TW201945471A - Polyimide precursor resin composition - Google Patents

Abstract

A resin composition which contains, as mentioned in the description of the present application, a polyimide precursor that contains a structural unit represented by general formula (1) and a structural unit represented by general formula (2), and at least either one of the compounds represented by general formula (3-1) or (3-2) wherein m is an integer of 3 or more, and which optionally contains a compound represented by general formula (4). The total amount of the compound represented by general formula (3-1) or (3-2) wherein m is an integer of 3 or more is more than 0 ppm but 1,100 ppm or less based on the mass of the resin composition; or alternatively, the total amount of the compound represented by general formula (3-1) or (3-2) wherein m is an integer of 3 or more and the compound represented by general formula (4) wherein n is an integer of 3 or more is more than 0 ppm but 1,300 ppm or less based on the mass of the resin composition.

Description

Polyfluorene imide precursor resin composition

The present invention relates to a polyfluorene imide precursor resin composition and a polyfluorene imide film. The present invention further relates to a method for manufacturing a polyimide film, a display, a laminate, and a flexible device.

Polyimide resin is an insoluble and insoluble super heat-resistant resin, which has excellent properties such as heat-resistant oxidation resistance, heat resistance, radiation resistance, low temperature resistance, and chemical resistance. Therefore, polyimide resins are used in a wide range of fields including electronic materials. Examples of the application of the polyimide resin in the field of electronic materials include, for example, an insulating coating material, an insulating film, a semiconductor, and an electrode protective film of a thin film transistor liquid crystal display (TFT-LCD). Recently, the industry is also continuously researching the use of the light weight and flexibility of polyimide films as flexible substrates to replace glass substrates previously used in the field of display materials.

For example, Patent Document 1 describes a resin precursor (weight average molecular weight 30,000 to 90,000) having a siloxane unit and polymerized by bis (diaminodiphenyl) fluorene (hereinafter, also referred to as DAS). . Patent Document 1 describes that the polyimide obtained by hardening the precursor has low residual stress between glass and a support such as glass, is excellent in chemical resistance, and has a yellowing resistance caused by the oxygen concentration during the curing step. The degree of influence (YI) value and total light transmittance are small. Patent Document 2 describes a resin precursor which is polymerized by 2,2′-bis (trifluoromethyl) benzidine (hereinafter, also referred to as TFMB) and has a siloxane unit. Patent Document 2 describes that the polyimide film obtained by curing the precursor has a specific glass transition temperature, has low residual stress between the inorganic film, and has excellent mechanical properties and thermal stability.
[Prior technical 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 No. 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 Publication No. 2007-512568
[Patent Document 7] Japanese Patent Publication No. 2012-511173
[Patent Document 8] Japanese Patent 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] Shin-Etsu Chemical Industry Co., Ltd. Homepage, "Q & A", "About silicone grease, oil compounds", [online], [Retrieved March 13, 2018], Internet < URL: https://www.silicone.jp/contact/qa/qa103.shtml ＞

[Problems to be solved by the invention]

Patent Documents 1 and 2 use a siloxane-containing compound as a monomer of a polyimide precursor, but such a siloxane-containing compound contains a low molecular weight cyclic siloxane (hereinafter, also referred to as a low molecular ring) Like siloxane). It is known that this low-molecular-weight cyclic siloxane is volatile, and there is a possibility that a contact point of a manufacturing device in a manufacturing process may be defective. For example, refer to Non-Patent Document 1.

Examples of prior art documents related to polyimide precursors that reduce the low-molecular-weight cyclic siloxane by purification include patent documents 3 to 5. In the prior art 3, it is described that after adding a siloxane-containing compound to acetone, centrifugal separation and decantation are performed to remove low-molecular cyclic siloxane, and the obtained polyimide is transparent Sex, less outgassing. Patent Documents 4 and 5 describe that by subjecting a siloxane-containing compound to stripping under specific conditions, or dissolving a siloxane-containing compound in 2-butanone and reprecipitating with methanol, The siloxane-containing compound is refined, and the adhesiveness of the obtained polyimide is improved.

The present inventors synthesized a polyfluorene imide precursor using a siloxane-containing compound purified by the same purification method as described in the aforementioned Patent Documents 3 to 5, and used it to produce a polyfluorene imine. As a result, it was found that when a large number of polyimide precursors were processed in the polyimide manufacturing process, the number of foreign matter attached to the polyimide film was poorly evaluated, and compared with unrefined products. In the case of using refined products, the degree of improvement in yellowness (YI value) is insufficient. Therefore, an object of the present invention is to provide a polyimide which can further improve the yellowness (YI value) compared with the case of using an unrefined siloxane compound, and can reduce the amount of foreign matter generated in the polyimide manufacturing process. Amine precursor resin composition.
[Technical means to solve the problem]

The present inventors conducted diligent research, and as a result, they focused on that the low-molecular-weight cyclic siloxanes reduced in Patent Documents 3 to 5 are methyl side chains (general formula (4) below) instead of the phenyl side. A chain body (the following general formula (3-1) or (3-2)). In addition, it has been found that by purifying a siloxane compound, a siloxane compound obtained by reducing the phenyl side chain of a low-molecular cyclic siloxane to a specific amount as a polyimide precursor can solve the above problem. Topic. Examples of the embodiments of the present invention are listed in the following [1] to [34].
[1]
A resin composition comprising the following components:
A polyimide precursor comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2);
At least any one compound of the following general formula (3-1) or (3-2) in which m is an integer of 3 or more; and any of the compounds represented by the following general formula (4); and Based on mass, the total amount of compounds in which m is an integer of 3 or more in the following general formula (3-1) or (3-2) is more than 0 ppm and 1,100 ppm or less,
Based on the mass of the above resin composition, a compound in which m in the following general formula (3-1) or (3-2) is an integer of 3 or more and a compound in which n in the following general formula (4) is an integer of 3 or more The total amount of compounds is more than 0 ppm and less than 1,300 ppm.
[Chemical 1]

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

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

{Where m is an integer of 1 or more}
[Chemical 4]

{Where n is an integer of 2 or more}
[2]
The resin composition according to item 1, wherein the total amount of the compound in which m is an integer of 3 or more in the above general formula (3-1) or (3-2) is based on the mass of the above-mentioned resin composition. 0 ppm to 300 ppm.
[3]
A resin composition comprising the following components:
A polyimide precursor comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2);
At least one compound in which m is 3 or 4 in the following general formula (3-1) or (3-2); and any compound represented by the following general formula (4); and based on the mass of the resin composition As a reference, the total amount of compounds in which m is 3 in the following general formula (3-1) or (3-2) is more than 0 ppm and 650 ppm or less, or
Based on the mass of the above-mentioned resin composition, the total amount of compounds in which m is 4 in the following general formula (3-1) or (3-2) is more than 0 ppm and 350 ppm or less.
[Chemical 5]

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer}
[Chemical 6]

{In the formula, P ₃ and P ₄ are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms, or a monovalent aromatic group having 6 to 10 carbon atoms, and q is an integer of 1 to 200}
[Chemical 7]

{Where m is an integer of 1 or more}
[Chemical 8]

{Where n is an integer of 2 or more}
[4]
A resin composition comprising the following components:
A polyimide precursor comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2);
In the following general formula (3-1) or (3-2), at least any one compound in which m is an integer of 3 or more; and any one of the compounds represented by the following general formula (4); and in the above resin composition Based on the mass of the solid component, the total amount of compounds in which m is an integer of 3 or more in the following general formula (3-1) or (3-2) is more than 0 ppm and 7,500 ppm or less,
Based on the mass of the solid component in the resin composition, a compound in which m in the following general formula (3-1) or (3-2) is an integer of 3 or more and n in the following general formula (4) is The total number of compounds with an integer of 3 or more is more than 0 ppm and 8,600 ppm or less.
[Chemical 9]

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer}
[Chemical 10]

{In the formula, P ₃ and P ₄ are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms, or a monovalent aromatic group having 6 to 10 carbon atoms, and q is an integer of 1 to 200}
[Chemical 11]

{Where m is an integer of 1 or more}
[Chemical 12]

{Where n is an integer of 2 or more}
[5]
A resin composition comprising the following components:
A polyimide precursor comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2);
In the following general formula (3-1) or (3-2), m is at least any one compound of 3 or 4; and any of the compounds represented by the following general formula (4); and Based on the mass of the solid component, the total amount of the compound in which m is 3 in the following general formula (3-1) or (3-2) is more than 0 ppm and 4,500 ppm or less, or,
Based on the mass of the solid component in the resin composition, the total amount of the compound in which m is 4 in the following general formula (3-1) or (3-2) is more than 0 ppm and less than 2,500 ppm.
[Chemical 13]

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer}
[Chemical 14]

{In the formula, P ₃ and P ₄ are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms, or a monovalent aromatic group having 6 to 10 carbon atoms, and q is an integer of 1 to 200}
[Chemical 15]

{Where m is an integer of 1 or more}
[Chemical 16]

[6]
The resin composition according to any one of items 1, 2 and 4, wherein m is an integer of 3 to 5 in the compound represented by the general formula (3-1) or (3-2).
[7]
The resin composition according to any one of items 1, 2, and 4, wherein in the compound represented by the general formula (4), n is an integer of 3 to 8.
[8]
The resin composition according to any one of items 1 to 7, wherein the polyimide resin film obtained by curing the polyimide precursor is used for a flexible substrate.
[9]
The resin composition according to any one of items 1 to 7, wherein the polyimide resin film obtained by curing the polyimide precursor is used for a flexible display.
[10]
A resin composition comprising the following components:
A polyimide precursor comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2);
At least any one compound in which m is an integer of 3 or more in the following general formula (3-1) or (3-2); and any compound represented by the following general formula (4); and the resin composition is borrowed Manufactured by the following method including the following steps:
Containing: a silicon-containing compound represented by the following general formula (5);
Raw material composition and tetracarboxylic acid of at least any one compound of m in the following general formula (3-1) or (3-2) and an integer of 3 or more, and any of the compounds represented by the following general formula (4) Polycondensation reaction of dianhydride and diamine to provide polyimide precursors;
Based on the total mass of the silicon-containing compound represented by the following general formulae (3-1), (3-2), (4), and (5), the following general formula (3- 1) or (3-2) The total amount of compounds in which m is an integer of 3 or more is more than 0 ppm and 46,000 ppm or less,
Based on the total mass of the silicon-containing compound of the general formulae (3-1), (3-2), (4), and (5) above, the following general formula (3-1) contained in the raw material composition Or, the total amount of the compound in which m is an integer of 3 or more in (3-2) and the compound in which n is an integer of 3 or more in the following general formula (4) is more than 0 ppm and 47,000 ppm or less.
[Chemical 17]

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer}
[Chemical 18]

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


[Chemical 19]

{Where m is an integer of 1 or more}
[Chemical 20]

{Where n is an integer of 2 or more}
[Chemical 21]

{Wherein R _{1 is} each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one of them is a carbon number A monovalent aliphatic hydrocarbon group of 1 to 5, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms, R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one is an organic group having an unsaturated aliphatic hydrocarbon group, and L ₁ and L ₂ are each independently an amine group, an acid anhydride group, an isocyanate group, a carboxyl group, Ester group, fluorenyl halide group, hydroxyl group, epoxy group, or mercapto group, i and j are each independently an integer of 1 to 200, k is an integer of 0 to 200, and 0.05 ≦ j / (i + j + k) ≦ 0.50}
[11]
The resin composition according to item 10, wherein, in the compound represented by the general formula (3-1) or (3-2), m is an integer of 3 to 5.
[12]
The resin composition according to item 10, wherein in the compound represented by the general formula (4), n is an integer of 3 to 8.
[13]
A resin composition comprising the following components:
A polyimide precursor comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2);
In the following general formula (3-1) or (3-2), m is at least any one compound of 3 or 4; and any of the compounds represented by the following general formula (4); The following methods are produced by the following steps:
Containing: a silicon-containing compound represented by the following general formula (5);
A raw material composition of at least one compound in which m is 3 or 4 in the following general formula (3-1) or (3-2), and any one of the compounds represented by the following general formula (4), and tetracarboxylic acid di Anhydride and diamine undergo polycondensation reaction to provide polyimide precursors;
Based on the total mass of the silicon-containing compound of the following general formulae (3-1), (3-2), (4), and (5), the following general formula (3-1) contained in the above raw material composition Or the total amount of compounds in which m is 3 in (3-2) is more than 0 ppm and less than 25,000 ppm, or
Based on the total mass of the silicon-containing compound of the following general formulae (3-1), (3-2), (4), and (5), the following general formula (3-1) contained in the above raw material composition Or, the total amount of the compound in which m is 4 in (3-2) is more than 0 ppm and 15,000 ppm or less.
[Chemical 22]

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer}
[Chemical 23]

{In the formula, P ₃ and P ₄ are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms, or a monovalent aromatic group having 6 to 10 carbon atoms, and q is an integer of 1 to 200}
[Chemical 24]

{Where m is an integer of 1 or more}
[Chemical 25]

{Where n is an integer of 2 or more}
[Chemical 26]

{Wherein R _{1 is} each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one of them is a carbon number A monovalent aliphatic hydrocarbon group of 1 to 5, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms, R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one is an organic group having an unsaturated aliphatic hydrocarbon group, and L ₁ and L ₂ are each independently an amine group, an acid anhydride group, an isocyanate group, a carboxyl group, Ester group, sulfonyl halide, hydroxyl, epoxy, or mercapto group, i and j are each independently an integer of 1 to 200, k is an integer of 0 to 200, and 0.05 ≦ j / (i + j + k) ≦ 0.50}
[14]
The resin composition according to any one of items 10 to 13, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (5) are each independently selected from the group consisting of an amine group, an acid anhydride group, and an epoxy group. Group of people.
[15]
The resin composition according to any one of items 10 to 14, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (5) are amine groups.
[16]
The resin composition according to any one of items 10 to 15, wherein the compound represented by the general formula (3-1) or (3-2) is a compound represented by the general formula (3-1).
[17]
The resin composition according to any one of items 10 to 16, wherein the tetracarboxylic dianhydride is selected from the group consisting of pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride At least one of 4, 4'-oxydiphthalic dianhydride, cyclohexanetetracarboxylic dianhydride, and cyclobutanetetracarboxylic dianhydride.
[18]
The resin composition according to any one of items 10 to 17, wherein the diamine is selected from the group consisting of 4,4'-diaminodiphenylphosphonium, m-toluidine, p-phenylenediamine, 2,2 ' -At least one of the group consisting of bis (trifluoromethyl) benzidine and 2,2'-bis [4- (4-aminophenoxy) phenyl] propane.
[19]
A method for manufacturing a resin composition includes the following steps:
Containing: a silicon-containing compound represented by the following general formula (5);
A raw material composition and a tetracarboxylic acid of at least any one compound in which m is an integer of 3 or more in the following general formula (3-1) or (3-2) The polyanhydride precursor is provided by a polycondensation reaction of a dianhydride and a diamine; and the total mass of the silicon-containing compound represented by the following general formulae (3-1), (3-2), (4), and (5) As a reference, the total amount of compounds in which m in the following general formula (3-1) or (3-2) in the raw material composition is an integer of 3 or more is more than 0 ppm and 46,000 ppm or less,
Based on the total mass of the silicon-containing compound of the general formulae (3-1), (3-2), (4), and (5) above, the following general formula (3-1) contained in the raw material composition Or, the total amount of the compound in which m is an integer of 3 or more in (3-2) and the compound in which n is an integer of 3 or more in the following general formula (4) is more than 0 ppm and 47,000 ppm or less.
[Chemical 27]

