to 24, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (4) are each independently selected from the group consisting of an amino group, an acid anhydride group, an epoxy group, a hydroxyl group and a mercapto group.

26. The method according to any one of claims 20 to 24, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (4) are amino groups.

27. The method according to any one of claims 20 to 26, wherein the tetracarboxylic dianhydride is at least one selected from the group consisting of pyromellitic dianhydride (PMDA), 3', 4' -biphenyl tetracarboxylic dianhydride (BPDA), 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride (BPAF), 4' -oxydiphthalic anhydride (ODPA), 1,2,4, 5-cyclohexane tetracarboxylic dianhydride (HPMDA) and 1,2,3, 4-cyclobutane tetracarboxylic dianhydride (CBDA).

28. The method of any one of claims 20-26, wherein the diamine is at least one selected from the group consisting of 4,4' -diaminodiphenyl sulfone (4, 4' -DAS), 3' -diaminodiphenyl sulfone (3, 3' -DAS), 9-bis (4-aminophenyl) fluorene (BAFL), 2' -dimethylbenzidine (mTB), p-Phenylenediamine (PDA), diaminobis (trifluoromethyl) biphenyl (TFMB), 2' -bis [4- (4-aminophenoxy) phenyl ] propane (BAPP), 4' -diaminodiphenyl ether (ODA), and 1, 4-Cyclohexanediamine (CHDA).

29. A method for producing a polyimide film, comprising:

a coating step of coating the resin composition according to any one of claims 1 to 19 on a surface of a support;

And a peeling step of peeling the polyimide resin film from the support.

30. The method according to claim 29, further comprising an irradiation step of irradiating the resin composition with laser light from the support side before the peeling step.

31. A method of manufacturing a display, comprising:

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

And a peeling step of peeling the polyimide resin film having the element formed thereon from the support.

32. A method for producing a laminate, comprising:

And an element forming step of forming an element on the polyimide resin film.

33. The method for producing a laminate according to claim 32, further comprising a step of peeling the polyimide resin film on which the element is formed from the support.

34. A method of manufacturing a flexible device comprising manufacturing a laminate using the method of claim 32 or 33.

35. A polyimide film which is a cured product of the resin composition according to any one of claims 1 to 19.