{Where m is an integer of 1 or more}
[Chemical 28]

{Where n is an integer of 2 or more}
[Chemical 29]

{Wherein R _{1 is} each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one of them is a carbon number A monovalent aliphatic hydrocarbon group of 1 to 5, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms, R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one is an organic group having an unsaturated aliphatic hydrocarbon group, and L ₁ and L ₂ are each independently an amine group, an acid anhydride group, an isocyanate group, a carboxyl group, Ester group, fluorenyl halide group, hydroxyl group, epoxy group, or mercapto group, i and j are each independently an integer of 1 to 200, k is an integer of 0 to 200, and 0.05 ≦ j / (i + j + k) ≦ 0.50}
[20]
The method according to item 19, wherein in the compound represented by the general formula (3-1) or (3-2), m is an integer of 3 to 5.
[twenty one]
The method according to item 19, wherein in the compound represented by the general formula (4), n is an integer of 3 to 8.
[twenty two]
A method for manufacturing a resin composition includes the following steps:
Containing: a silicon-containing compound represented by the following general formula (5);
A raw material composition of at least one compound in which m is 3 or 4 in the following general formula (3-1) or (3-2), and any one of the compounds represented by the following general formula (4), and tetracarboxylic acid di An anhydride and a diamine are subjected to a polycondensation reaction to provide a polyimide precursor; and based on the total mass of the silicon-containing compound of the following general formulae (3-1), (3-2), (4), and (5), The total amount of the compound in which m is 3 in the following formula (3-1) or (3-2) contained in the above raw material composition is more than 0 ppm and 25,000 ppm or less,
Based on the total mass of the silicon-containing compound of the following general formulae (3-1), (3-2), (4), and (5), the following general formula (3-1) contained in the above raw material composition Or, the total amount of the compound in which m is 4 in (3-2) is more than 0 ppm and 15,000 ppm or less.


[Chemical 30]

{Where m is an integer of 1 or more}
[Chemical 31]

{Where n is an integer of 2 or more}
[Chemical 32]

{Wherein R _{1 is} each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one of them is a carbon number A monovalent aliphatic hydrocarbon group of 1 to 5, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms, R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one is an organic group having an unsaturated aliphatic hydrocarbon group, and L ₁ and L ₂ are each independently an amine group, an acid anhydride group, an isocyanate group, a carboxyl group, Ester group, fluorenyl halide group, hydroxyl group, epoxy group, or mercapto group, i and j are each independently an integer of 1 to 200, k is an integer of 0 to 200, and 0.05 ≦ j / (i + j + k) ≦ 0.50}
[twenty three]
The method according to any one of items 19 to 22, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (5) are each independently selected from the group consisting of an amine group, an acid anhydride group, and an epoxy group. group.
[twenty four]
The method according to any one of items 19 to 23, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (5) are amine groups.
[25]
The method according to any one of items 19 to 24, wherein the compound represented by the general formula (3-1) or (3-2) is a compound represented by the general formula (3-1).
[26]
The method according to any one of items 19 to 25, wherein the tetracarboxylic dianhydride is selected from the group consisting of pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 4 , At least one of the group consisting of 4'-oxydiphthalic dianhydride, cyclohexanetetracarboxylic dianhydride, and cyclobutanetetracarboxylic dianhydride.
[27]
The method according to any one of items 19 to 26, wherein the diamine is selected from the group consisting of 4,4'-diaminodiphenylphosphonium, m-toluidine, p-phenylenediamine, 2,2'-bis (Trifluoromethyl) benzidine and at least one member of the group consisting of 2,2'-bis [4- (4-aminophenoxy) phenyl] propane.
[28]
A method for manufacturing a polyimide film includes the following steps:
A coating step of coating the resin composition according to any one of items 1 to 18 on the surface of the support;
A film forming step of heating the resin composition to form a polyimide resin film; and a peeling step of peeling the polyimide resin film from the support.
[29]
The method for producing a polyimide film according to item 28, further comprising an irradiation step of irradiating the resin composition with a laser from the support side before the peeling step.
[30]
A method for manufacturing a display, comprising the following steps: a coating step of coating the resin composition according to any one of items 1 to 18 on a 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 on which the element is formed from the support.
[31]
A method for manufacturing a laminated body includes the following steps:
A coating step of coating the resin composition according to any one of items 1 to 18 on the surface of the support;
A film forming step of heating the resin composition to form a polyimide resin film; and an element forming step of forming an element on the polyimide resin film.
[32]
The manufacturing method of the laminated body as described in the item 31, further including the step of peeling the said polyimide resin film in which the said element was formed from the said support.
[33]
A method for manufacturing a flexible device includes the steps of manufacturing a laminated body by a method as described in item 31 or 32.
[34]
A polyimide film is a cured product of the resin composition according to any one of items 1 to 18.
[Effect of the invention]

According to the present invention, it is possible to provide a polyimide precursor that can further improve yellowness (YI value) compared with a case where an unrefined siloxane compound is used, and can reduce foreign substances generated in a polyimide manufacturing process. Body resin composition. Furthermore, the above description cannot be regarded as revealing all the embodiments of the present invention and all the advantages related to the present invention. Further embodiments and advantages of the present invention will be made clear by referring to the following description.

Hereinafter, an exemplary embodiment of the present invention (hereinafter, simply referred to as "this embodiment") will be described in detail. The present invention is not limited to this embodiment, and can be implemented with various changes within the scope of the gist thereof. In the description of this case, the upper limit value and lower limit value of each numerical range can be arbitrarily combined.

<< Resin Composition >>
<Polyimide precursor>
Structural Unit of General Formula (1) First Embodiment In the first embodiment, the resin composition of the present embodiment includes a polyimide precursor containing a structural unit represented by the following general formula (1).

[Chemical 33]

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

The polyimide precursor having a structure represented by the general formula (1) is preferably a copolymer 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, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3 ' -Biphenyltetracarboxylic dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride, 5- (2,5-dioxatetrahydro-3-furanyl) -3 -Methyl-cyclohexene-1,2 dicarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride Anhydride, 2,2 ', 3,3'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, methylene-4,4 ' -Diphthalic dianhydride, 1,1-ethylene-4,4'-diphthalic dianhydride, 2,2-propylene-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, 4,4'-oxydiphthalic dianhydride, para- Diphenylene bis (trimellitic anhydride), thio-4,4'-diphthalic dianhydride, sulfo-4,4'-diphthalic dianhydride, 1,3- Bis (3,4-dicarboxyphenyl) phthalic anhydride, 1,3-bis (3,4-dicarboxyphenoxy) phthalic anhydride, 1,4-bis (3,4-Dicarboxyphenoxy) phthalic anhydride, 1,3-bis [2- (3,4-dicarboxyphenyl) -2-propyl] phthalic anhydride, 1,4-bis [2 -(3,4-dicarboxyphenyl) -2-propyl] phthalic anhydride, bis [3- (3,4-dicarboxyphenoxy) phenyl] methane dianhydride, bis [4- (3, 4-dicarboxyphenoxy) phenyl] methane dianhydride, 2,2-bis [3- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [4- ( 3,4-dicarboxyphenoxy) phenyl] propane dianhydride, bis (3,4-dicarboxyphenoxy) dimethylsilane dianhydride, 1,3-bis (3,4-dicarboxyphenyl) ) -1,1,3,3-tetramethyldisiladian dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-pyridinetetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, and 1,2, 7,8-phenanthrenetetracarboxylic dianhydride.

The acid dianhydride may be used singly or in combination of two or more kinds. Among these, from the viewpoints of the mechanical properties of the polyimide film, optical characteristics such as lower thickness direction retardation (Rth) and lower yellowness (YI value), and higher glass transition temperature, Pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic dianhydride (BPDA) are preferred. The polyimide precursor having a structure represented by the general formula (1) is a copolymer of tetracarboxylic dianhydride and diamine, and the tetracarboxylic dianhydride preferably includes pyromellitic dianhydride (PMDA).

Regarding the total content of pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic dianhydride (BPDA) in all acid dianhydrides, the lower the Rth and YI values of the polyimide film, and the higher the From the viewpoint of glass transition temperature, it is preferably 60 mol% or more, more preferably 80 mol% or more, and still more preferably 100 mol%.

Regarding the content of pyromellitic dianhydride (PMDA) in all acid dianhydrides, from the viewpoint of the higher glass transition temperature of the polyimide film, it is preferably 0 mol% or more, and more preferably 10 Molar% or more, preferably 20 Molar% or more, and preferably 100 Molar% or less, and more preferably 90 Molar% or less.

Regarding the content of biphenyltetracarboxylic dianhydride (BPDA) in all acid dianhydrides, from the viewpoint of the lower Rth and YI values of the polyfluorene imide film, it is preferably 0 mol% or more, more preferably It is 10 mol% or more, preferably 20 mol% or more, and preferably 100 mol% or less, and more preferably 90 mol% or less.

Regarding the pyromellitic dianhydride (PMDA): biphenyltetracarboxylic dianhydride (BPDA) content ratio in acid dianhydride, the lower Rth and YI values of the polyfluorene imide film and the higher From a viewpoint of glass transition temperature and elongation, it is preferably 20:80 to 80:20, and more preferably 30:70 to 70:30.

As a diamine containing a P ₁ group in the formula (1), diamines include diaminodiphenylphosphonium (for example, 4,4'-diaminodiphenylphosphonium, 3,3'-diamino) Diphenylhydrazone), p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 3,3'-diamine Diphenyl sulfide, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl Benzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diamine Diphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] fluorene, 4,4-bis (4-aminophenoxy) biphenyl, 4 , 4-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] Ether, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 9,10-bis (4-aminophenyl) anthracene, 2,2 -Bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl) propane ,2 , 2-bis [4- (4-aminophenoxy) phenyl) hexafluoropropane, and 1,4-bis (3-aminopropyldimethylsilyl) benzene.

As the diamine containing the P ₁ group in the formula (1), it is preferred to contain a diaminodiphenylsulfonium, such as 4,4'-diaminodiphenylsulfonium, and / or 3,3'-diamine. Aminodiphenylphosphonium.

The content of diaminodiphenylphosphonium in all diamines may be 50 mol% or more, or 70 mol% or more, or 90 mol% or more, or 95 mol% or more. The greater the amount of diaminodiphenylphosphonium, the lower the YI value of the polyfluoreneimide film, and the higher the glass transition temperature, the better. From the viewpoint of lowering the YI value, the diaminodiphenylphosphonium is particularly preferably 4,4'-diaminodiphenylphosphonium.

The diamine may be used singly or in combination of two or more kinds. It is preferred to copolymerize diaminodiphenylphosphonium with other diamines. As the other diamine copolymerized with diaminodiphenylfluorene, from the viewpoint of the higher heat resistance of the polyfluoreneimide film and the lower YI value, diamine biphenyls are preferably exemplified. More preferred examples include diaminobis (trifluoromethyl) biphenyl (TFMB). Regarding the content of diaminobis (trifluoromethyl) biphenyl (TFMB) in all diamines, from the viewpoint of the lower YI value of the polyfluoreneimide film, it is preferably 20 mol% or more, More preferably, it is 30 mol% or more. From the viewpoint of designing the diamine to include other diamines such as diaminodiphenylsulfonium, the content of TFMB is preferably 80 mol% or less, and more preferably 70 mol% or less.

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

[Chem 34]

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

Using the mass of the polyimide precursor as a reference, regarding the lower limit of the ratio of the structural parts represented by the general formula (2), from the viewpoint of reducing the residual stress of the polyimide film generated between the support and the support It is preferably 5 mass% or more, more preferably 6 mass% or more, and even more preferably 7 mass% or more. Using the mass of the polyimide precursor as a reference, the upper limit of the ratio of the structural site represented by the general formula (2) is preferably 40 in terms of the transparency and heat resistance of the polyimide film. Mass% or less, more preferably 30 mass% or less, and still more preferably 25 mass% or less.
In the general formula (2), q is an integer of 1 to 200, and from the viewpoint of the heat resistance of the obtained polyimide, it is preferably an integer of 3 to 200.

The polyimide precursor may have a structure of the general formula (2) at any position in the molecule. From the viewpoint of the type and cost of the siloxane monomer and the molecular weight of the obtained polyimide precursor, In other words, the structure of the general formula (2) is preferably a silicon-containing compound, for example, derived from a silicon-containing diamine. As the silicon-containing diamine, for example, a diamine (poly) siloxane represented by the following formula (6) is preferred.

[Chemical 35]

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

The general formula (2) in the P ₅ of the preferred structure include: a methylene group, an ethyl stretching, stretching propyl, butyl stretch, phenylene and the like. Preferable structures of P ₃ and P ₄ include methyl, ethyl, propyl, butyl, and phenyl. In the above general formula (6), l is an integer of 1 to 200, and from the viewpoint of heat resistance of the polyimide of (6), an integer of 3 to 200 is preferred.

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

Specific examples of the compound represented by the general formula (6) include: amine modified methylphenyl polysiloxane (made by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400), X22) -9409 (number average molecular weight 1340)), acid anhydride modified methylphenyl polysiloxane (made by Shin-Etsu Chemical Co., Ltd .: X22-168-P5-B (number average molecular weight 4200)), epoxy modified at both ends Methylphenyl polysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-2000 (number average molecular weight 1240)), amine modified dimethyl polysiloxane at both ends (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-161A (Quantity average molecular weight) 1600), X22-161B (number average molecular weight 3000), KF8021 (number average molecular weight 4400), manufactured by Dow Corning Toray: BY16-835U (number average molecular weight 900), manufactured by Chisso: SilaplaneFM3311 (number average molecular weight 1000)), and the like. Among these, from the viewpoints of improvement in chemical resistance and improvement in Tg, both terminal amine-modified methylphenylpolysiloxanes are preferred.

The copolymerization ratio of the silicon-containing diamine is preferably 0.5 to 30% by mass, more preferably 1.0% to 25% by mass, and even more preferably 1.5% by mass to the total mass of the polyimide precursor. 20% by mass. When the diamine containing silicon is 0.5% by mass or more, the residual stress generated between the diamine and the support can be effectively reduced. When the silicon-containing diamine is less than 30% by mass, the transparency (especially low haze) of the obtained polyimide film is good, with respect to the realization of a higher total light transmittance and a higher From a viewpoint of glass transition temperature, it is preferable.

The dicarboxylic acid is used as an acid component for forming the polyimide precursor in this embodiment, and the acid dianhydride (such as the tetracarboxylic dianhydride exemplified above) is removed within a range that does not impair its performance. In addition, dicarboxylic acids may be used. That is, the polyimide precursor of the present invention may also be a polyimide precursor. The film obtained by using such a polyfluorene imide precursor may have various properties such as mechanical elongation, glass transition temperature Tg, and YI value. Examples of the dicarboxylic acid to be used include a dicarboxylic acid having an aromatic ring and an alicyclic dicarboxylic acid. Particularly preferred is at least one compound selected from the group consisting of an aromatic dicarboxylic acid having 8 to 36 carbon atoms and an alicyclic dicarboxylic acid having 6 to 34 carbon atoms. The number of carbons referred to here also includes the number of carbons contained in the carboxyl group. Among these, a dicarboxylic acid having an aromatic ring is preferred.

Specific examples of the dicarboxylic acid having an aromatic ring include isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid, 3,4'-biphenyldicarboxylic acid, and 3 , 3'-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-sulfonyl Bisbenzoic acid, 3,4'-sulfofluorenylbisbenzoic acid, 3,3'-sulfofluorenylbisbenzoic acid, 4,4'-oxybisbenzoic acid, 3,4'-oxybisbenzoic acid, 3,3'-oxybisbenzoic acid, 2,2-bis (4-carboxyphenyl) propane, 2,2-bis (3-carboxyphenyl) propane, 2,2'-dimethyl-4, 4'-biphenyldicarboxylic acid, 3,3'-dimethyl-4,4'-biphenyldicarboxylic acid, 2,2'-dimethyl-3,3'-biphenyldicarboxylic acid, 9 , 9-bis (4- (4-carboxyphenoxy) phenyl) fluorene, 9,9-bis (4- (3-carboxyphenoxy) phenyl) fluorene, 4,4'-bis (4- Carboxyphenoxy) biphenyl, 4,4'-bis (3-carboxyphenoxy) biphenyl, 3,4'-bis (4-carboxyphenoxy) biphenyl, 3,4'-bis (3 -Carboxyphenoxy) biphenyl, 3,3'-bis (4-carboxyphenoxy) biphenyl, 3,3'-bis (3-carboxyphenoxy) biphenyl, 4,4'-bis ( 4-carboxyphenoxy) -p-terphenyl, 4,4'-bis (4-carboxyphenoxy) -m-terphenyl, 3,4'-bis (4-carboxybenzene ) -P-terphenyl, 3,3'-bis (4-carboxyphenoxy) -p-terphenyl, 3,4'-bis (4-carboxyphenoxy) -m-terphenyl, 3,3 ' -Bis (4-carboxyphenoxy) -m-terphenyl, 4,4'-bis (3-carboxyphenoxy) -p-terphenyl, 4,4'-bis (3-carboxyphenoxy)- M-terphenyl, 3,4'-bis (3-carboxyphenoxy) -p-terphenyl, 3,3'-bis (3-carboxyphenoxy) -p-terphenyl, 3,4'-bis ( (3-carboxyphenoxy) -m-terphenyl, 3,3'-bis (3-carboxyphenoxy) -m-terphenyl, 1,1-cyclobutanedicarboxylic acid, 1,4-cyclohexyl Alkanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4,4'-benzophenone dicarboxylic acid, 1,3-benzenediacetic acid, 1,4-benzenediacetic acid, etc .; and published internationally 5-aminoisophthalic acid derivatives and the like described in 2005/068535. When the dicarboxylic acid is actually copolymerized with the polymer, it can be used in the form of an ammonium chloride body, an active ester body, or the like derived from thionyl chloride.

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

[Chemical 36]

{Wherein R _{1 is} each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one of them is a carbon number A monovalent aliphatic hydrocarbon group of 1 to 5, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms, R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one is an organic group having an unsaturated aliphatic hydrocarbon group, and L ₁ and L ₂ are each independently an amine group, an acid anhydride group, an isocyanate group, a carboxyl group, Ester group, fluorenyl halide group, hydroxyl group, epoxy group, or mercapto group, i and j are each independently an integer of 1 to 200, k is an integer of 0 to 200, and 0.05 ≦ j / (i + j + k) ≦ 0.50}

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

In the general formula (5), R _{1 is} each independently a single bond or a divalent organic group having 1 to 10 carbon atoms. The divalent organic group having 1 to 10 carbon atoms may be any of linear, cyclic, and branched, and may be saturated or unsaturated. Examples of the divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms include methylene, ethylene, n-propyl, n-isopropyl, n-butyl, second-butyl, third-butyl, Straight or branched chain alkylene groups such as n-pentyl, neo-pentyl, hexyl, heptyl, octyl, nonyl, and decyl; and cyclopropyl, cyclobutyl, Cyclopentyl, such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. The divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferably at least one selected from the group consisting of ethylene, n-propyl, and isopropyl.

In the general formula (5), R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one of them is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms. The monovalent organic group having 1 to 10 carbon atoms may be any of linear, cyclic, and branched, and may be saturated or unsaturated. Examples of the monovalent organic group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, n-pentyl, and neo Linear or branched alkyl groups such as pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; and cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl And aromatic groups such as cycloalkyl, such as cyclooctyl, phenyl, tolyl, xylyl, α-naphthyl, and β-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 methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, n-pentyl, And linear or branched alkyl such as neopentyl; cycloalkyl 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.

In the general formula (5), R ₄ and R ₅ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one of them is a monovalent aromatic group having 6 to 10 carbon atoms. The monovalent organic group having 1 to 10 carbon atoms may be any of linear, cyclic, and branched, and may be saturated or unsaturated. Examples of the monovalent organic group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, n-pentyl, and neo Linear or branched alkyl groups such as pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; and cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl And aromatic groups such as cycloalkyl, such as cyclooctyl, phenyl, tolyl, xylyl, α-naphthyl, and β-naphthyl. Examples of the monovalent aromatic group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an α-naphthyl group, and a β-naphthyl group, and the like is preferably a phenyl group, a tolyl group, or a di-naphthyl group. Tolyl.

In the general formula (5), R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one of them is an organic group having an unsaturated aliphatic hydrocarbon group. The monovalent organic group having 1 to 10 carbon atoms may be any of linear, cyclic, and branched, and examples thereof include methyl, ethyl, n-propyl, isopropyl, and n-butyl. Straight or branched chain alkyl groups such as, second butyl, third butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; and cyclopropyl Aromatic groups such as cycloalkyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, phenyl, tolyl, xylyl, α-naphthyl, and β-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 linear, cyclic, and branched. Examples of the unsaturated aliphatic hydrocarbon group having 3 to 10 carbon atoms include vinyl, allyl, propenyl, 3-butenyl, 2-butenyl, pentenyl, cyclopentenyl, and hexene. Base, cyclohexenyl, heptenyl, octenyl, nonenyl, decenyl, ethynyl, propynyl, butynyl, pentynyl, and hexynyl. The unsaturated aliphatic hydrocarbon group having 3 to 10 carbon atoms is preferably at least one selected from the group consisting of a vinyl group, an allyl group, and a 3-butenyl group.

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

i and j are each independently an integer of 1 to 200, preferably an integer of 2 to 100, more preferably an integer of 4 to 80, and even more preferably an integer of 8 to 40. k is 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 tetracarboxylic dianhydride in the second embodiment may be the tetracarboxylic dianhydride listed for the general formula (1). The tetracarboxylic dianhydride in the second embodiment is preferably selected from the group consisting of pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, and 4,4'-oxodiphthalic acid. At least one of the group consisting of dicarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, and cyclobutanetetracarboxylic dianhydride.

The diamine in the second embodiment may be the diamines listed for the general formula (1). Two of the second embodiment are preferably amine 4,4'-diaminodiphenylphosphonium, m-toluidine, p-phenylenediamine, 2,2'-bis (trifluoromethyl) benzidine, and At least one member of the group consisting of 2,2'-bis [4- (4-aminophenoxy) phenyl] propane.

Weight average molecular weight In the present embodiment, the weight average molecular weight of the polyimide precursor is preferably 50,000 or more, and more preferably 60,000 or more, from the viewpoint of reducing the YI value of the polyimide film. From the viewpoint of reducing the haze of the polyimide film, the weight average molecular weight of the polyimide precursor is preferably 150,000 or less, and more preferably 120,000 or less. The preferable weight average molecular weight of the polyimide precursor can be determined according to the required application, the type of the polyimide precursor, the solid content content of the resin composition, and the kind of solvent that the resin composition can contain. different.

Preferred Embodiments of the Polyfluorene Imide Precursor The polyfluorene imide precursor which is particularly preferred in this embodiment includes the following (1) to (9).
(1) The acid dianhydride component is pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic dianhydride (BPDA), and the diamine component is diaminodiphenylphosphonium (DAS) and silicon-containing diamine Of polycondensate. More preferably, the weight average molecular weight is 80,000 to 100,000, and the solid content content is 10 to 25% by mass.
(2) The acid dianhydride components are pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic dianhydride (BPDA), and the diamine component is diaminobis (trifluoromethyl) biphenyl (TFMB) and Polycondensate of silicon-containing diamine. More preferably, the weight average molecular weight is 65,000 to 90,000, and the solid content content is 10 to 25% by mass.
(3) The acid dianhydride component is pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic dianhydride (BPDA), and the diamine component is diaminodiphenylphosphonium (DAS), diamine bis ( Polycondensate of trifluoromethyl) biphenyl (TFMB) and silicon-containing diamine. More preferably, the weight average molecular weight is 95,000 to 120,000, and the solid content content is 10 to 25% by mass.
(4) The acid dianhydride component is pyromellitic dianhydride (PMDA), and the diamine component is a polycondensate of diaminodiphenylphosphonium (DAS) and silicon-containing diamine. More preferably, the weight average molecular weight is 100,000 to 110,000, and the solid content content is 10 to 25% by mass.
(5) The acid dianhydride component is pyromellitic dianhydride (PMDA), and the diamine component is a polycondensate of diamine bis (trifluoromethyl) biphenyl (TFMB) and silicon-containing diamine. More preferably, the weight average molecular weight is 100,000 to 110,000, and the solid content content is 10 to 25% by mass.
(6) The acid dianhydride component is pyromellitic dianhydride (PMDA), and the diamine component is diaminodiphenylphosphonium (DAS), diaminobis (trifluoromethyl) biphenyl (TFMB), and Polycondensate of silicon-containing diamine. More preferably, the weight average molecular weight is 110,000 to 120,000, and the solid content content is 10 to 25% by mass.

(7) The acid dianhydride component is biphenyltetracarboxylic dianhydride (BPDA), and the diamine component is a polycondensate of diaminodiphenylphosphonium (DAS) and silicon-containing diamine. More preferably, the weight average molecular weight is 70,000 to 80,000, and the solid content content is 10 to 25% by mass.
(8) The acid dianhydride component is biphenyltetracarboxylic dianhydride (BPDA), and the diamine component is diaminodiphenylphosphonium (DAS), diaminobis (trifluoromethyl) biphenyl (TFMB) And polycondensates of silicon-containing diamines. More preferably, the weight average molecular weight is 90,000 to 100,000, and the solid content content is 10 to 25% by mass.
(9) The acid dianhydride component is biphenyltetracarboxylic dianhydride (BPDA), and the diamine component is a polycondensate of diamine bis (trifluoromethyl) biphenyl (TFMB) and silicon-containing diamine. More preferably, the weight average molecular weight is 70,000 to 80,000, and the solid content content is 10 to 25% by mass.

Among the material components of the polycondensates of the above (1) to (9), the diamine containing silicon is preferably a diamine (poly) siloxane represented by the general formula (6). In this case, the number average molecular weight of the diamine (poly) siloxane is preferably from 500 to 12,000, and more preferably, the diamine (poly) siloxane is a amine modified methylphenyl polysiloxane at both ends. oil.

＜ Low-molecular cyclic siloxane ＞
The compound of the general formula (3) The resin composition according to this embodiment includes a low-molecular-weight cyclic siloxane represented by the following general formula (3-1) or (3-2), where m is an integer of 3 or more At least any one of low-molecular-weight cyclic siloxanes (hereinafter referred to as "(3)" means "(3-1) or (3-2)"). The composition of this embodiment may contain the compound of which m is 1 or 2 in general formula (3-1) or (3-2), and may not contain it. The resin composition of this embodiment may contain only one of the general formula (3-1) or (3-2), and may contain both. The compound represented by general formula (3-1) or (3-2) is preferably a compound represented by general formula (3-1). That is, the resin composition of the present embodiment preferably contains at least a compound represented by the general formula (3-1).

[Chemical 37]

{Where m is an integer of 1 or more}

Regarding the total amount of compounds in which m is an integer of 3 or more in the general formula (3), based on the mass of the resin composition, it is preferably more than 0 ppm and 1,100 ppm or less, more preferably more than 0 ppm and is 800 ppm or less, more preferably 0 ppm and 600 ppm or less, particularly preferably more than 0 ppm and 300 ppm or less, even more preferably more than 0 ppm and 180 ppm or less. Here, the total amount of the compound represented by the general formula (3) refers to the general formula (3) when the resin composition includes only one of the general formula (3-1) or (3-2). The total of either -1) or (3-2), when including both, means the total of both.

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

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

When the mass of the solid component in the resin composition is used as a reference, the total amount of the compound in which m is an integer of 3 or more in the general formula (3) is preferably more than 0 ppm and 7,500 ppm or less, more It is preferably more than 0 ppm and 2,000 ppm or less, and still more preferably more than 0 ppm and 1,100 ppm or less. When the mass of the solid component in the resin composition is used as a reference, the total amount of the compound in which m is 3 in the general formula (3) is preferably more than 0 ppm and 4,500 ppm or less, more preferably more than 0 ppm and 1,000 ppm or less, more preferably more than 0 ppm and 500 ppm or less. When the mass of the solid component in the resin composition is used as a reference, the total amount of the compound in which m is 4 in the general formula (3) is preferably more than 0 ppm and 2,500 ppm or less, more preferably more than 0 ppm and 700 ppm or less, more preferably more than 0 ppm and 400 ppm or less. If the total amount of the compound represented by the general formula (3) is within the above range, the YI value of the polyimide resin film obtained by using the resin composition is further reduced, which is preferable.

In the specification of the present case, the so-called "solid content component" refers to all components other than the solvent in the resin composition, and the liquid monomer component is also included in the mass of the solid content component. When the resin composition contains only a solvent and a polyimide precursor, the polyimide precursor corresponds to a solid component. When the resin composition contains only a solvent and a polyimide precursor, the mass of the solid component is equal to the total amount of the mass of all the monomers contained in the polyimide precursor. The mass of the solid component can also be determined by analyzing the resin composition by gas chromatography (hereinafter also referred to as GC) to determine the mass of the solvent, and subtracting from the mass of the resin composition. The quality of the solvent. The mass of the solid component can also be determined by heating the resin composition to volatilize and remove the solvent, determine the mass of the solvent, and subtract the mass of the solvent from the mass of the resin composition.

The polyfluorene imide precursor according to this embodiment may contain a silicon-containing compound represented by the general formula (5), a compound represented by the general formula (3-1) or (3-2), and a general formula (4). The raw material composition of the compound represented by) is obtained by a polycondensation reaction with tetracarboxylic dianhydride and diamine. In this case, regarding the total amount of compounds in which m in the above-mentioned general formula (3) contained in the raw material composition is an integer of 3 or more, the formulas (3), (4), and (5) are used. As a reference, the mass of the silicon-containing compound is preferably more than 0 ppm and less than 280 ppm, more preferably more than 0 ppm and less than 30 ppm, and still more preferably more than 0 ppm and less than 6 ppm. Based on the total mass of the silicon-containing compound represented by the general formulae (3), (4), and (5) as a reference, the total amount of the compound in which m is 3 in the general formula (3) is preferably more than 0 ppm and 200 ppm or less, more preferably 0 ppm and 25 ppm or less, still more preferably 0 ppm and 3 ppm or less. When the total mass of the silicon-containing compound of the general formulae (3), (4), and (5) is used as a reference, the total amount of the compound in which m is 4 in the general formula (3) is preferably more than 0 ppm and It is 80 ppm or less, more preferably 0 ppm and 5 ppm or less, and still more preferably 0 ppm and 3 ppm or less. If the total amount of the compound represented by the general formula (3) is within the above range, the YI value of the polyimide resin film obtained by using the resin composition is further reduced, which is preferable.

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

[Chemical 38]

{Where n is an integer of 2 or more}

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

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

Regarding the total amount of the compound in which m is an integer of 3 or more in the general formula (3) and the compound in which n is an integer of 3 or more in the general formula (4), based on the mass of the resin composition, preferably more than 0 ppm is 1,300 ppm or less, more preferably 0 ppm and 400 ppm or less, still more preferably 0 ppm and 230 ppm or less. Preferably, the total amount of the compound in which m is an integer of 3 or more in the general formula (3) and the compound in which n is an integer of 3 or more in the general formula (4) is within the above range, and The total amount of the compound having an integer of 3 or more, based on the mass of the resin composition, preferably more than 0 ppm and 1,100 ppm or less, more preferably more than 0 ppm and 800 ppm or less, and further preferably More than 0 ppm and less than 600 ppm, more preferably more than 0 ppm and less than 300 ppm, even more preferably more than 0 ppm and less than 180 ppm.

It is preferable that the total amount of the compound in which m is an integer of 3 or more in the general formula (3) and the compound in which n is an integer of 3 or more in the general formula (4) is within the above range, and about m in the general formula (3) The total amount of the compound is 3 to 5, based on the mass of the resin composition, preferably more than 0 ppm and less than 1,100 ppm, more preferably more than 0 ppm and less than 800 ppm, and more preferably more 0 ppm to 600 ppm, more preferably 0 ppm to 300 ppm, and even more preferably 0 ppm to 180 ppm. If the total amount of the compound represented by the general formula (3) and the compound represented by the general formula (4) is within the above range, the total number of foreign matters adhering to the manufacturing process of the polyimide resin film is reduced. Speak better.

When the mass of the solid content component in the resin composition is used as a reference, the total amount of compounds in which n in the general formula (4) is an integer of 3 or more is preferably more than 0 ppm and 1,100 ppm or less, and more preferably It is more than 0 ppm and 700 ppm or less, and more preferably more than 0 ppm and 400 ppm or less. When the mass of the solid component in the resin composition is used as a reference, the total amount of the compound in which m is an integer of 3 or more in the general formula (3) and the compound in which n is an integer of 3 or more in the general formula (4) It is preferably more than 0 ppm and 8,600 ppm or less, more preferably more than 0 ppm and 2,700 ppm or less, and still more preferably more than 0 ppm and 1,500 ppm or less. If the total amount of the compound represented by the general formula (3) and the compound represented by the general formula (4) is within the above range, the total number of foreign matters adhering to the manufacturing process of the polyimide resin film is reduced. Speak better.

In the case where the mass of the silicon-containing compound of the general formulae (3), (4), and (5) is used as a reference, the total amount of the compounds of which n is an integer of 3 or more in the general formula (4) is preferably more than 0. ppm is 200 ppm or less, more preferably 0 ppm and 100 ppm or less, and still more preferably 0 ppm and 50 ppm or less. When the total mass of the silicon-containing compound of the general formulae (3), (4), and (5) is used as a reference, the compound of the general formula (3) in which m is an integer of 3 or more and the n of the general formula (4) The total amount of the compound having an integer of 3 or more is preferably more than 0 ppm and 4,700 ppm or less, more preferably more than 0 ppm and 1,100 ppm or less, still more preferably more than 0 ppm and 6,300 ppm or less. If the total amount of the compound represented by the general formula (3) and the compound represented by the general formula (4) is within the above range, the total number of foreign matters adhering to the manufacturing process of the polyimide resin film is reduced. Speak better.

The foreign matter counts are based on the mass of the resin composition, solid components, and silicon-containing compounds, respectively. The cyclic siloxane and m in the general formula (3) are integers of 3 or more (preferably m is 3 to 5) and The smaller the total amount of cyclic siloxanes in the general formula (4) where n is an integer of 3 or more (preferably n is 3 to 8), the more foreign substances adhered to the polyimide resin film during the manufacturing process. A small amount is preferred. Although the mechanism is not clear, the inventors and others presume the following. That is, in the production of a polyimide resin film, the following operation is typically performed: a resin composition containing a polyimide precursor composition is coated on a support such as a glass substrate, and in an oven, for example, in It is heated at 100 ° C for 30 minutes to remove the solvent, and continuously heated in the same oven at a higher temperature, for example, 350 ° C for 1 hour, thereby performing amidation to form a polyimide resin film. Here, the cyclic siloxane of the general formula (4) is more volatile than the cyclic siloxane of the general formula (3). Therefore, it is considered that the cyclic siloxane of the general formula (4) is volatilized when the solvent is removed, and the cyclic siloxane of the general formula (3) is volatile and attached to the oven when the amidine is imidized. In particular, when the number of samples put into the oven is large, it is considered that the cyclic siloxanes of the general formulae (3) and (4) accumulate more in the oven and become attached to Foreign matter of polyimide resin film. Therefore, it is considered that the smaller the total amount of the cyclic siloxane of the general formula (3) and the cyclic siloxane of the general formula (4), the smaller the amount of foreign matter attached in the manufacturing process of the polyimide resin film. .

<Solvent>
The resin composition typically contains a solvent. As the solvent, it is preferred that the polyfluorene imide precursor has good solubility and the solution viscosity of the resin composition can be appropriately controlled, and a reaction solvent of the polyfluorene imide precursor can be used as the solvent of the composition. Among them, N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), a compound represented by the general formula (4), and the like are preferred. Specific examples of the solvent composition include N-methyl-2-pyrrolidone (NMP) alone or a mixture of N-methyl-2-pyrrolidone (NMP) and γ-butyrolactone (GBL) Solvents, etc. The mass ratio of NMP to GBL may be, for example, NMP: GBL (mass ratio) = 10: 90 to 90:10.

＜ Additional ingredients ＞
The resin composition of this embodiment may further contain an additional component in addition to a polyimide precursor, a low-molecular cyclic siloxane, and a solvent. Examples of the additional component include a surfactant and an alkoxysilane compound.

Surfactant By adding a surfactant to the resin composition of this embodiment, the coating property of the resin composition can be improved. Specifically, the occurrence of streaks in the coating film can be prevented.
Examples of such a surfactant include a polysiloxane-based surfactant, a fluorine-based surfactant, and a nonionic surfactant other than these. Examples of the polysiloxane-based surfactant include organosiloxane polymers KF-640, 642, 643, KP341, X-70-092, and X-70-093 (trade names, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) ; SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (trade name, manufactured by Dow Corning Toray Silicone); SILWET L-77, L-7001, FZ -2105, FZ-2120, FZ-2154, FZ-2164, FZ-2166, L-7604 (trade name, manufactured by Nippon Unicar); DBE-814, DBE-224, DBE-621, CMS-626, CMS- 222, KF-352A, KF-354L, KF-355A, KF-6020, DBE-821, DBE-712 (Gelest), BYK-307, BYK-310, BYK-378, BYK-333 (brand name, BYK- (Manufactured by Chemie Japan); Glano (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), and the like. Examples of the fluorine-based surfactant include MEGAFACF171, F173, and R-08 (manufactured by Dainippon Ink Chemical Industry Co., Ltd., trade name); Fluorad FC4430, FC4432 (Sumitomo 3M Co., Ltd., trade name), and the like. Examples of non-ionic surfactants other than these include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenol ether.

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

When the alkoxysilane compound is used in a flexible substrate or the like with a polyimide film obtained by using the resin composition of this embodiment, the support in the manufacturing process and the polyimide film are good. From the viewpoint of adhesion, the resin composition may contain 0.01 to 20 parts by mass of the alkoxysilane compound relative to 100 parts by mass of the polyfluorene imide precursor. The content of the alkoxysilane compound is 0.01 parts by mass or more relative to 100 parts by mass of the polyfluorene imide precursor, and good adhesion can be obtained between the support and the polyimide film. From the viewpoint of storage stability of the resin composition, the content of the alkoxysilane compound is preferably 20 parts by mass or less. The content of the alkoxysilane compound is preferably 0.02 to 15 parts by mass, more preferably 0.05 to 10 parts by mass, and still more preferably 0.1 to 8 parts by mass based on 100 parts by mass of the polyfluorene imide precursor. By using an alkoxysilane compound, in addition to the above-mentioned improvement in adhesiveness, it is possible to improve the coating properties of the resin composition (striping unevenness suppression), and to reduce the polyisocyanate caused by the oxygen concentration at the time of curing. Influence of YI value of amine film.

Examples of the alkoxysilane compound include 3-ureidopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, and 3-glycidyloxy Propyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltripropoxysilane, γ-aminopropyltributoxysilane, γ-aminoethyltriethyl Oxysilane, γ-aminoethyltripropoxysilane, γ-aminoethyltributoxysilane, γ-aminobutyltriethoxysilane, γ-aminobutyltrimethoxysilane , Γ-aminobutyltripropoxysilane, γ-aminobutyltributoxysilane, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy (p-tolyl) silane, diphenyl Silyldiol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and alkoxy groups represented by the following structures, respectively Silane compounds, etc. The alkoxysilane compound may be used singly or in combination of two or more kinds.

[Chemical 39]

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

＜ Refining of silicon-containing compounds ＞
The resin composition according to this embodiment can be produced by subjecting a polycondensation component including an acid dianhydride, a diamine, and a silicon-containing compound to a polycondensation reaction. As a method for reducing the total amount of the compound of the general formula (3) contained in the resin composition of this embodiment, for example, before the polycondensation reaction, a silicon-containing compound is purified to reduce the compound of the general formula (3) Total. Alternatively, after the polycondensation reaction, the resin composition may be purified to reduce the total amount of the compound of the general formula (3).

As a method for purifying the silicon-containing compound, for example, stripping may be performed while blowing an inert gas such as nitrogen into the silicon-containing compound in an arbitrary container. The stripping temperature is preferably 200 ° C or higher and 300 ° C or lower, more preferably 220 ° C or higher and 300 ° C or lower, and still more preferably 240 ° C or higher and 300 ° C or lower. The lower the vapor pressure, the better. It is 1,000 Pa or less, more preferably 300 Pa or less, still more preferably 200 Pa or less, and still more preferably 133.32 Pa (1 mmHg) or less. The stripping time is preferably 4 hours or more and 12 hours or less, and more preferably 6 hours or more and 10 hours or less. By adjusting to the above conditions, the compound of the general formula (3) can be efficiently removed, and the total amount of the general formulae (3) and (4) can be controlled within a preferable range.

＜ Synthesis of Polyimide Precursor ＞
The polyfluorene imide precursor of this embodiment can be synthesized by subjecting a polycondensation component including an acid dianhydride, a diamine, and a silicon-containing compound to a polycondensation reaction. The silicon-containing compound is preferably one which has been purified as described above. In a preferred aspect, the polycondensation component includes an acid dianhydride, a diamine, and a silicon-containing compound. The polycondensation reaction is preferably performed in a suitable solvent. Specifically, for example, a method in which a specific amount of a diamine component and a silicon-containing compound are dissolved in a solvent, and a specific amount of an acid dianhydride is added to the obtained diamine solution, and the method is stirred.

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

The molecular weight of the polyimide precursor can be adjusted by the types of acid dianhydride, diamine, and silicon-containing compound, the molar ratio of acid dianhydride to diamine, the addition of blocking agent, and the adjustment of reaction conditions. control. The closer the molar ratio of the acid dianhydride component to the diamine component is to 1: 1, and the smaller the amount of end-capping agent used, the more the polyimide precursor polymer can be quantified.

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 even more preferably 99.5% by mass or more. By reducing the water content in the acid dianhydride component and the diamine component, high purity can also be achieved. When a plurality of acid dianhydride components and / or a plurality of diamine components are used, it is preferable that the acid dianhydride component has the above-mentioned purity as a whole, and the diamine component as a whole has the above-mentioned purity, and more preferably All types of acid dianhydride components and diamine components used have the aforementioned purity.

The solvent used for the reaction is not particularly limited as long as it is a solvent capable of dissolving the acid dianhydride component and the diamine component and the produced polyimide precursor to obtain a polymer having a high molecular weight. Examples of such a solvent include aprotic solvents, phenol-based solvents, ethers, and glycol-based solvents. Examples of the aprotic solvent include N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), and N-methyl-2-pyrrolidone (NMP ), N-methylcaprolactam, 1,3-dimethylimidazolidone, tetramethylurea, and amidamine-based solvents of the following general formula (6):
[Chemical 40]

{In the formula, R ₁₂ = Equamide M100 (trade name: manufactured by Idemitsu Kosan Co., Ltd.) represented by methyl, and R ₁₂ = Equamide B100 (trade name: manufactured by Idemitsu Kosan Co., Ltd.) represented by n-butyl}} -Lactone solvents such as butyrolactone, γ-valerolactone; phosphonium amine solvents such as hexamethylphosphoramidene and hexamethylphosphinetriamine; dimethylphosphonium, dimethylsulfonium, Sulfur-based solvents such as cyclobutane; ketone solvents such as cyclohexanone and methylcyclohexanone; tertiary amine solvents such as methylpyridine and pyridine; acetic acid (2-methoxy-1-methylethyl) Ester-based solvents such as esters.
Examples of the phenol-based solvent include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, and 2,6 -Xylenol, 3,4-xylenol, 3,5-xylenol, etc.
Examples of the ether and glycol-based solvent include 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, and 1,2-bis (2-methoxyethoxy) Ethane, bis [2- (2-methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,4-dioxane, and the like.
These solvents may be used alone or in combination of two or more.

The boiling point of the solvent used in the synthesis of the polyimide precursor under normal pressure is preferably 60 to 300 ° C, more preferably 140 to 280 ° C, and still more preferably 170 to 270 ° C. With the boiling point of the solvent below 300 ° C, the drying step becomes short. If the boiling point of the solvent is 60 ° C. or higher, in the drying step, it is not easy to cause the generation of roughness on the surface of the resin film, the mixing of air bubbles into the resin film, and the like, and a more uniform film can be obtained. In particular, from the viewpoint of reducing solubility and edge abnormality at the time of coating, it is preferable to use a solvent having a boiling point of 170 to 270 ° C and / or a vapor pressure of 250 Pa or less at 20 ° C. More specifically, it is preferably selected from the group consisting of N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), and a compound represented by the general formula (6). More than that.

The water content in the solvent is preferably 3,000 ppm by mass or less in order to perform the polycondensation reaction well. In the resin composition in this embodiment, the content of molecules having a molecular weight of less than 1,000 is preferably not more than 5% by mass. The reason is considered to be that the presence of a molecular weight of less than 1,000 in the resin composition is related to the water content of the solvent or raw materials (acid dianhydride, diamine) used in the synthesis. That is, the reason is considered to be that an acid anhydride group of a part of the acid dianhydride monomer is hydrolyzed with water to become a carboxyl group, and it remains in a low-molecular state without being quantified by a high molecular weight. Therefore, the smaller the water content of the solvent used in the above-mentioned polycondensation reaction, the better. The water content of the solvent is preferably 3,000 mass ppm or less, and more preferably 1,000 mass ppm or less. Similarly, the amount of water contained in the raw material is preferably 3,000 mass ppm or less, and more preferably 1,000 mass ppm or less.

It is considered that the water content of the solvent is the grade of the solvent used (dehydration grade, general grade, etc.), the solvent container (bottle, 18 L can, canister, etc.), the storage state of the solvent (with or without rare gases, etc.), The time from opening to use (use immediately after opening, or use after time, etc.). It is also considered to be related to the replacement of rare gases in the reactor before synthesis, and the presence or absence of rare gas circulation during synthesis. Therefore, in the synthesis of polyimide precursors, it is recommended to take measures such as using high-purity products as raw materials, using solvents with less water content, and not mixing water from the environment into the system before and during the reaction. .

When each polycondensation component is dissolved in a solvent, heating may be performed as necessary. From the viewpoint of obtaining a polyimide precursor having a high degree of polymerization, the reaction temperature at the time of synthesis of the polyimide precursor is preferably 0 ° C to 120 ° C, 40 ° C to 100 ° C, or 60 to The polymerization time at 100 ° C is preferably 1 to 100 hours, or 2 to 10 hours. The polyimide precursor having a uniform polymerization degree can be obtained by setting the polymerization time to 1 hour or more, and the polyimide precursor having a higher polymerization degree can be obtained by setting the polymerization time to 100 hours or less.

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

The polyfluorene imide precursor in this embodiment may be partially fluorinated (partially fluorinated). By partially imidizing the polyfluorene imide precursor, the viscosity stability during storage of the resin composition can be improved. Regarding the fluorene imidization rate in this case, from the viewpoint of obtaining a balance between the solubility of the polyfluorene imide precursor in the resin composition and the storage stability of the solution, it is preferably 5% or more, and more preferably It is 8% or more, and preferably 80% or less, more preferably 70% or less, and even more preferably 50% or less. The partial fluorene imidization can be obtained by heating the polyfluorene imine precursor and dehydrating and closing the ring. The heating may be performed at a temperature of preferably 120 to 200 ° C, more preferably 150 to 180 ° C, preferably 15 minutes to 20 hours, and more preferably 30 minutes to 10 hours.

It is possible to use by adding N, N-dimethylformamide dimethyl acetal or N, N-dimethylformamide diethyl acetal to the polyamine obtained by the above reaction. Then, heating is performed, and a part or all of the carboxylic acid is obtained as a polyimide precursor of this embodiment. By esterification, viscosity stability during storage can be improved. These ester-modified polyamidoacids can also be obtained by the following method: the acid dianhydride component and a monohydric alcohol equivalent to 1 equivalent to the acid anhydride group, and thionyl chloride and dicyclohexylcarbodifluoride After a dehydration condensation agent such as an amine is sequentially reacted, it is subjected to a condensation reaction with a diamine component.

<Preparation of resin composition>
When the solvent used in synthesizing the polyfluorene imide precursor is the same as the solvent contained in the resin composition, the synthesized polyfluorine imide precursor solution may be directly used as the resin composition. If necessary, in a temperature range from room temperature (25 ° C) to 80 ° C, one or more further solvents and additional components are added to the polyimide precursor, and the resin composition is prepared by stirring and mixing. This stirring and mixing can be performed using an appropriate device such as a Trinity Motor (made by Shinto Chemical Co., Ltd.) having a stirring blade, a revolution orbit mixer, and the like. If necessary, the resin composition can be heated to 40 ° C to 100 ° C.

On the other hand, when the solvent used in synthesizing the polyimide precursor is different from the solvent contained in the resin composition, for example, the synthesized compound can be removed by appropriate methods such as reprecipitation and solvent distillation. Solvent in the polyimide precursor solution, so that the polyimide precursor is isolated. Then, in a temperature range from room temperature (25 ° C) to 80 ° C, the required solvent and optional additional components are added to the isolated polyimide precursor, and the mixture is stirred and mixed to prepare a resin. combination.

After preparing the resin composition as described above, by heating the resin composition at 130 to 200 ° C., for example, for 5 minutes to 2 hours, a part of the polyimide precursor can be partially dehydrated and imidized (partially).醯 imidization) to the extent that it does not cause polymer precipitation. By controlling the heating temperature and heating time, the rate of fluorene imidization can be controlled. By partially imidizing the polyfluorene imide precursor, the viscosity stability during storage of the resin composition can be improved.

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

Regarding the solution viscosity of the resin composition at the time of synthesis of the polyimide precursor, if it is higher than 200,000 mPa · s, there is a possibility that the problem of agitation during synthesis may not be easily produced. Among them, even if the solution has a high viscosity at the time of synthesis, a resin composition having a good viscosity can be obtained by adding a solvent and stirring after the reaction is completed. The solution viscosity of the resin composition in this embodiment is a value measured at 23 ° C. using an E-type viscometer (for example, VISCONICEHD, manufactured by Toki Sangyo).

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

"Polyimide film and its manufacturing method"
A polyimide film (hereinafter, also referred to as a polyimide resin film) can be provided using the resin composition of this embodiment. The method for manufacturing a polyimide film according to this embodiment includes the following steps: a coating step of coating the resin composition of this embodiment on a surface of a support; and a film forming step of heating the resin composition A polyimide resin film is formed; and a peeling step that peels the polyimide resin film from the support.

<Coating step>
In the coating step, the resin composition of this embodiment is coated on the surface of the support. The support has heat resistance to the heating temperature of the subsequent film formation step (heating step), and is not particularly limited as long as the peelability in the peeling step is good. Examples of the support include a glass substrate, such as an alkali-free glass substrate; a silicon wafer; PET (polyethylene terephthalate), OPP (extended polypropylene), polyethylene terephthalate, Polyethylene glycol naphthalate, polycarbonate, polyimide, polyimide, imine, polyether, imine, polyether ether ketone, polyether, polyphenylene sulfonium, polyphenylene sulfide Resin substrates such as ether; metal substrates such as stainless steel, aluminum oxide, copper, and nickel.

In the case of forming a thin polyimide molded body, for example, a glass substrate or a silicon wafer is preferred, and in the case of forming a thick film-like polyimide formed body or a sheet, for example, Supports containing PET (polyethylene terephthalate), OPP (extended polypropylene), and the like are preferred.

Examples of the coating method include a blade coater, an air knife coater, a roll coater, a rotary coater, a flow coater, a die coater, and a bar coater. Coating methods such as coating methods, spin coating, spray coating, and dip coating; printing technologies typified by screen printing and gravure printing. The resin composition of this embodiment is preferably applied by slit coating. The coating thickness is appropriately adjusted according to the required thickness of the resin film and the content of the polyimide precursor in the resin composition, and is preferably about 1 to 1,000 μm. The temperature of the coating step may be room temperature, but in order to reduce viscosity and improve workability, the resin composition may be heated to, for example, 40 to 80 ° C.

＜ Any drying step ＞
After the coating step, a drying step may be performed, or the drying step may be omitted and the process may be directly performed to the following film formation step (heating step). The drying step is performed to remove an organic solvent from the resin composition. When the drying step is performed, for example, a suitable device such as a hot plate, a box-type dryer, or a conveyor-type dryer can be used. The temperature in the drying step is preferably 80 to 200 ° C, and more preferably 100 to 150 ° C. The implementation time of the drying step is preferably 1 minute to 10 hours, and more preferably 3 minutes to 1 hour. A coating film containing a polyfluorene imide precursor was formed on the support in the manner described above.

<Film formation step>
Then, a film formation step (heating step) is performed. The heating step is a step of obtaining the polyimide resin film by removing the organic solvent contained in the coating film, and performing a polyimide reaction of a polyimide precursor in the coating film. This heating step can be performed using, for example, an inert gas oven, a hot plate, a box-type dryer, or a conveyor-type dryer. This step may be performed simultaneously with the drying step, or two steps may be performed sequentially.

The heating step can be performed in an air environment, but from the viewpoints of safety and obtaining good transparency of the obtained polyimide film, lower thickness direction retardation (Rth), and lower YI value, It is preferably performed under an inert gas environment. Examples of the inert gas include nitrogen and argon. The heating temperature can be appropriately set according to the type of the polyimide precursor and the type of the solvent in the resin composition, and is preferably 250 ° C to 550 ° C, and more preferably 300 to 450 ° C. If it is 250 ° C or higher, the fluorene imidization proceeds well, and if it is 550 ° C or lower, it is possible to avoid disadvantages such as reduction in transparency of the obtained polyimide film and deterioration in heat resistance. The heating time is preferably about 0.1 to 10 hours.

In this embodiment, the oxygen concentration in the surrounding environment in the heating step is preferably 2,000 mass ppm or less, and more preferably 100 in terms of the transparency and YI value of the obtained polyimide film. Mass ppm or less, more preferably 10 mass ppm or less. By heating in an environment with an oxygen concentration of 2,000 mass ppm or less, the YI value of the obtained polyimide film can be set to 30 or less.

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

(1) A structure including a polyimide resin film / support is produced by the method described above, and then a laser is irradiated from the support side of the structure to ablate the interface between the support and the polyimide resin film. In this way, the method of peeling the polyfluorene imide resin is performed. Examples of the type of laser include a solid (YAG) laser, and a gas (UV (Ultra Violet) excimer) laser. It is preferable to use a spectrum such as a wavelength of 308 nm (refer to Japanese Patent Publication No. 2007-512568, Japanese Patent Publication No. 2012-511173, etc.).
(2) Before coating the resin composition on the support, a release layer is formed on the support, and thereafter a structure including a polyimide resin film / release layer / support is obtained, and the polyimide film is peeled off. method. Examples of the release layer include Parylene (registered trademark, manufactured by Parylene Japan LLC) and tungsten oxide; release agents such as vegetable oil-based, polysiloxane-based, fluorine-based, and alkyd-based can be used (see Japanese Patent Laid-Open No. 2010-067957). (Japanese Patent Publication No. 2013-179306).
The laser irradiation of this method (2) and method (1) can be used together.

(3) A method of obtaining a polyimide resin film by using an etchable metal substrate as a support to obtain a structure including a polyimide resin film / support, and then etching the metal with an etchant. As the metal, for example, copper (as a specific example, electrolytic copper foil "DFF" manufactured by Mitsui Metals Mining Co., Ltd.), aluminum, and the like can be used. As the etchant, ferric chloride or the like can be used for copper, and dilute hydrochloric acid or the like can be used for aluminum.
(4) By the method described above, a structure including a polyimide film / support is obtained, and then an adhesive film is attached to the surface of the polyimide film, and the adhesive film / polyimide film is separated from the support. Method for separating polyfluorene imide film from self-adhesive film

Among these peeling methods, the method (1) or (2) is preferable from the viewpoints of the refractive index difference, the YI value, and the elongation of the front and back surfaces of the obtained polyimide resin film. From the viewpoint of the difference in refractive index between the front and back sides of the obtained polyimide resin film, the method (1) is more preferable, that is, the irradiation step of radiating laser light from the support side is performed before the peeling step. Furthermore, in the method (3), when copper is used as a support, the YI value of the obtained polyimide resin film tends to increase and the elongation tends to decrease. This is considered to be the effect of copper ions.

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

<Yellowness (YI value)>
The YI value of the polyimide film obtained by using the resin composition of this embodiment at a film thickness of 10 μm is preferably 20 or less, more preferably 18 or less, from the viewpoint of obtaining good optical characteristics. It is preferably 16 or less, particularly preferably 14 or less, particularly preferably 13 or less, particularly preferably 10 or less, and even more preferably 7 or less. The YI value varies depending on the monomer skeleton of the polyimide precursor. If the monomer skeleton is the same, the larger the weight average molecular weight of the polyimide precursor, the smaller the YI value.

For example, the YI value affects the amine value of the silicon-containing compound used. If the amine value is higher, the YI value tends to be larger, and if the amine value is smaller, the YI value also tends to decrease. However, using a purified silicon-containing compound, that is, a compound represented by the general formula (3) in which the total amount of the polyimide precursor is within the above-mentioned range and the polymer using an unrefined silicon-containing compound having the same amine value Compared with the fluorene imide precursor, the YI value of the obtained fluorene imide resin film tends to be lower. Although the mechanism is not clear, the inventors and others presume the following. That is, in the previous purification method, the non-cyclic low-molecular-weight diamine residue used in the production of polyimide precursors is decomposed when the polyimide hardens to generate free radicals, which may cause free radicals. The YI value is increased (deteriorated). It is considered that, by reducing the amount of the cyclic siloxane represented by the general formula (3), not only the cyclic siloxane represented by the general formula (3) is removed during purification, but also the amine value which is increased by two is removed. Among the amines, relatively low molecular weight diamines are relatively volatile. Therefore, it is presumed that the polyimide precursor in which the total amount of the compound represented by the general formula (3) according to this embodiment is reduced further improves the YI value of the polyimide resin film. In the previous purification method, it is difficult to reduce the diamine which is not a cyclic low-molecular-weight diamine. Therefore, even if purification is performed, the improvement degree of the YI value of the polyfluoreneimide resin film is less than that in this embodiment.

In this embodiment, the difference between the YI values of the polyfluorene imide precursor using a refined silicon-containing compound and the polyfluorine imide precursor using an unrefined silicon-containing compound is determined by the following formula.
(Difference in YI value) = (YI value of a polyimide resin film obtained by curing a polyimide resin precursor obtained by using an unrefined silicon compound)-(obtained by using a refined silicon compound (YI value of polyimide resin film hardened by polyimide precursor)
The larger the difference in YI value, the better the YI is, which is better. In this embodiment, the difference in YI value is preferably 1.5 or more, more preferably 2 or more, and even more preferably 2.5 or more. For the method of measuring the YI value, please refer to the column of the examples.

"Application of Polyimide Film"
The polyimide film obtained by using the resin composition of this embodiment can be used, for example, as a semiconductor insulating film, a thin-film transistor liquid crystal display (TFT-LCD) insulating film, and an electrode protection film, and can also be used as a liquid crystal display or an organic electronic device. Transparent substrates for display devices such as electroluminescence displays, field emission displays, and electronic paper. In particular, the polyimide film obtained by using the resin composition of this embodiment can be suitably used as a thin film transistor (TFT) substrate, a color filter substrate, a touch panel substrate, and the like in the manufacture of flexible devices. A substrate of a transparent conductive film (ITO (Indium Tin Oxide, Indium Tin Oxide)). Examples of the flexible device to which the polyimide film of this embodiment can be applied include a TFT device for a flexible display, a flexible solar cell, a flexible touch panel, flexible lighting, and a flexible device. Batteries, flexible printed circuit boards, flexible color filters, surface housing lenses for smartphones, etc.

The step of forming a TFT on a flexible substrate using a polyimide film is typically performed at a wide range of temperatures from 150 to 650 ° C. Specifically, in the case of manufacturing a TFT device using amorphous silicon, a process temperature of 250 ° C to 350 ° C is usually required. Since the polyimide film of this embodiment must be able to withstand this temperature, specifically, it must be Appropriately select a polymer structure with a glass transition temperature above the process temperature and a thermal decomposition onset temperature.

When manufacturing a TFT device using a metal oxide semiconductor (IGZO, etc.), a process temperature of 320 ° C to 400 ° C is usually required. Since the polyimide film of this embodiment must be able to withstand this temperature, it must be appropriately selected. Polymer structure with glass transition temperature and thermal decomposition onset temperature above the maximum temperature of TFT manufacturing process.

When manufacturing a TFT device using low temperature polycrystalline silicon (LTPS), a process temperature of 380 ° C to 520 ° C is usually required. Since the polyimide film of this embodiment must be able to withstand this temperature, it must be appropriately selected to have TFT fabrication Polymer structure with glass transition temperature and thermal decomposition onset temperature above the highest temperature of the process.
On the other hand, due to these thermal history, the optical characteristics (especially light transmittance, retardation characteristics, and YI value) of polyimide films tend to decrease as they are exposed to high-temperature processes. However, the polyfluorene imide obtained using the polyfluorene imide precursor of this embodiment has good optical characteristics even after thermal history.

Hereinafter, as a use example of the polyimide film of this embodiment, a method for manufacturing a display and a laminated body will be described.

＜ Manufacturing method of display ＞
The method for manufacturing a display of this embodiment includes the following steps: a coating step of coating the resin composition of this embodiment on a surface of a support; and a film forming step of heating the resin composition to form a polyfluorene An imine resin film; an element forming step that forms an element on the polyfluorene imine resin film; and a peeling step that peels the polyfluorene imine resin film on which the element is formed from the support.

Manufacturing Example of Flexible Organic EL Display FIG. 1 is a schematic diagram showing the structure of a top portion of a flexible polyimide substrate of a top-emission type flexible organic EL display as an example of the display of this embodiment. The organic EL structure section 25 in FIG. 1 will be described. For example, the organic EL element 250a that emits red light, the organic EL element 250b that emits green light, and the organic EL element 250c that emits blue light are arranged as a unit, and are arranged in a matrix shape. The light emitting range of each organic EL element is determined. Each organic EL element includes a lower electrode (anode) 252, a hole transporting layer 253, a light emitting layer 254, and an upper electrode (cathode) 255. On the lower layer 2a of a CVD (Chemical Vapor Deposition) cladding film (multiple barrier layer) containing silicon nitride (SiN) or silicon oxide (SiO), a plurality of layers are provided to drive the organic The TFT 256 (selected from low temperature polycrystalline silicon (LTPS) or metal oxide semiconductor (IGZO)) of the EL element, an interlayer insulating film 258 having a contact hole 257, and a lower electrode 259. The organic EL element is sealed with a sealing substrate 2b, and a hollow portion 261 is formed between each organic EL element and the sealing substrate 2b.

The manufacturing steps of the flexible organic EL display include the following steps: a step of fabricating a polyimide film on a glass substrate support, and manufacturing the organic EL substrate shown in FIG. 1 above; a step of manufacturing a sealing substrate; An assembly step of combining two substrates; and an peeling step of an organic EL display produced by peeling a glass substrate support from a polyimide film. The organic EL substrate manufacturing step, the sealing substrate manufacturing step, and the assembly step can be performed using well-known manufacturing steps. An example is given below, but it is not limited to this. The peeling step may be the same as the peeling step of the polyfluoreneimide film.

For example, referring to FIG. 1, firstly, a polyimide film is prepared on a support by the above method, and a silicon nitride (SiN) and silicon oxide (SiO) are produced on the upper part by a CVD method or a sputtering method. ) With multiple barrier layers (lower substrate 2a in FIG. 1), and a photoresist or the like is used on the upper part to make a metal wiring layer for driving the TFT. An active buffer layer such as SiO is formed on the upper part by CVD method, and a TFT device such as metal oxide semiconductor (IGZO) or low temperature polycrystalline silicon (LTPS) is formed on the upper part (TFT256 in FIG. 1). After the TFT substrate for a flexible display is produced, an interlayer insulating film 258 having a contact hole 257 is formed using a photosensitive acrylic resin or the like. A ITO film is formed by a sputtering method or the like, and a lower electrode 259 is formed as a pair with the TFT.

Next, after forming a partition wall (touching row) 251 with a photosensitive polyimide or the like, a hole transporting layer 253 and a light emitting layer 254 are formed in each space divided by the partition wall. An upper electrode (cathode) 255 is formed so as to cover the light-emitting layer 254 and the partition wall (contact bank) 251. Thereafter, a fine metal mask or the like is used as a mask, and an organic EL material emitting red light (corresponding to the organic EL element 250a emitting red light in FIG. 1) and an organic light emitting green light are vapor-deposited by a known method. An EL material (corresponding to the organic EL element 250b emitting green light in FIG. 1) and an organic EL material emitting blue (corresponding to the organic EL element 250c emitting blue light in FIG. 1), thereby producing an organic EL A substrate, thereby producing an organic EL substrate. The organic EL substrate is sealed with a sealing film or the like (seal substrate 2b in FIG. 1), and the device on the upper part of the polyimide substrate is peeled from the glass substrate support by a known peeling method such as laser peeling, thereby making the top Light-emitting flexible organic EL display. When the polyimide of this embodiment is used, a see-through type flexible organic EL display can be manufactured. A bottom-emission type flexible organic EL display can be manufactured by a known method.

In the manufacturing example of a flexible liquid crystal display, a flexible liquid crystal display can be produced using the polyimide film of this embodiment. As a specific manufacturing method, a polyimide film is prepared on the glass substrate support by the above method, and a TFT substrate including, for example, amorphous silicon, metal oxide semiconductor (IGZO, etc.), and low-temperature polycrystalline silicon is manufactured using the above method. . In addition, according to the coating step and film forming step of this embodiment, a polyimide film is produced on a glass substrate support, and a color filter with a polyimide film is produced in accordance with a known method using a polyimide film. Light sheet glass substrate (CF substrate). On one of the TFT substrate and the CF substrate, a sealing material containing a thermosetting epoxy resin or the like is coated into a frame-like pattern lacking a liquid crystal injection port by screen printing, and has a liquid crystal layer A thick spacer having a diameter and containing plastic or silicon dioxide is scattered on another substrate.

Then, the TFT substrate and the CF substrate are bonded together, and the sealing material is hardened. Then, a liquid crystal material is injected into the space surrounded by the TFT substrate, the CF substrate, and the sealing material by a reduced pressure method, a thermosetting resin is applied to the liquid crystal injection port, and the liquid crystal material is sealed by heating to form a liquid crystal layer. . Finally, the laser peeling method is equivalent to peeling the glass substrate on the CF side and the glass substrate on the TFT side at the interface between the polyimide film and the glass substrate, thereby making a flexible liquid crystal display.

＜ Manufacturing method of laminated body ＞
The manufacturing method of the laminated body of this embodiment includes the following steps: a coating step of coating the resin composition of this embodiment on the surface of a support; and a film forming step of heating the resin composition to form a polymer. An imine resin film; and an element forming step for forming an element on the polyfluorene imine resin film.

As a component in a laminated body, the thing exemplified in the manufacture of the said flexible device is mentioned. As a support body, a glass substrate can be used, for example. The preferable specific order of the coating step and the film forming step is the same as that described in the above-mentioned method for producing a polyimide film. In the element forming step, the above elements are formed on a polyimide film as a flexible substrate formed on a support. After that, the polyimide resin film and the device may be detached from the support in an optional step.
[Example]

Hereinafter, the embodiments of the present invention will be specifically described using examples and comparative examples, but the present invention is not limited to these examples and comparative examples.

《Measurement and Evaluation Method》
＜ Solid matter composition ＞
The total mass of the monomers used in the polyimide precursor can be used as the mass of the solid component contained in the resin composition. Alternatively, the mass of the solid component can be obtained by analyzing the resin composition by gas chromatography (hereinafter also referred to as GC) to determine the mass of the solvent, and subtracting from the mass of the resin composition. Desolvent quality.
The GC conditions include the following conditions.
Device: Gas chromatograph (manufactured by Agilent, gas chromatograph 6890N)
Note inlet temperature: 280 ℃
Injection volume: 1 μL
Oven temperature: After being held at 50 ° C. for 1 minute, the temperature was increased to 350 ° C. at a heating rate of 20 ° C./min, and maintained at 350 ° C. for 5 minutes.
Carrier gas: Helium, 1.0 ml / min
Column: made by SGE, BPX5 (0.25 mm × 30 m, film thickness 0.25 μm)
Split ratio: 50: 1
Detector: Hydrogen flame ionization detector Detector temperature: 355 ° 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) under the following conditions.
As a solvent, NMP (manufactured by Wako Pure Chemical Industries, Ltd., for high-speed liquid chromatography, 24.8 mmol / L 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-speed liquid chromatography) and dissolved). A calibration curve for calculating the weight average molecular weight was prepared using standard polystyrene (manufactured by Tosoh Corporation).
Column: Shodex KD-806M (manufactured by Showa Denko)
Flow rate: 1.0 mL / min
Column temperature: 40 ℃
Pump: PU-2080Plus (manufactured by JASCO)
Detectors: RI-2031Plus (RI: differential refractometer, manufactured by JASCO) and UV-2075Plus (UV-VIS: ultraviolet-visible absorbance meter, manufactured by JASCO)

＜ Analysis of low-molecular-weight cyclic siloxane concentration ＞
Low-molecular-weight cyclic siloxane concentration of general formula (3) and general formula (4) contained in a resin composition containing a polyimide precursor and a silicon-containing compound (general formulas (3) and (4)) The analysis was performed by GC (gas chromatography) analysis as shown below (refer to the analysis of the low-molecular-weight cyclic siloxane concentration described below (based on silicon-containing compounds)).

＜ Analysis of low-molecular-weight cyclic siloxane concentration (composition standard, solid content component standard) ＞
(1) Briefly make a calibration curve to quantify the amount of cyclic siloxane. The calibration curve was prepared by using a sample (manufactured by Tokyo Chemical Industry Co., Ltd.) of a cyclic siloxane (hereinafter, also referred to as D4 body) with n = 4 in the general formula (4), and was prepared according to the following method.
The amount of the low-molecular-weight cyclic siloxane in the resin composition was determined by heating the resin composition at 150 ° C and 200 ° C for 30 minutes in a pyrolyzer, and by GC / MS (Gas Chromatography Mass Spectrometry (gas chromatography mass spectrometry) analysis and measurement of the volatile components generated. Using a previously prepared calibration curve, the peak area of each compound obtained was converted into D4 body concentration.
GC / MS measurement was performed using the following apparatus.
Pyrolyzer: Py-3030iD (Frontier Laboratories)
GC system: 7890B (Agilent Technologies)
MSD: 5977A (Agilent Technologies)
Column: UA-1 (inner diameter 0.25 mm, length 15 m, liquid phase thickness 0.25 μm) (Frontier Laboratories)
The GC / MS measurement was performed under the following measurement conditions.
Column temperature: Hold at 40 ° C for 5 minutes, heat up at 20 ° C / min, hold at 320 ° C for 11 minutes, total 30 minutes. Injection port temperature: 320 ° C
Injection method: split method (split ratio 1/20)
Interface temperature: 320 ℃
Ion source temperature: 230 ° C
Ionization method: Electron ionization method (EI)
Measurement method: Scan (SCAN) method (m / z 10-800)

(2) Production amount of calibration curve A sample (hereinafter referred to as D4 body) of a compound of general formula (4) where n = 4 (hereinafter referred to as D4 body) was placed in a 10 mL volumetric flask, and chloroform was used as a solvent. A sample of D4 body with a concentration of 0.1 mg / mL and a sample of 0.01 mg / mL were prepared.
A sampler for a liquid sample was installed on a pyrolyzer set to 400 ° C. A micro syringe was used to measure 1 μL of the sample with the adjusted concentration and inject it into the pyrolyzer. During the heating of the pyrolyzer to 400 ° C, the column was immersed in liquid nitrogen to capture volatile components into the column. After 1 minute from the end of heating, the column was taken out of the liquid nitrogen and subjected to GC / MS measurement. The slope of the calibration curve of the D4 body was obtained from the concentration of the D4 body and the obtained peak area.
The retention time of the cyclic siloxane in the GC / MS measurement using the apparatus and measurement conditions used is shown in Table 1 below. The same applies to the following GC / MS measurement.

[Table 1]

Dn (n = 3 to 8) in the above Table 1 is a cyclic siloxane corresponding to n = 3 to 8 in the general formula (4). Dimethyl m biphenyls 1, Dm in Table 1 above (m = 3 to 5) is a cyclic siloxane corresponding to m = 3 to 5 in the general formula (3).

(3) Analysis of low-molecular-weight cyclic siloxane concentration of the general formulae (3) and (4) in the resin composition The concentration of the phenyl side chain of the general formula (3) contained in the resin composition is determined by The resin composition was heated to 200 ° C. and the GC / MS measurement of the generated volatile component was performed to measure. The concentration of the methyl side chain in the general formula (4) was measured by heating the resin composition to 150 ° C. and measuring the generated volatile components by GC / MS. The concentration of each compound was calculated from the peak area of the volatile component measurement result of the resin composition. If the peak of each compound does not overlap with other compounds, the peak area obtained from the total ion chromatogram (TIC) is used. When overlapping with other compounds, the peak area obtained from the mass spectrum chromatogram (MS) of m / z = 281 was used.

A. Analysis of the low-molecular-weight cyclic siloxane concentration of the general formula (3) (phenyl side chain body) in the resin composition To a heating furnace (helium atmosphere) of a pyrolyzer set at 200 ° C, add A sample cup of about 1 mg of the resin composition was added and heated at 200 ° C for 30 minutes. The measurement was performed by analyzing the generated volatile components by GC / MS. Using a previously prepared calibration curve, the peak area of each compound obtained was converted into D4 body concentration. The amount of the low-molecular-weight cyclic siloxane of the general formula (3) is calculated based on the following formula.
Dm (μg / g) = (Dm (GC-area)} / {Slope of calibration curve of D4 body} / {mass of resin composition weighed (mg)} × 1000
M in the formula corresponds to the carbon number m of the general formula (3), and m is an integer of 3 or more.

B. Analysis of the low-molecular-weight cyclic siloxane concentration of the general formula (4) (methyl side chain body) in the resin composition To a heating furnace (helium atmosphere) of a pyrolyzer set to 150 ° C, add A sample cup containing about 1 mg of the resin composition was added and heated at 150 ° C for 30 minutes. The measurement was performed by analyzing the generated volatile components by GC / MS. Using a previously prepared calibration curve, the peak area of each compound obtained was converted into D4 body concentration.
Dn (μg / g) = {Dn (GC-area)} / {Slope of D4 volume calibration curve} / {mass of resin composition weighed (mg)} × 1000
N in the formula corresponds to the carbon number n of the general formula (4), and n is an integer of 3 or more.

(5) Analysis of low-molecular-weight cyclic siloxane concentration of the general formulae (3) and (4) in the solid matter component contained in the resin composition The general formulae (3) and (4) contained in the solid matter component The analysis of the low-molecular-weight cyclic siloxane concentration in) is calculated based on the low-molecular-weight cyclic siloxane concentration of the general formulae (3) and (4) in the resin composition. That is, the total mass of the monomers used in the polyimide precursors of the respective examples and comparative examples is defined as the mass of the solid component contained in the resin composition, and according to the general formula (3 The cyclic siloxane concentration in) and (4) and the total mass thereof were used to calculate the cyclic siloxane concentration in formula (3) and (4) in the solid component. The mass of the solid component contained in the resin composition can also be determined by the following: As described above, the mass of the solvent is obtained by GC analysis of the resin composition, and is subtracted from the mass of the resin composition. The mass of the solvent; or heating the resin composition to evaporate the solvent to obtain the mass of the solvent, and subtracting the mass of the solvent from the mass of the resin composition.

<Analysis of the concentration of low-molecular-weight cyclic siloxanes contained in the raw material composition (based on silicon-containing compounds)>
(summary)
The analysis of the low-molecular-weight cyclic siloxane concentration was performed by using GC to analyze silicon-containing compounds (containing general formulae (3), (4), and (5)) dissolved in acetone (including n-tetradecane as an internal standard substance). Solution containing silicon compounds). Based on the peak area of each compound obtained, and using the peak area of n-tetradecane as a reference, the concentration of each compound was determined.
The GC measurement was performed using the following apparatus.
GC system: 7890A (Agilent Technologies)
Column: J & W Scientific Durabond DB-5MS (MEGABORE inner diameter 0.53 mm, length 30 m, liquid phase thickness 1.0 μm)
All GC measurements were performed under the following measurement conditions.
Column temperature: 50 ° C, heating at 10 ° C / min, holding at 280 ° C for 17 minutes, total 40 minutes Injection port temperature: 270 ° C
Carrier gas: Helium injection method: Split method (split ratio 1/10)
Detector: FID (Flame Ionization Detector) (300 ℃)

(Calculation of Low-molecular-weight Cyclosiloxane)
The amount of the low-molecular-weight cyclic siloxane of the general formula (3) is calculated based on the following formula.
Dm (μm / g) = {Total amount of compounds of general formula (3) (μg)) / {Total mass of compounds of general formula (3-1), (3-2), (4), and (5) ( g)} = {Dm (GC-area)} / {n-tetradecane (GC-area) × GC-area coefficient} × 20 × 100
M in the formula corresponds to the carbon number m of the general formula (3), and m is an integer of 3 or more.
The GC-area coefficient in the formula is calculated based on the following formula.
GC-area coefficient = molecular weight / carbon number

The amount of the low-molecular-weight cyclic siloxane of the general formula (4) is calculated based on the following formula.
Dn (μg / g) = {Total amount of compounds of general formula (4) (μg)) / {Total mass of compounds of general formula (3-1), (3-2), (4) and (5) (g)} = {Dn (GC-area)} / {n-tetradecane (GC-area) × GC-area coefficient} × 20 × 100
N in the formula corresponds to the carbon number n of the general formula (4), and n is an integer of 3 or more.
The GC-area coefficient in the formula is calculated based on the following formula.
GC-area coefficient = 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 following GC measurement.

[Table 2]

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

(Analysis of Low-Molecular Cyclosiloxane)
The analysis of the low-molecular-weight cyclic siloxane concentration of the general formulae (3) and (4) contained in the silicon-containing compound was performed in the following order. 0.1 g of the silicon-containing compound was dissolved in 10 mL of acetone (containing 20 μg / mL of n-tetradecane as an internal standard substance), and left for 16 hours. 1 μL of the left solution was measured with a micro syringe, and introduced into a GC (Gas Chromatography, gas chromatograph) for measurement. In the obtained chromatogram, use the software attached to GC to calculate the peak area of each low-molecular cyclic siloxane and n-tetradecane, and use the calculation formula shown above to find the low-molecular cyclic siloxane concentration .

＜ Evaluation of foreign matter count of polyimide resin film ＞
In this evaluation, after a large number of polyimide precursors were dried and hardened using an oven, when the polyimide resin film was produced in the same oven, the surface attached to the polyimide resin film was evaluated. How many foreign objects.
The resin compositions of the examples and comparative examples were applied to a 200 mm square alkali-free glass substrate (hereinafter, also referred to as a glass substrate) so that the film thickness after curing became 10 μm to form a coating film. For the coating system, a slit coater (TN25000, manufactured by Tokyo Chemical Industry Co., Ltd.) was used. At this time, for each resin composition, a resin composition formed on 50 glass substrates was prepared. One piece of a glass substrate having a coating film of a resin composition was dried in an oven (KLO-30NH, manufactured by Koyo Thermo Systems) under a nitrogen atmosphere (oxygen concentration of 300 ppm or less) at 100 ° C for 30 minutes, and Remove the solvent. Then, a polyimide resin film was formed on a glass substrate by heating at 350 ° C. for 1 hour under a nitrogen environment (oxygen concentration of 300 ppm or less). Using a microscope (VHX-6000, manufactured by Keyence), the size and number of foreign objects were counted on a 50 mm square center of the obtained 200 mm square polyimide resin film.
The observation conditions are as follows.
Lens: 100x Threshold: Automatically, the number of foreign objects with a long diameter of 50 μm or more and less than 1000 μm was evaluated by the following criteria.
The number of foreign objects is 10 or more and less than 50: A (good)
The number of foreign objects is 50 or more and less than 100: B (possible)
The number of foreign objects is more than 100: C (bad)
Using a scanning electron microscope (JSM-IT500HR, manufactured by Japan Electronics Co., Ltd.), EDS analysis (Energy Dispersive X-Ray Spectroscopy) (elemental analysis) of the observed foreign matter was performed. As a result, C, Si, O elements, etc., N elements were not observed. Based on the results, it is presumed that the low-molecular-weight cyclic siloxane that volatilized during vacuum drying adhered to the inner wall of the dryer, and was dropped, adhered, or the like.
In addition, when evaluating different types of resin compositions, the evaluation was performed after the oven was baked at 600 ° C for 5 hours or more.

＜ Evaluation of difference of YI value ＞
In this evaluation, a polyimide resin film obtained by curing a polyimide precursor obtained using a refined silicon compound and a polyimide precursor obtained using an unrefined silicon compound are evaluated. The difference in YI value.
The resin compositions of the examples and comparative examples were applied to a 200 mm square alkali-free glass substrate (hereinafter, also referred to as a glass substrate) so that the film thickness after curing became 10 μm to form a coating film. The coating was performed using a slit coater (TN25000, Tokyo Chemical Industry Co., Ltd.). One of the obtained glass substrates having a coating film of a resin composition was dried in an oven (KLO-30 NH, Koyo Thermo Systems) under a nitrogen atmosphere (oxygen concentration of 300 ppm or less) at 100 ° C for 30 minutes. The solvent was removed in minutes. After that, the polyimide resin film was formed on the glass substrate by heating at 400 ° C. for 1 hour under a nitrogen environment (oxygen concentration: 300 ppm or less).
Using the obtained polyimide resin film, a YI value was measured using Nippon Denshoku Industries Co., Ltd. (spectrophotometer: SE600). The light source is a D65 light source. The difference between the YI values is obtained by the following formula.
(Difference in YI value) = (YI value of a polyimide resin film obtained by curing a polyimide resin precursor obtained by using an unrefined silicon compound)-(obtained by using a refined silicon compound (YI value of polyimide resin film hardened by polyimide precursor)
Furthermore, when the difference between the YI values is determined, the hardening of the polyimide precursor obtained using the unrefined silicon compound and the hardening of the polyimide precursor obtained using the refined silicon compound are performed by The same batch of ovens are used for heat treatment to eliminate device errors.

"Refining method of silicon-containing compounds"
The silicon-containing compounds described in the following examples and comparative examples are treated by the following purification methods to reduce the low-molecular-weight cyclic siloxane contained therein. The concentration of the purified low-molecular-weight cyclic siloxane was analyzed by the above method.
＜ Refined A ＞
10 kg of a silicon-containing compound was added to the flask, and stripping was performed at a temperature of 160 ° C. and a pressure of 270 Pa for 8 hours while blowing nitrogen gas.
＜ Refined B-1 ＞
1 kg of a silicon-containing compound was added to the flask, and stripping was performed at a temperature of 200 ° C. and a pressure of 200 Pa for 8 hours while blowing nitrogen gas.
＜ Refined B-2 ＞
10 kg of a silicon-containing compound was added to the flask, and stripping was performed at a temperature of 200 ° C. and a pressure of 200 Pa for 8 hours while blowing nitrogen gas.
＜ Refined C ＞ According to the synthesis example of the two-terminal amine-modified polysiloxane oil (refined product) described in Japanese Patent Laid-Open No. 2016-029126, 1000 g of acetone was added to 100 g of a silicon-containing compound, and the temperature was maintained at room temperature Stir for 30 minutes. Centrifuge at 2500 rpm for 15 minutes with a centrifugal separator. After separating acetone from polysiloxane, acetone was removed by decantation. After repeating this operation three times, acetone was distilled off by an evaporator to obtain a refined silicon-containing compound.
<Refinement D> Purification example 1 described in Japanese Patent Laid-Open No. 2006-028533
500 g of a silicon-containing compound was added to the flask, and stripping was performed at a temperature of 250 ° C. and a pressure of 1,330 Pa for 8 hours while blowing nitrogen gas.
<Refinement E> Purification Example 2 described in Japanese Patent Laid-Open No. 2006-028533
100 g of a silicon-containing compound was added to 300 g of 2-butanone to dissolve it uniformly. While the solution was being stirred, it was slowly poured into methanol and reprecipitated. After the above-mentioned reprecipitation was repeated three times in total, it was dried to obtain a purified silicon-containing compound.

<< Example 1 >>
As described in Table 2, the silicon-containing compound (1) (in the general formula (1), L ₁ and L ₂ are amine groups, and R ₁ is -CH ₂ CH ₂ CH _2- R ₂ , R ₃ , R ₆ , and R ₇ are methyl groups, R ₄ and R ₅ are phenyl groups, and j / (i + j + k) = 0.15, and a compound having a number average molecular weight of 4,400) is purified. Into a 3 L separable flask with a stir bar, while introducing nitrogen, and stirring while adding NMP (332 g) as a solvent, 4,4'-DAS (14.2 g) as a diamine, and TFMB (37.8 g ), And the refined silicon-containing compound (1) (10.56 g), and then PMDA (21.8 g) as an acid dianhydride was added. The molar ratio of acid dianhydride and diamine is 100: 97. The mixture was stirred at room temperature for 48 hours to obtain a transparent NMP solution of polyamic acid (hereinafter, also referred to as a varnish). The obtained varnish was stored in a freezer (set at -20 ° C, the same applies hereinafter), and thawed before evaluation, and then used.

"Examples 2 to 32 and Comparative Examples 17 to 19"
In Example 1, it carried out similarly to Example 1 except having changed the kind and quantity of a solvent, an acid dianhydride, a diamine, and a silicon-containing compound to those described in Tables 2 and 3.
The types of silicon-containing compounds in Table 3 are as follows.
Silicon-containing compound (2): In the general formula (1), L ₁ and L ₂ are amine groups, R ₁ is -CH ₂ CH ₂ CH _2- , and R ₂ , R ₃ , R ₆ , and R ₇ are methyl groups. , R ₄ and R ₅ are phenyl, j / (i + j + k) = 0.15, silicon-containing compound (3) having a number average molecular weight of 1340: In the general formula (1), L ₁ and L ₂ are anhydride groups, and R ₁ is -CH ₂ CH ₂ CH _2- , R ₂ , R ₃ , R ₆ , and R ₇ are methyl groups, R ₄ and R ₅ are phenyl groups, j / (i + j + k) = 0.15, and the compound having a number average molecular weight of 4200 contains Silicon compound (4): In the general formula (1), L ₁ and L ₂ are epoxy groups, R ₁ is -CH ₂ CH ₂ CH _2- , and R ₂ , R ₃ , R ₆ , and R ₇ are methyl groups. Compounds in which R ₄ and R ₅ are phenyl groups, j / (i + j + k) = 0.15, and a number average molecular weight of 1240

Comparative Example 1
As described in Table 3, a 3 L separable flask with a stir bar was introduced with nitrogen while stirring, and NMP (319 g) as a solvent and 4,4'-DAS (diamine) were added while stirring. 14.3 g), TFMB (12.3 g), unrefined silicon-containing compound (in the general formula (1), L ₁ and L ₂ are amine groups, R ₁ is -CH ₂ CH ₂ CH _2- , R ₂ , R _3, R _6, R ₇ is methyl, R _4, R ₅ is phenyl, j is 15, 10, compound number average molecular weight 4400 i + j + k as) (5.72 g), followed by added as PMDA dianhydride of (15.3 g). The molar ratio of acid dianhydride to diamine is 100: 97. Next, the mixture was stirred at room temperature for 48 hours to obtain a transparent NMP solution of polyamic acid (hereinafter, also referred to as a varnish). The obtained varnish was stored in a freezer (set at -20 ° C, the same applies hereinafter), and thawed before evaluation, and then used.

"Comparative Example 2 to Comparative Example 16"
In Comparative Example 1, it carried out similarly to Comparative Example 1, except having changed the kind and quantity of a solvent, an acid dianhydride, a diamine, and a silicon-containing compound into the thing described in Table 3.

For the resin compositions of the examples and comparative examples, the low-molecular-weight cyclic siloxane concentration based on the resin composition standard, the solid component standard, and the silicon-containing compound standard was evaluated; the molecular weight of the polyimide precursor; the foreign matter count evaluation; And YI value. The results are shown in Tables 5 and 6. In Tables 5 and 6, the "compound of formula (3)" corresponds to the compound of general formula (3), and m is 3 to 5, and the "compound of formula (4)" corresponds to the compound of general formula (4) , N is 3 to 8.

[table 3]

[Table 4]

[table 5]

[TABLE 6]

2a‧‧‧ lower substrate

2b‧‧‧Sealed substrate

25‧‧‧Organic EL Structure Department

250a‧‧‧ Organic EL element emitting red light

250b‧‧‧ Organic EL element emitting green light

250c‧‧‧Organic EL element emitting blue light

251‧‧‧ partition wall (touch the row)

252‧‧‧Lower electrode (anode)

253‧‧‧Electric hole transport layer

254‧‧‧Light-emitting layer

255‧‧‧upper electrode (cathode)

256‧‧‧TFT

257‧‧‧contact hole

258‧‧‧Interlayer insulation film

259‧‧‧Lower electrode

261‧‧‧Hollow Department

FIG. 1 is a schematic diagram showing a structure of a top part of a polyimide substrate of a top-emission type flexible organic EL (Electroluminescence) display as an example of the display of this embodiment.

Claims (34)

A resin composition comprising the following components: a polyimide precursor comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2); 3-1) or (3-2) at least any one compound in which m is an integer of 3 or more; and any compound represented by the following general formula (4); and based on the mass of the above resin composition, the following In the general formula (3-1) or (3-2), the total amount of compounds in which m is an integer of 3 or more is more than 0 ppm and 1,100 ppm or less, or, based on the mass of the resin composition, the following The total amount of the compound in which m is an integer of 3 or more in the general formula (3-1) or (3-2) and the compound in which n is an integer of 3 or more in the following general formula (4) is more than 0 ppm and 1,300 ppm Following, [化 1] {In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer} [化 2] {In the formula, P ₃ and P ₄ are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms, or a monovalent aromatic group having 6 to 10 carbon atoms, and q is an integer of 1 to 200} [化 3] {Where m is an integer greater than or equal to 1} [化 4] {Where n is an integer of 2 or more}. If the resin composition of claim 1 is based on the mass of the above-mentioned resin composition, the total amount of compounds in which m in the general formula (3-1) or (3-2) is an integer of 3 or more is more than 0 ppm It is 300 ppm or less. A resin composition comprising the following components: a polyimide precursor comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2); 3-1) or (3-2) at least one compound in which m is 3 or 4; and any compound represented by the following general formula (4); and based on the mass of the resin composition, the following In the general formula (3-1) or (3-2), the total amount of the compound in which m is 3 is more than 0 ppm and 650 ppm or less, or, based on the mass of the resin composition, the following general formula (3 -1) or (3-2) The total amount of compounds in which m is 4 is more than 0 ppm and less than 350 ppm. {In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer} [化 6] {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} [Chem. 7] {Where m is an integer greater than 1} [化 8] {Where n is an integer of 2 or more}. A resin composition comprising the following components: a polyimide precursor comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2); 3-1) or (3-2) at least any one compound in which m is an integer of 3 or more; and any compound represented by the following general formula (4); and the solid component in the resin composition described above Based on the mass, the total amount of compounds in which m is an integer of 3 or more in the following general formula (3-1) or (3-2) is more than 0 ppm and 7,500 ppm or less. Based on the mass of the solid component, the compound of m in the following general formula (3-1) or (3-2) is an integer of 3 or more and the compound of n in the following general formula (4) is an integer of 3 or more The total amount is more than 0 ppm and less than 8,600 ppm. {In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer} [化 10] {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} [Chem. 11] {Where m is an integer of 1 or more} [化 12] {Where n is an integer of 2 or more}. A resin composition comprising the following components: a polyimide precursor comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2); 3-1) or (3-2) at least one compound in which m is 3 or 4; and any compound represented by the following general formula (4); and based on the mass of the solid component in the resin composition As a reference, the total amount of compounds in which m is 3 in the following general formula (3-1) or (3-2) is more than 0 ppm and 4,500 ppm or less, or based on the solid content of the resin composition. Based on mass, the total amount of compounds in which m is 4 in the following general formula (3-1) or (3-2) is more than 0 ppm and less than 2,500 ppm, [Chem. 13] {In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer} [化 14] {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} [Chem. 15] {Where m is an integer of 1 or more} [化 16] . The resin composition according to any one of 2 and 4, wherein m is an integer of 3 to 5 in the compound represented by the general formula (3-1) or (3-2). The resin composition according to any one of 2 and 4, wherein n is an integer of 3 to 8 in the compound represented by the general formula (4). The resin composition according to any one of claims 1 to 7, wherein the polyimide resin film obtained by curing the polyimide precursor is used for a flexible substrate. The resin composition according to any one of claims 1 to 7, wherein the polyimide resin film obtained by curing the polyimide precursor is used for a flexible display. A resin composition comprising the following components: a polyimide precursor comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2); 3-1) or (3-2) at least any one compound in which m is an integer of 3 or more; and any compound represented by the following general formula (4); and the above resin composition includes the following by It is produced by a method of steps: containing at least any one of a silicon-containing compound represented by the following general formula (5), and m in the following general formula (3-1) or (3-2): an integer of 3 or more And a raw material composition of a compound represented by any of the following general formula (4) is subjected to a polycondensation reaction with tetracarboxylic dianhydride and diamine to provide a polyfluorene imine precursor; represented by the following general formula (3-1), The total mass of the silicon-containing compound represented by (3-2), (4), and (5) is based on the following general formula (3-1) or (3-2) m The total amount of the compound having an integer of 3 or more is more than 0 ppm and 46,000 ppm or less, or the silicon-containing compound of the general formulae (3-1), (3-2), (4), and (5) Based on total mass The total amount of a compound in which m is an integer of 3 or more in the following general formula (3-1) or (3-2) and a compound in which n is an integer of 3 or more in the following general formula (4) More than 0 ppm and less than 47,000 ppm, [Chem. 17] {In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer} [化 18] {In the formula, P ₃ and P ₄ are each independently a monovalent aliphatic hydrocarbon having 1 to 5 carbon atoms, or a monovalent aromatic group having 6 to 10 carbon atoms, and q is an integer of 1 to 200} [Chem. 19] {Where m is an integer of 1 or more} [化 20] {Where n is an integer greater than 2} [化 21] {Wherein R _{1 is} each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one of them is a carbon number A monovalent aliphatic hydrocarbon group of 1 to 5, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms, R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one is an organic group having an unsaturated aliphatic hydrocarbon group, and L ₁ and L ₂ are each independently an amine group, an acid anhydride group, an isocyanate group, a carboxyl group, Ester group, sulfonyl halide group, hydroxyl group, epoxy group, or mercapto group, i and j are each independently an integer of 1 to 200, k is an integer of 0 to 200, and 0.05 ≦ j / (i + j + k) ≦ 0.50}. The resin composition according to claim 10, wherein in the compound represented by the general formula (3-1) or (3-2), m is an integer of 3 to 5. The resin composition according to claim 10, wherein in the compound represented by the general formula (4), n is an integer of 3 to 8. A resin composition comprising the following components: a polyimide precursor comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2); 3-1) or (3-2) at least any one compound in which m is 3 or 4; and any compound represented by the following general formula (4); and the above resin composition includes the following steps by the following It is produced by a method of: containing at least any one of the silicon-containing compound represented by the following general formula (5), m at 3 or 4 in the following general formula (3-1) or (3-2), and A raw material composition of a compound represented by any of the following general formula (4) is subjected to a polycondensation reaction with tetracarboxylic dianhydride and diamine to provide a polyfluorene imide precursor; the following general formulae (3-1), (3 -2), (4) and (5) The total mass of the silicon-containing compound is based on the compound in which m is 3 in the following general formula (3-1) or (3-2) contained in the above raw material composition The total amount is more than 0 ppm and 25,000 ppm or less, or based on the total mass of the silicon-containing compound of the following general formulae (3-1), (3-2), (4), and (5). The following general formula (3-1) or (3-2) contained in the composition m is the total amount of the compound of 4 of more than 0 ppm and 15,000 ppm or less, [Chem. 22] {In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer} [化 23] {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} [Chem. 24] {Where m is an integer of 1 or more} [化 25] {Where n is an integer greater than 2} [化 26] {Wherein R _{1 is} each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one of them is a carbon number A monovalent aliphatic hydrocarbon group of 1 to 5, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms, R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one is an organic group having an unsaturated aliphatic hydrocarbon group, and L ₁ and L ₂ are each independently an amine group, an acid anhydride group, an isocyanate group, a carboxyl group, Ester group, sulfonyl halide group, hydroxyl group, epoxy group, or mercapto group, i and j are each independently an integer of 1 to 200, k is an integer of 0 to 200, and 0.05 ≦ j / (i + j + k) ≦ 0.50}. The resin composition according to any one of claims 10 to 13, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (5) are each independently selected from the group consisting of an amine group, an acid anhydride group, and an epoxy group. Group. The resin composition according to any one of claims 10 to 14, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (5) are amine groups. The resin composition according to any one of claims 10 to 15, wherein the compound represented by the general formula (3-1) or (3-2) is a compound represented by the general formula (3-1). The resin composition according to any one of claims 10 to 16, wherein the tetracarboxylic dianhydride is selected from the group consisting of pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, At least one of 4,4'-oxydiphthalic dianhydride, cyclohexanetetracarboxylic dianhydride, and cyclobutanetetracarboxylic dianhydride. The resin composition according to any one of claims 10 to 17, wherein the diamine is selected from the group consisting of 4,4'-diaminodiphenylphosphonium, m-toluidine, p-phenylenediamine, 2,2'- At least one of the group consisting of bis (trifluoromethyl) benzidine and 2,2'-bis [4- (4-aminophenoxy) phenyl] propane. A method for producing a resin composition, comprising the steps of: containing a silicon-containing compound represented by the following general formula (5), and m is 3 or more in the following general formula (3-1) or (3-2) A raw material composition of at least any one of the integers and any of the compounds represented by the following general formula (4) is subjected to a polycondensation reaction with tetracarboxylic dianhydride and diamine to provide a polyimide precursor; and Based on the total mass of the silicon-containing compound represented by the general formulae (3-1), (3-2), (4), and (5), the following general formula (3-1) contained in the raw material composition is based on Or the total amount of the compound in which m is an integer of 3 or more in (3-2) is more than 0 ppm and 46,000 ppm or less, or the general formulae (3-1), (3-2), (4) and (5) The total mass of the silicon-containing compound is based on the following general formula (3-1) or (3-2) in the above-mentioned raw material composition. (4) The total amount of compounds in which n is an integer of 3 or more is more than 0 ppm and 47,000 ppm or less, [Chem. 27] {Where m is an integer greater than or equal to 1} [化 28] {Where n is an integer greater than or equal to 2} [化 29] {Wherein R _{1 is} each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one of them is a carbon number A monovalent aliphatic hydrocarbon group of 1 to 5, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms, R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one is an organic group having an unsaturated aliphatic hydrocarbon group, and L ₁ and L ₂ are each independently an amine group, an acid anhydride group, an isocyanate group, a carboxyl group, Ester group, sulfonyl halide group, hydroxyl group, epoxy group, or mercapto group, i and j are each independently an integer of 1 to 200, k is an integer of 0 to 200, and 0.05 ≦ j / (i + j + k) ≦ 0.50}. The method according to claim 19, wherein in the compound represented by the general formula (3-1) or (3-2), m is an integer of 3 to 5. The method according to claim 19, wherein in the compound represented by the general formula (4), n is an integer of 3 to 8. A method for producing a resin composition, comprising the steps of: containing: a silicon-containing compound represented by the following general formula (5); m in the following general formula (3-1) or (3-2) is 3 or A raw material composition of at least any one of 4 and any of the compounds represented by the following general formula (4) is subjected to a polycondensation reaction with tetracarboxylic dianhydride and diamine to provide a polyfluorene imide precursor; and Based on the total mass of the silicon-containing compound of the formulae (3-1), (3-2), (4), and (5), the following general formula (3-1) or (3) contained in the raw material composition is based on -2) The total amount of compounds in which m is 3 is more than 0 ppm and less than 25,000 ppm, or silicon-containing compounds having the following general formulae (3-1), (3-2), (4), and (5) Based on the total mass of the compound, the total amount of the compound in which m is 4 in the following general formula (3-1) or (3-2) contained in the above raw material composition is more than 0 ppm and 15,000 ppm or less, [ Hua 30] {Where m is an integer of 1 or more} [化 31] {Where n is an integer greater than or equal to 2} [化 32] {Wherein R _{1 is} each independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one of them is a carbon number A monovalent aliphatic hydrocarbon group of 1 to 5, R ₄ and R ₅ are each independently a monovalent organic group of 1 to 10 carbon atoms, and at least one is a monovalent aromatic group of 6 to 10 carbon atoms, R ₆ and R ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one is an organic group having an unsaturated aliphatic hydrocarbon group, and L ₁ and L ₂ are each independently an amine group, an acid anhydride group, an isocyanate group, a carboxyl group, Ester group, sulfonyl halide group, hydroxyl group, epoxy group, or mercapto group, i and j are each independently an integer of 1 to 200, k is an integer of 0 to 200, and 0.05 ≦ j / (i + j + k) ≦ 0.50}. The method according to any one of claims 19 to 22, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (5) are independently selected from the group consisting of an amine group, an acid anhydride group, and an epoxy group . The method according to any one of claims 19 to 23, wherein L ₁ and L ₂ of the silicon-containing compound represented by the general formula (5) are amine groups. The method according to any one of claims 19 to 24, wherein the compound represented by the general formula (3-1) or (3-2) is a compound represented by the general formula (3-1). The method according to any one of claims 19 to 25, wherein the tetracarboxylic dianhydride is selected from the group consisting of pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, At least one of the group consisting of 4'-oxydiphthalic dianhydride, cyclohexanetetracarboxylic dianhydride, and cyclobutanetetracarboxylic dianhydride. The method according to any one of claims 19 to 26, wherein the diamine is selected from the group consisting of 4,4'-diaminodiphenylphosphonium, m-toluidine, p-phenylenediamine, 2,2'-bis ( At least one member of the group consisting of trifluoromethyl) benzidine and 2,2'-bis [4- (4-aminophenoxy) phenyl] propane. A method for manufacturing a polyimide film includes the following steps: A coating step of coating the resin composition according to any one of claims 1 to 18 on the surface of the support; A film forming step of heating the resin composition to form a polyimide resin film; and In a peeling step, the polyimide resin film is peeled from the support. The method for producing a polyimide film according to claim 28, further comprising an irradiation step of irradiating the resin composition with a laser from the support side before the peeling step. A method for manufacturing a display, comprising the following steps: a coating step of coating the resin composition according to any one of claims 1 to 18 on a 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 In the peeling step, the polyimide resin film on which the above-mentioned element is formed is peeled from the support. A method for manufacturing a laminated body includes the following steps: A coating step of coating the resin composition according to any one of claims 1 to 18 on the surface of the support; A film forming step of heating the resin composition to form a polyimide resin film; and An element forming step for forming an element on the polyimide resin film. The method for producing a laminated body according to claim 31, further comprising the step of peeling the polyimide resin film on which the above-mentioned element is formed from the support. A method for manufacturing a flexible device includes the steps of: manufacturing a laminated body by a method such as claim 31 or 32. A polyimide film is a cured product of the resin composition according to any one of claims 1 to 18.